Science.gov

Sample records for fluorescent aromatic compounds

  1. Fluorescence spectroscopy of polynuclear aromatic compounds in environmental monitoring.

    PubMed

    Kumke, M U; Löhmannsröben, H G; Roch, T

    1995-06-01

    The occurrence of polynuclear aromatic compounds (PAC) in the environment and experimental techniques suitable for the detection of PAC in environmental compartments are briefly reviewed. The specific requirements for on-site andin situ environmental analysis are outlined. Particular emphasis is given to fluorescence spectroscopic techniques for the investigation of humic acid- and soil-containing samples. Some examples of studies in the literature on Shpol'skii and jet spectroscopy and on laser-induced fluorescence (OF) measurements of PAC and mineral oils are highlighted. Contaminants in the environment are usually encountered as multicomponent mixtures in very complex matrices. Total fluorescence analysis in combination with the chemometrical technique of rank annihilation factor analysis (RAFA) was employed for the evaluation of a six-component PAC mixture in toluene. It was shown that even in the presence of strong spectral overlap the qualitative identification of all compounds and the reliable quantification of five substances was possible. Results are presented from our stationary and time-resolved fluorescence investigations of the interactions between pyrene and humic acid in water. The Stern-Volmer analysis showed a significant effect of pH on the static quenching efficiency which can be explained by the pH-dependent macromolecular structure of humic acids. Preliminary results from studies of the deactivation of triplet PAC and quenching of delayed fluorescence by humic acid are reported. LIF measurements of mineral oils directly from soil surfaces and of a model oil in a soil column were performed with a fiber-optic coupled multichannel spectrometer. The fluorescence intensity/ concentration relationships were established for a crude and a fuel oil; the corresponding lower limits of detection (LOD) were determined to be 0.025 and 0.125% m/m (mass/mass percentages). These detection limits are compared with realistic oil contaminations of soils. In a soil

  2. Interaction of aromatic compounds with Photobacterium leiognathi luciferase: fluorescence anisotropy study.

    PubMed

    Kudryasheva, N S; Nemtseva, E V; Visser, A J W G; Van Hoek, A

    2003-01-01

    The time-resolved and steady-state fluorescence techniques were employed to elucidate possible interactions of four aromatic compounds (anthracene, POPOP, MSB and 1,4-naphthalendiol) with bacterial luciferase. Fluorescence spectra and fluorescence anisotropy decays of these compounds were studied in ethanol, water-ethanol solutions and in the presence of bacterial luciferase. Shifts of fluorescent spectra and differences in rotational correlation times are interpreted in terms of weak (hydrophobic) interactions of the molecules with the enzyme. These interactions suggest the feasibility of intermolecular energy transfer by an exchange resonance mechanism with a collision-interaction radius as a way of excitation of these compounds in the reaction catalysed by bacterial luciferase.

  3. Two-stage bile preparation with acetone for recovery of fluorescent aromatic compounds (FACs).

    PubMed

    Karami, Ali; Syed, Mohd A; Christianus, Annie; Willett, Kristine L; Mazzeo, Jeffrey R; Courtenay, Simon C

    2012-07-15

    In this study we sought to optimize recovery of fluorescent aromatic compounds (FACs) from the bile of African catfish (Clarias gariepinus) injected with 10mg/kg benzo[a]pyrene (BaP). Fractions of pooled bile were hydrolyzed, combined with ten volumes of methanol, ethanol, acetonitrile, or acetone, centrifuged and supernatants were analyzed by high-performance liquid chromatography with fluorescent detection (HPLC/FL). As well, to test whether FACs were being lost in solids from the centrifugation, pellets were resuspended, hydrolyzed and mixed with six volumes of the organic solvent that produced best FAC recovery from the supernatant, and subjected to HPLC/FL. Highest FAC concentrations were obtained with 2000μl and 1250μl acetone for supernatants and resuspended pellets respectively. FACs concentrations were negatively correlated with biliary protein content but were unaffected by addition of bovine serum albumin (BSA) followed by no incubation indicating that the presence of proteins in the biliary mixture does not simply interfere with detection of FACs. In another experiment, efficiency of acetone addition was compared to two different liquid-liquid extractions (L-LEs). Acetone additions provided significantly higher biliary FACs than the L-LE methods. The new two-stage bile preparation with acetone is an efficient, inexpensive and easily performed method.

  4. Development of a flow-injection fluorescence method for estimation of total polycyclic aromatic compounds in asphalt fumes.

    PubMed

    Neumeister, Charles E; Olsen, Larry D; Dollberg, Donald D

    2003-01-01

    Traditionally, measurements of specific polycyclic aromatic compounds (PACs) have been attempted as an estimate of asphalt fume exposure. However, asphalt fumes contain numerous alkyl substituted PACs, including PACs containing heteroatoms of nitrogen, oxygen, and sulfur. Many of these compounds coelute precluding the resolution of the individual compounds resulting in ambiguous data. Moreover, many researchers believe that some observed health hazards are associated with PACs overall and not just a few select PACs. Therefore, NIOSH method 5800 was developed to evaluate total PACs as a chemical class in asphalt fumes. Asphalt fume samples were collected on a poly(tetrafluoroethylene) filter backed by an XAD-2 sorbent tube. The samples were extracted with hexane; then, a cyano-solid-phase-extraction column was used to remove the polar compounds while the aliphatic and aromatic compounds were eluted with hexane. An equal volume of dimethyl sulfoxide (DMSO) was added to the hexane extract, causing the aromatic compounds to partition into the DMSO, thus isolating the PACs. The PACs were then analyzed for fluorescence using a flow-injection method with two fluorescence detectors. Wavelength settings for the first detector (254-nm excitation, 370-nm emission) emphasized the 2- to 4-ring PACs that may cause eye and respiratory tract irritation. Wavelength settings of the second detector (254-nm excitation, 400-nm emission) emphasized the 4- and higher-ring PACs that are often mutagenic and possibly carcinogenic.

  5. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, Amy A.

    1996-01-01

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

  6. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, A.A.

    1996-02-06

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

  7. Fluorescent imprinted polymers for detection of explosive nitro-aromatic compounds

    NASA Astrophysics Data System (ADS)

    Stringer, R. Cody; Gangopadhyay, Shubhra; Grant, Sheila A.

    2009-05-01

    Molecular recognition is an important aspect of any biosensor system. Due to increased stability in a variety of environmental conditions, molecular imprinted polymer (MIP) technology is an attractive alternative to biological-based recognition. This is particularly true in the case of improvised explosive device detection, in which the sensor must be capable of detecting trace amounts of airborne nitroaromatic compounds. In an effort to create a sensor for detection of explosive devices via nitroaromatic vapor, MIPs have been deployed as a molecular recognition tool in a fluorescence-based optical biosensor. These devices are easily scalable to a very small size, and are also robust and durable. To achieve such a sensor scheme, polymer microparticles synthesized using methacrylic acid monomer and imprinted with a 2,4-dinitrotoluene (DNT) template were fabricated. These microparticles were then conjugated with green CdSe/ZnS quantum dots, creating fluorescent MIP microparticles. When exposed to the DNT template, rebinding occurred between the DNT and the imprinted sites of the MIP microparticles. This brings the nitroaromatic DNT into close proximity to the quantum dots, allowing the DNT to accept electrons from the fluorescent species, thereby quenching the fluorescence of the quantum dot. Results indicate that this novel method for synthesizing fluorescent MIPs and their integration into an optical biosensor produced observable fluorescence quenching upon exposure to DNT.

  8. Significance of Cytochrome P450 System Responses and Levels of Bile Fluorescent Aromatic Compounds in Marine Wildlife Following Oil Spills

    SciTech Connect

    Lee, Richard F.; Anderson, Jack W.

    2005-07-01

    The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 in marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to

  9. Significance of cytochrome P450 system responses and levels of bile fluorescent aromatic compounds in marine wildlife following oil spills.

    PubMed

    Lee, Richard F; Anderson, Jack W

    2005-07-01

    The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 in marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to

  10. Device for aqueous detection of nitro-aromatic compounds

    DOEpatents

    Reagen, W.K.; Schulz, A.L.; Ingram, J.C.; Lancaster, G.D.; Grey, A.E.

    1994-04-26

    This invention relates to a compact and portable detection apparatus for nitro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound. 4 figures.

  11. Device for aqueous detection of nitro-aromatic compounds

    DOEpatents

    Reagen, William K.; Schulz, Amber L.; Ingram, Jani C.; Lancaster, Gregory D.; Grey, Alan E.

    1994-01-01

    This invention relates to a compact and portable detection apparatus for ro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound.

  12. Bacterial Degradation of Aromatic Compounds

    PubMed Central

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

    2009-01-01

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

  13. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

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

  14. Alkylation of organic aromatic compounds

    DOEpatents

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

    1994-01-01

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

  15. Alkylation of organic aromatic compounds

    DOEpatents

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

    1993-09-07

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

  16. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

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

  17. Alkylation of organic aromatic compounds

    DOEpatents

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

    1993-01-01

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

  18. Alkylation of organic aromatic compounds

    DOEpatents

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

    1994-06-14

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

  19. Time-resolved detection of aromatic compounds on planetary surfaces by ultraviolet laser induced fluorescence and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Eshelman, E.; Daly, M. G.; Slater, G.; Cloutis, E.

    2015-12-01

    Raman spectroscopic instruments are highly capable in the search for organics on Mars due to the potential to perform rapid and nondestructive measurements on unprepared samples. Upcoming and future Raman instruments are likely to also incorporate laser-induced fluorescence (LIF) capabilities, which can be added for modest cost and complexity. We demonstrate that it is possible to obtain sub-ns fluorescence lifetime measurements of Mars-relevant organics and minerals if a fast time-gating capability is used with an intensified detector and a short ultraviolet laser pulse. This serves a primary purpose of discriminating mineral from short-lived (less than 10 ns) organic fluorescence, considered a potential biosignature. Additionally, lifetime measurements may assist in determining if more than one fluorescing species is present and provide information concerning the molecular structure as well as the local environment. Fast time-gating is also useful at longer visible or near-IR wavelengths, as this approach increases the sensitivity of the instrument to organic material by removing the majority of the fluorescence background from the Raman signal and reducing the effect of ambient light.

  20. Alkylation of organic aromatic compounds

    DOEpatents

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

    1993-01-05

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

  1. Alkylation of organic aromatic compounds

    DOEpatents

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

    1993-01-01

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

  2. Heterogeneous photocatalytic reactions of sulfur aromatic compounds.

    PubMed

    Samokhvalov, Alexander

    2011-11-18

    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.

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

    PubMed

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

    2015-09-21

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

  4. Label-free fluorescence detection of aromatic compounds in chip electrophoresis applying two-photon excitation and time-correlated single-photon counting.

    PubMed

    Beyreiss, Reinhild; Geißler, David; Ohla, Stefan; Nagl, Stefan; Posch, Tjorben Nils; Belder, Detlev

    2013-09-03

    In this study, we introduce time-resolved fluorescence detection with two-photon excitation at 532 nm for label-free analyte determination in microchip electrophoresis. In the developed method, information about analyte fluorescence lifetimes is collected by time-correlated single-photon counting, improving reliable peak assignment in electrophoretic separations. The determined limits of detection for serotonin, propranolol, and tryptophan were 51, 37, and 280 nM, respectively, using microfluidic chips made of fused silica. Applying two-photon excitation microchip separations and label-free detection could also be performed in borosilicate glass chips demonstrating the potential for label-free fluorescence detection in non-UV-transparent devices. Microchip electrophoresis with two-photon excited fluorescence detection was then applied for analyses of active compounds in plant extracts. Harmala alkaloids present in methanolic plant extracts from Peganum harmala could be separated within seconds and detected with on-the-fly determination of fluorescence lifetimes.

  5. Biodegradation of Aromatic Compounds by Escherichia coli

    PubMed Central

    Díaz, Eduardo; Ferrández, Abel; Prieto, María A.; García, José L.

    2001-01-01

    Although Escherichia coli has long been recognized as the best-understood living organism, little was known about its abilities to use aromatic compounds as sole carbon and energy sources. This review gives an extensive overview of the current knowledge of the catabolism of aromatic compounds by E. coli. After giving a general overview of the aromatic compounds that E. coli strains encounter and mineralize in the different habitats that they colonize, we provide an up-to-date status report on the genes and proteins involved in the catabolism of such compounds, namely, several aromatic acids (phenylacetic acid, 3- and 4-hydroxyphenylacetic acid, phenylpropionic acid, 3-hydroxyphenylpropionic acid, and 3-hydroxycinnamic acid) and amines (phenylethylamine, tyramine, and dopamine). Other enzymatic activities acting on aromatic compounds in E. coli are also reviewed and evaluated. The review also reflects the present impact of genomic research and how the analysis of the whole E. coli genome reveals novel aromatic catabolic functions. Moreover, evolutionary considerations derived from sequence comparisons between the aromatic catabolic clusters of E. coli and homologous clusters from an increasing number of bacteria are also discussed. The recent progress in the understanding of the fundamentals that govern the degradation of aromatic compounds in E. coli makes this bacterium a very useful model system to decipher biochemical, genetic, evolutionary, and ecological aspects of the catabolism of such compounds. In the last part of the review, we discuss strategies and concepts to metabolically engineer E. coli to suit specific needs for biodegradation and biotransformation of aromatics and we provide several examples based on selected studies. Finally, conclusions derived from this review may serve as a lead for future research and applications. PMID:11729263

  6. Biodegradation of aromatic compounds by Escherichia coli.

    PubMed

    Díaz, E; Ferrández, A; Prieto, M A; García, J L

    2001-12-01

    Although Escherichia coli has long been recognized as the best-understood living organism, little was known about its abilities to use aromatic compounds as sole carbon and energy sources. This review gives an extensive overview of the current knowledge of the catabolism of aromatic compounds by E. coli. After giving a general overview of the aromatic compounds that E. coli strains encounter and mineralize in the different habitats that they colonize, we provide an up-to-date status report on the genes and proteins involved in the catabolism of such compounds, namely, several aromatic acids (phenylacetic acid, 3- and 4-hydroxyphenylacetic acid, phenylpropionic acid, 3-hydroxyphenylpropionic acid, and 3-hydroxycinnamic acid) and amines (phenylethylamine, tyramine, and dopamine). Other enzymatic activities acting on aromatic compounds in E. coli are also reviewed and evaluated. The review also reflects the present impact of genomic research and how the analysis of the whole E. coli genome reveals novel aromatic catabolic functions. Moreover, evolutionary considerations derived from sequence comparisons between the aromatic catabolic clusters of E. coli and homologous clusters from an increasing number of bacteria are also discussed. The recent progress in the understanding of the fundamentals that govern the degradation of aromatic compounds in E. coli makes this bacterium a very useful model system to decipher biochemical, genetic, evolutionary, and ecological aspects of the catabolism of such compounds. In the last part of the review, we discuss strategies and concepts to metabolically engineer E. coli to suit specific needs for biodegradation and biotransformation of aromatics and we provide several examples based on selected studies. Finally, conclusions derived from this review may serve as a lead for future research and applications.

  7. Water-soluble constituents of caraway: aromatic compound, aromatic compound glucoside and glucides.

    PubMed

    Matsumura, Tetsuko; Ishikawa, Toru; Kitajima, Junichi

    2002-10-01

    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.

  8. Nucleophilic fluorination of aromatic compounds

    SciTech Connect

    Satyamurthy, Nagichettiar; Barrio, Jorge R

    2014-03-18

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

  9. Production of aromatic compounds in bacteria.

    PubMed

    Gosset, Guillermo

    2009-12-01

    The aromatic class of chemicals includes a large number of industrially important products. In bacteria and plants, the shikimate pathway and related biosynthetic pathways are a source of aromatic compounds having commercial value. Bacterial strains for the production of aromatic compounds from simple carbon sources as raw material have been generated by applying metabolic engineering and random/combinatorial strategies that modify central metabolism, aromatic biosynthetic pathways, transport, and regulatory functions. These strategies are complemented with heterologous gene expression and protein engineering. Engineered Escherichia coli and Pseudomonas putida strains are enabling the development of sustainable processes for the manufacture of 2-phenylethanol, p-hydroxycinnamic acid, p-hydroxystyrene, p-hydroxybenzoate, anthranilate, and cyclohexadiene-transdiols, among other useful chemicals.

  10. Reaction of disubstituted aromatic compounds with styrene

    SciTech Connect

    Grushin, A.I.; Grigor'ev, V.V.; Prokof'ev, K.V.; Kozlova, N.M.

    1988-03-20

    Hydrocarbons of the 1,1-diphenylethane type were obtained by the reaction of styrene with various disubstituted derivatives of benzene in the presence of titanium tetrachloride. It was found that the yield of the desired compound depends on the strength of the electron-donating substituents and on steric factors in the aromatic ring.

  11. Overview of Polycyclic Aromatic Compounds (PAC)

    PubMed Central

    Achten, Christine; Andersson, Jan T.

    2015-01-01

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

  12. Overview of Polycyclic Aromatic Compounds (PAC).

    PubMed

    Achten, Christine; Andersson, Jan T

    2015-03-15

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

  13. Fluorescent aromatic sensors and their methods of use

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor); Tyson, Daniel S. (Inventor); Ilan, Ulvi F. (Inventor)

    2012-01-01

    Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

  14. Chemotaxis of Azospirillum species to aromatic compounds

    SciTech Connect

    Lopez-de-Victoria, G.; Lovell, C.R. )

    1993-09-01

    Azospirillum sspeciesare free-living nitrogen fixing bacteria commonly found in soils and in association with plant roots, including important agricultural crops. Rhizosphere colonization my Azospirillum species has been shown to stimulate growth of a variety of plant species. Chemotaxis is one of the properties which may contribute to survival, rhizosphere colonization and the initiation of mutualistic interactions by Azospirillum species. This study evaluates the chemotactic responses of three Azospirillum stains to a variety of aromatic compounds:benzoate, catechol, 4-HB, and PCA. Results indicate that the same aromatic substance can elicit different chemotactic responses from different Azospirillum species, and that Azospirillum can detect aromatic substrates at concentrations similar to those they encounter naturally. 36 refs., 1 fig., 6 tabs.

  15. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  16. 40 CFR 721.875 - Aromatic nitro compound.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aromatic nitro compound. 721.875... Substances § 721.875 Aromatic nitro compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic nitro compound (PMN P-86-335) is subject to reporting...

  17. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  18. 40 CFR 721.875 - Aromatic nitro compound.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aromatic nitro compound. 721.875... Substances § 721.875 Aromatic nitro compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic nitro compound (PMN P-86-335) is subject to reporting...

  19. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  20. 40 CFR 721.875 - Aromatic nitro compound.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aromatic nitro compound. 721.875... Substances § 721.875 Aromatic nitro compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic nitro compound (PMN P-86-335) is subject to reporting...

  1. 40 CFR 721.875 - Aromatic nitro compound.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aromatic nitro compound. 721.875... Substances § 721.875 Aromatic nitro compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic nitro compound (PMN P-86-335) is subject to reporting...

  2. 40 CFR 721.750 - Aromatic amine compound.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aromatic amine compound. 721.750... Substances § 721.750 Aromatic amine compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aromatic amine compound (PMN P-86-334) is subject to reporting...

  3. «Оn-off» fluorescent sensors for aromatic analytes based on zinc(II) bis(dipyrromethenate)s

    NASA Astrophysics Data System (ADS)

    Ksenofontov, A. A.; Guseva, G. B.; Antina, E. V.; Nuraneeva, E. N.

    2017-02-01

    This paper presents the results of spectral-luminescence research of binuclear zinc(II) helicates with tetra-, octa-, and decamethylsubstituted 3,3‧-bis(dipyrromethene)s ([Zn2L2]) in binary mixtures of cyclohexane with aromatic hydrocarbons (benzene, toluene, and m-xylene). Structure effects of zinc(II) helicates, and aromaticity criteria of analytes (HOMA, NICS, δ) on the fluorescence quenching efficiency of [Zn2L2] in the presence of aromatic compounds was considered. It was found that decamethylsubstituted 3,3‧-bis(dipyrromethenate)s compared to tetra-, and octamethylsubstituted-analogs shows the highest fluorescence sensitivity to the presence of aromatic compounds. High specificity of spectral-luminescence characteristics changing in the presence of particular aromatic analytes provides the possibility of using [Zn2L2] helicates as new fluorescent sensors of aromatic compounds trace amount (120 ppb to 56 ppm) in organic media.

  4. Aromatic molecule-like fluorescence from Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Galande, Charudatta; Mohite, Aditya; Naumov, Anton; Gao, Wei; Ci, Lijie; Ajayan, Anakha; Gao, Hui; Srivastava, Anchal; Weisman, R. Bruce; Ajayan, Pulickel M.

    2011-03-01

    Graphene Oxide (GO) is a functionalized derivative of graphene, obtained by chemical exfoliation and chemical oxidation of graphite. Recent NMR studies on GO have revealed presence of hydroxyl, epoxy, carbonyl, carboxyl and lactols. Although there have been several studies on electronic and optical properties of GO, the role of functional groups in determining the electronic density of states is still unclear. Here we report pH dependent fluorescence and excitation spectra of GO, with spectroscopic signatures indicating the presence of molecule-like fluorophores in GO. In acidic medium, a single, broad emission peak is observed at ca. 660nm. In contrast, relatively sharp emission at lower wavelengths (480nm-515nm) appears in a short pH range between 7.6 and 8.0, while the broad peak is completely quenched in basic conditions. The fluorescence and excitation spectra have pH-dependence strikingly similar to several aromatic carboxylic acids. The observed spectral features are proposed to arise from quasi-molecular fluorophores, similar to polycyclic aromatic compounds that are formed by the electronic coupling of carboxylic acid groups with nearby carbon atoms of the graphene.

  5. Metabolism of aromatic compounds by Caulobacter crescentus

    SciTech Connect

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

    1987-05-01

    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.

  6. Bioremediation technologies for polycyclic aromatic hydrocarbon compounds

    SciTech Connect

    Alleman, B.C.; Leeson, A.

    1999-11-01

    Polycyclic aromatic hydrocarbon compounds (PAHs) are common and challenging contaminants that affect soil and sediments. Methods for treating PAHs have undergone change and refinement in the recent past, and this volume presents the latest trends in PAH remediation theory and practice. The papers in this volume cover topics ranging from the remediation of manufactured gas plant (MGP) sites to the remediation of sediments. The papers present lab and field studies, characterization studies, comparison studies, and descriptions of technologies ranging from composting to thermally enhanced bioremediation to fungal technologies and other innovative approaches.

  7. Two-photon excited fluorescence detection at 420 nm for label-free detection of small aromatics and proteins in microchip electrophoresis.

    PubMed

    Schulze, Philipp; Schüttpelz, Mark; Sauer, Markus; Belder, Detlev

    2007-12-01

    Two photon excited (TPE) fluorescence detection was applied to native fluorescence detection of aromatics in microchip electrophoresis (MCE). This technique was evaluated as an alternative to common one photon excitation in the deep UV spectral range. TPE enables fluorescence detection of unlabeled aromatic compounds, even in non-deep UV-transparent microfluidic chips. In this study, we demonstrate the proof of concept of native TPE fluorescence detection of small aromatics in commercial microfluidic glass chips. Label-free TPE fluorescence detection of native proteins and small aromatics in MCE was achieved within the micromolar concentration range, utilising 420 nm excitation light.

  8. Comparison of high-performance liquid chromatography/fluorescence screening and gas chromatography/mass spectrometry analysis for aromatic compounds in sediments sampled after the Exxon Valdez oil spill

    SciTech Connect

    Krahn, M.M.; Ylitalo, G.M.; Buzitis, J.; Chan, S.L.; Varanasi, U. ); Wade, T.L.; Jackson, T.J.; Brooks, J.M. ); Wolfe, D.A.; Manen, C.A. )

    1993-04-01

    After the grounding of the Exxon Valdez, sediment samples were collected to determine the degree and distribution of the oiling. Sixty sediments from 10 sites in Prince William Sound, AK, were analyzed for Prudhoe Bay crude oil (PBCO) using a rapid HPLC screening method that measured fluorescence at wavelength pairs specific for two- and three-ring petroleum-related aromatic compounds (ACs). Concentrations of individual ACs in the sediments were also determined by GC/MS to compare the results of the two methods. Concentrations of ACs measured by HPLC screening were highly correlated with the sums of ACs determined by GC/MS, thus validating the screening method as an effective tool for estimating concentrations of petroleum-related ACs in sediments. Moreover, differences in HPLC chromatographic patterns among sediments suggested different sources of contamination, e.g., crude oil or diesel fuel. Finally, GC/MS analyses confirmed that PBCO was a primary source of contamination in many sediments. 21 refs., 5 figs., 2 tabs.

  9. Interstellar Polycyclic Aromatic Compounds and Astrophysics

    NASA Technical Reports Server (NTRS)

    Hudgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role polycyclic aromatic compounds (PAC) in the interstellar medium (ISM). Twenty years ago, the notion of an abundant population of large, carbon rich molecules in the ISM was considered preposterous. Today, the unmistakable spectroscopic signatures of PAC - shockingly large molecules by previous interstellar chemistry standards - are recognized throughout the Universe. In this paper, we will examine the interstellar PAC model and its importance to astrophysics, including: (1) the evidence which led to inception of the model; (2) the ensuing laboratory and theoretical studies of the fundamental spectroscopic properties of PAC by which the model has been refined and extended; and (3) a few examples of how the model is being exploited to derive insight into the nature of the interstellar PAC population.

  10. Prediction of seawater solubility of aromatic compounds

    SciTech Connect

    Hashimoto, Y.; Tokura, K.; Kishi, H.; Strachan, W.M.J.

    1984-01-01

    The salting-out effect by seawater constituents on the water solubilities of 11 aromatic compounds, anthracene, pyrene, phenanthrene, biphenyl, naphthalene, p-nitrotoluene, p-toluidine, o-nitrophenol, m-nitrophenol, p-nitrophenol and phenol was investigated. A best fit equation for the salting-out parameters, K, and distilled water solubilities, S/sub 0/, at 20/sup 0/C was found to be K = -0.0298 log S/sub 0/ + 0.114. Seawater solubilities, S, predicted for solutions of ionic strength, I, using the equation log S = (0.0298 I + 1)logS/sub 0/ - 0.114 I were in agreement with observed values within 13% and there were no significant differences between values from the Pacific Ocean seawater and those from 35% NaCl solutions. It was concluded that dissolved organic matter in seawater had an insignificant effect for the test chemicals.

  11. Lanthanide magneto-luminescent and plasmonic (Gd2O3:Eu@AuNR) nanoassembly for the turn-on fluorescence detection of nitro aromatic compound

    NASA Astrophysics Data System (ADS)

    Praveen, G. L.; Lekha, G. M.; Visakh, V. M.; Reshma, L. R.; George, Sony

    2014-08-01

    In this study, we design a nanoassembly-based chemosensor possessing the fluorescence in the visible region which comes into play for analyte detection in aqueous medium. Here, Mercaptopropionic acid-functionalised nanophosphor (Gd2O3:Eu @ MPA) acts as donor, and the Cysteamine functionalised gold nanorod (AuNR @ Cysteamine) acts as the acceptor molecule. The working principle of this nanoassembly is the FRET phenomenon which happens between nanophosphors and gold nanorods through amine-carboxyl attractive interactions (Turn-Off) followed by the Meisenheimer complex formation between -NO2 groups of TNT and primary amines of the Cysteamine functionalised AuNR (Turn-On) which gives corresponding fluorescent signals in the visible regions. The fluorescence turn-on is immediate, and the limit of detection is as low as 11.88 x 10-9 M. The above-mentioned phenomena were substantiated using the UV-Visible, Photoluminescence, and Time-Correlated Single Photon Counting spectroscopic techniques. The size, morphology, particle interactions, charge, and functionalisations were substantiated through TEM, DLS, Zeta potential, and FTIR techniques. The size variations happened to the AuNR in three different stages are evident from the TEM images. (i) when AuNR (Gold nanorod) is present alone, i.e. LnNp and TNT free system, the average size of AuNR was 15.17 nm (ii) When LnNp (Lanthanide Nanophosphor) was added (attached), i.e. AuNR + LnNp involved state, the average size of AuNR was increased to 23.05 nm (iii) When TNT was introduced to AuNR + LnNp system (Analyte attachment and LnNp detachment happening state) i.e. AuNR + LnNp + TNT involved state, the average size of AuNR was decreased to16.3 nm as it was in its pristine form. The same trend was obtained for the DLS measurements.

  12. Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Thomas, J. D.; Witt, A. N.

    2006-01-01

    The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

  13. Aerobic biodegradation of trichloroethylene by microorganisms that degrade aromatic compounds

    SciTech Connect

    Lu, C.J.; Chang, C.Y.; Lee, C.M.

    1995-12-31

    Aerobic biodegradation of trichloroethylene (TCE) at an initial concentration of 80 mg/L with and without the presence of an aromatic compound was conducted with a series of batch reactors. The target aromatic compounds were benzene, toluene, and catechol. The aromatics-acclimated microorganisms were used as the cell source for the batch study. The results indicated that the presence of an aromatic compound was required to initiate the aerobic biodegradation of TCE by the aromatic-utilizing microorganisms. The addition of benzene or toluene initiated the removal of TCE. However, TCE removal was not proportional to the initial concentration of the aromatic compounds. The presence of an aromatic compound at an initial concentration of 5 mg/L resulted in better TCE removal in comparison with that at 1 or 20 mg/L. TCE removal was still significant after the depletion of the aromatic compound, but at a lower rate. The presence of catechol, an intermediate of the biodegradation of an aromatic compound, did not initiate the biodegradation of TCE by the catechol-utilizing microorganisms.

  14. Anaerobic Catabolism of Aromatic Compounds: a Genetic and Genomic View

    PubMed Central

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

    2009-01-01

    Summary: 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. PMID:19258534

  15. Determination of Aromatic Ring Number Using Multi-Channel Deep UV Native Fluorescence

    NASA Technical Reports Server (NTRS)

    Bhartia, R.; McDonald, G. D.; Salas, E.; Conrad, P.

    2004-01-01

    The in situ detection of organic material on an extraterrestrial surface requires both effective means of searching a relatively large surface area or volume for possible organic carbon, and a more specific means of identifying and quantifying compounds in indicated samples. Fluorescence spectroscopy fits the first requirement well, as it can be carried out rapidly, with minimal or no physical contact with the sample, and with sensitivity unmatched by any other organic analytical technique. Aromatic organic compounds with know fluorescence signatures have been identified in several extraterrestrial samples, including carbonaceous chondrites, interplanetary dust particles, and Martian meteorites. The compound distributions vary among these sources, however, with clear differences in relative abundances by number of aromatic rings and by degree of alkylation. This relative abundance information, therefore, can be used to infer the source of organic material detected on a planetary surface.

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

    DOEpatents

    Smith, Robert E.; Dolbeare, Frank A.

    1979-01-01

    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.

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

    DOEpatents

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

    1980-10-21

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

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

    DOEpatents

    Smith, Robert E. [557 Escondido Cir., Livermore, CA 94550; Dolbeare, Frank A. [5178 Diane La., Livermore, CA 94550

    1980-10-21

    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes.

  19. Process for producing high purity aromatic compounds

    SciTech Connect

    Mayes, W.W.

    1980-05-20

    High-purity C7 and/or C8 aromatic hydrocarbons are produced by reforming a C7 or C8 full boiling carbon number naphtha feed fraction or combinations thereof under reforming conditions of sufficient severity to convert essentially all of the nonaromatic portion of the naphtha feed boiling in the C7 to C8 aromatic boiling range to C7 and/or C8 aromatics, and then separating the reformate by fractional distillation into highpurity fractions of C7 and/or C8 aromatic hydrocarbons. Preferably, the C7 and/or C8 full boiling carbon number naphtha feed fraction is reformed in a plurality of reformer reaction stages with increasingly more severe conditions in order to maximize the yield of the C7 and C8 aromatics.

  20. Assessing Uncertainty of Interspecies Correlation Estimation Models for Aromatic Compounds

    EPA Science Inventory

    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 ...

  1. Fluorescent derivatization of aromatic carboxylic acids with horseradish peroxidase in the presence of excess hydrogen peroxide.

    PubMed

    Odo, Junichi; Inoguchi, Masahiko; Aoki, Hiroyuki; Sogawa, Yuto; Nishimura, Masahiro

    2015-01-01

    The fluorescent derivatization of aromatic carboxylic acids by the catalytic activity of horseradish peroxidase (HRP) in the presence of excess H2O2 was investigated. Four monocarboxylic acids, nine dicarboxylic acids, and two tricarboxylic acids, all of which are non- or weakly fluorescent, were effectively converted into fluorescent compounds using this new method. This technique was further developed for the fluorometric determination of trace amounts of terephthalic acid (3c) and lutidinic acid (2b), and linear calibration curves for concentrations between 2.5 and 20.0 nmol of terephthalic acid (3c) and 1.0 and 10.0 nmol of lutidinic acid (2b) were demonstrated. Compound III, an intermediate of HRP, played an essential role in this process. Additionally, lactoperoxidase and manganese peroxidase, peroxidases similar to HRP, showed successful fluorescent derivatization of nicotinic acid (1b), lutidinic acid (2b), and hemimellitic acid (4a) in the presence of excess H2O2.

  2. Terahertz Spectroscopy of Biochars and Related Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Lepodise, L. M.; Horvat, J.; Lewis, R. A.

    2016-12-01

    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.

  3. Synthesis of Functional Fluorescent BODIPY‐based Dyes through Electrophilic Aromatic Substitution: Straightforward Approach towards Customized Fluorescent Probes

    PubMed Central

    Schoenmakers, Daniël C.; Veranič, Peter; Muševič, Igor

    2016-01-01

    Abstract Fluorescent materials are widely used in biological and material applications as probes for imaging or sensing; however, their customization is usually complicated without the support of an organic chemistry laboratory. Here, we present a straightforward method for the customization of BODIPY cores, which are among the most commonly used fluorescent probes. The method is based on the formation of a new C−C bond through Friedel–Crafts electrophilic aromatic substitution carried out at room temperature. The method presented can be used to obtain completely customized fluorescent materials in one or two steps from commercially available compounds. Examples of the preparation of fluorescent materials for cell staining and functionalization of silica colloids are also presented. PMID:27777837

  4. Aromatic metabolism of filamentous fungi in relation to the presence of aromatic compounds in plant biomass.

    PubMed

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

    2015-01-01

    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.

  5. Transformations of aromatic compounds by nitrosomonas europaea

    SciTech Connect

    Keener, W.K.; Arp, D.J.

    1994-06-01

    The soil bacterium Nitrosomonas europaea is an obligate autotroph which uses O2 as an electron acceptor and ammonia as its sole natural energy source. The ubiquity of nitrifying bacteria may facilitate their use in bioremediation applications, but such applications will require a thorough knowledge of the substrate range of Ammonia monooxygenase (AMO) (catalyzing the oxidation of ammonia). This study extends the know substrate range of N. europaea to include alkylbenzenes, halobenzenes, and various N- and O-containing aromatics. Evidence is also presented that oxidation of p-cresol and ring-substituted benzylic alcohols to corresponding aldehydes joccures even in the absence of AMO activity. 33 refs., 7 figs.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  7. Microbial remediation of nitro-aromatic compounds: an overview.

    PubMed

    Kulkarni, Meenal; Chaudhari, Ambalal

    2007-10-01

    Nitro-aromatic compounds are produced by incomplete combustion of fossil fuel or nitration reactions and are used as chemical feedstock for synthesis of explosives, pesticides, herbicides, dyes, pharmaceuticals, etc. The indiscriminate use of nitro-aromatics in the past due to wide applications has resulted in inexorable environmental pollution. Hence, nitro-aromatics are recognized as recalcitrant and given Hazardous Rating-3. Although several conventional pump and treat clean up methods are currently in use for the removal of nitro-aromatics, none has proved to be sustainable. Recently, remediation by biological systems has attracted worldwide attention to decontaminate nitro-aromatics polluted sources. The incredible versatility inherited in microbes has rendered these compounds as a part of the biogeochemical cycle. Several microbes catalyze mineralization and/or non-specific transformation of nitro-aromatics either by aerobic or anaerobic processes. Aerobic degradation of nitro-aromatics applies mainly to mono-, dinitro-derivatives and to some extent to poly-nitro-aromatics through oxygenation by: (i) monooxygenase, (ii) dioxygenase catalyzed reactions, (iii) Meisenheimer complex formation, and (iv) partial reduction of aromatic ring. Under anaerobic conditions, nitro-aromatics are reduced to amino-aromatics to facilitate complete mineralization. The nitro-aromatic explosives from contaminated sediments are effectively degraded at field scale using in situ bioremediation strategies, while ex situ techniques using whole cell/enzyme(s) immobilized on a suitable matrix/support are gaining acceptance for decontamination of nitrophenolic pesticides from soils at high chemical loading rates. Presently, the qualitative and quantitative performance of biological approaches of remediation is undergoing improvement due to: (i) knowledge of catabolic pathways of degradation, (ii) optimization of various parameters for accelerated degradation, and (iii) design of microbe

  8. The oxidation degradation of aromatic compounds

    NASA Technical Reports Server (NTRS)

    Brezinsky, Kenneth; Glassman, Irvin

    1987-01-01

    A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained.

  9. Airborne Exposures to Polycyclic Aromatic Compounds Among Workers in Asphalt Roofing Manufacturing Facilities.

    PubMed

    Trumbore, David C; Osborn, Linda V; Johnson, Kathleen A; Fayerweather, William E

    2015-01-01

    We studied exposure of 151 workers to polycyclic aromatic compounds and asphalt emissions during the manufacturing of asphalt roofing products-including 64 workers from 10 asphalt plants producing oxidized, straight-run, cutback, and wax- or polymer-modified asphalts, and 87 workers from 11 roofing plants producing asphalt shingles and granulated roll roofing. The facilities were located throughout the United States and used asphalt from many refiners and crude oils. This article helps fill a gap in exposure data for asphalt roofing manufacturing workers by using a fluorescence technique that targets biologically active 4-6 ring polycyclic aromatic compounds and is strongly correlated with carcinogenic activity in animal studies. Worker exposures to polycyclic aromatic compounds were compared between manufacturing plants, at different temperatures and using different raw materials, and to important external benchmarks. High levels of fine limestone particulate in the plant air during roofing manufacturing increased polycyclic aromatic compound exposure, resulting in the hypothesis that the particulate brought adsorbed polycyclic aromatic compounds to the worker breathing zone. Elevated asphalt temperatures increased exposures during the pouring of asphalt. Co-exposures in these workplaces which act as confounders for both the measurement of total organic matter and fluorescence were detected and their influence discussed. Exposures to polycyclic aromatic compounds in asphalt roofing manufacturing facilities were lower than or similar to those reported in hot-mix paving application studies, and much below those reported in studies of hot application of built-up roofing asphalt. These relatively low exposures in manufacturing are primarily attributed to air emission controls in the facilities, and the relatively moderate temperatures, compared to built-up roofing, used in these facilities for oxidized asphalt. The exposure to polycyclic aromatic compounds was a very

  10. Global atmospheric budget of simple monocyclic aromatic compounds

    NASA Astrophysics Data System (ADS)

    Cabrera-Perez, David; Taraborrelli, Domenico; Sander, Rolf; Pozzer, Andrea

    2016-06-01

    The global atmospheric budget and distribution of monocyclic aromatic compounds is estimated, using an atmospheric chemistry general circulation model. Simulation results are evaluated with an ensemble of surface and aircraft observations with the goal of understanding emission, production and removal of these compounds.Anthropogenic emissions provided by the RCP database represent the largest source of aromatics in the model (≃ 23 TgC year-1) and biomass burning from the GFAS inventory the second largest (≃ 5 TgC year-1). The simulated chemical production of aromatics accounts for ≃ 5 TgC year-1. The atmospheric burden of aromatics sums up to 0.3 TgC. The main removal process of aromatics is photochemical decomposition (≃ 27 TgC year-1), while wet and dry deposition are responsible for a removal of ≃ 4 TgC year-1.Simulated mixing ratios at the surface and elsewhere in the troposphere show good spatial and temporal agreement with the observations for benzene, although the model generally underestimates mixing ratios. Toluene is generally well reproduced by the model at the surface, but mixing ratios in the free troposphere are underestimated. Finally, larger discrepancies are found for xylenes: surface mixing ratios are not only overestimated but also a low temporal correlation is found with respect to in situ observations.

  11. Fluorescent compounds for plastic scintillation applications

    SciTech Connect

    Pla-Dalmau, A.; Bross, A.D.

    1994-04-01

    Several 2-(2{prime}-hydroxyphenyl)benzothiazole, -benzoxazole, and -benzimidazole derivatives have been prepared. Transmittance, fluorescence, light yield, and decay time characteristics of these compounds have been studied in a polystyrene matrix and evaluated for use in plastic scintillation detectors. Radiation damage studies utilizing a {sup 60}C source have also been performed.

  12. 40 CFR 721.9620 - Aromatic sulfonic acid compound with amine.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aromatic sulfonic acid compound with... Specific Chemical Substances § 721.9620 Aromatic sulfonic acid compound with amine. (a) Chemical substance... aromatic sulfonic acid compound with amine (PMN P-93-832) is subject to reporting under this section...

  13. 40 CFR 721.9620 - Aromatic sulfonic acid compound with amine.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aromatic sulfonic acid compound with... Specific Chemical Substances § 721.9620 Aromatic sulfonic acid compound with amine. (a) Chemical substance... aromatic sulfonic acid compound with amine (PMN P-93-832) is subject to reporting under this section...

  14. 40 CFR 721.9620 - Aromatic sulfonic acid compound with amine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aromatic sulfonic acid compound with... Specific Chemical Substances § 721.9620 Aromatic sulfonic acid compound with amine. (a) Chemical substance... aromatic sulfonic acid compound with amine (PMN P-93-832) is subject to reporting under this section...

  15. 40 CFR 721.9620 - Aromatic sulfonic acid compound with amine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic sulfonic acid compound with... Specific Chemical Substances § 721.9620 Aromatic sulfonic acid compound with amine. (a) Chemical substance... aromatic sulfonic acid compound with amine (PMN P-93-832) is subject to reporting under this section...

  16. 40 CFR 721.9620 - Aromatic sulfonic acid compound with amine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aromatic sulfonic acid compound with... Specific Chemical Substances § 721.9620 Aromatic sulfonic acid compound with amine. (a) Chemical substance... aromatic sulfonic acid compound with amine (PMN P-93-832) is subject to reporting under this section...

  17. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  18. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  19. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  20. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  1. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  2. Amination of electrophilic aromatic compounds by vicarious nucleophilic substitution

    SciTech Connect

    Mitchell, Alexander R.; Pagoria, Philip F.; Schmidt, Robert D.

    2000-01-01

    The present invention relates to a process to aminate electrophilic aromatic compounds by vicarious nucleophilic substitution of hydrogen using quaternary hydrazinium salts. The use of trialkylhydrazinium halide, e.g., trimethylhydrazinium iodide, as well as hydroxylamine, alkoxylamines, and 4-amino-1,2,4-triazole to produce aminated aromatic structures, such as 1,3-diamino-2,4,6-trinitrobenzene (DATB), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and 3,5-diamino-2,4,6-trinitrotoluene (DATNT), is described. DATB and TATB are useful insensitive high explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

  3. Detection of Aromatic Nitro Compounds Using Preconcentrator and SPR Immunosensor

    NASA Astrophysics Data System (ADS)

    Onodera, Takeshi; Miyahara, Kazuhisa; Iwakura, Munehiro; Hayashi, Kenshi; Miura, Norio; Matsumoto, Kiyoshi; Toko, Kiyoshi

    In this study, we report the sensitive detection of aromatic nitro compounds using a surface plasmon resonance (SPR) immunosensor based on the indirect competitive method. The vapors from the substances were sampled with a preconcentrator developed here. The solutions of the sampled vapors were measured using SPR immunosensor. Three kinds of explosives such as 2,4-dinitrobenzene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene were detected at 1 ppb. Sampling time at 1 l/min was 3 min. Total detection time was brought down to 5 min, which is relatively short for second scanning in landmine detection. Efforts are being made to integrate the SPR immunosensor and preconcentrator for rapid sensitive detection of nitro aromatic compounds under simulated field conditions.

  4. Biological Treatment of Groundwater Contaminated with Mixtures of Aromatic Compounds

    DTIC Science & Technology

    1993-03-01

    bioreactor to biodegrade chlorinated aromatic compounds. The site at Kelly AFB, TX is an abandoned waste storage area where the soil and groundwater is...scale submerged fixed- film bioreactors were tested with groundwater containing benzene, naphthalene, phenol, toluene, ortho and para- cresol , 2,4...strain JS150 could aerobically biodegrade complex mixtures of solvents if appropriate dissolved oxygen levels were maintained. After the initial 5 days

  5. Aromatic fluorine compounds. VII. Replacement of aromatic -Cl and -NO2 groups by -F

    USGS Publications Warehouse

    Finger, G.C.; Kruse, C.W.

    1956-01-01

    Replacement of -Cl by -F in aryl chlorides with potassium fluoride has been extended from 2,4-dinitrochlorobenzene to less activated halides by the use of non-aqueous solvents, especially dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Also replacement of -NO2 by -F in substituted nitrobenzenes was studied in DMF. As a direct result of this study, many aromatic fluorine compounds can now be obtained by a relatively simple synthetic route.

  6. (Anaerobic metabolism of aromatic compounds by phototrophic bacteria: Biochemical aspects)

    SciTech Connect

    Gibson, J.

    1989-01-01

    Two aspects of the work proposed have received major emphasis during the period since the grant was activated: isolation and characterization of transposon insertion mutants of Rhodopseudomonas palusrtis defective in phototrophic growth on aromatic compounds, and attempts to purify and characterize the Coenzyme A ligase enzyme involved in activating 4-hydroxybenzoate. The HPLC apparatus was installed in August, and calibration of columns both for metabolite and for protein separations has been initiated. A start has also been made on synthesis of Coenzyme A thioesters of compounds that are potential intermediates in the anaerobic degradation pathways. 1 tab.

  7. Microwave-assisted extraction of polycyclic aromatic compounds from coal.

    PubMed

    Kerst, M; Andersson, J T

    2001-08-01

    Microwave-assisted extraction (MAE) of polycyclic aromatic compounds (PACs) from coal is shown to give the same pattern of compounds as Soxhlet extraction. MAE requires only 10 mL solvent and 10 min extraction time whereas Soxhlet uses 200 mL and takes 24 h. Although the yields were lower, dichloromethane (DCM) was preferred to pyridine, N-methyl-2-pyrrolidone (NMP), and NMP with CS2 because the pattern of the PACs is shown to be independent of solvent and DCM is a much more convenient solvent to work with.

  8. Detection of polycyclic aromatic hydrocarbons (PAHs) in raw menhaden fish oil using fluorescence spectroscopy: Method development.

    PubMed

    Pena, Edwin A; Ridley, Lauren M; Murphy, Wyatt R; Sowa, John R; Bentivegna, Carolyn S

    2015-09-01

    Raw menhaden fish oil was developed for biomonitoring polycyclic aromatic hydrocarbons (PAHs) using fluorescence spectroscopy. Menhaden (Genus Brevoortia) were collected in 2010 and/or 2011 from Delaware Bay, New Jersey, USA; James River, Virginia, USA; Vermillion Bay, Louisiana, USA (VBLA); and Barataria Bay, Louisiana, USA (BBLA). Barataria Bay, Louisiana received heavy oiling from the Deepwater Horizon oil spill. Method development included determining optimal wavelengths for PAH detection, fish oil matrix interferences, and influence of solvent concentration on extraction. Results showed that some fish oils contained high molecular weight PAH-like compounds in addition to other fluorescent compounds such as albumin and vitamin A and vitamin E. None of these naturally occurring compounds interfered with detection of high molecular weight PAHs. However, data suggested that the lipid component of fish oil was altering fluorescence spectra by supporting the formation of PAH excimers. For example, the most intense excitation wavelength for hydroxypyrene shifted from Ex285/Em430 to Ex340/Em430. Comparison of Deepwater Horizon crude oil and fish oil spectra indicated that some fish oils contained crude oil-like PAHs. Using wavelengths of Ex360/Em430, fish oil concentrations were calculated as 3.92 μg/g, 0.61 μg/g, and 0.14 μg/g for a Delaware Bay sample, BBLA 2011, and VBLA 2011, respectively. Overall, these results supported using menhaden fish oil to track PAH exposures spatially and temporally.

  9. [Efficient synthesis of multisubstituted aromatic compounds from phenol derivatives].

    PubMed

    Ikawa, Takashi

    2014-01-01

    Phenols are abundant in nature and diverse phenols are readily available commercially at low cost. Thus, phenols can be used as the raw materials for the synthesis of valuable multisubstituted aromatic compounds by the direct activation of phenolic hydroxyl groups (C-O bond activation), followed by substitutions with other substituents. Although the derivatization of phenolic hydroxyl groups to sulfonates, such as triflates, nonaflates, tosylates and mesylates, followed by the transition-metal-catalyzed coupling reactions has been extensively investigated for this purpose, the direct C-O bond activation of phenols for subsequent functional group transformation has been a long-standing challenge in modern organic synthesis. In this review, I have summarized my recent studies on the formal direct C-O bond activation of phenols using nonafluorobutanesulfonyl fluoride (NfF) for the synthesis of multisubstituted aromatics. I have focused on the dual use of NfF, a less expensive commercially available reagent, including the tentative formation of highly reactive nonaflates from phenols and the use of the liberated fluoride ion as a nucleophile to promote the reactions of nonaflates. The following four topics are discussed: 1) palladium-catalyzed coupling reactions of phenols, 2) novel preparation of benzynes from 2-silylphenols, 3) synthesis of fluorinated aromatic compounds via the formation of benzynes, and 4) Hiyama coupling of (tert-butyldimethylsilyl)arenes activated by internal phenolic hydroxyl groups.

  10. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G.; Sims, R.C.

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  11. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. ); Sims, R.C. . Dept. of Civil and Environmental Engineering)

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  12. Development of genetically engineered bacteria for production of selected aromatic compounds

    DOEpatents

    Ward, Thomas E.; Watkins, Carolyn S.; Bulmer, Deborah K.; Johnson, Bruce F.; Amaratunga, Mohan

    2001-01-01

    The cloning and expression of genes in the common aromatic pathway of E. coli are described. A compound for which chorismate, the final product of the common aromatic pathway, is an anabolic intermediate can be produced by cloning and expressing selected genes of the common aromatic pathway and the genes coding for enzymes necessary to convert chorismate to the selected compound. Plasmids carrying selected genes of the common aromatic pathway are also described.

  13. Polycyclic aromatic hydrocarbons from U.S. and Antarctic sites analyzed with synchronous fluorescence spectrometry

    SciTech Connect

    Amick, E.N.; Pollard, J.E.; Engelmann, W.H.; Brown, K.W.; Alarie, J.P.; Watts, W.; Vo-Dinh, T.; Akindele, F.M.; Crockett, A.B.

    1995-12-31

    Synchronous ultraviolet-visible (UV-vis) fluorescence spectrometry is currently being evaluated as a field screening technology by the US Environmental Protection Agency`s (EPA) Environmental Monitoring Systems Laboratory in Las Vegas, Nevada (EMSL-LV). This method can provide compound or class-selective results on site at a reasonable cost. A prototype field-portable spectrofluorometer capable of excitation, emission, and synchronous scans was field tested at the American Creosote Works Superfund Site (a wood preservation facility) in Jackson, Tennessee. The instrument was also tested in the laboratory with sediment samples collected from Antarctica. The UV-vis fluorescence spectra of various polycyclic aromatic hydrocarbons (PAHs) were clearly seen in the synchronous spectra of soil samples extracted on site at American Creosote Works. The spectra for the Antarctic sediment samples were nearly identical to that of motor oil. The results of this study demonstrate the utility of synchronous fluorescence to provide evidence of the presence and identity of hydrocarbon contamination in environmental samples. The technique allows flexibility in selection of optimum extraction and instrumental procedures for site-specific matrices.

  14. Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

    DOEpatents

    Baker, E.G.; Elliott, D.C.

    1993-01-19

    The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compounds as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

  15. Bacterial Transcriptional Regulators for Degradation Pathways of Aromatic Compounds

    PubMed Central

    Tropel, David; van der Meer, Jan Roelof

    2004-01-01

    Human activities have resulted in the release and introduction into the environment of a plethora of aromatic chemicals. The interest in discovering how bacteria are dealing with hazardous environmental pollutants has driven a large research community and has resulted in important biochemical, genetic, and physiological knowledge about the degradation capacities of microorganisms and their application in bioremediation, green chemistry, or production of pharmacy synthons. In addition, regulation of catabolic pathway expression has attracted the interest of numerous different groups, and several catabolic pathway regulators have been exemplary for understanding transcription control mechanisms. More recently, information about regulatory systems has been used to construct whole-cell living bioreporters that are used to measure the quality of the aqueous, soil, and air environment. The topic of biodegradation is relatively coherent, and this review presents a coherent overview of the regulatory systems involved in the transcriptional control of catabolic pathways. This review summarizes the different regulatory systems involved in biodegradation pathways of aromatic compounds linking them to other known protein families. Specific attention has been paid to describing the genetic organization of the regulatory genes, promoters, and target operon(s) and to discussing present knowledge about signaling molecules, DNA binding properties, and operator characteristics, and evidence from regulatory mutants. For each regulator family, this information is combined with recently obtained protein structural information to arrive at a possible mechanism of transcription activation. This demonstrates the diversity of control mechanisms existing in catabolic pathways. PMID:15353566

  16. Gas and Particulate Sampling of Airborne Polycyclic Aromatic Compounds

    SciTech Connect

    Lane, D.A.; Gundel, L.A.

    1995-10-01

    The denuder surfaces of the gas and particle (GAP) sampler (developed at the Atmospheric Environment Service of Environment Canada) have been modified by coating with XAD-4 resin, using techniques developed at Lawrence Berkeley National Laboratory (LBNL) for the lower capacity integrated organic vapor/particle sampler (IOVPS). The resulting high capacity integrated organic gas and particle sampler (IOGAPS) has been operated in ambient air at 16.7 L min{sup -1} for a 24-hour period in Berkeley, California, USA. Simultaneous measurements were made at the same collection rate with a conventional sampler that used a filter followed by two sorbent beds. Gas and particle partition measurements were determined for 13 polycyclic aromatic hydrocarbons (PAH) ranging from 2-ring to 6-ring species. The IOGAPS indicated a higher particle fraction of these compounds than did the conventional sampler, suggesting that the conventional sampler suffered from 'blow-off' losses from the particles collected on the filter.

  17. The metabolism of aromatic compounds by Rhodopseudomonas palustris. A new, reductive, method of aromatic ring metabolism

    PubMed Central

    Dutton, P. L.; Evans, W. C.

    1969-01-01

    1. Rhodopseudomonas palustris grows both aerobically and photosynthetically on aromatic acids. p-Hydroxybenzoate and protocatechuate are able to support aerobic growth; these compounds are metabolized by the protocatechuate 4,5-oxygenase pathway. 2. The photoassimilation of benzoate and hydroxybenzoates and the effects of air and darkness on the photoassimilation of benzoate are described. 3. Evidence in conflict with the pathway previously proposed for the photometabolism of benzoate is discussed. 4. The photometabolism of benzoate is accomplished by a novel reductive pathway involving its reduction to cyclohex-1-ene-1-carboxylate, followed by hydration to 2-hydroxycyclohexanecarboxylate and after dehydrogenation to 2-oxocyclohexanecarboxylate further hydration results in ring-fission and the production of pimelate. 5. Attempts were made to prepare cell-free extracts capable of dissimilating benzoate. PMID:5807211

  18. Quenching of fluorescence of phenolic compounds and modified humic acids by cadmium ions.

    PubMed

    Tchaikovskaya, O N; Nechaev, L V; Yudina, N V; Mal'tseva, E V

    2016-08-01

    The interaction of a number of phenolic compounds, being 'model fragments' of humic acids, with cadmium ions was investigated. The fluorescence quenching method was used to determine the complexation constants of these compounds with cadmium ions. It was established that bonding of phenolic compounds by cadmium ions at рН 7 is weak and reaches a maximum value of 15% for interaction with resorcinol. It was demonstrated that modification of humic acids by the mechanoactivation method increases by three times bonding of cadmium ions, which is caused by strengthening the acid properties of carboxyl and hydroxyl groups at the aromatic ring. Copyright © 2016 John Wiley & Sons, Ltd.

  19. Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

    DOEpatents

    Baker, Eddie G.; Elliott, Douglas C.

    1993-01-01

    The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compouns as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

  20. Biotechnological production of aromatic compounds of the extended shikimate pathway from renewable biomass.

    PubMed

    Lee, Jin-Ho; Wendisch, Volker F

    2016-11-18

    Aromatic chemicals that contain an unsaturated ring with alternating double and single bonds find numerous applications in a wide range of industries, e.g. paper and dye manufacture, as fuel additives, electrical insulation, resins, pharmaceuticals, agrochemicals, in food, feed and cosmetics. Their chemical production is based on petroleum (BTX; benzene, toluene, and xylene), but they can also be obtained from plants by extraction. Due to petroleum depletion, health compliance, or environmental issues such as global warming, the biotechnological production of aromatics from renewable biomass came more and more into focus. Lignin, a complex polymeric aromatic molecule itself, is a natural source of aromatic compounds. Many microorganisms are able to catabolize a plethora of aromatic compounds and interception of these pathways may lead to the biotechnological production of value-added aromatic compounds which will be discussed for Corynebacterium glutamicum. Biosynthesis of aromatic amino acids not only gives rise to l-tryptophan, L-tyrosine and l-phenylalanine, but also to aromatic intermediates such as dehydroshikimate or chorismate from which value-added aromatic compounds can be derived. In this review, we will summarize recent strategies for the biotechnological production of aromatic and related compounds from renewable biomass by Escherichia coli, Pseudomonas putida, C. glutamicum and Saccharomyces cerevisiae. In particular, we will focus on metabolic engineering of the extended shikimate pathway.

  1. Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

    ERIC Educational Resources Information Center

    Leung, Sam H.

    2000-01-01

    Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

  2. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, [OH]dt) of the different VOC. It is found that [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform [OH]dt for VOC with different reactivity is not justified and that the observed values for [OH]dt are the result of mixing of VOC from air masses with different values for [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine [OH]dt would result in values for [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform [OH]dt for an air mass has to be replaced by the concept of individual values of an average [OH]dt for VOC with different reactivity.

  3. Correlation and prediction of adsorption capacity and affinity of aromatic compounds on carbon nanotubes.

    PubMed

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

    2016-01-01

    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.

  4. Determination of polycyclic aromatic compounds and dioxin receptor ligands present in diesel exhaust particulate extracts

    NASA Astrophysics Data System (ADS)

    Li, Hang; Banner, Carol D.; Mason, Grant G.; Westerholm, Roger N.; Rafter, Joseph J.

    Polycyclic aromatic compounds and dioxin receptor ligands present in diesel particulate extract fractions and subfractions were determined. A crude model diesel particulate extract was fractionated into five fractions (I-V), fractions I, II and III were further fractionated into subfractions (I-1, I-2, II-1 to II-7 and III-1 to III-6). The amounts of 33 PAC present in fraction II and its subfractions were determined by gas chromatography-mass spectrometry. The amounts of 1-nitropyrene present in fraction III and its subfractions were analysed by high performance liquid chromatography with fluorescence detection. The ability of each fraction and subfraction to compete with 2,3,7,8-tetrachloro[1,6-[ 3H

  5. Biodegradation of aromatic compounds: current status and opportunities for biomolecular approaches.

    PubMed

    Cao, Bin; Nagarajan, Karthiga; Loh, Kai-Chee

    2009-11-01

    Biodegradation can achieve complete and cost-effective elimination of aromatic pollutants through harnessing diverse microbial metabolic processes. Aromatics biodegradation plays an important role in environmental cleanup and has been extensively studied since the inception of biodegradation. These studies, however, are diverse and scattered; there is an imperative need to consolidate, summarize, and review the current status of aromatics biodegradation. The first part of this review briefly discusses the catabolic mechanisms and describes the current status of aromatics biodegradation. Emphasis is placed on monocyclic, polycyclic, and chlorinated aromatic hydrocarbons because they are the most prevalent aromatic contaminants in the environment. Among monocyclic aromatic hydrocarbons, benzene, toluene, ethylbenzene, and xylene; phenylacetic acid; and structurally related aromatic compounds are highlighted. In addition, biofilms and their applications in biodegradation of aromatic compounds are briefly discussed. In recent years, various biomolecular approaches have been applied to design and understand microorganisms for enhanced biodegradation. In the second part of this review, biomolecular approaches, their applications in aromatics biodegradation, and associated biosafety issues are discussed. Particular attention is given to the applications of metabolic engineering, protein engineering, and "omics" technologies in aromatics biodegradation.

  6. Linear and nonlinear optical properties of new materials based on DNA-CTMA and aromatic compounds (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Lazar, Cosmina Andreea; Kajzar, François; Rau, Ileana; Puntus, Lada N.; Manea, Ana-Maria

    2016-10-01

    In order to find eco-friendly materials for different applications an important research effort was devoted to the materials science in the last decade. A particular attention attracted the deoxyribonucleic acid (DNA). The interest is due to its versatility, biodegradability, abundance and their origin from renewable sources. DNA based new materials, functionalized with hexadecyltrimethylammonium chloride (CTMA) and aromatic compounds were prepared. Solutions with two different concentrations of aromatic compounds were obtained in butanol. The obtained, new complexes were processed into good optical quality thin films by spin coating method. Films were deposited on glass substrates and characterized for their spectroscopic, linear and nonlinear optical properties. The third-order nonlinear optical (NLO) properties of thin films were determined by the optical third-harmonic generation technique at 1 064.2 nm fundamental wavelength. The obtained materials, with improved fluorescence efficiency, present a potential interest for application in photonics.

  7. NIR fluorescent ytterbium compound for in vivo fluorescence molecular imaging.

    PubMed

    Aita, Kazuki; Temma, Takashi; Kuge, Yuji; Seki, Koh-ichi; Saji, Hideo

    2010-01-01

    We have developed a new NIR fluorescent probe based on an ytterbium(III) (E)-1-(pyridin-2-yl-diazenyl)naphthalen-2-ol (PAN) complex. This probe emits near-infrared luminescence derived from the Yb ion through excitation of the PAN moiety with visible light (lambda(ex)= 530 nm, lambda(em)= 975 nm). The results support the possible utility of the probe for in vivo fluorescence molecular imaging.

  8. Primary photochemistry of nitrated aromatic compounds: excited-state dynamics and NO· dissociation from 9-nitroanthracene.

    PubMed

    Plaza-Medina, Eddy F; Rodríguez-Córdoba, William; Morales-Cueto, Rodrigo; Peon, Jorge

    2011-02-10

    We report results of femtosecond-resolved ex-periments which elucidate the time scale for the primary photoinduced events in the model nitroaromatic compound 9-nitroanthracene. Through time-resolved fluorescence measurements, we observed the ultrafast decay of the initially excited singlet state, and through transient absorption experiments, we observed the spectral evolution associated with the formation of the relaxed phosphorescent T(1) state. Additionally, we have detected for the first time the accumulation of the anthryloxy radical which results from the nitro-group rearrangement and NO(•) dissociation from photoexcited 9-nitroanthracene, a photochemical channel which occurs in parallel with the formation of the phosphorescent state. The spectral evolution in this molecule is highly complex since both channels take place in similar time ranges of up to a few picoseconds. Despite this complexity, our experiments provide the general time scales in which the primary products are formed. In addition, we include calculations at the time-dependent density functional level of theory which distinguish the molecular orbitals responsible for the n-π* character of the "receiver" vibronic triplet states that couple with the first singlet state and promote the ultrafast transfer of population between the two manifolds. Comparisons with the isoelectronic compounds anthracene-9-carboxylic acid and its conjugated base, which are highly fluorescent, show that in these two compounds the near-isoenergeticity of the S(1) with an appropriate "receiver" triplet state is disrupted, providing support to the idea that a specific energy coincidence is important for the ultrafast population of the triplet manifold, prevalent in polycyclic nitrated aromatic compounds.

  9. Self-Assembly of New Arene-Ruthenium Rectangles Containing Triptycene Building Block and Their Application in Fluorescent Detection of Nitro Aromatics

    PubMed Central

    Dubey, Abhishek; Mishra, Anurag; Min, Jin Wook; Lee, Min Hyung; Kim, Hyunuk; Stang, Peter J.; Chi, Ki-Whan

    2014-01-01

    A suite of two new tetraruthenium metallarectangles 5 and 6 have been obtained from [2 + 2] self-assemblies between dipyridylethynyltriptycene 2 and one of the two dinuclear arene ruthenium clips, [Ru2 (μ-η4-OO∩OO) (η6-p-cymene)2][OTf]2 ; (OO∩OO = oxalate 3; 6,11-dihydroxy-5,12-naphthacenedionato (dotq) 4; OTf = triflate). These molecular rectangles are fully characterized by 1H NMR spectroscopy, electrospray mass spectrometry. A single crystal of 6 was suitable for X-ray diffraction structural characterization. These new metallarectangles showed fluorescence behavior in solution, have been examined for emission quenching effects with various aromatic compounds, and show high quenching selectivity and sensitivity towards nitroaromatics, particularly picric acid and trinitrotoluene. Excited-state charge transfer from the rectangles to nitro aromatic substrates can be used to develop selective fluorescent sensors for nitro aromatics. PMID:26321767

  10. Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

    ERIC Educational Resources Information Center

    Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

    2004-01-01

    A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

  11. Synthesis of a Fluorescent Acridone Using a Grignard Addition, Oxidation, and Nucleophilic Aromatic Substitution Reaction Sequence

    ERIC Educational Resources Information Center

    Goodrich, Samuel; Patel, Miloni; Woydziak, Zachary R.

    2015-01-01

    A three-pot synthesis oriented for an undergraduate organic chemistry laboratory was developed to construct a fluorescent acridone molecule. This laboratory experiment utilizes Grignard addition to an aldehyde, alcohol oxidation, and iterative nucleophilic aromatic substitution steps to produce the final product. Each of the intermediates and the…

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

    DOEpatents

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

    1983-09-20

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

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

    DOEpatents

    Googin, John M.; Napier, John M.; Travaglini, Michael A.

    1983-01-01

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

  14. Possible Mechanism of Liver Necrosis Caused by Aromatic Organic Compounds

    PubMed Central

    Brodie, Bernard B.; Reid, Watson D.; Cho, Arthur K.; Sipes, Glenn; Krishna, Gopal; Gillette, James R.

    1971-01-01

    Treatment of rats with phenobarbital, which stimulates the activity of the drug-metabolizing enzymes in the liver, potentiates hepatic necrosis elicited by bromobenzene and a number of other chemically inert halogenated aromatic hydrocarbons. Radioautographic studies indicate that [14C]bromobenzene is covalently bound at the sites of necrosis. From these results, it is inferred that the hepatotoxic effects of the halogenated aromatic hydrocarbons are mediated by chemically active metabolites formed in hepatocytes. In accord with this view, a number of aromatic halogenated hydrocarbons are converted by microsomes in vitro to active intermediates which form covalent complexes with glutathione (GSH). Images PMID:4395686

  15. Binding phenomena and fluorescence quenching. II: Photophysics of aromatic residues and dependence of fluorescence spectra on protein conformation

    NASA Astrophysics Data System (ADS)

    Callis, Patrik R.

    2014-12-01

    The three amino acids with aromatic ring side chains-phenylalanine (Phe), tyrosine (Tyr), and especially tryptophan (Trp) have played a long and productive role in helping unlock the secrets of protein behavior by optical spectroscopy (absorption, fluorescence, circular dichroism, etc.) In principle, an appropriately placed Trp will undergo fluorescence wavelength and/or intensity changes upon whatever functional process a protein performs. Although perceived to be enigmatic and not well understood, Trp is arguably now better understood than many of the extrinsic probes currently in use. Basic principles of intrinsic tryptophan fluorescence quenching and wavelength shifts in proteins are presented, with strong emphasis on the importance of electrostatics. The condensed description of findings from recent experiments and simulations of tryptophan fluorescence and intrinsic quenching in proteins is designed to help authors in planning and interpreting experimental results of ligand binding studies.

  16. Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry.

    PubMed

    Gaik, Urszula; Sillanpää, Mika; Witkiewicz, Zygfryd; Puton, Jarosław

    2017-03-03

    Limits of detection (LODs) in ion mobility spectrometry (IMS) strictly depend on ionization of the analyte. Especially challenging is ionization of compounds with relatively low proton affinity (PA) such as aromatic compounds. To change the course of ion-molecule reactions and enhance the performance of the IMS spectrometer, substances called dopants are introduced into the carrier gas. In this work, we present the results of studies of detection using nitrogen oxides (NOx) dopants. Three aromatic compounds, benzene, toluene, toluene diisocyanate and, for comparison, two compounds with high PA, dimethyl methylphosphonate (DMMP) and triethyl phosphate (TEP), were selected as analytes. The influence of water vapour on these analyses was also studied. Experiments were carried out with a generator of gas mixtures that allowed for the simultaneous introduction of three substances into the carrier gas. The experiments showed that the use of NOx dopants significantly decreases LODs for aromatic compounds and does not affect the detection of compounds with high PA. The water vapour significantly disturbs the detection of aromatic compounds; however, doping with NOx allows to reduce the effect of humidity. Graphical Abstract Two possible ionization mechanisms of aromatic compounds in ion mobility spectrometry: proton transfer reaction and adduct formation.

  17. Bond cleavage of lignin model compounds into aromatic monomers using supported metal catalysts in supercritical water

    PubMed Central

    Yamaguchi, Aritomo; Mimura, Naoki; Shirai, Masayuki; Sato, Osamu

    2017-01-01

    More efficient use of lignin carbon is necessary for carbon-efficient utilization of lignocellulosic biomass. Conversion of lignin into valuable aromatic compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units. The catalytic cleavage of C–O bonds is still challenging, and cleavage of C–C bonds is even more difficult. Here, we report cleavage of the aromatic C–O bonds in lignin model compounds using supported metal catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of the aromatic rings. The cleavage of the C–C bond in bibenzyl was also achieved with Rh/C as a catalyst. Use of this technique may greatly facilitate the conversion of lignin into valuable aromatic compounds. PMID:28387304

  18. Volatile compounds in dry dog foods and their influence on sensory aromatic profile.

    PubMed

    Koppel, Kadri; Adhikari, Koushik; Di Donfrancesco, Brizio

    2013-02-27

    The aim of this study was to determine volatile compounds in dry dog foods and their possible influence on sensory aromatic profile. Grain-free dry dog foods were compared to dry dog foods manufactured with grain, but also with different protein sources for their aromatic volatiles. Solid-phase microextraction/gas chromatography/mass spectrometry was used to determine the aromatic compounds present in the headspace of these samples. Partial Least Squares regression was performed to correlate the instrumental aromatic data with the descriptive aroma analysis data. A total of 54 aromatic compounds were tentatively identified in the dry dog food samples, with aldehydes and ketones being the most represented organic volatiles group. Grain-added products were on the average higher in total volatiles than grain-free products. Partial Least Squares regression analysis indicated possible connections with sensory aromatic profile and grain-added samples, such as rancid aroma and aldehydes, especially hexanal. The results of this study showed that dry dog foods are products with complex odor characteristics and that grain-free products are less aromatic.

  19. Degradation and assimilation of aromatic compounds by Corynebacterium glutamicum: another potential for applications for this bacterium?

    PubMed

    Shen, Xi-Hui; Zhou, Ning-Yi; Liu, Shuang-Jiang

    2012-07-01

    With the implementation of the well-established molecular tools and systems biology techniques, new knowledge on aromatic degradation and assimilation by Corynebacterium glutamicum has been emerging. This review summarizes recent findings on degradation of aromatic compounds by C. glutamicum. Among these findings, the mycothiol-dependent gentisate pathway was firstly discovered in C. glutamicum. Other important knowledge derived from C. glutamicum would be the discovery of linkages among aromatic degradation and primary metabolisms such as gluconeogenesis and central carbon metabolism. Various transporters in C. glutamicum have also been identified, and they play an essential role in microbial assimilation of aromatic compounds. Regulation on aromatic degradation occurs mainly at transcription level via pathway-specific regulators, but global regulator(s) is presumably involved in the regulation. It is concluded that C. glutamicum is a very useful model organism to disclose new knowledge of biochemistry, physiology, and genetics of the catabolism of aromatic compounds in high GC content Gram-positive bacteria, and that the new physiological properties of aromatic degradation and assimilation are potentially important for industrial applications of C. glutamicum.

  20. Selective Fluorescence Detection of Polycyclic AromaticHydrocarbons in Environmental Tobacco Smoke and Other AirborneParticles

    SciTech Connect

    Mahanama, K.R.R.; Gundel, L.A.; Daisey, J.M.

    1992-11-01

    An analytical method is described for the simultaneous quantitation of polycyclic aromatic hydrocarbons [pAHs] and alkylderivatives [alkyl-PAHs] in 'real world' samples using microbore reversed-phase high performance liquid chromatography in conjunction with two programmable fluorescence detectors. Sensitivity and selectivity were enhanced by analyzing PAHs under their optimum fluorescence wavelengths. The accuracy of the analytical method was evaluated by determination of PAHs in 5 mg of standard reference material SRM 1649. The method was also successfilly employed to analyze major parent PAHs and some alkyl-PAHs from environmental tobacco smoke [ETS] with a sample size of 2 mg using class-selective fluorescence wavelengths. Some alkyl-PAHs were tentatively identified even in the absence of standard compounds. Coeluting pairs were identified and analyzed by careful selection of excitation and emission wavelengths for each compound. Identities of the signals were confirmed by comparing both the retention behavior and the peak-height ratios at two or more different excitation and emission wavelength combinations.

  1. The potential production of aromatic compounds in flowers of Vanda tricolor

    NASA Astrophysics Data System (ADS)

    Darmasiwi, Sari; Indriani, Vitri; Innata, Dita; Semiarti, Endang

    2015-09-01

    Vanda tricolor is a famous natural orchid that has beautiful flowers with fragrance, therefore analysis of aromatic compounds of this orchid are important. The objective of this research was to isolate and identify the aromatic compounds of Vanda tricolor flower. The flower petals were picked at various developmental stages (0,4,7, and 10 days of flower opened) at 12.00 noon. It was then extracted using solvent extraction method and enfleurage method. The hexane:acetone (9:1) extract was considered as concrete extract, while some parts of concrete that were further extracted with ethanol, considered as absolute extract. The olive oil extract was considered as enfleurage extract. Those extracts were then evaporated using nitrogen gas, and analyzed by GC/MS (GC/MS-QP 2010S Shimadzu, Agilent HP-5 MS UI column, 30 m ID length: 0.25 mm, Helium gas carrier). The results showed that aromatic compounds composition in Vanda tricolor flower extracts were consisted of fatty acid derivates, monoterpenoids, sesquiterpenoids, benzenoids, phenylpropanoids, hydrocarbons and other oxygenated compounds. The highest diversity of aromatic compounds were found at the 10th days after floral opened, and the sensory test among those 3 (three) extracts showed that the absolute extract had more similarity with the original flower scent profile rather than the other extracts. This research showed that Vanda tricolor has potential production of aromatic compounds which was different compare to another species of Vanda.

  2. Synthesis of a Fluorescent Acridone using a Grignard Addition, Oxidation, and Nucleophilic Aromatic Substitution Reaction Sequence.

    PubMed

    Goodrich, Samuel; Patel, Miloni; Woydziak, Zachary R

    2015-07-14

    A three-pot synthesis oriented for an undergraduate organic chemistry laboratory was developed to construct a fluorescent acridone molecule. This laboratory experiment utilizes Grignard addition to an aldehyde, alcohol oxidation, and iterative nucleophilic aromatic substitution steps to produce the final product. Each of the intermediates and the acridone product of the synthesis are analyzed by common techniques available in most undergraduate chemistry laboratories, such as melting point, TLC, IR spectroscopy, UV-Vis spectroscopy, and fluorescence spectroscopy. Yields for each transformation in the synthesis are generally moderately low to good (20-90%) and nearly all of the students (>90%) who attempted the synthesis were able to produce the final acridone product.

  3. SOLVENT-FREE REDUCTION OF AROMATIC NITRO COMPOUNDS WITH ALUMINA-SUPPORTED HYDRAZINE UNDER MICROWAVE IRRADIATION

    EPA Science Inventory

    In a solvent-free microwave-expedited process, aromatic nitro compounds are readily reduced to the corresponding amino compounds in good yield with hydrazine hydrate supported on alumina in presence of FeCl3, 6H2), Fe(III) oxide hydroxide or Fe(III) oxides.

  4. Metabolic engineering for microbial production of aromatic amino acids and derived compounds.

    PubMed

    Bongaerts, J; Krämer, M; Müller, U; Raeven, L; Wubbolts, M

    2001-10-01

    Metabolic engineering to design and construct microorganisms suitable for the production of aromatic amino acids and derivatives thereof requires control of a complicated network of metabolic reactions that partly act in parallel and frequently are in rapid equilibrium. Engineering the regulatory circuits, the uptake of carbon, the glycolytic pathway, the pentose phosphate pathway, and the common aromatic amino acid pathway as well as amino acid importers and exporters that have all been targeted to effect higher productivities of these compounds are discussed.

  5. New methods for the synthesis of aromatic fluorine compounds from industrial freons and polyfluorinated olefins

    SciTech Connect

    Nefedov, O.M.; Volchkov, N.V.

    1995-01-10

    The results from investigations into the development and application of a strategy and new methods for the synthesis of aromatic fluorine compounds, using fluorohalogenomethanes and polyfluorinated olefins as initial fluorine-containing substrates or structural units, are summarized. Two general methods for the production of fluoroarenes, involving the synthetic assembly of fluorobenzenoid structures through the cycloaddition of fluorocarbenes and fluoroalkenes to various 1,3-diene substrates and subsequent aromatization of the obtained fluorinated cyclopropane, cyclobutane, or cyclohexene adducts, are examined.

  6. Photoactivation and toxicity of mixtures of polycyclic aromatic hydrocarbon compounds in marine sediment

    SciTech Connect

    Swartz, R.C.; Ferraro, S.P.; Lamberson, J.O.; Cole, F.A.; Ozretich, R.J.; Boese, B.L.; Schults, D.W.; Behrenfeld, M.; Ankley, G.T.

    1997-10-01

    The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration series of either single compounds or as approximately equitoxic mixtures of all four compounds. Standard 10-d sediment toxicity tests were conducted under fluorescent lighting. After 10 d, survivors were exposed for 1 h to ultraviolet (UV) radiation in the absence of sediment and then tested for their ability to bury in uncontaminated sediment. The 10-d median lethal concentrations (LC50s) were 2.31 mg acenaphthene/g organic carbon (OC), 2.22 mg phenanthrene/g OC, 3.31 mg fluoranthene/g OC, and 2.81 mg pyrene/g OC. These LC50s were used to calculate the sum of toxic units ({Sigma}TU) of the four PAHs in the approximately equitoxic mixtures. The {Sigma}TU LC50 was then calculated for the mixture treatments. If the toxicologic interaction of a mixture of contaminants is additive, {Sigma}TU LC50 = 1.0. The observed LC50 (1.55 {Sigma}TU) was slightly, but significantly, greater than unity, indicating that the interaction of PAHs in the mixture was less than additive. Exposure to UV radiation enhanced the toxic effects of fluoranthene and pyrene, but did not affect the toxicity of acenaphthene and phenanthrene. Effects of UV radiation on the toxicity of the mixture of four PAHs could be explained by the photoactivation of fluoranthene and pyrene alone. These results are consistent with predictions based on photophysical properties of PAH compounds.

  7. Inversion and rotation processes involving non-planar aromatic compounds catalyzed by extended polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Karton, Amir

    2014-10-01

    Using accurate quantum chemical calculations, we show that extended planar polycyclic aromatic hydrocarbons (PAHs) can efficiently catalyze a range of chemical processes involving non-planar aromatic systems. These include (i) bowl-to-bowl inversion of curved PAHs (e.g. corannulene and sumanene), (ii) 'flip-flop' inversion of helicenes (e.g. benzo[c]phenanthrene), and (iii) rotation about the Phsbnd Ph bond in biphenyls. Non-covalent π-π interactions between the planar catalyst and the substrate stabilize the planar transition structures to a greater extent than they stabilize the non-planar reactants. These result in surprisingly large catalytic enhancements (namely, the reaction barrier heights are reduced by 21-63% of the uncatalyzed reaction barriers).

  8. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part A-Monocyclic and Polycyclic Aromatic Hydrocarbons.

    PubMed

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty

    2015-08-01

    Present study focused on the screening of bacterial consortium for biodegradation of monocyclic aromatic hydrocarbon (MAH) and polycyclic aromatic hydrocarbons (PAHs). Target compounds in the present study were naphthalene, acenaphthene, phenanthrene (PAHs), and benzene (MAH). Microbial consortia enriched with the above target compounds were used in screening experiments. Naphthalene-enriched consortium was found to be the most efficient consortium, based on its substrate degradation rate and its ability to degrade other aromatic pollutants with significantly high efficiency. Substrate degradation rate with naphthalene-enriched culture followed the order benzene > naphthalene > acenaphthene > phenanthrene. Chryseobacterium and Rhodobacter were discerned as the predominant species in naphthalene-enriched culture. They are closely associated to the type strain Chryseobacterium arthrosphaerae and Rhodobacter maris, respectively. Single substrate biodegradation studies with naphthalene (PAH) and benzene (MAH) were carried out using naphthalene-enriched microbial consortium (NAPH). Phenol and 2-hydroxybenzaldehyde were identified as the predominant intermediates during benzene and naphthalene degradation, respectively. Biodegradation of toluene, ethyl benzene, xylene, phenol, and indole by NAPH was also investigated. Monod inhibition model was able to simulate biodegradation kinetics for benzene, whereas multiple substrate biodegradation model was able to simulate biodegradation kinetics for naphthalene.

  9. Biodegradation of soluble aromatic compounds of jet fuel under anaerobic conditions: laboratory batch experiments.

    PubMed

    Zheng, Z; Breedveld, G; Aagaard, P

    2001-11-01

    Laboratory batch experiments were performed with contaminated aquifer sediments and four soluble aromatic components of jet fuel to assess their biodegradation under anaerobic conditions. The biodegradation of four aromatic compounds, toluene, o-xylene, 1,2,4-trimethylbenzene (TMB), and naphthalene, separately or together, was investigated under strictly anaerobic conditions in the dark for a period of 160 days. Of the aromatic compounds, toluene and o-xylene were degraded both as a single substrate and in a mixture with the other aromatic compounds, while TMB was not biodegraded as a single substrate, but was biodegraded in the presence of the other aromatic hydrocarbons. Substrate interaction is thus significant in the biodegradation of TMB. Biodegradation of naphthalene was not observed, either as a single substrate or in a mixture of other aromatic hydrocarbons. Although redox conditions were dominated by iron reduction, a clear relation between degradation and sulfate reduction was observed. Methanogenesis took place during the later stages of incubation. However, the large background of Fe(II) masked the increase of Fe(II) concentration due to iron reduction. Thus, although microbial reduction of Fe(III) is an important process, the evidence is not conclusive. Our results have shown that a better understanding of the degradation of complex mixtures of hydrocarbons under anaerobic conditions is important in the application of natural attenuation as a remedial method for soil and groundwater contamination.

  10. Environmental diagnostic analysis of ground water bacteria and their involvement in utilization of aromatic compounds

    SciTech Connect

    Wear, J.E. Jr.

    1993-05-01

    The objective of this study was to examine the hypothesis that select functional groups of bacteria from pristine sites have an innate ability to degrade synthetic aromatics that often contaminate groundwater environments,due to exposure to naturally occurring recalcitrant aromatics in their environment. This study demonstrates that subsurface microbial communities are capable of utilizing lignin and humic acid breakdown products. Utilizers of these compounds were found to be present in most all the wells tested. Even the deepest aquifer tested had utilizers present for all six of the aromatics tested. Highest counts for the aromatics tested were observed with the naturally occurring breakdown products of either lignin or humic acid. Carboxylic acids were found to be an important sole carbon source for groundwater bacteria possibly explained by the fact that they are produced by the oxidative cleavage of aromatic ring structures. The carbohydrate sole carbon sources that demonstrated the greatest densities were ones commonly associated with humics. This study indicates that utilization of naturally occurring aromatic compounds in the subsurface is an important nutritional source for groundwater bacteria. In addition, it suggests that adaptation to naturally occurring recalcitrant substrates is the origin of degradative pathways for xenobiotic compounds with analogous structure. This work has important implications for in situ bioremediation as a method of environmental cleanup.

  11. Light emission from compound eye with conformal fluorescent coating

    NASA Astrophysics Data System (ADS)

    Martín-Palma, Raúl J.; Miller, Amy E.; Pulsifer, Drew P.; Lakhtakia, Akhlesh

    2015-03-01

    Compound eyes of insects are attractive biological systems for engineered biomimicry as artificial sources of light, given their characteristic wide angular field of view. A blowfly eye was coated with a thin conformal fluorescent film, with the aim of achieving wide field-of-view emission. Experimental results showed that the coated eye emitted visible light and that the intensity showed a weaker angular dependence than a fluorescent thin film deposited on a flat surface.

  12. Electron-transfer fluorescence quenching of aromatic hydrocarbons by europium and ytterbium ions in acetonitrile.

    PubMed

    Inada, Taeko; Funasaka, Yoko; Kikuchi, Koichi; Takahashi, Yasutake; Ikeda, Hiroshi

    2006-03-02

    To make the effects of molecular size on photoinduced electron-transfer (ET) reactions clear, the ET fluorescence quenching of aromatic hydrocarbons by trivalent lanthanide ions M3+ (europium ion Eu3+ and ytterbium ion Yb3+) and the following ET reactions such as the geminate and free radical recombination were studied in acetonitrile. The rate constant k(q) of fluorescence quenching, the yields of free radical (phi(R)) and fluorescer triplet (phi(T)) in fluorescence quenching, and the rate constant k(rec) of free radical recombination were measured. Upon analysis of the free energy dependence of k(q), phi(R), phi(T), and k(rec), it was found that the switchover of the fluorescence quenching mechanism occurs at deltaG(fet) = -1.4 to -1.6 eV: When deltaG(fet) < -1.6 eV, the fluorescence quenching by M3+ is induced by a long-distance ET yielding the geminate radical ion pairs. When deltaG(fet) > -1.4 eV, it is induced by an exciplex formation. The exciplex dissociates rapidly to yield either the fluorescer triplet or the geminate radical ion pairs. The large shift of switchover deltaG(fet) from -0.5 eV for aromatic quenchers to -1.4 to -1.6 eV for lanthanide ions is almost attributed to the difference in the molecular size of the quenchers. Furthermore, it was substantiated that the free energy dependence of ET rates for the geminate and free radical recombination is satisfactorily interpreted within the limits of the Marcus theory.

  13. Demonstration of the interactions between aromatic compound-loaded lipid nanocapsules and Acinetobacter baumannii bacterial membrane.

    PubMed

    Montagu, A; Joly-Guillou, M-L; Guillet, C; Bejaud, J; Rossines, E; Saulnier, P

    2016-06-15

    Acinetobacter baumannii is an important nosocomial pathogen that is resistant to many commonly-used antibiotics. One strategy for treatment is the use of aromatic compounds (carvacrol, cinnamaldehyde) against A. baumannii. The aim of this study was to determine the interactions between bacteria and lipid nanocapsules (LNCs) over time based on the fluorescence of 3,3'-Dioctadecyloxacarbocyanine Perchlorate-LNCs (DiO-LNCs) and the properties of trypan blue to analyse the physicochemical mechanisms occurring at the level of the biological membrane. The results demonstrated the capacity of carvacrol-loaded LNCs to interact with and penetrate the bacterial membrane in comparison with cinnamaldehyde-loaded LNCs and unloaded LNCs. Modifications of carvacrol after substitution of hydroxyl functional groups by fatty acids demonstrated the crucial role of hydroxyl functions in antibacterial activity. Finally, after contact with the efflux pump inhibitor, carbonylcyanide-3-chlorophenyl hydrazine (CCCP), the results indicated the total synergistic antibacterial effect with Car-LNCs, showing that CCCP is associated with the action mechanism of carvacrol, especially at the level of the efflux pump mechanism.

  14. Capricious selectivity in electrophilic deuteration of methylenedioxy substituted aromatic compounds.

    PubMed

    Pohjoispää, Monika; Mera-Adasme, Raúl; Sundholm, Dage; Heikkinen, Sami; Hase, Tapio; Wähälä, Kristiina

    2014-11-07

    Ring deuteration via the SEAr mechanism, which is usually problem-free, is found to be troublesome with methylenedioxy substituent aromatics. We report a case where the deuteration not only partially fails at one of the ortho positions but also is completely prevented by a conformation dependent effect at the other o-position. Such selectivity discrepancies are important due to the widespread occurrence of methylenedioxy substituted natural products. Density functional theory calculations were used to elucidate the exchange reaction mechanism in 1,2-dialkoxybenzenes.

  15. Double fluorescence conversion in ultraviolet and visible region for some praseodymium complexes of aromatic carboxylates.

    PubMed

    Yan, Bing; Wang, Wei-Jing; Song, Yi-Shan

    2006-07-01

    Four praseodymium complexes of aromatic carboxylates (benzoate, 4-tert-butylbenzoate, 2-benzoylbe-noate, and benzimidazole-5-carboxylate) have been synthesized and characterized, whose photophysical properties have been studied with ultraviolet spectra, phosphorescence spectra, and fluorescence spectra. The fluorescent emission spectra of all praseodymium complexes show two emission peaks under the excitation band of 245 nm at about 395 and 595 nm respectively, while one peak under 415 nm at about 595 nm, which attributed to be 1S0 --> 1I6 (395 nm) transition and the characteristic emission 1D2 --> 3H4 (595 nm) transition of Pr3+ ion. The 1S0 --> 1I6 transition can be ascribed as the transition of charge transfer state, and the 1D2 --> 3H4 can be further proved that there exists an antenna effect in the fluorescence of praseodymium with aromatic carboxylic acids. In conclusion, the praseodymium complexes systems can realize the double fluorescent conversion in both ultraviolet and visible region and can be further studied the application of this conversion.

  16. Fluorescence quenching method for the determination of carbazochrome sodium sulfonate with aromatic amino acids.

    PubMed

    Gan, Xiao-Juan; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li; Tian, Jing; Xue, Jia-Xing

    2013-01-01

    In Britton-Robinson (BR) buffer medium (pH 3.3), carbazochrome sodium sulfonate (CSS) can react with some aromatic amino acids such as tryptophan (Trp), tyrosine (Tyr) and phenylalanine (Phe) to form a 1:1 complex by electrostatic attraction, aromatic stacking interaction and Van der Waals' force, resulting in fluorescence quenching of these amino acids. Maximum quenching wavelengths were located at 352 nm (CSS-Trp system), 303 nm (CSS-Tyr system) and 284 nm (CSS-Phe system), respectively. The fluorescence quenching value (ΔF) was proportional to the concentration of CSS in a certain range. The fluorescence quenching method for the determination of CSS showed high sensitivity, with detection limits of 31.3 ng/mL (CSS-Trp system), 44.6 ng/mL (CSS-Tyr system) and 315.0 ng/mL (CSS-Phe system), respectively. The optimum conditions of the reaction conditions and the effect of coexisting substances were investigated and results showed that the method had good selectivity. The method was successfully applied for the rapid determination of CSS in blood and urine samples. Based on the bimolecular quenching constant Kq , the effect of temperature and Stern-Volmer plots, this study showed that quenching of fluorescence of amino acids by CSS was a static quenching process.

  17. Determining heats of detonation of non-aromatic energetic compounds without considering their heats of formation.

    PubMed

    Keshavarz, Mohammad Hossein

    2007-04-02

    A new procedure is introduced for calculating heats of detonation of non-aromatic energetic compounds through ratios of oxygen to carbon and hydrogen to oxygen as well as the contribution of some structural parameters. There is no need to use heats of formation of non-aromatic energetic compounds that are usually needed by the other methods. Moreover, this much simple method does not use any experimental and computed data of energetic materials. Predicted heats of detonation for 28 non-aromatic energetic compounds have a root mean square (rms) of deviation of 0.54 kJ/g from experiment, which show good agreement with respect to measured values. The new method is the simplest procedure for predicting heats of detonation and provides reliable results which are comparable with the other methods.

  18. Process for reducing aromatic compounds in ethylenediamine with calcium

    DOEpatents

    Benkeser, R.A.; Laugal, J.A.; Rappa, A.

    1985-08-06

    Olefins are produced by containing an organic compound having at least one benzene ring with ethylenediamine and calcium metal, the calcium metal being used in large excess or alternatively in conjunction with an inert abrasive particulate substance. Substantially all of the organic compounds are converted to corresponding cyclic olefins, largely mono-olefins.

  19. Process for reducing aromatic compounds in ethylenediamine with calcium

    DOEpatents

    Benkeser, Robert A.; Laugal, James A.; Rappa, Angela

    1985-01-01

    Olefins are produced by containing an organic compound having at least one benzene ring with ethylenediamine and calcium metal, the calcium metal being used in large excess or alternatively in conjunction with an inert abrasive particulate substance. Substantially all of the organic compounds are converted to corresponding cyclic olefins, largely mono-olefins.

  20. Simultaneous analysis of riboflavin and aromatic amino acids in beer using fluorescence and multivariate calibration methods.

    PubMed

    Sikorska, Ewa; Gliszczyńska-Swigło, Anna; Insińska-Rak, Małgorzata; Khmelinskii, Igor; De Keukeleire, Denis; Sikorski, Marek

    2008-04-21

    The study demonstrates an application of the front-face fluorescence spectroscopy combined with multivariate regression methods to the analysis of fluorescent beer components. Partial least-squares regressions (PLS1, PLS2, and N-way PLS) were utilized to develop calibration models between synchronous fluorescence spectra and excitation-emission matrices of beers, on one hand, and analytical concentrations of riboflavin and aromatic amino acids, on the other hand. The best results were obtained in the analysis of excitation-emission matrices using the N-way PLS2 method. The respective correlation coefficients, and the values of the root mean-square error of cross-validation (RMSECV), expressed as percentages of the respective mean analytic concentrations, were: 0.963 and 14% for riboflavin, 0.974 and 4% for tryptophan, 0.980 and 4% for tyrosine, and 0.982 and 19% for phenylalanine.

  1. Fluorescent Analysis of Photosynthetic Microbes and Polycyclic Aromatic Hydrocarbons Linked to Optical Remote Sensing

    NASA Astrophysics Data System (ADS)

    Zhang, D.; Muller, J.-P.; Lavender, S.; Walton, D.; Dartnell, L. R.

    2012-07-01

    Fluorescence analysis, being a non-invasive technique, has become one of the most powerful and widely used techniques for microbiologists and chemists to study various types of sample from photosynthetic microbes to hydrocarbons. The work reported here focuses on experimental results of fluorescent features of photosynthetic microbial species (cyanobacteria) and also five different crude oil samples. The cyanobacteria samples were collected from the Baltic Sea at the end of July 2011 and were associated with cyanobacterial bloom events, and the crude oil samples were from various oil spill events. The aim of the study was to find fluorescent biosignatures of cyanobacteria (initially a species specific to the Baltic Sea) and the fingerprints of crude oil; oil spills can be difficult to differentiate from biogenic films when using Synthetic Aperture Radar (SAR) or sunglint contaminated optical imagery. All samples were measured using a Perkin Elmer LS55 Luminescence spectrometer over a broad range of excitation and emission wavelength from ultraviolet (UV) to near infrared (NIR). The results are presented in Excitation Emission Matrices (EEMs) that exhibit the fluorescent features of each sample. In the EEM of the seawater sample containing cyanobacteria, there is an intense emission peak from tryptophan with fluorescent excitation and emission peaks at 285 and 345 nm respectively. In addition, fluorescent signatures of phycocyanin and chlorophyll-a are present with excitation and emission centre wavelengths at 555 nm, 645 nm and 390 nm, 685 nm, respectively. Additionally, the fluorescence signatures of Polycyclic Aromatic Hydrocarbons (PAHs) are present in the EEMs of crude oil samples with excitation and emission peaks at 285 nm and 425 nm. This study underpins further research on how to distinguish cyanobacteria species by their fluorescence signatures and the potential role that PAHs play in detection of cyanobacteria fluorescence features.

  2. Aromatic fluorine compounds. VIII. Plant growth regulators and intermediates

    USGS Publications Warehouse

    Finger, G.C.; Gortatowski, M.J.; Shiley, R.H.; White, R.H.

    1959-01-01

    The preparation and properties of 41 fluorophenoxyacetic acids, 4 fluorophenoxypropionic acids, 2 fluorobenzoic acids, several indole derivatives, and a number of miscellaneous compounds are described. Data are given for many intermediates such as new fluorinated phenols, anisoles, anilines and nitrobenzenes. Most of the subject compounds are related to a number of well-known herbicides or plant growth regulators such as 2,4-D, 2,4,5-T and others.

  3. Azoarcus sp. CIB, an Anaerobic Biodegrader of Aromatic Compounds Shows an Endophytic Lifestyle

    PubMed Central

    Fernández, Helga; Prandoni, Nicolás; Fernández-Pascual, Mercedes; Fajardo, Susana; Morcillo, César; Díaz, Eduardo; Carmona, Manuel

    2014-01-01

    Background Endophytic bacteria that have plant growth promoting traits are of great interest in green biotechnology. The previous thought that the Azoarcus genus comprises bacteria that fit into one of two major eco-physiological groups, either free-living anaerobic biodegraders of aromatic compounds or obligate endophytes unable to degrade aromatics under anaerobic conditions, is revisited here. Methodology/Principal Findings Light, confocal and electron microscopy reveal that Azoarcus sp. CIB, a facultative anaerobe β-proteobacterium able to degrade aromatic hydrocarbons under anoxic conditions, is also able to colonize the intercellular spaces of the rice roots. In addition, the strain CIB displays plant growth promoting traits such nitrogen fixation, uptake of insoluble phosphorus and production of indoleacetic acid. Therefore, this work demonstrates by the first time that a free-living bacterium able to degrade aromatic compounds under aerobic and anoxic conditions can share also an endophytic lifestyle. The phylogenetic analyses based on the 16S rDNA and nifH genes confirmed that obligate endophytes of the Azoarcus genus and facultative endophytes, such as Azoarcus sp. CIB, locate into different evolutionary branches. Conclusions/Significance This is the first report of a bacterium, Azoarcus sp. CIB, able to degrade anaerobically a significant number of aromatic compounds, some of them of great environmental concern, and to colonize the rice as a facultative endophyte. Thus, Azoarcus sp. CIB becomes a suitable candidate for a more sustainable agricultural practice and phytoremediation technology. PMID:25340341

  4. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Compounds and their Ions. 6; Polycyclic Aromatic Nitrogen Heterocycles

    NASA Technical Reports Server (NTRS)

    Mattioda, A. L.; Hudgins, Douglas M.; Bauschlicher, C. W., Jr.; Rosi, M.; Allamandola, L. J.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    The matrix-isolation technique has been employed to measure the mid-infrared spectra of several polycyclic aromatic nitrogen heterocycles in both neutral and cationic forms. The species studied include: 7,8 benzoquinoline (C13H9N); 2-azapyrene (C15H9N); 1- and 2-azabenz(a)anthracene (C17H11N); and 1-, 2-, and 4-azachrysene (also C17H11N). The experimentally measured band frequencies and intensities for each molecule are tabulated and compared with their theoretically calculated values computed using density functional theory at the B3LYP/4-31G level. The overall agreement between experiment and theory is quite good, in keeping with previous investigations involving the parent aromatic hydrocarbons. Several interesting spectroscopic trends are found to accompany nitrogen substitution into the aromatic framework of these compounds. First, for the neutral species, the nitrogen atom produces a significant increase in the total integrated infrared intensity across the 1600 - 1100/cm region and plays an essential role in the molecular vibration that underlies an uncharacteristically intense, discrete feature that is observed near 1400/cm in the spectra of 7,8 benzoquinoline, 1-azabenz(a)anthracene, and 4-azachrysene. The origin of this enhanced infrared activity and the nature of the new 1400/cm vibrational mode are explored. Finally, in contrast to the parent hydrocarbon species, these aromatic nitrogen heterocycles possess a significant permanent dipole moment. Consequently, these dipole moments and the rotational constants are reported for these species in their neutral and ionized forms.

  5. Comamonas testosteroni uses a chemoreceptor for tricarboxylic acid cycle intermediates to trigger chemotactic responses towards aromatic compounds.

    PubMed

    Ni, Bin; Huang, Zhou; Fan, Zheng; Jiang, Cheng-Ying; Liu, Shuang-Jiang

    2013-11-01

    Bacterial chemotaxis towards aromatic compounds has been frequently observed; however, knowledge of how bacteria sense aromatic compounds is limited. Comamonas testosteroni CNB-1 is able to grow on a range of aromatic compounds. This study investigated the chemotactic responses of CNB-1 to 10 aromatic compounds. We constructed a chemoreceptor-free, non-chemotactic mutant, CNB-1Δ20, by disruption of all 19 putative methyl-accepting chemotaxis proteins (MCPs) and the atypical chemoreceptor in strain CNB-1. Individual complementation revealed that a putative MCP (tagged MCP2201) was involved in triggering chemotaxis towards all 10 aromatic compounds. The recombinant sensory domain of MCP2201 did not bind to 3- or 4-hydroxybenzoate, protocatechuate, catechol, benzoate, vanillate and gentisate, but bound oxaloacetate, citrate, cis-aconitate, isocitrate, α-ketoglutarate, succinate, fumarate and malate. The mutant CNB-1ΔpmdF that lost the ability to metabolize 4-hydroxybenzoate and protocatechuate also lost its chemotactic response to these compounds, suggesting that taxis towards aromatic compounds is metabolism-dependent. Based on the ligand profile, we proposed that MCP2201 triggers taxis towards aromatic compounds by sensing TCA cycle intermediates. Our hypothesis was further supported by the finding that introduction of the previously characterized pseudomonad chemoreceptor (McpS) for TCA cycle intermediates into CNB-1Δ20 likewise triggered chemotaxis towards aromatic compounds.

  6. Detection of Medium-Sized Polycyclic Aromatic Hydrocarbons via Fluorescence Energy Transfer

    PubMed Central

    Serio, Nicole; Prignano, Lindsey; Peters, Sean; Levine, Mindy

    2015-01-01

    Reported herein is the use of proximity-induced non-covalent energy transfer for the detection of medium-sized polycyclic aromatic hydrocarbons (PAHs). This energy transfer occurs within the cavity of γ-cyclodextrin in various aqueous environments, including human plasma and coconut water. Highly efficient energy transfer was observed, and the efficiency of the energy transfer is independent of the concentration of γ-cyclodextrin used, demonstrating the importance of hydrophobic binding in facilitating such energy transfer. Low limits of detection were also observed for many of the PAHs investigated, which is promising for the development of fluorescence-based detection schemes. PMID:25821390

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

    PubMed

    Lim, Seung Joo; Fox, Peter

    2014-02-01

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

  8. Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

    PubMed Central

    Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

    1995-01-01

    Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found. PMID:7487007

  9. Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent.

    PubMed

    Hoffmann, Norbert

    2012-11-01

    Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

  10. Native Fluorescence Detection Methods and Detectors for Naphthalene and/or Other Volatile Organic Compound Vapors

    NASA Technical Reports Server (NTRS)

    Hug, William F. (Inventor); Bhartia, Rohit (Inventor); Reid, Ray D. (Inventor); Lane, Arthur L. (Inventor)

    2014-01-01

    Naphthalene, benzene, toluene, xylene, and other volatile organic compounds have been identified as serious health hazards. This is especially true for personnel working with JP8 jet fuel and other fuels containing naphthalene as well as other hazardous volatile organic compounds (VOCs). Embodiments of the invention are directed to methods and apparatus for near-real-time in-situ detection and accumulated dose measurement of exposure to naphthalene vapor and other hazardous gaseous VOCs. The methods and apparatus employ excitation of fluorophors native or endogenous to compounds of interest using light sources emitting in the ultraviolet below 300 nm and measurement of native fluorescence emissions in distinct wavebands above the excitation wavelength. The apparatus of some embodiments are cell-phone-sized sensor/dosimeter "badges" to be worn by personnel potentially exposed to naphthalene or other hazardous VOCs. The badge sensor of some embodiments provides both real time detection and data logging of exposure to naphthalene or other VOCs of interest from which both instantaneous and accumulated dose can be determined. The badges employ a new native fluorescence based detection method to identify and differentiate VOCs. The particular focus of some embodiments are the detection and identification of naphthalene while other embodiments are directed to detection and identification of other VOCs like aromatic hydrocarbons such as benzene, toluene, and xylene.

  11. Detection of polycyclic aromatic hydrocarbons (PAHs) in Medicago sativa L. by fluorescence microscopy.

    PubMed

    Alves, Wilber S; Manoel, Evelin A; Santos, Noemi S; Nunes, Rosane O; Domiciano, Giselli C; Soares, Marcia R

    2017-04-01

    Green technologies, such as phytoremediation, are effective for removing organic pollutants derived from oil and oil products, including polycyclic aromatic hydrocarbons (PAHs). Given the increasing popularity of these sustainable remediation techniques, methods based on fluorescence microscopy and multiphoton microscopy for the environmental monitoring of such pollutants have emerged in recent decades as effective tools for phytoremediation studies aimed at understanding the fate of these contaminants in plants. However, little is known about the cellular and molecular mechanisms involved in PAH uptake, responses and degradation by plants. Thus, the present study aimed to detect the location of pyrene, anthracene and phenanthrene using fluorescence microscopy techniques in shoots and roots of Medicago sativa L. (alfalfa) plants grown in artificially contaminated soil (150ppm PAHs) for 40days. Leaflet and root samples were then collected and observed under a fluorescence microscope to detect the presence of PAHs in various tissues. One important finding of the present study was intense fluorescence in the glandular secreting trichomes (GSTs) of plants grown in contaminated soil. These trichomes, with a previously unknown function, may be sites of PAH conjugation and degradation.

  12. Effect of halogenated fluorescent compounds on bioluminescent reactions.

    PubMed

    Kirillova, Tamara N; Gerasimova, Marina A; Nemtseva, Elena V; Kudryasheva, Nadezhda S

    2011-04-01

    The paper investigates an application of luminescent bioassays to monitor the toxicity of organic halides. Effects of xanthene dyes (fluorescein, eosin Y, and erythrosin B), used as model compounds, on bioluminescent reactions of firefly Luciola mingrelica, marine bacteria Photobacterium leiognathi, and hydroid polyp Obelia longissima were studied. Dependence of bioluminescence quenching constants on the atomic weight of halogen substituents in dye molecules was demonstrated. Bacterial bioluminescence was shown to be most sensitive to heavy halogen atoms involved in molecular structure; hence, it is suitable for construction of sensors to monitor toxicity of halogenated compounds. Mechanisms of bioluminescence quenching--energy transfer processes, collisional interactions, and enzyme-dye binding--were considered. Changes of bioluminescence (BL) spectra in the presence of the dyes were analyzed. Interactions of the dyes with enzymes were studied using fluorescence characteristics of the dyes in steady-state and time-resolved experiments. The dependences of fluorescence anisotropy of enzyme-bound dyes, the average fluorescence lifetime, and the number of exponential components in fluorescence decay on the atomic weight of halogen substituents were demonstrated. The results are discussed in terms of "dark effect of heavy halogen atom" in the process of enzyme-dye binding; hydrophobic interactions were assumed to be responsible for the effect.

  13. Quenching of red cell tryptophan fluorescence by mercurial compounds.

    PubMed

    Verkman, A S; Lukacovic, M F; Tinklepaugh, M S; Dix, J A

    1986-01-01

    Intrinsic tryptophan fluorescence in red cell ghost membranes labeled with N-ethylmaleimide (N-EM) is quenched in a dose-dependent manner by the organic mercurial p-chloromercuribenzene sulfonate (p-CMBS). Fluorescence lifetime analysis shows that quenching occurs by a static mechanism. Binding of p-CMBS occurs by a rapid (less than 5 s) biomolecular association (dissociation constant K1 = 1.8 mM) followed by a slower unimolecular transition with forward rate constant k2 = 0.015 s-1 and reverse rate constant k-2 = 0.0054 s-1. Analysis of the temperature dependence of k2 gives delta H = 6.5 kcal/mol and delta S = -21 eu. The mercurial compounds p-chloromercuribenzoic acid, p-aminophenylmercuric acetate, and mercuric chloride quench red cell tryptophan fluorescence by the same mechanism as p-CMBS does; the measured k2 value was the same for each compound, whereas K1 varied. p-CMBS also quenches the tryptophan fluorescence in vesicles reconstituted with purified band 3, the red cell anion exchange protein, in a manner similar to that in ghost membranes. These experiments define a mercurial binding site on band 3 in ghosts treated with N-EM and establish the binding mechanism to this site. The characteristics of this p-CMBS binding site on band 3 differ significantly from those of the p-CMBS binding site involved in red cell water and urea transport inhibition.

  14. Biosynthesis of polybrominated aromatic organic compounds by marine bacteria

    PubMed Central

    Agarwal, Vinayak; El Gamal, Abrahim A.; Yamanaka, Kazuya; Poth, Dennis; Kersten, Roland D.; Schorn, Michelle; Allen, Eric E.; Moore, Bradley S.

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs) and polybrominated bipyrroles are natural products that bioaccumulate in the marine food chain. PBDEs have attracted widespread attention due to their persistence in the environment and potential toxicity to humans. However, the natural origins of PBDE biosynthesis are not known. Here we report marine bacteria as producers of PBDEs and establish a genetic and molecular foundation for their production that unifies paradigms for the elaboration of bromophenols and bromopyrroles abundant in marine biota. We provide biochemical evidence of marine brominase enzymes revealing decarboxylative-halogenation enzymology previously unknown among halogenating enzymes. Biosynthetic motifs discovered in our study were used to mine sequence databases to discover unrealized marine bacterial producers of organobromine compounds. PMID:24974229

  15. [Analysis of Three Polycyclic Aromatic Hydrocarbons in Solution Based on Two-Dimensional Fluorescence Correlation Spectroscopy].

    PubMed

    Zhou, Chang-hong; Zhao, Mei-rong; Yang, Ren-jie; Zhu, Wen-bi; Dong, Gui-mei

    2016-02-01

    Polycyclic aromatic hydrocarbons (PAHs) are listed as the priority pollutants. It is difficult to resolve effectively the peaks of PAHs by conventional one-dimensional fluorescence spectroscopy due to its low content and the overlapping fluorescence three mixed ystems and a total of 27 samples, are to be prepared with different concentrations of three PAHs. Concentrations of three PAHS are monotonically increasing or decreasing in each mixed system. Then the 2D fluorescence correlation spectrum of each mixed systems will be calculated under the perturbation of the concentration of anthracene, phenanthrene and pyrene in solution. There are seven strong autopeaks at 425, 402, 381, 373, 365, 393 and 347 nm in synchronous 2D correlation spectrum. The fluorescence peak of phenanthrene at 347 nm is uncovered in three mixed systems, so the band at 347 nm is to be used as clues for further assignment. According to positive or negative cross peaks at 347 nm in synchronous 2D correlation spectrum, we can know that the peaks at 402, 381, 425 and 452 nm are assigned to anthracene, the peaks at 373 and 393 nm are assigned to pyrene, and the peaks at 365, 356 and 347 nm are assigned to phenanthrene. The fluorescence peak of phenanthrene at 385 nm is shown in asynchronous 2D correlation spectrum; it means the spectral resolution of asynchronous spectrum is better than the synchronous spectrum. The results are that it is feasible to analyze serious overlapping multi-component PAHs using two-dimensional fluorescence correlation spectroscopy, which can be extended to the detection of other pollutants in the air.

  16. Aromatic compound glucosides, alkyl glucoside and glucide from the fruit of anise.

    PubMed

    Fujimatu, Eiko; Ishikawa, Toru; Kitajima, Junichi

    2003-07-01

    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.

  17. Antitumor and antiparasitic activity of novel ruthenium compounds with polycyclic aromatic ligands.

    PubMed

    Miserachs, Helena Guiset; Cipriani, Micaella; Grau, Jordi; Vilaseca, Marta; Lorenzo, Julia; Medeiros, Andrea; Comini, Marcelo A; Gambino, Dinorah; Otero, Lucía; Moreno, Virtudes

    2015-09-01

    Five novel ruthenium(II)-arene complexes with polycyclic aromatic ligands were synthesized, comprising three compounds of the formula [RuCl(η(6)-p-cym)(L)][PF6], where p-cym = 1-isopropyl-4-methylbenzene and L are the bidentate aromatic ligands 1,10-phenanthroline-5,6-dione, 1, 5-amine-1,10-phenanthroline, 4, or 5,6-epoxy-5,6-dihydro-phenanthroline, 5. In the other two complexes [RuCl2(η(6)-p-cym)(L')], the metal is coordinated to a monodentate ligand L', where L' is phenanthridine, 2, or 9-carbonylanthracene, 3. All compounds were fully characterized by mass spectrometry and elemental analysis, as well as NMR and IR spectroscopic techniques. Obtained ruthenium compounds as well as their respective ligands were tested for their antiparasitic and antitumoral activities. Even though all compounds showed lower Trypanosoma brucei activity than the free ligands, they also resulted less toxic on mammalian cells. Cytotoxicity assays on HL60 cells showed a moderate antitumoral activity for all ruthenium compounds. Compound 1 was the most potent antitumoral (IC50 = 1.26±0.78 μM) and antiparasitic (IC50 = 0.19 ± 0.05 μM) agent, showing high selectivity towards the parasites (selectivity index >100). As complex 1 was the most promising antitumoral compound, its interaction with ubiquitin as potential target was also studied. In addition, obtained ruthenium compounds were found to bind DNA, and they are thought to interact with this macromolecule mainly through intercalation of the aromatic ligand.

  18. Removal of aromatic hydrocarbon compounds by hydroxypropyl-cyclodextrin

    SciTech Connect

    1999-09-15

    Activated carbon has been used for the recovery and removal of benzene, toluene, and xylenes in air and water for a long time. However, removal of benzene, toluene, and xylenes from soil is very difficult. They can be removed by an increase in the apparent solubility of organic compounds in soil. The apparent solubilities of benzene, toluene, and xylene were investigated to estimate their inclusion behavior into natural cyclodextrins (CDs) and hydroxypropyl-cyclodextrins (HP-CDs) in the liquid phase. The apparent solubilities of benzene, toluene, and xylenes did not increase by adding natural CDs but did increase when HP-CDs were added. Benzene, toluene, and xylenes in a HP-CD solution depended on the relationship between the molecular diameter of benzene, toluene, and xylenes, the CD cavity size, and the 1-octanol-water partition coefficient. That of p-xylene was larger than that of o-xylene and m-xylene because of the smallest steric hindrance of p-xylene.

  19. Analysis of preference for carbon source utilization among three strains of aromatic compounds degrading Pseudomonas.

    PubMed

    Karishma, M; Trivedi, Vikas D; Choudhary, Alpa; Mhatre, Akanksha; Kambli, Pranita; Desai, Jinal; Phale, Prashant S

    2015-10-01

    Soil isolates Pseudomonas putida CSV86, Pseudomonas aeruginosa PP4 and Pseudomonas sp. C5pp degrade naphthalene, phthalate isomers and carbaryl, respectively. Strain CSV86 displayed a diauxic growth pattern on phenylpropanoid compounds (veratraldehyde, ferulic acid, vanillin or vanillic acid) plus glucose with a distinct second lag-phase. The glucose concentration in the medium remained constant with higher cell respiration rates on aromatics and maximum protocatechuate 3,4-dioxygenase activity in the first log-phase, which gradually decreased in the second log-phase with concomitant depletion of the glucose. In strains PP4 and C5pp, growth profile and metabolic studies suggest that glucose is utilized in the first log-phase with the repression of utilization of aromatics (phthalate or carbaryl). All three strains utilize benzoate via the catechol 'ortho' ring-cleavage pathway. On benzoate plus glucose, strain CSV86 showed preference for benzoate over glucose in contrast to strains PP4 and C5pp. Additionally, organic acids like succinate were preferred over aromatics in strains PP4 and C5pp, whereas strain CSV86 co-metabolizes them. Preferential utilization of aromatics over glucose and co-metabolism of organic acids and aromatics are found to be unique properties of P. putida CSV86 as compared with strains PP4 and C5pp and this property of strain CSV86 can be exploited for effective bioremediation.

  20. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    PubMed Central

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.

    1994-01-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  1. Leaching of styrene and other aromatic compounds in drinking water from PS bottles.

    PubMed

    Ahmad, Maqbool; Bajahlan, Ahmad S

    2007-01-01

    Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene (PS) bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as "purge and trap" and analysed by gas chromatograph-mass spectrometer (GC/MS). Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 microg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 microg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.

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

    PubMed Central

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

    2007-01-01

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

  3. Photocatabolism of aromatic compounds by the phototrophic purple bacterium Rhodomicrobium vannielii

    SciTech Connect

    Wright, G.E.; Madigan, M.T. )

    1991-07-01

    The phototrophic purple non-sulfur bacterium Thodomicrobium vannielii grew phototrophically (illuminated anaerobic conditions) on a variety of aromatic compounds (in the presence of CO{sub 2}). Benzoate was universally photocatabolized by all five strains of R. vannielii examined, and benzyl alcohol was photocatabolized by four of the five strains. Catabolism of benzyl alcohol by phototrophic bacteria has not been previously reported. Other aromatic substrates supporting reasonably good growth of R. vannielii strains were the methozylated benzoate derivatives vanillate (4-hydroxy-3-methoxybenzoate) and syringate (4-hydroxy-3,5-dimethoxybenzoate). However, catabolism of vanillate and syringate led to significant inhibition of bacteriochlorophyll synthesis in R. vannielii cells, eventually causing cultures to cease growing. No such effect on photopigment synthesis in cells grown on benzoate or benzyl alcohol was observed. Along with a handful of other species of anoxygenic phototrophic bacteria, the ability of the species R. vannielii to photocatabolize aromatic compounds indicates that this organism may also be ecologically significant as a consumer of aromatic derivatives in illuminated anaerobic habitats in nature.

  4. Mass spectrometry investigation of Titan aerosols analogs formed with traces of aromatic compounds

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Trainer, Melissa; Sebree, Joshua; Li, Xiang; Pinnick, Veronica; Getty, Stephanie; Brinckerhoff, Will

    2016-06-01

    The detection of benzene at ppm levels in Titan's atmosphere [1] by Cassini's Ion and Neutral Mass Spectrometer (INMS) supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titan's aerosols formation. In laboratory studies it has been shown that these aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation [2] and be used to dope the production of aerosol analogs [3]. In this work we investigate the effect on the aerosol composition and growth pattern of the chemical nature of the aromatic reactant used to produce aerosol. Analysis are performed using Laser Desorption-Time of Flight mass spectrometry (LD-TOF) and Fourier Transform Infrared Spectroscopy (FTIR) Infrared analysis of our samples shows that inclusion of aromatic compounds as trace precursors allows to better fit laboratory data to Titan aerosol spectra observed by Cassini [3,4]. The improvement is especially visible on the far infrared (˜200 cm-1) bands observed by CIRS [5]. LDMS results show that the aerosol growth patterns depend both on the number of rings and on the nitrogen content of the trace precursor used. We also perform MS/MS analysis on some prominent peaks of aerosol mass spectra. This MS/MS approach allows us to identify some of the key compounds in the aerosol growth processes.

  5. The studies on the aromaticity of fullerenes and their holmium endohedral compounds.

    PubMed

    Tan, Bisheng; Peng, Rufang; Li, Hongbo; Wang, Bing; Jin, Bo; Chu, Shijin; Long, Xinping

    2011-02-01

    Density functional theory BLYP/DNP was employed to optimize a series of fullerenes and their holmium endohedral compounds, including C(20), Ho@C(20), Ho(3+)@C(20), C(60), Ho@C(60), Ho(3+)@C(60),C(70), Ho@C(70), Ho(3+)@C(70) C(78), Ho@C(78), Ho(3+)@C(78), C(82),Ho@C(82) and Ho(3+)@C(82). DFT semi core pseudospot approximation was taken into consideration in the calculations of the element holmium because of its particular electronic structure. Fullerenes and their holmium endohedral compounds' aromaticity were studied in terms of structural criteria, energetic criteria, and reactivity criteria. The results indicate that the aromaticity of fullerenes was reduced when a holmium atom was introduced into the carbon cage, and the endohedral fullerenes' reactive activity enhance; but the aromaticity of the carbon cage increased when a Ho(3+) cation was encapsulated into a fullerene. Calculations of aromaticity and stability indicate that two paths can lead to the similar aim of preparing holmium endohedral fullerenes; that is, they can form from either a holmium atom or a holmium cation (Ho(3+)) reacting with fullerenes, respectively, and the latter is more favorable.

  6. Pseudomonads biodegradation of aromatic compounds in oil sands process-affected water.

    PubMed

    Zhang, Yanyan; McPhedran, Kerry N; Gamal El-Din, Mohamed

    2015-07-15

    Aromatic naphthenic acids (NAs) have been shown to be more toxic than the classical NAs found in oil sands process-affected water (OSPW). To reduce this toxicity, Pseudomonas fluorescens and Pseudomonas putida were used to determine their ability to biodegrade aromatic compounds including treatments considering the impacts of external carbon and iron addition. Results showed that with added carbon P. fluorescens and P. putida have the capability of biodegrading these aromatics. In the presence of external carbon, gene expression of a functional PAH-ring hydroxylating dioxygenase (PAH-RHDα) was determined through reverse transcription real-time PCR, suggesting active degradation of OSPW aromatic compounds. Although no significant classical NAs removal was observed during this process, toxicity was reduced by 49.3% under optimal conditions. OSPW toxicity was eliminated with the combination of ozonation at a dose of 80 mg/L followed by biodegradation, indicating that it is a promising combined OSPW treatment approach for the safe discharge to the aquatic environment.

  7. [Macromolecular aromatic network characteristics of Chinese power coal analyzed by synchronous fluorescence and X-ray diffraction].

    PubMed

    Ye, Cui-Ping; Feng, Jie; Li, Wen-Ying

    2012-07-01

    Coal structure, especially the macromolecular aromatic skeleton structure, has a strong influence on coke reactivity and coal gasification, so it is the key to grasp the macromolecular aromatic skeleton coal structure for getting the reasonable high efficiency utilization of coal. However, it is difficult to acquire their information due to the complex compositions and structure of coal. It has been found that the macromolecular aromatic network coal structure would be most isolated if small molecular of coal was first extracted. Then the macromolecular aromatic skeleton coal structure would be clearly analyzed by instruments, such as X-ray diffraction (XRD), fluorescence spectroscopy with synchronous mode (Syn-F), Gel permeation chromatography (GPC) etc. Based on the previous results, according to the stepwise fractional liquid extraction, two Chinese typical power coals, PS and HDG, were extracted by silica gel as stationary phase and acetonitrile, tetrahydrofuran (THF), pyridine and 1-methyl-2-pyrollidinone (NMP) as a solvent group for sequential elution. GPC, Syn-F and XRD were applied to investigate molecular mass distribution, condensed aromatic structure and crystal characteristics. The results showed that the size of aromatic layers (La) is small (3-3.95 nm) and the stacking heights (Lc) are 0.8-1.2 nm. The molecular mass distribution of the macromolecular aromatic network structure is between 400 and 1 130 amu, with condensed aromatic numbers of 3-7 in the structure units.

  8. Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in the Cosmic Simulation Chamber

    NASA Technical Reports Server (NTRS)

    Bejaoui, Salma; Salama, Farid; Contreras, Cesar; Sciamma O'Brien, Ella; Foing, Bernard; Pascale, Ehrenfreund

    2015-01-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser induced fluorescence (LIF) technique and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates a plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examined.

  9. Quick estimation of heats of detonation of aromatic energetic compounds from structural parameters.

    PubMed

    Keshavarz, Mohammad Hossein

    2007-05-08

    In this paper, a simple procedure is introduced for a quick and reliable estimation of detonation heats of aromatic energetic compounds without considering heats of formation of energetic compounds. This method does not use any experimental or computed data of energetic materials. The methodology assumes that the heat of detonation of an energetic compound with composition of C(a)H(b)N(c)O(d) can be obtained from the number of nitrogens, ratios of oxygen to carbon and hydrogen to oxygen as well as the contribution of some specific functional groups. There is no need to use any assumed decomposition products to calculate heats of detonation for energetic compounds. Predicted heats of detonation of pure energetic compounds with the product H(2)O in the liquid state for 31 aromatic energetic compounds have a root mean square (rms) of deviation of 0.32 kJ/g from experiment. The new method gives good results with respect to two empirical methods which use measured heats of formation of explosives with two sets of decomposition gases.

  10. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part B--Nitrogen-, Sulfur-, and Oxygen-Containing Heterocyclic Aromatic Compounds.

    PubMed

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty

    2015-07-01

    Present study focused on the biodegradation of various heterocyclic nitrogen, sulfur, and oxygen (NSO) compounds using naphthalene-enriched culture. Target compounds in the study were pyridine, quinoline, benzothiophene, and benzofuran. Screening studies were carried out using different microbial consortia enriched with specific polycyclic aromatic hydrocarbon (PAH) and NSO compounds. Among different microbial consortia, naphthalene-enriched culture was the most efficient consortium based on high substrate degradation rate. Substrate degradation rate with naphthalene-enriched culture followed the order pyridine > quinoline > benzofuran > benzothiophene. Benzothiophene and benzofuran were found to be highly recalcitrant pollutants. Benzothiophene could not be biodegraded when concentration was above 50 mg/l. It was observed that 2-(1H)-quinolinone, benzothiophene-2-one, and benzofuran-2,3-dione were formed as metabolic intermediates during biodegradation of quinoline, benzothiophene, and benzofuran, respectively. Quinoline-N and pyridine-N were transformed into free ammonium ions during the biodegradation process. Biodegradation pathways for various NSO compounds are proposed. Monod inhibition model was able to simulate single substrate biodegradation kinetics satisfactorily. Benzothiophene and benzofuran biodegradation kinetics, in presence of acetone, was simulated using a generalized multi-substrate model.

  11. Application of BDD thin film electrode for electrochemical decomposition of heterogeneous aromatic compounds

    NASA Astrophysics Data System (ADS)

    Czupryniak, Justyna; Fabiańska, Aleksandra; Stepnowski, Piotr; Ossowski, Tadeusz; Bogdanowicz, Robert; Gnyba, Marcin; Siedlecka, Ewa M.

    2012-10-01

    The aim of the presented study is to investigate the applicability of electrochemical oxidation of aromatic compounds containing heteroatoms, e.g. waste from production of pesticides or pharmaceutics, at a borondoped diamond (BDD) electrode. The BDD electrodes were synthesized by microwave plasma enhanced chemical vapour deposition (MW PE CVD). Investigation of the electrode surface by optical microscopy and scanning electron microscopy (SEM) confirmed that the synthesized layer was continuous and formed a densely packed grain structure with an average roughness of less than 0 :5 μm. The influence of important electrochemical parameters: current density, kind of reactor, pH or mixing operation, on the efficiency of the oxidation was investigated. The fouling of electrode's surface caused by the deposition of organic material was observed during CV and galvanostatic experiments. At low current density the oxidation rate constant k was low, but the current efficiency was relatively high. The BDD can be used successfully to remove heterogeneous aromatic compounds existing either as molecules or cations. During 4 h of electrolysis 95% of aromatic compounds were electrochemically decomposed to mineral forms. It was observed that the influence of the initial pH on mineralization was marginal.

  12. Application of BDD thin film electrode for electrochemical decomposition of heterogeneous aromatic compounds

    NASA Astrophysics Data System (ADS)

    Czupryniak, Justyna; Fabiańska, Aleksandra; Stepnowski, Piotr; Ossowski, Tadeusz; Bogdanowicz, Robert; Gnyba, Marcin; Siedlecka, Ewa

    2012-10-01

    The aim of the presented study is to investigate the applicability of electrochemical oxidation of aromatic compounds containing heteroatoms, e.g. waste from production of pesticides or pharmaceutics, at a borondoped diamond (BDD) electrode. The BDD electrodes were synthesized by microwave plasma enhanced chemical vapour deposition (MW PE CVD). Investigation of the electrode surface by optical microscopy and scanning electron microscopy (SEM) confirmed that the synthesized layer was continuous and formed a densely packed grain structure with an average roughness of less than 0:5 μm. The influence of important electrochemical parameters: current density, kind of reactor, pH or mixing operation, on the efficiency of the oxidation was investigated. The fouling of electrode's surface caused by the deposition of organic material was observed during CV and galvanostatic experiments. At low current density the oxidation rate constant k was low, but the current efficiency was relatively high. The BDD can be used successfully to remove heterogeneous aromatic compounds existing either as molecules or cations. During 4 h of electrolysis 95% of aromatic compounds were electrochemically decomposed to mineral forms. It was observed that the influence of the initial pH on mineralization was marginal.

  13. Structural and functional characterization of solute binding proteins for aromatic compounds derived from lignin: p-coumaric acid and related aromatic acids.

    PubMed

    Tan, Kemin; Chang, Changsoo; Cuff, Marianne; Osipiuk, Jerzy; Landorf, Elizabeth; Mack, Jamey C; Zerbs, Sarah; Joachimiak, Andrzej; Collart, Frank R

    2013-10-01

    Lignin comprises 15-25% of plant biomass and represents a major environmental carbon source for utilization by soil microorganisms. Access to this energy resource requires the action of fungal and bacterial enzymes to break down the lignin polymer into a complex assortment of aromatic compounds that can be transported into the cells. To improve our understanding of the utilization of lignin by microorganisms, we characterized the molecular properties of solute binding proteins of ATP-binding cassette transporter proteins that interact with these compounds. A combination of functional screens and structural studies characterized the binding specificity of the solute binding proteins for aromatic compounds derived from lignin such as p-coumarate, 3-phenylpropionic acid and compounds with more complex ring substitutions. A ligand screen based on thermal stabilization identified several binding protein clusters that exhibit preferences based on the size or number of aromatic ring substituents. Multiple X-ray crystal structures of protein-ligand complexes for these clusters identified the molecular basis of the binding specificity for the lignin-derived aromatic compounds. The screens and structural data provide new functional assignments for these solute-binding proteins which can be used to infer their transport specificity. This knowledge of the functional roles and molecular binding specificity of these proteins will support the identification of the specific enzymes and regulatory proteins of peripheral pathways that funnel these compounds to central metabolic pathways and will improve the predictive power of sequence-based functional annotation methods for this family of proteins.

  14. Theoretical and experimental study of polycyclic aromatic compounds as β-tubulin inhibitors.

    PubMed

    Olazarán, Fabian E; García-Pérez, Carlos A; Bandyopadhyay, Debasish; Balderas-Rentería, Isaias; Reyes-Figueroa, Angel D; Henschke, Lars; Rivera, Gildardo

    2017-03-01

    In this work, through a docking analysis of compounds from the ZINC chemical library on human β-tubulin using high performance computer cluster, we report new polycyclic aromatic compounds that bind with high energy on the colchicine binding site of β-tubulin, suggesting three new key amino acids. However, molecular dynamic analysis showed low stability in the interaction between ligand and receptor. Results were confirmed experimentally in in vitro and in vivo models that suggest that molecular dynamics simulation is the best option to find new potential β-tubulin inhibitors. Graphical abstract Bennett's acceptance ratio (BAR) method.

  15. A New Aromatic Compound from the Stem Bark of Terminalia catappa.

    PubMed

    Pertuit, David; Mitaine-Offer, Anne-Claire; Miyamoto, Tomofumi; Tanaka, Chiaki; Delemasure, Stéphanie; Dutartre, Patrick; Lacaille-Dubois, Marie-Aleth

    2015-06-01

    A new aromatic compound 3,4,5-trimethoxyphenyl-1-O-(4-sulfo)-β-D-glucopyranoside (1), in addition to two triterpenoid saponins (chebuloside II, arjunoglucoside II), two triterpenes (arjunolic acid and 3-betulinic acid) and sitosterol-3-O-β-D-glucopyranoside have been isolated from the barks of Terminalia catappa. Their structures have been established on the basis of spectroscopic techniques (1D/2D NMR) and MS. Their cytotoxicity and antiinflammatory activity, together with the antioxidant capacity of compound 1 were also evaluated.

  16. Langmuir films of asphaltene model compounds and their fluorescent properties.

    PubMed

    Nordgård, Erland L; Landsem, Eva; Sjöblom, Johan

    2008-08-19

    The relationship between the physicochemical properties of asphaltenes and asphaltene structure is an issue of increasing focus. Surface pressure-area isotherms of asphaltene model compounds have been investigated to gain more knowledge of their arrangement at an aqueous surface. Variations in interfacial activity have been correlated to proposed arrangements. The presence of a carboxylic acid has shown to be crucial for their interfacial activity and film properties. The acid group directs the molecules normal to the surface, forming a stable monolayer film. The high stability was absent when no acidic groups were present. Fluorescence spectra of deposited Langmuir-Blodgett films showed only the presence of the excimer emission for thin films of acidic model compounds, indicating a close face-to-face arrangement of the molecules. Time-correlated single photon counting (TCSPC) of the model compounds in toluene indicated the presence of aggregates for two of four compounds at low concentrations. However, a sudden drop of interfacial tension observed could not be correlated to the aggregation. Instead, aggregation induced by addition of a "poor" solvent showed decreased interfacial activity when aggregated due to decrease of monomers in bulk. The findings regarding these asphaltene model compounds and their structural differences show the great effect an acidic group has on their physicochemical properties.

  17. Ultraviolet-stimulated fluorescence and phosphorescence of aromatic hydrocarbons in water ice.

    PubMed

    Johnson, Paul V; Hodyss, Robert; Bolser, Diana K; Bhartia, Rohit; Lane, Arthur L; Kanik, Isik

    2011-03-01

    A principal goal of astrobiology is to detect and inventory the population of organic compounds on extraterrestrial bodies. Targets of specific interest include the wealth of icy worlds that populate our Solar System. One potential technique for in situ detection of organics trapped in water ice matrices involves ultraviolet-stimulated emission from these compounds. Here, we report a preliminary investigation into the feasibility of this concept. Specifically, fluorescence and phosphorescence of pure benzene ice and 1% mixtures of benzene, toluene, p-xylene, m-xylene, and o-xylene in water ice, respectively, were studied at temperatures ranging from ∼17 K up to 160 K. Spectra were measured from 200-500 nm (50,000-20,000 cm(-1)) while ice mixtures were excited at 248.6 nm. The temperature dependence of the fluorescence and phosphorescence intensities was found to be independent of the thermal history and phase of the ice matrix in all cases examined. All phosphorescent emissions were found to decrease in intensity with increasing temperature. Similar behavior was observed for fluorescence in pure benzene, while the observed fluorescence intensity in water ices was independent of temperature.

  18. Correlations and adsorption mechanisms of aromatic compounds on a high heat temperature treated bamboo biochar.

    PubMed

    Yang, Kun; Yang, Jingjing; Jiang, Yuan; Wu, Wenhao; Lin, Daohui

    2016-03-01

    Adsorption of aromatic compounds, including polycyclic aromatic hydrocarbons, nitrobenzenes, phenols, and anilines, on a bamboo biochar produced at 700 °C (Ba700) was investigated with the mechanism discussion by isotherm fitting using the Polanyi-theory based Dubinin-Ashtakhov (DA) model. Correlations of adsorption capacity (Q(0)) of organic compounds with their molecular sizes and melting points, as well as correlations of adsorption affinity (E) with their solvatochromic parameters (i.e., π* and αm), on the biochar, were developed and indicating that adsorption is captured by the pore filling mechanism and derived from the hydrophobic effects of organic compounds and the forming of π-π electron donor-acceptor (EDA) interactions and hydrogen bonding interactions of organic molecules with surface sites of the biochar. The effects of organic molecular sizes and melting points on adsorption capacity are ascribed to the molecular sieving effect and the packing efficiency of the organic molecules in the biochar pores, respectively. These correlations can be used to quantitatively estimate the adsorption of organic compounds on biochars from their commonly physicochemical properties including solvatochromic parameters, melting points and molecular cross-sectional area. The prediction using these correlations is important for assessing the unknown adsorption behaviors of new organic compounds and also helpful to guide the surface modification of biochars and make targeted selection in the environmental applications of biochars as adsorbents.

  19. Phenotypic profiling and gene expression analyses for aromatic and volatile compounds in Chamoes (Cucumis melo).

    PubMed

    Lee, Jeongyeo; Kim, Min Keun; Hwang, Seung Hwan; Kim, Jungeun; Ahn, Jong Moon; Min, Sung Ran; Park, Sang Un; Lim, Soon Sung; Kim, HyeRan

    2014-05-01

    Gotgam chamoe (GgC), a native oriental melon in Korea, is known to possess the aroma of a dried persimmon, an agronomic relevance for melon breeding program. The volatile compounds and the transcript levels of aromatic compound genes in cultivar (Ohbokggul chamoe [OC]) and GgC were profiled. A total of 62 volatile compounds were identified and quantified. Twenty-eight volatile compounds were specific to either the OC or the GgC. The amounts of volatile alcohol, saturated hydrocarbon, and unsaturated hydrocarbon compounds were 2.2, 2.7, and 1.1 times higher in OC, respectively. The amounts of ketone volatiles were 1.2 times higher in GgC, whereas the total amounts of esters were similar. In the shikimate pathway, transcriptional patterns with the fruit parts were different between the two chamoes for CmDAHPS, CmDHD/SDH, and CmEPSPS. The expression levels of all six genes investigated, especially CmCS, were highest in the peel of both chamoes compared to the other parts. The transcript levels of the aromatic amino acid biosynthesis genes demonstrate that phenylalanine and tyrosine are present more in edible parts of the chamoe, while tryptophan may be accumulated low in the chamoe. In addition, phenylalanine and tryptophan are synthesized more in GgC than the OC.

  20. Pseudomonas putida as a platform for the synthesis of aromatic compounds.

    PubMed

    Molina-Santiago, Carlos; Cordero, Baldo F; Daddaoua, Abdelali; Udaondo, Zulema; Manzano, Javier; Valdivia, Miguel; Segura, Ana; Ramos, Juan-Luis; Duque, Estrella

    2016-09-01

    Aromatic compounds such as l-phenylalanine, 2-phenylethanol and trans-cinnamate are aromatic compounds of industrial interest. Current trends support replacement of chemical synthesis of these compounds by 'green' alternatives produced in microbial cell factories. The solvent-tolerant Pseudomonas putida DOT-T1E strain was genetically modified to produce up to 1 g l-1 of l-phenylalanine. In order to engineer this strain, we carried out the following stepwise process: (1) we selected random mutants that are resistant to toxic phenylalanine analogues; (2) we then deleted up to five genes belonging to phenylalanine metabolism pathways, which greatly diminished the internal metabolism of phenylalanine; and (3) in these mutants, we overexpressed the pheAfbr gene, which encodes a recombinant variant of PheA that is insensitive to feedback inhibition by phenylalanine. Furthermore, by introducing new genes, we were able to further extend the diversity of compounds produced. Introduction of histidinol phosphate transferase (PP_0967), phenylpyruvate decarboxylase (kdc) and an alcohol dehydrogenase (adh) enabled the strain to produce up to 180 mg l-1 2-phenylethanol. When phenylalanine ammonia lyase (pal) was introduced, the resulting strain produced up to 200 mg l-1 of trans-cinnamate. These results demonstrate that P. putida can serve as a promising microbial cell factory for the production of l-phenylalanine and related compounds.

  1. Investigation of aromatic compound degradation under atmospheric conditions in the outdoor simulation chamber SAPHIR

    NASA Astrophysics Data System (ADS)

    Nehr, Sascha; Bohn, Birger; Rohrer, Franz; Tillmann, Ralf; Wegener, Robert; Dorn, Hans-Peter; Häseler, Rolf; Brauers, Theo; Wahner, Andreas

    2010-05-01

    Ozone is produced in the lower troposphere by the OH-initiated photooxidation of volatile organic compounds in the presence of NOx. Aromatic hydrocarbons from anthropogenic sources are a major contributor to the OH-reactivity and thus to ozone formation in urban areas [1]. Moreover, their degradation leads to formation of secondary organic aerosol. Aromatic compounds are therefore important trace constituents with regard to air quality. We will present the results of photooxidation experiments which were conducted in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. The experiments were designed to investigate the degradation mechanisms of benzene and p-xylene, which are among the most abundant aromatics in urban air samples. Benzene and p-xylene were selected because they have high structural symmetry which limits the number of potential isomers of secondary products. The experiments were performed under low-NOx-conditions (≤ 2 ppb). SAPHIR was equipped with instruments for the measurement of the parent aromatics and their major oxidation products, OH radicals, important radical precursors (O3, HONO, HCHO), photolysis frequencies and particulate matter. As shown in previous studies, simulation chamber data from the photooxidation of aromatics cannot be explained satisfactorily with current photochemistry mechanisms. For example the MCMv3.1 tends to overestimate the ozone-concentration and to underestimate the OH-concentration [2]. In this study, we will contrast model calculations with experimental results to check if similar discrepancies can be observed in SAPHIR and how they can be resolved. Based on the results of this preparatory study, further simulation chamber experiments with special emphasis on the radical budget are scheduled in 2010. References: [1] J. G. Calvert, R. Atkinson, K.H. Becker, R.M. Kamens, J.H. Seinfeld, T.J. Wallington, G. Yarwood: The mechanisms of atmospheric oxidation of aromatic hydrocarbons, Oxford University

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

    PubMed

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

    Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

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

    DOEpatents

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

    1982-03-31

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

  4. Native Fluorescence Detection Methods, Devices, and Systems for Organic Compounds

    NASA Technical Reports Server (NTRS)

    Hug, William F. (Inventor); Bhartia, Rohit (Inventor); Reid, Ray D. (Inventor); Lane, Arthur L. (Inventor)

    2016-01-01

    Naphthalene, benzene, toluene, xylene, and other volatile organic compounds VOCs have been identified as serious health hazards. Embodiments of the invention are directed to methods and apparatus for near-real-time in-situ detection and accumulated dose measurement of exposure to naphthalene vapor and other hazardous gaseous VOCs. The methods and apparatus employ excitation of fluorophors native or endogenous to compounds of interest using light sources emitting in the ultraviolet below 300 nm and measurement of native fluorescence emissions in distinct wavebands above the excitation wavelength. The apparatus of some embodiments are cell-phone-sized sensor/dosimeter "badges" to be worn by personnel potentially exposed to hazardous VOCs. The badge sensor of some embodiments provides both real time detection and data logging of exposure to naphthalene or other VOCs of interest from which both instantaneous and accumulated dose can be determined.

  5. Analysis of industrial contaminants in indoor air: part 1. Volatile organic compounds, carbonyl compounds, polycyclic aromatic hydrocarbons and polychlorinated biphenyls.

    PubMed

    Barro, Ruth; Regueiro, Jorge; Llompart, María; Garcia-Jares, Carmen

    2009-01-16

    This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.

  6. Enhancing trichloroethylene degradation using non-aromatic compounds as growth substrates.

    PubMed

    Kim, Seungjin; Hwang, Jeongmin; Chung, Jinwook; Bae, Wookeun

    2014-06-30

    The effect of non-aromatic compounds on the trichloroethylene (TCE) degradation of toluene-oxidizing bacteria were evaluated using Burkholderia cepacia G4 that expresses toluene 2-monooxygenase and Pseudomonas putida that expresses toluene dioxygenase. TCE degradation rates for B. cepacia G4 and P. putida with toluene alone as growth substrate were 0.144 and 0.123 μg-TCE/mg-protein h, respectively. When glucose, acetate and ethanol were fed as additional growth substrates, those values increased up to 0.196, 0.418 and 0.530 μg-TCE/mg-protein h, respectively for B. cepacia G4 and 0.319, 0.219 and 0.373 μg-TCE/mg-protein h, respectively for P. putida. In particular, the addition of ethanol resulted in a high TCE degradation rate regardless of the initial concentration. The use of a non-aromatic compound as an additional substrate probably enhanced the TCE degradation because of the additional supply of NADH that is consumed in co-metabolic degradation of TCE. Also, it is expected that the addition of a non-aromatic substrate can reduce the necessary dose of toluene and, subsequently, minimize the potential competitive inhibition upon TCE co-metabolism by toluene.

  7. Production of aromatic compounds by metabolically engineered Escherichia coli with an expanded shikimate pathway.

    PubMed

    Koma, Daisuke; Yamanaka, Hayato; Moriyoshi, Kunihiko; Ohmoto, Takashi; Sakai, Kiyofumi

    2012-09-01

    Escherichia coli was metabolically engineered by expanding the shikimate pathway to generate strains capable of producing six kinds of aromatic compounds, phenyllactic acid, 4-hydroxyphenyllactic acid, phenylacetic acid, 4-hydroxyphenylacetic acid, 2-phenylethanol, and 2-(4-hydroxyphenyl)ethanol, which are used in several fields of industries including pharmaceutical, agrochemical, antibiotic, flavor industries, etc. To generate strains that produce phenyllactic acid and 4-hydroxyphenyllactic acid, the lactate dehydrogenase gene (ldhA) from Cupriavidus necator was introduced into the chromosomes of phenylalanine and tyrosine overproducers, respectively. Both the phenylpyruvate decarboxylase gene (ipdC) from Azospirillum brasilense and the phenylacetaldehyde dehydrogenase gene (feaB) from E. coli were introduced into the chromosomes of phenylalanine and tyrosine overproducers to generate phenylacetic acid and 4-hydroxyphenylacetic acid producers, respectively, whereas ipdC and the alcohol dehydrogenase gene (adhC) from Lactobacillus brevis were introduced to generate 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol producers, respectively. Expression of the respective introduced genes was controlled by the T7 promoter. While generating the 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol producers, we found that produced phenylacetaldehyde and 4-hydroxyphenylacetaldehyde were automatically reduced to 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol by endogenous aldehyde reductases in E. coli encoded by the yqhD, yjgB, and yahK genes. Cointroduction and cooverexpression of each gene with ipdC in the phenylalanine and tyrosine overproducers enhanced the production of 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol from glucose. Introduction of the yahK gene yielded the most efficient production of both aromatic alcohols. During the production of 2-phenylethanol, 2-(4-hydroxyphenyl)ethanol, phenylacetic acid, and 4-hydroxyphenylacetic acid, accumulation of some by

  8. Production of Aromatic Compounds by Metabolically Engineered Escherichia coli with an Expanded Shikimate Pathway

    PubMed Central

    Yamanaka, Hayato; Moriyoshi, Kunihiko; Ohmoto, Takashi; Sakai, Kiyofumi

    2012-01-01

    Escherichia coli was metabolically engineered by expanding the shikimate pathway to generate strains capable of producing six kinds of aromatic compounds, phenyllactic acid, 4-hydroxyphenyllactic acid, phenylacetic acid, 4-hydroxyphenylacetic acid, 2-phenylethanol, and 2-(4-hydroxyphenyl)ethanol, which are used in several fields of industries including pharmaceutical, agrochemical, antibiotic, flavor industries, etc. To generate strains that produce phenyllactic acid and 4-hydroxyphenyllactic acid, the lactate dehydrogenase gene (ldhA) from Cupriavidus necator was introduced into the chromosomes of phenylalanine and tyrosine overproducers, respectively. Both the phenylpyruvate decarboxylase gene (ipdC) from Azospirillum brasilense and the phenylacetaldehyde dehydrogenase gene (feaB) from E. coli were introduced into the chromosomes of phenylalanine and tyrosine overproducers to generate phenylacetic acid and 4-hydroxyphenylacetic acid producers, respectively, whereas ipdC and the alcohol dehydrogenase gene (adhC) from Lactobacillus brevis were introduced to generate 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol producers, respectively. Expression of the respective introduced genes was controlled by the T7 promoter. While generating the 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol producers, we found that produced phenylacetaldehyde and 4-hydroxyphenylacetaldehyde were automatically reduced to 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol by endogenous aldehyde reductases in E. coli encoded by the yqhD, yjgB, and yahK genes. Cointroduction and cooverexpression of each gene with ipdC in the phenylalanine and tyrosine overproducers enhanced the production of 2-phenylethanol and 2-(4-hydroxyphenyl)ethanol from glucose. Introduction of the yahK gene yielded the most efficient production of both aromatic alcohols. During the production of 2-phenylethanol, 2-(4-hydroxyphenyl)ethanol, phenylacetic acid, and 4-hydroxyphenylacetic acid, accumulation of some by

  9. The rate of photocatalytic oxidation of aromatic volatile organic compounds in the gas-phase

    NASA Astrophysics Data System (ADS)

    Boulamanti, Aikaterini K.; Korologos, Christos A.; Philippopoulos, Constantine J.

    In the present study, the gas-solid heterogeneous photocatalytic oxidation (PCO) of six aromatic species of volatile organic compounds (VOCs), benzene, toluene, ethylbenzene, m-, o- and p-xylene over illuminated titania was carried out at ambient temperature in a continuous stirring-tank reactor. Initial VOC concentrations were in the low parts per million (ppm) range. Maximum conversions were over 90% for all compounds except from benzene, ethylbenzene and o-xylene, while the residence time varied from 50 to 210 s. Intermediates were detected only in the case of the xylenes, but catalyst deactivation occurred for all six compounds. The PCO kinetics were well fit by a Langmuir-Hinshelwood (L-H) model for monomolecular surface reaction and it was proved that the reaction rate is related to both constants. The rate constants ranged from 0.147 ppm s -1 g cat-1 for benzene to 1.067 ppm s -1 g cat-1 for m-xylene, while the adsorption constants from 0.424 ppm -1 for ethylbenzene to 0.69 ppm -1 for toluene. The molecular structure of the compounds was found to play an important role in the reaction. Finally the efficiency of the procedure in the case of a mixture of these aromatic substances was tested.

  10. Aromatic-Hydroxyl Interaction of a Lignin Model Compound on SBA-15, Present at Pyrolysis Temperatures

    DOE PAGES

    Kandziolka, III, Michael V.; Kidder, Michelle; Gill, Lance W.; ...

    2014-07-14

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic–hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C–H stretches, as well as a red-shift and broadening of the surface hydroxyl O–H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ~400 °C whereupon themore » ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.« less

  11. Aromatic-Hydroxyl Interaction of a Lignin Model Compound on SBA-15, Present at Pyrolysis Temperatures

    SciTech Connect

    Kandziolka, III, Michael V.; Kidder, Michelle; Gill, Lance W.; Wu, Zili; Savara, Aditya Ashi

    2014-07-14

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic–hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C–H stretches, as well as a red-shift and broadening of the surface hydroxyl O–H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ~400 °C whereupon the ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.

  12. Transition-Metal Planar Boron Clusters: a New Class of Aromatic Compounds with High Coordination

    NASA Astrophysics Data System (ADS)

    Wang, Lai-Sheng

    2012-06-01

    Photoelectron spectroscopy in combination with computational studies over the past decade has shown that boron clusters possess planar or quasi-planar structures, in contrast to that of bulk boron, which is dominated by three-dimensional cage-like building blocks. All planar or quasi-planar boron clusters are observed to consist of a monocyclic circumference with one or more interior atoms. The propensity for planarity has been found to be due to both σ and π electron delocalization throughout the molecular plane, giving rise to concepts of σ and π double aromaticity. We have found further that the central boron atoms can be substituted by transition metal atoms to form a new class of aromatic compounds, which consist of a central metal atom and a monocyclic boron ring (M B_n). Eight-, nine-, and ten-membered rings of boron have been observed, giving rise to octa-, ennea-, and deca-coordinated aromatic transition metal compounds [1-3]. References: [1] ``Aromatic Metal-Centered Monocyclic Boron Rings: Co B_9^- and Ru B_9^-" (Constantin Romanescu, Timur R. Galeev, Wei-Li Li, A. I. Boldyrev, and L. S. Wang), Angew. Chem. Int. Ed. {50}, 9334-9337 (2011). [2] ``Transition-Metal-Centered Nine-Membered Boron Rings: M B_9 and M B_9^- (M = Rh, Ir)" (Wei-Li Li, Constantin Romanescu, Timur R. Galeev, Zachary Piazza, A. I. Boldyrev, and L. S. Wang), J. Am. Chem. Soc. {134}, 165-168 (2012). [3] ``Observation of the Highest Coordination Number in Planar Species: Decacoordinated Ta B10^- and Nb B_9^- Anions" (Timur R. Galeev, Constantin Romanescu, Wei-Li Li, L. S. Wang, and A. I. Boldyrev), Angew. Chem. Int. Ed. {51}, 2101-2105 (2012).

  13. Quinones and Aromatic Chemical Compounds in Particulate Matter Induce Mitochondrial Dysfunction: Implications for Ultrafine Particle Toxicity

    PubMed Central

    Xia, Tian; Korge, Paavo; Weiss, James N.; Li, Ning; Venkatesen, M. Indira; Sioutas, Constantinos; Nel, Andre

    2004-01-01

    Particulate pollutants cause adverse health effects through the generation of oxidative stress. A key question is whether these effects are mediated by the particles or their chemical compounds. In this article we show that aliphatic, aromatic, and polar organic compounds, fractionated from diesel exhaust particles (DEPs), exert differential toxic effects in RAW 264.7 cells. Cellular analyses showed that the quinone-enriched polar fraction was more potent than the polycyclic aromatic hydrocarbon (PAH)–enriched aromatic fraction in O2•− generation, decrease of membrane potential (ΔΨm), loss of mitochondrial membrane mass, and induction of apoptosis. A major effect of the polar fraction was to promote cyclosporin A (CsA)–sensitive permeability transition pore (PTP) opening in isolated liver mitochondria. This opening effect is dependent on a direct effect on the PTP at low doses as well as on an effect on ΔΨm at high doses in calcium (Ca2+)-loaded mitochondria. The direct PTP effect was mimicked by redox-cycling DEP quinones. Although the aliphatic fraction failed to perturb mitochondrial function, the aromatic fraction increased the Ca2+ retention capacity at low doses and induced mitochondrial swelling and a decrease in ΔΨm at high doses. This swelling effect was mostly CsA insensitive and could be reproduced by a mixture of PAHs present in DEPs. These chemical effects on isolated mitochondria could be reproduced by intact DEPs as well as ambient ultrafine particles (UFPs). In contrast, commercial polystyrene nanoparticles failed to exert mitochondrial effects. These results suggest that DEP and UFP effects on the PTP and ΔΨm are mediated by adsorbed chemicals rather than the particles themselves. PMID:15471724

  14. Bioactive compounds derived from the yeast metabolism of aromatic amino acids during alcoholic fermentation.

    PubMed

    Mas, Albert; Guillamon, Jose Manuel; Torija, Maria Jesus; Beltran, Gemma; Cerezo, Ana B; Troncoso, Ana M; Garcia-Parrilla, M Carmen

    2014-01-01

    Metabolites resulting from nitrogen metabolism in yeast are currently found in some fermented beverages such as wine and beer. Their study has recently attracted the attention of researchers. Some metabolites derived from aromatic amino acids are bioactive compounds that can behave as hormones or even mimic their role in humans and may also act as regulators in yeast. Although the metabolic pathways for their formation are well known, the physiological significance is still far from being understood. The understanding of this relevance will be a key element in managing the production of these compounds under controlled conditions, to offer fermented food with specific enrichment in these compounds or even to use the yeast as nutritional complements.

  15. Bioactive Compounds Derived from the Yeast Metabolism of Aromatic Amino Acids during Alcoholic Fermentation

    PubMed Central

    Guillamon, Jose Manuel; Torija, Maria Jesus; Beltran, Gemma; Troncoso, Ana M.; Garcia-Parrilla, M. Carmen

    2014-01-01

    Metabolites resulting from nitrogen metabolism in yeast are currently found in some fermented beverages such as wine and beer. Their study has recently attracted the attention of researchers. Some metabolites derived from aromatic amino acids are bioactive compounds that can behave as hormones or even mimic their role in humans and may also act as regulators in yeast. Although the metabolic pathways for their formation are well known, the physiological significance is still far from being understood. The understanding of this relevance will be a key element in managing the production of these compounds under controlled conditions, to offer fermented food with specific enrichment in these compounds or even to use the yeast as nutritional complements. PMID:24895623

  16. Atmospheric plasma-driven catalysis for the low temperature decomposition of dilute aromatic compounds

    NASA Astrophysics Data System (ADS)

    Kim, Hyun-Ha; Ogata, Atsushi; Futamura, Shigeru

    2005-04-01

    The decomposition of volatile organic compounds (VOCs)—six aromatic compounds of benzene derivatives and formic acid—was investigated using a plasma-driven catalysis (PDC) system at atmospheric pressure. In the PDC reactor, the decomposition efficiency of VOCs was mostly determined by the specific input energy (SIE) and insensitivity to the gas hourly space velocity from 11 000 to 55 000 h-1. Formic acid (HCOOH) was formed as a common intermediate from the decomposition of the tested aromatic compounds. Formic acid was also found to be an important intermediate for CO2 formation. Except for styrene, all the tested VOCs indicated zero-order kinetics, which confirm the dominant role of the catalytic reaction in the decomposition of VOCs using the PDC reactor. A simple kinetic model represents well the observed zero-order kinetics with respect to the SIE. Unlike conventional plasma reactors, no correlation between the ionization potential and the decomposition was found with the PDC reactor. Continuous operation tests indicated stable performance without deterioration of catalytic activity over 150 h.

  17. Predicting adsorption of aromatic compounds by carbon nanotubes based on quantitative structure property relationship principles

    NASA Astrophysics Data System (ADS)

    Rahimi-Nasrabadi, Mehdi; Akhoondi, Reza; Pourmortazavi, Seied Mahdi; Ahmadi, Farhad

    2015-11-01

    Quantitative structure property relationship (QSPR) models were developed to predict the adsorption of aromatic compounds by carbon nanotubes (CNTs). Five descriptors chosen by combining self-organizing map and stepwise multiple linear regression (MLR) techniques were used to connect the structure of the studied chemicals with their adsorption descriptor (K∞) using linear and nonlinear modeling techniques. Correlation coefficient (R2) of 0.99 and root-mean square error (RMSE) of 0.29 for multilayered perceptron neural network (MLP-NN) model are signs of the superiority of the developed nonlinear model over MLR model with R2 of 0.93 and RMSE of 0.36. The results of cross-validation test showed the reliability of MLP-NN to predict the K∞ values for the aromatic contaminants. Molar volume and hydrogen bond accepting ability were found to be the factors much influencing the adsorption of the compounds. The developed QSPR, as a neural network based model, could be used to predict the adsorption of organic compounds by CNTs.

  18. The pollution characteristics of odor, volatile organochlorinated compounds and polycyclic aromatic hydrocarbons emitted from plastic waste recycling plants.

    PubMed

    Tsai, Chung-Jung; Chen, Mei-Lien; Chang, Keng-Fu; Chang, Fu-Kuei; Mao, I-Fang

    2009-02-01

    Plastic waste treatment trends toward recycling in many countries; however, the melting process in the facilities which adopt material recycling method for treating plastic waste may emit toxicants and cause sensory annoyance. The objectives of this study were to analyze the pollution characteristics of the emissions from the plastic waste recycling plants, particularly in harmful volatile organochlorinated compounds, polycyclic aromatic hydrocarbons (PAHs), odor levels and critical odorants. Ten large recycling plants were selected for analysis of odor concentration (OC), volatile organic compounds (VOCs) and PAHs inside and outside the plants using olfactometry, gas chromatography-mass spectrometry and high performance liquid chromatography-fluorescence detector, respectively. The olfactometric results showed that the melting processes used for treating polyethylene/polypropylene (PE/PP) and polyvinyl chloride (PVC) plastic waste significantly produced malodor, and the odor levels at downwind boundaries were 100-229 OC, which all exceeded Taiwan's EPA standard of 50 OC. Toluene, ethylbenzene, 4-methyl-2-pentanone, methyl methacrylate and acrolein accounted for most odors compared to numerous VOCs. Sixteen organochlorinated compounds were measured in the ambient air emitted from the PVC plastic waste recycling plant and total concentrations were 245-553 microg m(-3); most were vinyl chloride, chloroform and trichloroethylene. Concentrations of PAHs inside the PE/PP plant were 8.97-252.16 ng m(-3), in which the maximum level were 20-fold higher than the levels detected from boundaries. Most of these recycling plants simply used filter to treat the melting fumes, and this could not efficiently eliminate the gaseous compounds and malodor. Improved exhaust air pollution control were strongly recommended in these industries.

  19. Factors that influence the response of the LysR type transcriptional regulators to aromatic compounds

    PubMed Central

    2011-01-01

    Background The transcriptional regulators DntR, NagR and NtdR have a high sequence identity and belong to the large family of LysR type transcriptional regulators (LTTRs). These three regulators are all involved in regulation of genes identified in pathways for degradation of aromatic compounds. They activate the transcription of these genes in the presence of an inducer, but the inducer specificity profiles are different. Results The results from this study show that NtdR has the broadest inducer specificity, responding to several nitro-aromatic compounds. Mutational studies of residues that differ between DntR, NagR and NtdR suggest that a number of specific residues are involved in the broader inducer specificity of NtdR when compared to DntR and NagR. The inducer response was also investigated as a function of the experimental conditions and a number of parameters such as the growth media, plasmid arrangement of the LTTR-encoding genes, promoter and gfp reporter gene, and the presence of a His6-tag were shown to affect the inducer response in E.coli DH5α. Furthermore, the response upon addition of both salicylate and 4-nitrobenzoate to the growth media was larger than the sum of responses upon addition of each of the compounds, which suggests the presence of a secondary binding site, as previously reported for other LTTRs. Conclusions Optimization of the growth conditions and gene arrangement resulted in improved responses to nitro-aromatic inducers. The data also suggests the presence of a previously unknown secondary binding site in DntR, analogous to that of BenM. PMID:21884597

  20. Flash Vacuum Pyrolysis of Lignin Model Compounds: Reaction Pathways of Aromatic Methoxy Groups

    SciTech Connect

    Britt, P.F.; Buchanan, A.C., III; Martineau, D.R.

    1999-03-21

    Currently, there is interest in utilizing lignin, a major constituent of biomass, as a renewable source of chemicals and fuels. High yields of liquid products can be obtained from the flash or fast pyrolysis of biomass, but the reaction pathways that lead to product formation are not understood. To provide insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds at 500 C. This presentation will focus on the FVP of {beta}-ether linkages containing aromatic methoxy groups and the reaction pathways of methoxy-substituted phenoxy radicals.

  1. Sono-bromination of aromatic compounds based on the ultrasonic advanced oxidation processes.

    PubMed

    Fujita, Mitsue; Lévêque, Jean-Marc; Komatsu, Naoki; Kimura, Takahide

    2015-11-01

    A novel, mild "sono-halogenation" of various aromatic compounds with potassium halide was investigated under ultrasound in a biphasic carbon tetrachloride/water medium. The feasibility study was first undertaken with the potassium bromide and then extended to chloride and iodide analogues. This methodology could be considered as a new expansion of the ultrasonic advanced oxidation processes (UAOPs) into a synthetic aspect as the developed methodology is linked to the sonolytic disappearance of carbon tetrachloride. Advantages of the present method are not only that the manipulation of the bromination is simple and green, but also that the halogenating agents used are readily available, inexpensive, and easy-handling.

  2. Antioxidant and Anti-Osteoporotic Activities of Aromatic Compounds and Sterols from Hericium erinaceum.

    PubMed

    Li, Wei; Lee, Sang Hyun; Jang, Hae Dong; Ma, Jin Yeul; Kim, Young Ho

    2017-01-11

    Hericium erinaceum, commonly called lion's mane mushroom, is a traditional edible mushroom widely used in culinary applications and herbal medicines in East Asian countries. In this study, a new sterol, cerevisterol 6-cinnamate (6), was isolated from the fruiting bodies of H. erinaceum together with five aromatic compounds 1-5 and five sterols 7-11. The chemical structures of these compounds were elucidated using chemical and physical methods and comparison of HRESIMS, ¹D-NMR (¹H, (13)C, and DEPT) and 2D-NMR (COSY, HMQC, HMBC, and NOESY) spectra with previously reported data. The antioxidant and anti-osteoporotic activities of extracts and the isolated compounds 1-11 were investigated. All compounds exhibited peroxyl radical-scavenging capacity but only compounds 1, 3, and 4 showed potent reducing capacity. Moreover, compounds 1, 2, 4, and 5 showed moderate effects on cellular antioxidant activity and inhibited the receptor activator of nuclear factor κB ligand (RANKL)-induced osteoclastic differentiation. These results suggested that H. erinaceum could be utilized in the development of natural antioxidant and anti-osteoporotic nutraceuticals and functional foods.

  3. Kinetics of oxidation of aliphatic and aromatic thiols by myeloperoxidase compounds I and II.

    PubMed

    Burner, U; Jantschko, W; Obinger, C

    1999-01-29

    Myeloperoxidase (MPO) is the most abundant protein in neutrophils and plays a central role in microbial killing and inflammatory tissue damage. Because most of the non-steroidal anti-inflammatory drugs and other drugs contain a thiol group, it is necessary to understand how these substrates are oxidized by MPO. We have performed transient kinetic measurements to study the oxidation of 14 aliphatic and aromatic mono- and dithiols by the MPO intermediates, Compound I (k3) and Compound II (k4), using sequential mixing stopped-flow techniques. The one-electron reduction of Compound I by aromatic thiols (e.g. methimidazole, 2-mercaptopurine and 6-mercaptopurine) varied by less than a factor of seven (between 1.39 +/- 0.12 x 10(5) M(-1) s(-1) and 9.16 +/- 1.63 x 10(5) M(-1) s(-1)), whereas reduction by aliphatic thiols was demonstrated to depend on their overall net charge and hydrophobic character and not on the percentage of thiol deprotonation or redox potential. Cysteamine, cysteine methyl ester, cysteine ethyl ester and alpha-lipoic acid showed k3 values comparable to aromatic thiols, whereas a free carboxy group (e.g. cysteine, N-acetylcysteine, glutathione) diminished k3 dramatically. The one-electron reduction of Compound II was far more constrained by the nature of the substrate. Reduction by methimidazole, 2-mercaptopurine and 6-mercaptopurine showed second-order rate constants (k4) of 1.33 +/- 0.08 x 10(5) M(-1) s(-1), 5.25 +/- 0.07 x 10(5) M(-1) s(-1) and 3.03 +/- 0.07 x 10(3) M(-1) s(-1). Even at high concentrations cysteine, penicillamine and glutathione could not reduce Compound II, whereas cysteamine (4.27 +/- 0.05 x 10(3) M(-1) s(-1)), cysteine methyl ester (8.14 +/- 0.08 x 10(3) M(-1) s(-1)), cysteine ethyl ester (3.76 +/- 0.17 x 10(3) M(-1) s(-1)) and alpha-lipoic acid (4.78 +/- 0.07 x 10(4) M(-1) s(-1)) were demonstrated to reduce Compound II and thus could be expected to be oxidized by MPO without co-substrates.

  4. Comparison of HPLC-MS interfaces in the determination of heterocyclic polycyclic aromatic compounds

    SciTech Connect

    Thomas, D.; Sim, P.G.; Benoit, F.M.

    1995-12-31

    Polycyclic aromatic compounds (PACs) are generally regarded as one of the most widely disseminated groups of chemical carcinogens. In this work, the authors are interested in the determination of some of the heteroatom substituted PACs, particularly those containing nitrogen (PANHs) or sulfur (PASHs) in the aromatic ring structure. The reason for interest in these compounds is the extreme carcinogenicity of many of them. Further, the relative carcinogenicity can vary markedly between different members of a set of isomeric compounds. Any reliable assessment of the hazards associated with exposure to mixtures of PACs must, therefore, include analysis of the levels of these compounds in the mixture. The analytical technique used must also yield information about the relative amounts of different isomeric compounds. The sample chosen for this study is an extract of PACs from the Sydney Tar Ponds, Sydney, Nova Scotia, Canada. The Tar Ponds represent the end result of approximately 80 years of the uncontrolled discharge of effluent from an industrial coking operation into a tidal lagoon. It is thus a rich source of PAC mixtures. In the present work, the authors have applied two HPLC-MS methods to the characterization of the PASH content of tar pond sample fractions. The methods differed in the nature of the interface between the HPLC and the MS, and in the ionization process. The two techniques studied were the moving belt with EI ionization, and the heated nebulizer with APCI. Comparison was made on the basis of a number of criteria, including ease of use (and of automation), quality of mass spectra provided, preservation of chromatographic integrity, and sensitivity.

  5. Determination of polynuclear aromatic hydrocarbons in seafood by liquid chromatography with fluorescence detection

    SciTech Connect

    Perfetti, G.A.; Nyman, P.J.; Fisher, S.; Joe, F.L. Jr.; Diachenko, G.W.

    1992-09-01

    Modification of a previously published method for determination of polynuclear aromatic hydrocarbons (PAHs) produces very clean seafood extracts in less than half the time. After alkaline digestion of the seafood, PAHs were partitioned into 1,2,3-trichlorotrifluoroethane. The resulting extract was cleaned up by solid-phase extraction on alumina, silica, and C{sub 18} adsorbents and then analyzed by gradient reversed-phase liquid chromatography with programmable fluorescence detection. Average recoveries of 12 PAHs [acenaphthene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)-fluoranthene, benzo(k)-fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene, benzo(ghi)perylene, and indeno(1,2,3-cd)pyrene] from 5 different matrixes (mussels, oysters, clams, crabmeat, and salmon)spiked at low parts-per-billion levels ranged from 76 to 94%. Estimated limits of quantitation ranged from 0.01 to 0.6 ppb PAHs in extracts that were free of matrix interferences. Results of analyses of a mussels standard reference material obtained from the National Institute of Standards and Technology were in good agreement with the certified values. 16 refs., 3 figs., 4 tabs.

  6. Fluorescence monitoring of polycyclic aromatic hydrocarbon biodegradation and effect of surfactants

    SciTech Connect

    Putcha, R.V.; Domach, M.M. )

    1993-05-01

    Polycyclic Aromatic Hydrocarbons (PAH) are ubiquitous environmental pollutants that are suspected to be carcinogenic. Because some PAHs can undergo metabolic degradation, an interest has emerged in bioremediating contaminated sites and incorporating surfactants into treatment processes because the release of slowing desorbing, soil-bound PAH may be promoted. The authors employed fluorescence spectroscopy and quenching experiments to investigate micelle-naphthalene interaction and the dynamics of biodegradation in the presence and absence of micelles. These experiments were envisioned to provide some molecular-level insights as well as constitute the basis for subsequent work where realistic model systems will be investigated in a noninvasive manner. In the absence of micelles, naphthalene was observed to be degraded within three days and intermediates were detected. Micelles protected naphthalene against copper quenching and also suppressed biodegradation. Additionally, the emission spectrum of the naphthalene associated with the micelles changed over the course of days. Based on prior quenching and polarization studies, this finding suggests that micelle maturation may occur over the time scale of days, resulting in increased sequestering of naphthalene in the micellar phase. 12 refs., 7 figs.

  7. Coupled LC-GC techniques for the characterisation of polycyclic aromatic compounds in fuel materials

    SciTech Connect

    Askey, S.A.; Holden, K.M.L.; Bartle, K.D.

    1995-12-31

    Exposure to polycyclic aromatic compounds (PAC) has long been identified as of considerable environmental concern. Originating from both natural and anthropogenic sources, many PAC exhibit significant carcinogenic and mutagenic properties. Multi-dimensional chromatographic techniques which provide separation by virtue of chemical class (group-type) or by molecular mass greatly simplifies the analysis of inherently complex fuel materials. In this study, on-line LC-GC techniques in which high resolution gas chromatography (HPLC) have been investigated. Comprehensive characterisation of fuel feedstocks and post-pyrolysis and combustion products was achieved by coupling LC-GC to low resolution ion trap mass spectrometry (ITD-MS) and atomic emission detection (AED). The identification of PAC in diesel and coal materials, as well as urban air and diesel exhaust particulate extracts has provided valuable insight into the source, formation and distribution of such compounds pre- and post processing.

  8. Sorption of polar and nonpolar aromatic compounds to two humic acids with varied structural heterogeneity

    SciTech Connect

    Sun, H.Y.; Zhu, D.Q.; Mao, J.D.

    2008-12-15

    The major objective of the present study was to evaluate the correlation between structural nature of humic acids (HAs) and sorption affinity of organic compounds with varied polarity. We compared the sorption behavior of three aromatic compounds-nonpolar phenanthrene (PHEN) and 1,2,4,5-tetrachlorobenzene (TeCB) and highly polar 2,4-dichlorophenol (DCP)-to a solid-phase coal humic acid (CHA) and a soil humic acid (SHA) suspended in aqueous solution. The structural nature of HAs was characterized using elemental analysis, ultraviolet absorbance, diffusive reflectance Fourier-transform infrared, and solid-state C-13 nuclear magnetic resonance. The two tested HAs have very different structural properties: CHA consists primarily of poly(methylene)-rich aliphatics with high aromatic content and some COO/N-C=O but low polarity, while SHA consists of young materials of lignin, carbohydrates, and peptides with high polarity. In response to the structural heterogeneity of HAs, sorption of nonpolar and more hydrophobic solutes (PHEN, TeCB) to CHA is much greater than that to SHA because of the predominance of hydrophobic effects; however, disparities in sorption affinity between the two HAs become smaller for polar and less hydrophobic DCP because of the major role played by polar interactions. The influence of pH on the sorption of different solutes to the two HAs was also discussed. The results of the present work highlight the importance of structural heterogeneity of both solutes and HAs in the sorption process.

  9. Phase equilibria in ionic liquid-aromatic compound mixtures, including benzene fluorination effects.

    PubMed

    Blesic, Marijana; Lopes, José N Canongia; Pádua, Agílio A H; Shimizu, Karina; Gomes, Margarida F Costa; Rebelo, Luís Paulo N

    2009-05-28

    This work extends the scope of previous studies on the phase behavior of mixtures of ionic liquids with benzenes or its derivatives by determining the solid-liquid and liquid-liquid phase diagrams of mixtures containing an ionic liquid and a fluorinated benzene. The systems studied include 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide plus hexafluorobenzene or 1,3,5-trifluorobenzene and 1-ethyl-3-methylimidazolium triflate or N-ethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide plus benzene. The phase diagrams exhibit different kinds of solid-liquid behavior: the (usual) occurrence of eutectic points; the (not-so-usual) presence of congruent melting points and the corresponding formation of inclusion crystals; or the observation of different ionic liquid crystalline phases (polymorphism). These different types of behavior can be controlled by temperature annealing during crystallization or by the nature of the aromatic compound and can be interpreted, at a molecular level, taking into account the structure of the crystals or liquid mixtures, together with the unique characteristics of ionic liquids, namely the dual nature of their interactions with aromatic compounds.

  10. Chlorophyll fluorescence as a bioindicator of effects on growth in aquatic macrophytes from mixtures of polycyclic aromatic hydrocarbons.

    PubMed

    Marwood, C A; Solomon, K R; Greenberg, B M

    2001-04-01

    Chlorophyll-a fluorescence induction is a rapid technique for measuring photosynthetic electron transport in plants. To assess chlorophyll-a fluorescence as a bioindicator of effects of polycyclic aromatic hydrocarbon mixtures, chlorophyll-a fluorescence parameters and plant growth responses to exposure to the wood preservative creosote were examined in the aquatic plants Lemna gibba and Myriophyllum spicatum. Exposure to creosote inhibited growth of L. gibba (EC50 = 7.2 mg/L total polycyclic aromatic hydrocarbons) and M. spicatum (EC50 = 2.6 mg/L) despite differences in physiology. Creosote also diminished maximum PSII efficiency (Fv/Fm) (EC50 = 36 and 13 mg/L for L. gibba and M. spicatum) and the effective yield of photosystem II photochemistry (deltaF/Fm') (EC50 = 13 and 15 mg/L for L. gibba and M. spicatum). The similarity between growth and chlorophyll-a fluorescence EC50s and slopes of the response curves suggests a close mechanistic link between these end points. The predictive power of chlorophyll-a fluorescence as a bioindicator of whole-organism effects applied to complex contaminant mixtures is discussed.

  11. Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in a Cosmic Simulation Chamber

    NASA Astrophysics Data System (ADS)

    Bejaoui, Salma; Salama, Farid

    2015-08-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs [1, 2]. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions [see 3 for a review]. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser-induced fluorescence (LIF) technique [4] and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examinedReferences[1] F. Salama, E. Bakes, L.J. Allamandola, A.G.G.M. Tielens, Astrophys. J., 458 (1996) p.621[2] F. Salama, The ISO Revolution, EDP Sciences, Les Ulis, France (1999) p.65[3] Salama F., In Organic Matter in Space, IAU Symposium 251, Kwok & Sandford Eds.Cambridge University Press,4, S251,(2008), p. 357 (2008) and references therein.[4

  12. Effects of gasoline aromatic content on emissions of volatile organic compounds and aldehydes from a four-stroke motorcycle.

    PubMed

    Yao, Yung-Chen; Tsai, Jiun-Horng

    2013-01-01

    A new four-stroke carburettor motorcycle engine without any engine adjustments was used to study the impact of fuel aromatic content on the exhaust emissions of organic air pollutants (volatile organic compounds and carbonyls). Three levels of aromatic content, i.e. 15, 25, and 50% (vol.) aromatics mixed with gasoline were tested. The emissions of aromatic fuel were compared with those of commercial unleaded gasoline. The results indicated that the A 15 (15 vol% aromatics in gasoline) fuel exhibited the greatest total organic emission improvement among these three aromatic fuels as compared with commercial gasoline, reaching 59%. The highest emission factors of alkanes, alkenes, and carbonyl groups appeared in the reference fuel (RF) among all of the test fuels. A 15 showed the highest emission reduction in alkanes (73%), aromatics (36%), and carbonyls (28%), as compared to those of the RF. The highest emission reduction ofalkenes was observed when using A25 as fuel. A reduction in fuel aromatic content from 50 to 25 and 15 vol% in gasoline decreased benzene and toluene emissions, but increased the aldehyde emissions. In general, the results showed that the highest emission reductions for the most of measured organic pollutants appeared when using A 15 as the fuel.

  13. Discovery of a novel family of polycyclic aromatic molecules with unique reactivity and members valuable for fluorescent sensing and medicinal chemistry.

    PubMed

    Xiao, Yi; Liu, Fengyu; Chen, Zhuo; Zhu, Weipin; Xu, Yufang; Qian, Xuhong

    2015-04-18

    A novel polycyclic aromatic molecule, i.e. 1-oxo-1H-phenalene-2,3-dicarbonitrile (compound 1, initially misidentified as 8-oxo-8H-acenaphtho[1,2-b]pyrrolecarbonitrile) was discovered by our group in 2005. This parent compound is highlighted for its unique oxidative S(N)Ar(H) (nucleophilic substitution of aromatic hydrogen) reactivity that provides easy approaches to diverse derivatives with different long-wavelength fluorescence and important biological activities. To date, a large number of derivatives have been synthesized and evaluated by several international research groups, indicating the formation of a new and valuable family of functional chemicals. Some members have been functionalized for molecular or nanoparticle-based probes applicable in chemical and environmental sensing, biomolecule imaging and tumor diagnosis. Others have qualified as high potency anticancer agents specifically targeting different functional proteins in tumor cells. With regard to the increasing attention paid to this new chemical family, it is a good time to review major achievements in order to promote further and deeper investigation.

  14. Evaluation of sampling and analytical methodology for polynuclear aromatic compounds in indoor air. Final report, 1 March-30 September 1985

    SciTech Connect

    Chuang, C.C.; Mack, G.A.; Mondron, P.J.; Petersen, B.A.

    1985-10-01

    The objective of this project was to develop a generic sampling and analytical methodology to characterize the polynuclear aromatic hydrocarbon (PAH) concentrations in air within various microenvironments. The following three studies were performed: evaluation of analytical methods, design of a sampling method, and design of a pilot study. Two analytical methods, high performance liquid chromatography with ultraviolet adsorption and fluorescence detection and gas chromatography/mass spectrometry, were evaluated for the determination of PAHs and their derivatives in air within microenvironments. The results showed that gas chromatography/positive chemical ionization massspectrometry with data acquisition in the selected ion-monitoring mode is the preferred analytical approach. A modified EPA high-volume sampler, consisting of a quartz fiber filter and a polyurethane foam cartridge, is proposed for use in a future experimental study. A literature review was conducted to determine what is known about the contribution of cigarette smoke to the levels of PAHs in air within microenvironments and to evaluate the use of quinoline and isoquinoline as possible marker compounds for the levels of cigarette smoke. A pilot study was designed to assess PAH levels in air found in residences. A study using this design, was conducted in Columbus, Ohio, during the winter of 1983/84. These results can then be applied to a future large-scale study involving the measurement of human exposure to PAH in air.

  15. Visual Recognition of Aliphatic and Aromatic Amines Using a Fluorescent Gel: Application of a Sonication-Triggered Organogel.

    PubMed

    Pang, Xuelei; Yu, Xudong; Lan, Haichuang; Ge, Xiaoting; Li, Yajuan; Zhen, Xiaoli; Yi, Tao

    2015-06-24

    A naphthalimide-based fluorescent gelator (N1) containing an alkenyl group has been designed and characterized. This material is able to gelate alcohols via a precipitate-to-gel transformation when triggered with ultrasound for less than 2 min (S-gel). The gelation process in n-propanol was studied by means of absorption, fluorescence, and IR spectra, scanning electron microscopy (SEM) images, and X-ray diffraction patterns. The fluorescence intensity of N1 decreased during the gelation process in a linear relationship with the sonication time. The S-gel of N1 could be used to sense aliphatic and aromatic amines by measuring the change in the signal output. For example, the addition of propylamine to the S-gel of N1 resulted in a dramatic enhancement of the fluorescence intensity, accompanied by a gel-to-sol transition. On the contrary, when the S-gel of N1 was treated with aromatic amines such as aniline, fluorescence was quenched and there was no gel collapse. The sensing mechanisms were studied by (1)H NMR, small-angle X-ray scattering, SEM and spectroscopic experiments. It is proposed that isomerization of the alkenyl group of N1 from the trans to cis form occurs when the S-gel is treated with propylamine, resulting in a gel-sol transition. However, the aromatic aniline molecules prefer to insert into the gel networks of N1 via hydrogen-bonding and charge-transfer interactions, maintaining the gel state. As potential applications, testing strips of N1 were prepared to detect aniline.

  16. The Effects of Molecular Properties on Ready Biodegradation of Aromatic Compounds in the OECD 301B CO2 Evolution Test.

    PubMed

    He, Mei; Mei, Cheng-Fang; Sun, Guo-Ping; Li, Hai-Bei; Liu, Lei; Xu, Mei-Ying

    2016-07-01

    Ready biodegradation is the primary biodegradability of a compound, which is used for discriminating whether a compound could be rapidly and readily biodegraded in the natural ecosystems in a short period and has been applied extensively in the environmental risk assessment of many chemicals. In this study, the effects of 24 molecular properties (including 2 physicochemical parameters, 10 geometrical parameters, 6 topological parameters, and 6 electronic parameters) on the ready biodegradation of 24 kinds of synthetic aromatic compounds were investigated using the OECD 301B CO2 Evolution test. The relationship between molecular properties and ready biodegradation of these aromatic compounds varied with molecular properties. A significant inverse correlation was found for the topological parameter TD, five geometrical parameters (Rad, CAA, CMA, CSEV, and N c), and the physicochemical parameter K ow, and a positive correlation for two topological parameters TC and TVC, whereas no significant correlation was observed for any of the electronic parameters. Based on the correlations between molecular properties and ready biodegradation of these aromatic compounds, the importance of molecular properties was demonstrated as follows: geometrical properties > topological properties > physicochemical properties > electronic properties. Our study first demonstrated the effects of molecular properties on ready biodegradation by a number of experiment data under the same experimental conditions, which should be taken into account to better guide the ready biodegradation tests and understand the mechanisms of the ready biodegradation of aromatic compounds.

  17. Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

    NASA Technical Reports Server (NTRS)

    Sawko, Paul M. (Inventor); Riccitiello, Salvatore R. (Inventor); Hamermesh, Charles L. (Inventor)

    1980-01-01

    Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

  18. Polymer-assisted deposition of co-doped zinc oxide thin films for the detection of aromatic organic compounds.

    PubMed

    Li, Wei; Kim, Dojin

    2011-12-01

    Co-doped Zinc oxide thin films are deposited onto SiO2/Si substrate by polymer-assisted deposition method. The surface morphology, structures and chemical states of the thin films are examined by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The gas-sensing properties of the thin films upon exposure to aromatic organic compound vapors are also investigated. Co-doping is shown to be very effective in enhancing the response of ZnO thin film to aromatic organic compound.

  19. Predicting accurate fluorescent spectra for high molecular weight polycyclic aromatic hydrocarbons using density functional theory

    NASA Astrophysics Data System (ADS)

    Powell, Jacob; Heider, Emily C.; Campiglia, Andres; Harper, James K.

    2016-10-01

    The ability of density functional theory (DFT) methods to predict accurate fluorescence spectra for polycyclic aromatic hydrocarbons (PAHs) is explored. Two methods, PBE0 and CAM-B3LYP, are evaluated both in the gas phase and in solution. Spectra for several of the most toxic PAHs are predicted and compared to experiment, including three isomers of C24H14 and a PAH containing heteroatoms. Unusually high-resolution experimental spectra are obtained for comparison by analyzing each PAH at 4.2 K in an n-alkane matrix. All theoretical spectra visually conform to the profiles of the experimental data but are systematically offset by a small amount. Specifically, when solvent is included the PBE0 functional overestimates peaks by 16.1 ± 6.6 nm while CAM-B3LYP underestimates the same transitions by 14.5 ± 7.6 nm. These calculated spectra can be empirically corrected to decrease the uncertainties to 6.5 ± 5.1 and 5.7 ± 5.1 nm for the PBE0 and CAM-B3LYP methods, respectively. A comparison of computed spectra in the gas phase indicates that the inclusion of n-octane shifts peaks by +11 nm on average and this change is roughly equivalent for PBE0 and CAM-B3LYP. An automated approach for comparing spectra is also described that minimizes residuals between a given theoretical spectrum and all available experimental spectra. This approach identifies the correct spectrum in all cases and excludes approximately 80% of the incorrect spectra, demonstrating that an automated search of theoretical libraries of spectra may eventually become feasible.

  20. Migration kinetics of primary aromatic amines from polyamide kitchenware: Easy and fast screening procedure using fluorescence.

    PubMed

    Sanllorente, S; Sarabia, L A; Ortiz, M C

    2016-11-01

    Primary aromatic amines, PAAs, and their derivatives constitute a health risk and control of their migration from food contact materials is the subject of permanent attention by the authorities. 25.1% of notifications made by Rapid Alert System for Food and Feed in the European Union between 2010 and 2015 concerned PAAs, polyamide cooking utensils being a common source. It is thus useful to have fast and efficient analytical methods for their control. In this work a non-separative, easy, fast and inexpensive spectrofluorimetric method based on the second order calibration of excitation-emission fluorescence matrices (EEMs) was proposed for the determination of aniline (ANL), 2,4-diaminotoluene (2,4-TDA) and 4,4'-methylenedianiline (4,4'-MDA) in polyamide cooking utensils. The procedure made it possible to identify unequivocally each analyte. Trilinearity of the data tensor guarantees the uniqueness of the solution obtained through parallel factor analysis (PARAFAC), so the factors of the decomposition match up with the analytes. The three analytes were unequivocally identified by the correlation between the pure spectra and the PARAFAC excitation and emission spectral loadings. The recovery percentages found were, 82.6%, 112.7% and 84.4% for ANL, 2,4-TDA and 4,4'-MDA respectively. The proposed method was applied to carry out a migration test from polyamide cooking utensils, using a 3% (w/v) acetic acid in aqueous solution as food simulant. Detectable levels of 4,4'-MDA were found in food simulant from some of the investigated cooking utensils. Finally, a kinetic model for the migration of 4,4'-MDA has been fitted to experimental data obtained in the migration test. Thanks to the selectivity of PARAFAC calibration, which greatly simplifies sample treatment avoiding the use of toxic solvents, the developed method follows most green analytical chemistry principles.

  1. Ozone-related fluorescent compounds in mouse liver and lung

    SciTech Connect

    Csallany, A.S.; Manwaring, J.D.; Menken, B.Z.

    1985-08-01

    Groups of ten female, weanling mice were fed a basal, vitamin E-deficient diet or a basal diet supplemented with RRR-alpha-tocopheryl acetate for 14 months. During the last month one group from each dietary regimen was exposed for 30-60 min/day to 1.5 ppm ozone (25 hr total ozone exposure) and the remaining groups to control ambient air. The liver and lung tissues were homogenized and extracted with 2:1 chloroform:methanol and water. Excitation and emission wavelengths for the eluting fractions were determined by continuous emission scans from 250 to 600 nm for each excitation wavelength between 250 and 500 nm. Ozone exposure did not effect the concentration of any of the fluorescent materials examined in the lung, but it resulted in a significant increase in two of four water-soluble compounds in the liver with excitation wavelength maxima/emission wavelength maxima of 270 nm/310 nm and 275 nm/350 nm (smaller molecular weight material) suggesting in vivo lipid oxidation.

  2. Sorption of aromatic ionizable organic compounds to montmorillonites modified by hexadecyltrimethyl ammonium and polydiallyldimethyl ammonium.

    PubMed

    Xu, Huaizhou; Wan, Yuqiu; Li, Hui; Zheng, Shourong; Zhu, Dongqiang

    2011-01-01

    Environmental residues of aromatic ionizable organic compounds (AIOCs) have received considerable attention due to their potential human health and ecological risks. The main objective of this study was to investigate the key factors and mechanisms controlling sorption of a series of anionic and zwitterionic AIOCs (two aromatic sulfonates, 4-methyl-2,6-dinitrophenol, tetracycline, sulfamethoxazole, and tannic acid) to montmorillonites modified with hexadecyltrimethyl ammonium (HDTMA) and polydiallyldimethyl ammonium (PDADMA). Compared with naphthalene (a nonpolar and nonionic solute), all AIOCs showed stronger sorption (the sorbent-to-solution distribution coefficient was in the order of 10-10 L kg) to the two organoclays in spite of the much lower hydrophobicity, indicating the predominance of electrostatic interaction in sorption. The proposed electrostatic mechanism of the tested AIOCs was supported by the pH dependency of sorption to the two organoclays. The two organoclays manifested weaker sorption affinity but faster sorption kinetics for bulky AIOCs than commercial activated carbon, resulting from the high accessibility of sorption sites in the open, ordered clay interlayer. The findings of this study highlight the potential of using HDTMA- and PDADMA-exchanged montmorillonites as effective sorbents for AIOCs in water and wastewater treatments.

  3. How aromatic compounds block DNA binding of HcaR catabolite regulator

    DOE PAGES

    Kim, Youngchang; Joachimiak, Grazyna; Bigelow, Lance; ...

    2016-04-25

    Bacterial catabolism of aromatic compounds from various sources including phenylpropanoids and flavonoids that are abundant in soil plays an important role in the recycling of carbon in the ecosystem. We have determined the crystal structures of apo-HcaR from Acinetobacter sp. ADP1, a MarR/SlyA transcription factor, in complexes with hydroxycinnamates and a specific DNA operator. The protein regulates the expression of the hca catabolic operon in Acinetobacter and related bacterial strains, allowing utilization of hydroxycinnamates as sole sources of carbon. HcaR binds multiple ligands, and as a result the transcription of genes encoding several catabolic enzymes is increased. The 1.9-2.4 Åmore » resolution structures presented here explain how HcaR recognizes four ligands (ferulate, 3,4-dihydroxybenzoate, p-coumarate, and vanillin) using the same binding site. The ligand promiscuity appears to be an adaptation to match a broad specificity of hydroxycinnamate catabolic enzymes while responding to toxic thioester intermediates. Structures of apo-HcaR and in complex with a specific DNA hca operator when combined with binding studies of hydroxycinnamates show how aromatic ligands render HcaR unproductive in recognizing a specific DNA target. Furthermore, the current study contributes to a better understanding of the hca catabolic operon regulation mechanism by the transcription factor HcaR.« less

  4. How aromatic compounds block DNA binding of HcaR catabolite regulator

    SciTech Connect

    Kim, Youngchang; Joachimiak, Grazyna; Bigelow, Lance; Babnigg, Gyorgy; Joachimiak, Andrzej

    2016-04-25

    Bacterial catabolism of aromatic compounds from various sources including phenylpropanoids and flavonoids that are abundant in soil plays an important role in the recycling of carbon in the ecosystem. We have determined the crystal structures of apo-HcaR from Acinetobacter sp. ADP1, a MarR/SlyA transcription factor, in complexes with hydroxycinnamates and a specific DNA operator. The protein regulates the expression of the hca catabolic operon in Acinetobacter and related bacterial strains, allowing utilization of hydroxycinnamates as sole sources of carbon. HcaR binds multiple ligands, and as a result the transcription of genes encoding several catabolic enzymes is increased. The 1.9-2.4 Å resolution structures presented here explain how HcaR recognizes four ligands (ferulate, 3,4-dihydroxybenzoate, p-coumarate, and vanillin) using the same binding site. The ligand promiscuity appears to be an adaptation to match a broad specificity of hydroxycinnamate catabolic enzymes while responding to toxic thioester intermediates. Structures of apo-HcaR and in complex with a specific DNA hca operator when combined with binding studies of hydroxycinnamates show how aromatic ligands render HcaR unproductive in recognizing a specific DNA target. Furthermore, the current study contributes to a better understanding of the hca catabolic operon regulation mechanism by the transcription factor HcaR.

  5. Enhanced Photoreduction of Nitro-aromatic Compounds by Hydrated Electrons Derived from Indole on Natural Montmorillonite.

    PubMed

    Tian, Haoting; Guo, Yong; Pan, Bo; Gu, Cheng; Li, Hui; Boyd, Stephen A

    2015-07-07

    A new photoreduction pathway for nitro-aromatic compounds (NACs) and the underlying degradation mechanism are described. 1,3-Dinitrobenzene was reduced to 3-nitroaniline by the widely distributed aromatic molecule indole; the reaction is facilitated by montmorillonite clay mineral under both simulated and natural sunlight irradiation. The novel chemical reaction is strongly affected by the type of exchangeable cation present on montmorillonite. The photoreduction reaction is initiated by the adsorption of 1,3-dinitrobenzene and indole in clay interlayers. Under light irradiation, the excited indole molecule generates a hydrated electron and the indole radical cation. The structural negative charge of montmorillonite plausibly stabilizes the radical cation hence preventing charge recombination. This promotes the release of reactive hydrated electrons for further reductive reactions. Similar results were observed for the photoreduction of nitrobenzene. In situ irradiation time-resolved electron paramagnetic resonance and Fourier transform infrared spectroscopies provided direct evidence for the generation of hydrated electrons and the indole radical cations, which supported the proposed degradation mechanism. In the photoreduction process, the role of clay mineral is to both enhance the generation of hydrated electrons and to provide a constrained reaction environment in the galley regions, which increases the probability of contact between NACs and hydrated electrons.

  6. Diffusion of aromatic compounds in nonaqueous solvents: a study of solute, solvent, and temperature dependences.

    PubMed

    Chan, T C; Tang, W K

    2013-06-14

    Tracer diffusivities (limiting mutual diffusion coefficients) of nonassociated aromatic compounds in n-hexane and cyclohexane have been measured at 298.2 K by Taylor's dispersion method. These new data, together with other diffusivities of nonassociated pseudoplanar solutes reported in the literature, are used to determine the separate effects of solute and solvent on tracer diffusion. The data show that for a given pseudoplanar solute diffusing in different solvents at 298.2 K, the tracer diffusivity is dependent not only on the fractional viscosity of the solvent but also on a function of the solvent's molar density, molecular mass, and free volume fraction. For different pseudoplanar aromatic solutes diffusing in a particular solvent at a constant temperature, there is a linear relationship between the reciprocal of the tracer diffusivity and the molecular volume of the solutes. The results are discussed in respect to relevant theories and experimental studies in the literature. An idealized relation, developed on the basis of the Einstein equation by incorporating the newly found solute and solvent dependences, is capable of describing a total of 176 diffusivities of nonassociated pseudoplanar solutes in various solvents at different temperatures to within an average error of ±2.8%.

  7. Synergistic and diminutive effects between halogen bond and lithium bond in complexes involving aromatic compounds.

    PubMed

    Liu, Mingxiu; Cai, Mengyang; Li, Qingzhong; Li, Wenzuo; Cheng, Jianbo

    2015-10-01

    Quantum chemical calculations have been performed to study the interplay between halogen bond and lithium bond in the ternary systems FX-C6H5CN-LiF, FLi-C6H5CN-XF, and FLi-C6H5X-NH3 (X = Cl, Br, and I) involving aromatic compounds. This effect was studied in terms of interaction energy, electron density, charge transfer, and orbital interaction. The results showed that both FX-C6H5CN-LiF and FLi-C6H5CN-XF exhibit diminutive effects with the weakening of halogen bond and lithium bond, while FLi-C6H5X-NH3 displays synergistic effects with the strengthening of halogen bond and lithium bond. The nature of halogen bond and lithium bond in the corresponding binary complexes has been unveiled by the quantum theory of atoms in molecules methodology and energy decomposition analysis.

  8. Screening of halogenated aromatic compounds in some raw material lots for an aluminium recycling plant.

    PubMed

    Sinkkonen, Seija; Paasivirta, Jaakko; Lahtiperä, Mirja; Vattulainen, Antero

    2004-05-01

    Four samples of scrap raw materials for an aluminium recycling plant were screened for the occurrence of persistent halogenated aromatic compounds. The samples contained waste from handling of electric and electronic plastics, filter dust from electronic crusher, cyclone dust from electronic crusher and light fluff from car shredder. In our screening analyses, brominated flame retardants were observed in all samples. Polybrominated diphenyl ethers (PBDE) were identified in all samples in amounts of 245-67450 ng/g. The major PBDE congeners found were decabromo- and pentabromodiphenyl ethers. 1,1-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, ethyl-pentabromobenzene, tetrabromobisphenol-A, pentabromotoluene and dimethyl tetrabromobenzene were observed in all scrap samples. The concentrations of PCBs, PCNs (polychlorinated naphthalenes) and nona- to undecachlorinated terphenyls in some of these scrap samples were remarkably high.

  9. Determining inhibition effects of some aromatic compounds on peroxidase enzyme purified from white and red cabbage

    NASA Astrophysics Data System (ADS)

    Öztekin, Aykut; Almaz, Züleyha; Özdemir, Hasan

    2016-04-01

    Peroxidases (E.C.1.11.1.7) catalyze the one electron oxidation of wide range of substrates. They are used in synthesis reaction, removal of peroxide from industrial wastes, clinical biochemistry and immunoassays. In this study, the white cabbage (Brassica Oleracea var. capitata f. alba) and red cabbage (Brassica oleracea L. var. capitata f. rubra) peroxidase enzymes were purified for investigation of inhibitory effect of some aromatic compounds on these enzymes. IC50 values and Ki constants were calculated for the molecules of 6-Amino nicotinic hydrazide, 6-Amino-5-bromo nicotinic hydrazide, 2-Amino-5-hydroxy benzohydrazide, 4-Amino-3-hydroxy benzohydrazide on purified enzymes and inhibition type of these molecules were determined. (This research was supported by Ataturk University. Project Number: BAP-2015/98).

  10. Simple determination of a strongly aromatic compound, sotolon, by capillary electrophoresis.

    PubMed

    Taga, Atsushi; Sato, Atsushi; Suzuki, Kentaro; Takeda, Manami; Kodama, Shuji

    2012-01-01

    A strongly aromatic compound, sotolon, was assessed by capillary zone electrophoresis within 9 min without specific pre-sample treatment. The calibration curve comprised a straight line with good linearity (R = 0.997) over a relatively wide range of 3.13 to 100 ppm. The precision of this system was excellent with relative standard deviations of 1.39% for migration time and 2.96 % for peak response over 10 repetitions at a concentration of 12.5 ppm. The limit of quantitation and limit of detection values were 3.13 ppm (S/N = 9) and 0.781 ppm (S/N = 3), respectively. Using this system, sotolon was clearly detected from a maple-flavored food additive.

  11. Evaluation of Aromatic Plants and Compounds Used to Fight Multidrug Resistant Infections

    PubMed Central

    Perumal Samy, Ramar; Manikandan, Jayapal; Al Qahtani, Mohammed

    2013-01-01

    Traditional medicine plays a vital role for primary health care in India, where it is widely practiced to treat various ailments. Among those obtained from the healers, 78 medicinal plants were scientifically evaluated for antibacterial activity. Methanol extract of plants (100 μg of residue) was tested against the multidrug resistant (MDR) Gram-negative and Gram-positive bacteria. Forty-seven plants showed strong activity against Burkholderia pseudomallei (strain TES and KHW) and Staphylococcus aureus, of which Tragia involucrata L., Citrus acida Roxb. Hook.f., and Aegle marmelos (L.) Correa ex Roxb. showed powerful inhibition of bacteria. Eighteen plants displayed only a moderate effect, while six plants failed to provide any evidence of inhibition against the tested bacteria. Purified compounds showed higher antimicrobial activity than crude extracts. The compounds showed less toxic effect to the human skin fibroblasts (HEPK) cells than their corresponding aromatic fractions. Phytochemical screening indicates that the presence of various secondary metabolites may be responsible for this activity. Most of the plant extracts contained high levels of phenolic or polyphenolic compounds and exhibited activity against MDR pathogens. In conclusion, plants are promising agents that deserve further exploration. Lead molecules available from such extracts may serve as potential antimicrobial agents for future drug development to combat diseases caused by the MDR bacterial strains as reported in this study. PMID:24223059

  12. Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

    PubMed

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

    2014-09-01

    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.

  13. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics

    NASA Astrophysics Data System (ADS)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof

    2015-12-01

    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  14. Soft X-ray absorption spectra in the 0 K region of microporous carbon and some reference aromatic compounds

    SciTech Connect

    Muramatsu, Yasuji; Kuramoto, Kentaro; Gullikson, Eric M.; Perera, Rupert C.C.

    2003-06-01

    To analyze the oxidation states of the graphitic surface of microporous carbon, soft X-ray absorption spectra in the 0 K region have been obtained for microporous carbon and various aromatic compounds. The aromatic molecules studied are substituted with one or more of the following oxygenated functional groups: hydroxy (-OH), carboxy (-COOH), carbonyl (>C=O), formyl (-CH=O), and ether (-O-). From comparison of the soft X-ray absorption spectra of microporous carbon and of reference aromatic compounds, the most probable chemical bonding states of oxygen in microporous carbon are found to be -COOH and >C(H)=O. Spectral features in the soft X-ray absorption spectra of microporous carbon are well explained by the O2p density of states in these oxygenated functional groups from discrete variational (DV)-X{alpha} molecular orbital calculations.

  15. BIODEGRADATION OF AROMATIC COMPOUNDS UNDER MIXED OXYGEN/DENITRIFYING CONDITIONS: A REVIEW

    EPA Science Inventory

    Bioremediation of aromatic hydrocarbons in groundwater and sediments is often limited by dissolved oxygen. Many aromatic hydrocarbons degrade very slowly or not at all under anaerobic conditions. Nitrate is a good alternative electron acceptor to oxygen, and denitrifying bacteria...

  16. Aqueous and Tissue Residue-Based Interspecies Correlation Estimation Models Provide Conservative Hazard Estimates for Aromatic Compounds

    EPA Science Inventory

    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...

  17. Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review

    NASA Astrophysics Data System (ADS)

    Blum, Philipp; Sagner, Anne; Tiehm, Andreas; Martus, Peter; Wendel, Thomas; Grathwohl, Peter

    2011-11-01

    NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250 m, but less than 1000 m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.

  18. Compounds having aromatic rings and side-chain amide-functionality and a method for transporting monovalent anions across biological membranes using the same

    DOEpatents

    Davis, Jeffery T.; Sidorov, Vladimir; Kotch, Frank W.

    2008-04-08

    A compound containing at least two aromatic rings covalently bonded together, with each aromatic ring containing at least one oxyacetamide-based side chain, the compound being capable of forming a chloride ion channel across a lipid bilayer, and transporting chloride ion across the lipid bilayer.

  19. Determination of aromatic tracer compounds for environmental tobacco smoke aerosol by two step laser mass spectrometry

    NASA Astrophysics Data System (ADS)

    Morrical, Brad D.; Zenobi, Renato

    Cigarette smoking is a major cause of indoor aerosol pollution. Determination of exposure to environmental tobacco smoke (ETS) aerosol is critical to understanding health effects. Sizing studies have shown that ETS has a size distribution that is efficiently deposited into the lungs and can therefore provide effective delivery of carcinogenic compounds into the human body. Two-step laser mass spectrometry is used to analyze aromatic compounds on aerosols collected from a smoking lobby. The determination and suitability of ETS tracers on aerosols is examined. Additionally, the transport of aerosol from the smoking lobby is examined to determine what effect deposition and dilution have on the mass spectrum observed. Results from the analysis of ETS, both from lobby samples and direct cigarette sampling, show that several unique peaks are present in the mass spectrum when compared to other combustion sources, such as automobiles and diesel trucks. In particular, ions at m/ z 118, 132, 146, and 160 are consistently present and are not found in other combustion sources. For the indoor environment, where chemical transformation is much less rapid than in the outdoor environment, these ions were found to be present as soon as the first smokers appeared and persisted over the course of the day. Aerosol samples taken in the morning prior to the presence of smokers in the lobby reveal the presence of skeletal PAHs, indicative of outdoor urban traffic aerosol penetration into the building.

  20. Induced production of brominated aromatic compounds in the alga Ceramium tenuicorne.

    PubMed

    Dahlgren, Elin; Enhus, Carolina; Lindqvist, Dennis; Eklund, Britta; Asplund, Lillemor

    2015-11-01

    In the Baltic Sea, high concentrations of toxic brominated aromatic compounds have been detected in all compartments of the marine food web. A growing body of evidence points towards filamentous algae as a natural producer of these chemicals. However, little is known about the effects of environmental factors and life history on algal production of brominated compounds. In this study, several congeners of methoxylated polybrominated diphenyl ethers (MeO-PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and brominated phenols (BPs) were identified in a naturally growing filamentous red algal species (Ceramium tenuicorne) in the Baltic Sea. The identified substances displayed large seasonal variations in the alga with a concentration peak in July. Production of MeO-/OH-PBDEs and BPs by C. tenuicorne was also established in isolated clonal material grown in a controlled laboratory setting. Based on three replicates, herbivory, as well as elevated levels of light and salinity in the culture medium, significantly increased the production of 2,4,6-tribromophenol (2,4,6-TBP). Investigation of differences in production between the isomorphic female, male and diploid clonal life stages of the alga grown in the laboratory revealed a significantly higher production of 2,4,6-TBP in the brackish water female gametophytes, compared to the corresponding marine gametophytes. Even higher concentrations of 2,4,6-TBP were produced by marine male gametophytes and sporophytes.

  1. The Highly Conserved Escherichia coli Transcription Factor YhaJ Regulates Aromatic Compound Degradation

    PubMed Central

    Palevsky, Noa; Shemer, Benjamin; Connolly, James P. R.; Belkin, Shimshon

    2016-01-01

    The aromatic compound 2,4-dinitrotoluene (DNT), a common impurity in 2,4,6-trinitrotoluene (TNT) production, has been suggested as a tracer for the presence of TNT-based landmines due to its stability and high volatility. We have previously described an Escherichia coli bioreporter capable of detecting the presence of DNT vapors, harboring a fusion of the yqjF gene promoter to a reporter element. However, the DNT metabolite which is the direct inducer of yqjF, has not yet been identified, nor has the regulatory mechanism of the induction been clarified. We demonstrate here that the YhaJ protein, a member of the LysR type family, acts as a transcriptional regulator of yqjF activation, as well as of a panel of additional E. coli genes. This group of genes share a common sequence motif in their promoters, which is suggested here as a putative YhaJ-box. In addition, we have linked YhaJ to the regulation of quinol-like compound degradation in the cell, and identified yhaK as playing a role in the degradation of DNT. PMID:27713734

  2. Deviations from Ideal Sublimation Vapor Pressure Behavior in Mixtures of Polycyclic Aromatic Compounds with Interacting Heteroatoms.

    PubMed

    Goldfarb, Jillian L; Suuberg, Eric M

    2010-08-01

    Despite the relatively small atomic fraction of a given heteroatom in a binary mixture of polycyclic aromatic compounds (PAC), the inclusion of heteroatomic substituted compounds can significantly impact mixture vapor pressure behavior over a wide range of temperatures. The vapor pressures of several binary PAC mixtures containing various heteroatoms show varying behavior, from practically ideal behavior following Raoult's law to significant deviations from ideality depending on the heteroatom(s) present in the mixture. Mixtures were synthesized using the quench-cool technique with equimolar amounts of two PAC, both containing heteroatoms such as aldehyde, carboxyl, nitrogen, and sulfur substituent groups. For some mixtures, deviation from ideality is inversely related to temperature, though in other cases we see deviations from ideality increasing with temperature, whereas some appear independent of temperature. Most commonly we see lower vapor pressures than predicted by Raoult's law, which indicates that the interacting heteroatoms prefer the solid mixture phase as opposed to the vapor phase. Although negative deviations predominate from Raoult's Law, the varying mixtures investigated show both higher and lower enthalpies and entropies of sublimation than predicted. In each mixture, a higher enthalpy of sublimation leads to higher entropy of sublimation than predicted, and vice versa.

  3. Bromination of aromatic compounds by residual bromide in sodium chloride matrix modifier salt during heated headspace GC/MS analysis.

    PubMed

    Fine, Dennis D; Ko, Saebom; Huling, Scott

    2013-12-15

    Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation reactions and contained aromatic compounds, hydrogen peroxide (H2O2), and ferric sulfate. Prior to GC/MS headspace analysis, the samples were acidified (pH<2), and sodium chloride was amended to the headspace vial as a matrix modifier. The brominated artifacts were generated during heated headspace analysis. Further, when samples were spiked with a mixture of volatile chlorinated and aromatic compounds (50 µg/L), poor spike recoveries of toluene and xylenes occurred, and in some cases complete loss of trimethylbenzenes and naphthalene resulted. Where poor recovery of aromatic spike compounds occurred, brominated aromatic compounds were found. The only significant source of bromine in the reaction scheme is the bromide typically present (<0.01% w/w) in the sodium chloride amended to the samples. Conversely, brominated artifacts were absent when a buffered salt mixture composed of sodium chloride and potassium phosphate dibasic/monobasic was used as a matrix modifier and raised the sample pH (pH~6). This indicated that the brominated artifacts resulted from the reaction of the aromatic compounds with BrCl, which was formed by the reaction of H2O2, chloride, and bromide under acidic conditions. An alternative matrix modifier salt is recommended that prevents the bromination reaction and avoids these deleterious effects on sample integrity during headspace analysis.

  4. Chromatography, Absorption, and Fluorescence: A New Instrumental Analysis Experiment on the Measurement of Polycyclic Aromatic Hydrocarbons in Cigarette Smoke

    NASA Astrophysics Data System (ADS)

    Wingen, Lisa M.; Low, Jason C.; Finlayson-Pitts, Barbara J.

    1998-12-01

    The recent approval by the American Chemical Society of an undergraduate chemistry degree with an option in environmental chemistry requires the development of new experiments that teach fundamental chemistry in the context of environmental issues. We present an experiment suitable for an undergraduate junior/senior-level instrumental analysis laboratory which illustrates the principles of high-performance liquid chromatography (HPLC) and its application to the identification and measurement of polycyclic aromatic hydrocarbons (PAH) in tobacco smoke. Absorption and fluorescence detection methods for PAH, especially the differences in sensitivity and selectivity of these methods, are clearly demonstrated along with the basic principles of HPLC.

  5. Dry deposition of polycyclic aromatic compounds to various land covers in the Athabasca oil sands region

    NASA Astrophysics Data System (ADS)

    Zhang, Leiming; Cheng, Irene; Wu, Zhiyong; Harner, Tom; Schuster, Jasmin; Charland, Jean-Pierre; Muir, Derek; Parnis, J. Mark

    2015-09-01

    A framework was developed to estimate dry deposition of polycyclic aromatic compounds (PACs), including 17 polycyclic aromatic hydrocarbons (PAHs), 21 alkylated PAHs, and 5 parent and alkylated dibenzothiophenes (DBTs), to various land covers surrounding three monitoring sites in the Athabasca oil sands region. Modeled dry deposition velocities for various gaseous PACs and over various land covers were mostly in the range of 0.01-0.5 cm s-1 with median and annual mean values between 0.08 and 0.24 cm s-1, comparable with literature values obtained from field studies. Annual dry deposition of the sum of PAHs was estimated to range from 330 to 560 μg m-2 over forested canopies surrounding the three sites and from 270 to 490 μg m-2 over grass and shrubs. The corresponding values are 3920-5380 and 2850-4920 μg m-2 for the sum of 21 alkylated PAHs, and are 230-1120 and 450-930 μg m-2 for the sum of 5 DBTs. The three monitoring sites are situated nearby the Athabasca River, and the direct annual atmospheric dry deposition to water surface was estimated to range from 350 to 500, 3170 to 4530, and 170 to 840 μg m-2 for PAHs, alkylated PAHs, and DBTs, respectively. Alkylated PAHs contributed 80% of the total dry and 60% of the total wet deposition budget, suggesting the importance of including this group of PAHs in the atmospheric deposition budget estimation for subsequent ecosystem impact studies.

  6. Electron delocalization and aromaticity in low-lying excited states of archetypal organic compounds.

    PubMed

    Feixas, Ferran; Vandenbussche, Jelle; Bultinck, Patrick; Matito, Eduard; Solà, Miquel

    2011-12-14

    Aromaticity is a property usually linked to the ground state of stable molecules. Although it is well-known that certain excited states are unquestionably aromatic, the aromaticity of excited states remains rather unexplored. To move one step forward in the comprehension of aromaticity in excited states, in this work we analyze the electron delocalization and aromaticity of a series of low-lying excited states of cyclobutadiene, benzene, and cyclooctatetraene with different multiplicities at the CASSCF level by means of electron delocalization measures. While our results are in agreement with Baird's rule for the aromaticity of the lowest-lying triplet excited state in annulenes having 4nπ-electrons, they do not support Soncini and Fowler's generalization of Baird's rule pointing out that the lowest-lying quintet state of benzene and septet state of cyclooctatetraene are not aromatic.

  7. Origin of the conformational modulation of the 13C NMR chemical shift of methoxy groups in aromatic natural compounds.

    PubMed

    Toušek, Jaromír; Straka, Michal; Sklenář, Vladimír; Marek, Radek

    2013-01-24

    The interpretation of nuclear magnetic resonance (NMR) parameters is essential to understanding experimental observations at the molecular and supramolecular levels and to designing new and more efficient molecular probes. In many aromatic natural compounds, unusual (13)C NMR chemical shifts have been reported for out-of-plane methoxy groups bonded to the aromatic ring (~62 ppm as compared to the typical value of ~56 ppm for an aromatic methoxy group). Here, we analyzed this phenomenon for a series of aromatic natural compounds using Density Functional Theory (DFT) calculations. First, we checked the methodology used to optimize the structure and calculate the NMR chemical shifts in aromatic compounds. The conformational effects of the methoxy group on the (13)C NMR chemical shift then were interpreted by the Natural Bond Orbital (NBO) and Natural Chemical Shift (NCS) approaches, and by excitation analysis of the chemical shifts, breaking down the total nuclear shielding tensor into the contributions from the different occupied orbitals and their magnetic interactions with virtual orbitals. We discovered that the atypical (13)C NMR chemical shifts observed are not directly related to a different conjugation of the lone pair of electrons of the methoxy oxygen with the aromatic ring, as has been suggested. Our analysis indicates that rotation of the methoxy group induces changes in the virtual molecular orbital space, which, in turn, correlate with the predominant part of the contribution of the paramagnetic deshielding connected with the magnetic interactions of the BD(CMet-H)→BD*(CMet-OMet) orbitals, resulting in the experimentally observed deshielding of the (13)C NMR resonance of the out-of-plane methoxy group.

  8. Sources of SOA gaseous precursors in contrasted urban environments: a focus on mono-aromatic compounds and intermediate volatility compounds

    NASA Astrophysics Data System (ADS)

    Salameh, Therese; Borbon, Agnès; Ait-Helal, Warda; Afif, Charbel; Sauvage, Stéphane; Locoge, Nadine; Bonneau, Stéphane; Sanchez, Olivier

    2016-04-01

    Among Volatile Organic Compounds (VOC), the mono-aromatic compounds so-called BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes) and the intermediate volatility organic compounds (IVOC) with C>12 are two remarkable chemical families having high impact on health, as well as on the production of secondary pollutants like secondary organic aerosols (SOA) and ozone. However, the nature and relative importance of their sources and, consequently, their impact on SOA formation at urban scale is still under debate. On the one hand, BTEX observations in urban areas of northern mid-latitudes do not reconcile with emission inventories; the latter pointing to solvent use as the dominant source compared to traffic. Moreover, a recent study by Borbon et al. (2013) has shown an enrichment in the C7-C9 aromatic fraction in Paris atmosphere by a factor of 3 compared to other cities. Causes would be: (i) differences in gasoline composition, (ii) differences in vehicle fleet composition, and (iii) differences in solvent use related sources. On the other hand, many smog chamber studies have highlighted IVOCs as important SOA precursors over the last decade but their origin and importance in urban areas relative to other precursors like BTEX is still poorly addressed. Here we combined large VOC datasets to investigate sources of BTEX and IVOC in contrasted urban areas by source-receptor approaches and laboratory experiments. Ambient data include multi-site speciated ambient measurements of C2 to C17 VOCs (traffic, urban background, and tunnel) from air quality networks (ie. AIRPARIF in Paris) and intensive field campaigns (MEGAPOLI-Paris, TRANSEMED in Beirut and Istanbul, PHOTOPAQ in Brussels). Preliminary results for Paris suggest that traffic dominates BTEX concentrations while traffic and domestic heating for IVOC (>70%). In parallel, the detailed composition of the fuel liquid phase was determined at the laboratory for typical fuels distributed in Ile de France region (diesel, SP95

  9. Trophic transfer of naturally produced brominated aromatic compounds in a Baltic Sea food chain.

    PubMed

    Dahlgren, Elin; Lindqvist, Dennis; Dahlgren, Henrik; Asplund, Lillemor; Lehtilä, Kari

    2016-02-01

    Brominated aromatic compounds (BACs) are widely distributed in the marine environment. Some of these compounds are highly toxic, such as certain hydroxylated polybrominated diphenyl ethers (OH-PBDEs). In addition to anthropogenic emissions through use of BACs as e.g. flame retardants, BACs are natural products formed by marine organisms such as algae, sponges, and cyanobacteria. Little is known of the transfer of BACs from natural producers and further up in the trophic food chain. In this study it was observed that total sum of methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and OH-PBDEs increased in concentration from the filamentous red alga Ceramium tenuicorne, via Gammarus sp. and three-spined stickleback (Gasterosteus aculeatus) to perch (Perca fluviatilis). The MeO-PBDEs, which were expected to bioaccumulate, increased in concentration accordingly up to perch, where the levels suddenly dropped dramatically. The opposite pattern was observed for OH-PBDEs, where the concentration exhibited a general trend of decline up the food web, but increased in perch, indicating metabolic demethylation of MeO-PBDEs. Debromination was also indicated to occur when progressing through the food chain resulting in high levels of tetra-brominated MeO-PBDE and OH-PBDE congeners in fish, while some penta- and hexa-brominated congeners were observed to be the dominant products in the alga. As it has been shown that OH-PBDEs are potent disruptors of oxidative phosphorylation and that mixtures of different congener may act synergistically in terms of this toxic mode of action, the high levels of OH-PBDEs detected in perch in this study warrants further investigation into potential effects of these compounds on Baltic wildlife, and monitoring of their levels.

  10. Photocatalytic oxidation of volatile organic compounds using fluorescent visible light.

    PubMed

    Chapuis, Yannick; Klvana, Danilo; Guy, Christophe; Kirchnerova, Jitka

    2002-07-01

    Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) is a highly attractive alternative technology for purification and deodorization of indoor air. The main objectives of this study were to demonstrate that a common fluorescent visible light (FVL) lamp can be used to effectively remove by PCO low concentrations of VOCs from slightly contaminated air and to provide some fundamental and technical details on the process. The target VOC was n-butanol, which is a standard reference odorant. Its PCO was studied under a long residence time in a 3.7-L cylindrical reactor with commercial titanium dioxide (TiO2) as the reference photocatalyst and using mostly FVL for illumination. For comparison only, a UV (black) light lamp was used. The gas-phase products were detected and quantified online by gas chromatography (GC). The effects of reactor residence time, of inlet concentration, and of the relative light intensity on the efficiency of the process were also evaluated. At a high n-butanol concentration (0.1 vol %), butanal and propanal were identified as the intermediate products of the process; ethanal appeared when the initial concentration was < or = 850 ppm(v). This indicates that PCO leading to CO2 and H2O is relatively slow and proceeds in a stepwise manner. Although the efficiency of the process with an FVL lamp was significantly lower than when using a UV black light, complete PCO of low concentrations was achieved for 100 ppm(v). In a search for a material with photoactivation extended to higher wavelengths or increased photoactivity, several samples of transition metal- or silver ion-doped (2 atomic %) TiO2 as well as SrTi(1-x-)Fe(x)O3 (x = 0.1 and 0.15) perovskites were included in the study. None of these materials was more active than pure TiO2. The results of this study open new horizons in the area of in door air quality (IAQ) control.

  11. Portable spotter for fluorescent contaminants on surfaces

    DOEpatents

    Schuresko, Daniel D.

    1980-01-01

    A portable fluorescence-based spotter for polynuclear aromatic hydrocarbon contamination on personnel and work area surfaces under ambient lighting conditions is provided. This instrument employs beam modulation and phase sensitive detection for discriminating between fluorescence from organic materials from reflected background light and inorganic fluorescent material. The device uses excitation and emission filters to provide differentiation between classes of aromatic organic compounds. Certain inorganic fluorescent materials, including heavy metal compounds, may also be distinguished from the organic compounds, despite both having similar optical properties.

  12. Influence of polychlorinated aromatic compounds on the biotransformation and toxicity of organophosphorus pesticides (OP) to the Daphnia magna

    SciTech Connect

    Tonkopii, V.; Zagrebin, A.; Sherstneva, L.

    1995-12-31

    The effect of different polychlorinated aromatics (DDT, Aroclor 1254, certain polychlorinated biphenyls and dibenzofurans) on the toxicity of OP (DDVP paraoxon, malaoxon) to Daphnia magna was studied. Pretreatment of daphnids with chlorinated compounds during 72 hours in nontoxic concentrations (1/5--1/20 CL{sub 50}) has been shown to reduce the toxicity of OP for hydrobionts. For study of influence of chlorinated compounds on biotransformation of OP the activity of enzymes which are hydrolyzing the OP was investigated in Daphnia`s homogenates or microsomes. The activity of carboxylesterase (tributyrinase, aliesterase) and arylesterase (phosphorylphosphatase) with usage as substrates accordingly {alpha}-naphthylacetate and paraoxon was measured. Besides that the activity of cholinesterase with application of propionylthiocholine as substrate was determined. After polychlorinated aromatic compounds treatment of daphnids activities of both aryl-and carboxylesterase increased markedly. It decreased the inhibition of Daphnia`s cholinesterase caused by incubation with OP in concentrations 0.5--1.0 CL{sub 50}. Thus the induction by chlorinate aromatics of OP metabolizing enzymes seems to play the important role in reduction of OP toxicity to Daphnia magna. Perhaps the aryl- and carboxylesterase of Daphnia can be used as biomarkers of pollution by polychlorinated aromatics in water.

  13. High-field FT-ICR-MS and aromaticity equivalent approach for structural identification of water soluble organic compounds (WSOC)

    NASA Astrophysics Data System (ADS)

    Harir, Mourad; Yassine, Mahmoud M.; Dabek-Zlotorzynska, Ewa; Hertkorn, Norbert; Schmitt-Kopplin, Philippe

    2015-04-01

    Organic aerosol (OA) makes up a large and often dominant fraction, (20 to 90%) of the submicron atmospheric particulate mass, and its effects are becoming increasingly important in determining climatic and health effects of atmospheric aerosols. Despite the abundance of OA, our understanding of the sources, formation processes and atmospheric properties of OA is limited. Atmospheric OA has both primary (directly emitted) and secondary (formed in the atmosphere from precursor gases) sources, which can be natural (e.g. vegetation) and/or anthropogenic (e.g. fossil-based vehicle exhaust or biomass burning). A significant fraction of OA contains as much as 20-70% of water soluble organic compounds (WSOC). The WSOC fraction is a very complex mixture of low volatility, polyfunctional aliphatic and aromatic compounds containing carboxyl, alcohol, carbonyl, sulfo, nitro, and other functionalities. This high degree of chemical complexity of atmospheric organics has inspired a number of sophisticated approaches that are capable of identifying and detecting a variety of different analytes in OA. Accordingly, one of the most challenging areas of atmospheric particulate matter (PM) analysis is to comprehend the molecular complexity of the OA, especially WSOC fraction, a significant component of atmospheric fine PM (PM2.5). The sources of WSOC are not well understood, especially the relative contributions of primary vs. secondary organic aerosol. Therefore, the molecular characterization of WSOC is important because it allows gaining insight into aerosol sources and underlying mechanisms of secondary organic aerosols (SOA) formation and transformation. In this abstract, molecular characterization of WSOC was achieved using high-field mass spectrometry FT-ICR-MS and aromaticity equivalent approach. Aromaticity equivalent (Xc), defined recently as a new parameter calculated from the assigned molecular formulas (complementary to the aromaticity index [1]), is introduced to improve

  14. Laser Sensor Development for Fluorescence Detection of Plastics and other Anthropogenic Compounds Dissolved in Seawater

    DTIC Science & Technology

    2016-06-07

    Laser Sensor Development for Fluorescence Detection of Plastics and other Anthropogenic Compounds Dissolved in Seawater Dr. Paula G. Coble Department...plastic and carbon compounds. Projected limits of sensitivity in situ are in the range of parts per trillion (pptr) for this sensor , an improvement of...orders of magnitude over existing fluorescence sensors . Oceanographic applications include UV-vis spectral characterization of dissolved and

  15. Polycyclic aromatic compound profiles from extracts of Dreissenid mussels and gammarid amphipods coexisting in Hamilton Harbor

    SciTech Connect

    Marvin, C.H.; McCarry, B.E.; Allan, L.; Bryant, D.W.

    1995-06-01

    Aggregates of dreissenid mussels were collected in Hamilton Harbour (western Lake Ontario) from a south shore site (Randle Reef) in an area characterized by coal tar-contaminated sediments, and from a site on the north shore exposed to particulates circulating in the harbour water column. Samples were separated into three components: dreissend mussels, gammarid amphipods (Gammarus fasciatus), and particulate material. The samples were freeze-dried, and extracted using ultrasonication in dichloromethane. The organic solvent extracts were subjected to an open-column alumina and Sephadex LH-20 gel column clean-up procedure, and characterized by gas chromatography-mass spectrometry (GC-MS). The chromatographic profiles of all sample extracts were dominated by polycyclic aromatic hydrocarbons (PAH). The concentrations of the individual compounds were normalized for contaminant profile comparison of the extracts of dreissenids, amphipods, and particulates associated with aggregates of dreissenid mussels. These profiles were also compared with extracts of coal tar-contaminated sediment from the Randle Reef area, and extracts of suspended particulates obtained from sediment traps. The similarities in the PAH profiles provide evidence of exposure to a common source of contaminants. These data also show that PAH associated with suspended particulates obtained from sediment traps. The similarities in the PAH profiles provide evidence of exposure to a common source of contaminants. These data also show that PAH associated with suspended particulates in Hamilton Harbour are being accumulated by dreissenid mussels and gammarid amphipods.

  16. Polarizable Empirical Force Field for Aromatic Compounds Based on the Classical Drude Oscillator

    PubMed Central

    Lopes, Pedro E. M.; Lamoureux, Guillaume; Roux, Benoit; MacKerell, Alexander D.

    2008-01-01

    The polarizable empirical CHARMM force field based on the classical Drude oscillator has been extended to the aromatic compounds benzene and toluene. Parameters were optimized for benzene and then transferred directly to toluene, with parameters for the methyl moiety of toluene taken from the previously published work on the alkanes. Optimization of all parameters was performed against an extensive set of quantum mechanical and experimental data. Ab initio data was used for determination of the electrostatic parameters, the vibrational analysis, and in the optimization of the relative magnitudes of the Lennard-Jones parameters. The absolute values of the Lennard-Jones parameters were determined by comparing computed and experimental heats of vaporization, molecular volumes, free energies of hydration and dielectric constants. The newly developed parameter set was extensively tested against additional experimental data such as vibrational spectra in the condensed phase, diffusion constants, heat capacities at constant pressure and isothermal compressibilities including data as a function of temperature. Moreover, the structure of liquid benzene, liquid toluene and of solutions of each in water were studied. In the case of benzene, the computed and experimental total distribution function were compared, with the developed model shown to be in excellent agreement with experiment. PMID:17388420

  17. Degradation of Monochlorinated and Nonchlorinated Aromatic Compounds under Iron-Reducing Conditions

    PubMed Central

    Kazumi, J.; Haggblom, M. M.; Young, L. Y.

    1995-01-01

    The capacity for Fe(sup3+) to serve as an electron acceptor in the microbial degradation of monochlorinated and nonchlorinated aromatic compounds was investigated in anoxic sediment enrichments. The substrates tested included phenol, benzoate, aniline, their respective monochlorinated isomers, o-, m-, and p-cresol, and all six dimethylphenol isomers. Phenol and 2-, 3-, and 4-chlorophenol were utilized by anaerobic microorganisms, with the concomitant reduction of Fe(sup3+) to Fe(sup2+). The amount of Fe(sup2+) produced in the enrichments was 89 to 138% of that expected for the stoichiometric degradation of these substrates to CO(inf2), suggesting complete mineralization at the expense of Fe reduction. Under Fe-reducing conditions, there was initial loss of benzoate and 3-chlorobenzoate but not of 2- or 4-chlorobenzoate. In addition, there was initial microbial utilization of aniline but not of the chloroaniline isomers. There was also initial loss of o-, m-, and p-cresol in our enrichments. None of the dimethylphenol isomers, however, was degraded within 300 days. Furthermore, we tested the capacity of an Fe-reducing, benzoate-grown culture of Geobacter metallireducens GS-15 to utilize monochlorinated benzoates and phenols. G. metallireducens was able to degrade benzoate and phenol but none of their chlorinated isomers, suggesting that the degradation of chlorophenols in our sediment enrichments may be due to novel Fe-reducing organisms that have yet to be isolated. PMID:16535169

  18. Remediation of polycyclic aromatic hydrocarbon compounds in groundwater using poplar trees.

    PubMed

    Widdowson, Mark A; Shearer, Sandra; Andersen, Rikke G; Novak, John T

    2005-03-15

    A seven-year study was conducted to assess the effectiveness of hybrid poplar trees to remediate polycyclic aromatic hydrocarbon (PAH) compounds in soil and groundwater at a creosote-contaminated site. A reduction in the areal extent of the PAH plume was observed in the upper half of the 2-m-thick saturated zone, and PAH concentration levels in the groundwater declined throughout the plume. PAH concentrations began to decline during the period between the third and fourth growing seasons, which coincided with the propagation of the tree roots to the water table region. Remediation was limited to naphthalene and several three-ring PAHs (acenaphthylene and acenaphthene). PAH concentrations in soil and aquifer sediment samples also declined over time; however, levels of four-ring PAHs persisted at the lower depths during the study period. The naphthalene to total PAH concentration ratio in the most contaminated groundwater decreased from >0.90 at the beginning of the second growing season to approximately 0.70 at the end the study. Remediation in the lower region of the saturated zone was limited bythe presence of a 0.3-m-thick layer of creosote present as a dense nonaqueous phase liquid (DNAPL). The nearly steady-state condition of the PAH concentrations observed during the last three years of the study suggests that the effectiveness of the phytoremediation system is limited by the rate of PAH dissolution from the DNAPL source.

  19. Volatile organic compounds, polycyclic aromatic hydrocarbons and elements in the air of ten urban homes.

    PubMed

    Van Winkle, M R; Scheff, P A

    2001-03-01

    Ten homes were monitored at regular intervals from June 1994 through April 1995 as part of a Public Health Assessment in Southeast Chicago for exposure to volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and elements. Simultaneous 24-h indoor and outdoor samples were collected. VOCs were and analyzed using USEPA Method TO-14 with Selected Ion Monitoring Mass Spectrometry (GC/MS). PAHs were analyzed using USEPA Method TO-13 with GC/MS. Elements were collected on quartz fiber filters and analyzed by Inductively Coupled Argon Plasma (ICP) spectroscopy or Graphite Furnace Atomic Absorption (GFAA). Continuous measurements of CO2 and temperature were recorded for each indoor sample. Twenty-four h total CO2 emissions were determined from occupancy and estimated gas stove usage and were moderately correlated (R2 = 0.19) with 24 h average indoor CO2 concentrations. Modeled 24-h air exchange rates ranged from 0.04 to 3.76 air changes h-1 (ACH), with mean of 0.52 ACH. Median particle penetration was 0.89. Emission rates were calculated for each pollutant sampled. Using a detailed housing survey and field sampling questionnaires, it was possible to evaluate associations between housing characteristics and source activities, and pollutant source rates. The data indicate that several predictor variables, including mothball storage, air freshner use, and cooking activities, are reasonable predictors for emission rates for specific pollutants in the homes studied.

  20. Solubilization and biodegradation of polycyclic aromatic hydrocarbon compounds in soil-water suspensions with surfactants

    SciTech Connect

    Laha, S.

    1992-01-01

    Hydrophobic organic compounds (HOCs) sorb strongly onto soil and sediment material, and the effectiveness of microbial treatment can be diminished by HOC phase partitioning and decreased substrate accessibility to microorganisms. Surfactant addition has been suggested as a technique for decreasing the interfacial tension and partitioning of the HOC with soil, and thereby increasing HOC mobility and bioavailability. However, this study indicates that nonionic surfactant solubilization of HOCs from soil may not be beneficial for the enhancement of soil bioremediation. The solubilization and microbial degradation of phenanthrene, a three-ring polycyclic aromatic hydrocarbon (PAH) compound, was examined in various soil-water systems with commercially-available surface-active agents. This was accomplished by a series of batch tests using radiolabeled techniques. The purpose of surfactant addition was to assess the effect of surfactant solubilization of PAHs on their biodegradation. For soil-water suspensions without surfactant approximately 50-60% of the phenanthrene was mineralized over the course of ten weeks. The addition of nonionic surface-active agents was observed not to be beneficial for microbial mineralization of phenanthrene in the soil-water systems, and for supra-CMC surfactant doses phenanthrene mineralization was completely inhibited for all the surfactants tested. Sub-CMC levels of surfactant in the soil-water systems generally did not have an inhibitory effect on phenanthrene mineralization, but neither did such doses serve to enhance the rate of degradation, which proceeded most rapidly in the absence of any surfactant. Companion tests suggest that the supra-CMC inhibitory effect is not a toxicity phenomenon, per se, of the surfactant or micellized PAH. An assessment of the results from the various experiments suggest that the inhibitory effect is probably related to a reversible physiological surfactant micelle-bacteria interaction.

  1. Carbon 13 chemical shift tensors in aromatic compounds. 3. Phenanthrene and triphenylene

    SciTech Connect

    Soderquist, A.; Hughes, C.D.; Horton, W.J.; Facelli, J.C.; Grant, D.M.

    1992-04-08

    Measurements of the principal values of the {sup 13}C chemical shift tensor are presented for the three carbons in triphenylene and for three different {alpha} carbons in phenanthrene. The measurements in triphenylene were made in natural abundance samples at room temperature, while the phenanthrene tensors were obtained from selectively labeled compounds (99% {sup 13}C) at low temperatures ({approx} 25 K). The principal values of the shift tensors were oriented in the molecular frame using ab initio LORG calculations. The steric compression at C{sub 4} in phenanthrene and in corresponding positions in triphenylene is manifested in sizable upfield shift in the {sigma} 33 component relative to the corresponding {sigma} 33 values at C{sub 1} and C{sub 9} in phenanthrene. The upfield shift in {sigma} 33 is mainly responsible for the well-known upfield shift of the isotropic chemical shifts of such sterically perturbed carbons. In phenanthrene c{sub 9} exhibits a unique {sigma} 22 value reflecting the greater localization of {pi}-electrons in the c{sub 9}-C{sub 10} bond. This localization of the {pi}-electrons at the C{sub 9}-C{sub 10} bond in the central ring of phenanthrene also corresponds with the most likely ordering of electrons described by the various Kekule structures in phenanthrene. The analysis of the {sup 13}C chemical shieldings of the bridgehead carbons in the triphenylene provides significant experimental information on bonding between rings in polycyclic aromatic compounds. 39 refs., 8 fig., 3 tab.

  2. Biological monitoring of exposure to polycyclic aromatic hydrocarbons by determination of unmetabolized compounds in urine.

    PubMed

    Campo, Laura; Addario, Liliana; Buratti, Marina; Scibetta, Licia; Longhi, Omar; Valla, Carla; Cirla, Piero E; Martinotti, Irene; Foà, Vito; Fustinoni, Silvia

    2006-04-10

    In this paper we evaluated the possibility to assess occupational exposure to polycyclic aromatic hydrocarbons (PAHs) measuring unmetabolized PAHs in urine. With this aim, 24 road paving (RP) workers, exposed to bitumen fumes, and 6 road construction workers (CW), exposed to diesel exhausts, were investigated. Median personal exposure to low boiling PAHs (from naphthalene to pyrene) during the work shift ranged from 0.5 to 369 ng/m(3), with naphthalene as the most abundant compound. Three urine samples were collected for each worker: baseline (after 2 days of vacation), before- and end-shift samples (in the second part of the work week). The following urinary compounds were measured by headspace-solid phase microextraction GC/MS: naphthalene (U-NAP), acenaphthylene (U-ACY), acenaphthene (U-ACE), fluorene (U-FLE), phenanthrene (U-PHE), anthracene (U-ANT), fluoranthene (U-FLU), pyrene (U-PYR). Urinary PAHs were detected in almost all samples. Median levels for U-NAP, U-PHE, U-PYR and U-FLE in end-shift samples were 82, 48, 54 and 21 ng/L in RP and 69, 14, 24 and 15 ng/L in CW, respectively. Significant differences in the levels of U-PHE, U-FLU and U-PYR were found between RP and CW (p<0.05). Moreover in RP samples the urinary excretion of most analytes increased during the work shift (p<0.05). These results suggest that urinary PAHs may be useful biomarkers of occupational exposure.

  3. Aromatic compound emissions from municipal solid waste landfill: Emission factors and their impact on air pollution

    NASA Astrophysics Data System (ADS)

    Liu, Yanjun; Lu, Wenjing; Guo, Hanwen; Ming, Zhongyuan; Wang, Chi; Xu, Sai; Liu, Yanting; Wang, Hongtao

    2016-08-01

    Aromatic compounds (ACs) are major components of volatile organic compounds emitted from municipal solid waste (MSW) landfills. The ACs emissions from the working face of a landfill in Beijing were studied from 2014 to 2015 using a modified wind tunnel system. Emission factors (EFs) of fugitive ACs emissions from the working face of the landfill were proposed according to statistical analyses to cope with their uncertainty. And their impacts on air quality were assessed for the first time. Toluene was the dominant AC with an average emission rate of 38.8 ± 43.0 μg m-2 s-1 (at a sweeping velocity of 0.26 m s-1). An increasing trend in AC emission rates was observed from 12:00 to 18:00 and then peaked at 21:00 (314.3 μg m-2 s-1). The probability density functions (PDFs) of AC emission rates could be classified into three distributions: Gaussian, log-normal, and logistic. EFs of ACs from the working face of the landfill were proposed according to the 95th percentile cumulative emission rates and the wind effects on ACs emissions. The annual ozone formation and secondary organic aerosol formation potential caused by AC emissions from landfills in Beijing were estimated to be 8.86 × 105 kg year-1 and 3.46 × 104 kg year-1, respectively. Toluene, m + p-xylene, and 1,3,5-trimethylbenzene were the most significant contributors to air pollution. Although ACs pollutions from landfills accounts for less percentage (∼0.1%) compared with other anthropogenic sources, their fugitive emissions which cannot be controlled efficiently deserve more attention and further investigation.

  4. Structural and replicative diversity of large plasmids from sphingomonads that degrade polycyclic aromatic compounds and xenobiotics.

    PubMed

    Basta, Tamara; Buerger, Sibylle; Stolz, Andreas

    2005-06-01

    The plasmids from 16 sphingomonads which degrade various xenobiotics and polycyclic aromatic compounds were compared with the previously sequenced plasmid pNL1 from Sphingomonas aromaticivorans F199. The replicase genes repAaAb from plasmid pNL1 were amplified by PCR and used as a gene probe for the identification of plasmids belonging to the same incompatibility group as plasmid pNL1. Plasmids were prepared from various sphingomonads and hybridized with the repA gene probe. Positive hybridization signals were obtained with plasmids of approximately 160-195 kb from Sphingomonas subterranea and S. aromaticivorans B0695, which had been isolated from the same subsurface location as S. aromaticivorans F199. The repA probe also hybridized with plasmids from Sphingomonas xenophaga BN6, Sphingomonas sp. HH69 and Sphingomonas macrogoltabidus, which had been isolated from different continents and which utilize different organic compounds than S. aromaticivorans F199 and the other subsurface strains. The results of the hybridization experiments were confirmed by PCR experiments using primers deduced from the repAaAb region of plasmid pNL1. Nucleotide sequence comparisons suggested that three gene clusters were conserved between plasmid pNL1 and plasmid pBN6 from the naphthalenesulfonate- degrading strain S. xenophaga BN6. From these sequence comparisons, PCR primers were derived in order to detect the respective gene clusters in the other strains and to deduce their position relative to each other. These experiments demonstrated that all analysed subsurface strains harboured the same three gene clusters, but that the position and distance from each other of the clusters varied considerably among the different strains.

  5. Diurnal variability of polycyclic aromatic compound (PAC) concentrations: Relationship with meteorological conditions and inferred sources

    NASA Astrophysics Data System (ADS)

    Alam, Mohammed S.; Keyte, Ian J.; Yin, Jianxin; Stark, Christopher; Jones, Alan M.; Harrison, Roy M.

    2015-12-01

    Polycyclic aromatic hydrocarbons (PAH) and their nitro and oxy derivatives have been sampled every three hours over one week in winter at two sites in Birmingham UK. One site is heavily influenced by road traffic and is close to residential dwellings, while the other site is a background urban location at some distance from both sources of emission. The time series of concentrations has been examined along with the ratio of concentrations between the two sampling sites. A comparison of averaged diurnal profiles has shown different patterns of behaviour which has been investigated through calculating ratios of concentration at 18:00-21:00 h relative to that at 06:00-09:00 h. This allows identification of those compounds with a strong contribution to a traffic-related maximum at 06:00-09:00 h which are predominantly the low molecular weight PAHs, together with a substantial group of quinones and nitro-PAHs. Changes in partitioning between vapour and particulate forms are unlikely to influence the ratio as the mean temperature at both times was almost identical. Most compounds show an appreciable increase in concentrations in the evening which is attributed to residential heating emissions. Compounds dominated by this source show high ratios of 18:00-21:00 concentrations relative to 06:00-09:00 concentrations and include higher molecular weight PAH and a substantial group of both quinones and nitro-PAH. The behaviour of retene, normally taken as an indicator of biomass burning, is suggestive of wood smoke only being one contributor to the evening peak in PAH and their derivatives, with coal combustion presumably being the other main contributor. Variations of PAH concentrations with wind speed show a dilution behaviour consistent with other primary pollutants, and high concentrations of a range of air pollutants were observed in an episode of low temperatures and low wind speeds towards the end of the overall sampling period consistent with poor local dispersion

  6. A novel aromatic oil compound inhibits microbial overgrowth on feet: a case study

    PubMed Central

    Misner, Bill D

    2007-01-01

    Background Athlete's Foot (Tinea pedis) is a form of ringworm associated with highly contagious yeast-fungi colonies, although they look like bacteria. Foot bacteria overgrowth produces a harmless pungent odor, however, uncontrolled proliferation of yeast-fungi produces small vesicles, fissures, scaling, and maceration with eroded areas between the toes and the plantar surface of the foot, resulting in intense itching, blisters, and cracking. Painful microbial foot infection may prevent athletic participation. Keeping the feet clean and dry with the toenails trimmed reduces the incidence of skin disease of the feet. Wearing sandals in locker and shower rooms prevents intimate contact with the infecting organisms and alleviates most foot-sensitive infections. Enclosing feet in socks and shoes generates a moisture-rich environment that stimulates overgrowth of pungent both aerobic bacteria and infectious yeast-fungi. Suppression of microbial growth may be accomplished by exposing the feet to air to enhance evaporation to reduce moistures' growth-stimulating effect and is often neglected. There is an association between yeast-fungi overgrowths and disabling foot infections. Potent agents virtually exterminate some microbial growth, but the inevitable presence of infection under the nails predicts future infection. Topical antibiotics present a potent approach with the ideal agent being one that removes moisture producing antibacterial-antifungal activity. Severe infection may require costly prescription drugs, salves, and repeated treatment. Methods A 63-y female volunteered to enclose feet in shoes and socks for 48 hours. Aerobic bacteria and yeast-fungi counts were determined by swab sample incubation technique (1) after 48-hours feet enclosure, (2) after washing feet, and (3) after 8-hours socks-shoes exposure to a aromatic oil powder-compound consisting of arrowroot, baking soda, basil oil, tea tree oil, sage oil, and clove oil. Conclusion Application of this

  7. Petroleum alteration by thermochemical sulfate reduction - A comprehensive molecular study of aromatic hydrocarbons and polar compounds

    NASA Astrophysics Data System (ADS)

    Walters, Clifford C.; Wang, Frank C.; Qian, Kuangnan; Wu, Chunping; Mennito, Anthony S.; Wei, Zhibin

    2015-03-01

    Thermochemical sulfate reduction (TSR) alters petroleum composition as it proceeds towards the complete oxidation of hydrocarbons to CO2. The effects of TSR on the molecular and isotopic composition of volatile species are well known; however, the non-volatile higher molecular weight aromatic and polar species have not been well documented. To address this deficiency, a suite of onshore Gulf coast oils and condensates generated from and accumulating in Smackover carbonates was assembled to include samples that experienced varying levels of TSR alteration and in reservoir thermal cracking. The entire molecular composition of aromatic hydrocarbons and NSO species were characterized and semi-quantified using comprehensive GC × GC (FID and CSD) and APPI-FTICR-MS. The concentration of thiadiamondoids is a reliable indicator of the extent of TSR alteration. Once generated by TSR, thiadiamondoids remain thermally stable in all but the most extreme reservoir temperatures (>180 °C). Hydrocarbon concentrations and distributions are influenced by thermal cracking and TSR. With increasing TSR alteration, oils become enriched in monoaromatic hydrocarbons and the distribution of high molecular weight aromatic hydrocarbons shifts towards more condensed species with a decrease in the number of alkyl carbons. Organosulfur compounds are created by the TSR process. In addition to the increase in benzothiophenes and dibenzothiophenes noted in previous studies, TSR generates condensed species containing one or more sulfur atoms that likely are composed of a single or multiple thiophenic cores. We hypothesize that these species are generated from the partial oxidation of PAHs and dealkylation reactions, followed by sulfur incorporation and condensation reactions. The organosulfur species remaining in the TSR altered oils are "proto-solid bitumen" moieties that upon further condensation, oxidation or sulfur incorporation result in highly sulfur enriched solid bitumen, which is

  8. Development of the New Approaches in Designing of Fluoroorganic Derivatives Sulfur (Unsaturated, Heterocyclic, Aromatic Molecular Systems and Polyfunctional Organic Compounds)

    DTIC Science & Technology

    2005-11-15

    electrophilic fluorinating agents R2N-F, [R3N-F]+ A-; Stage 3. The investigation of pentafluorosulfanylation of different unsaturated, aromatic and...study of reaction fluorination of ethers with pentafluorothio groups (SF5), nitro (NO2) groups and related compounds having electron-withdrawing...fragment 27 9. Exploring the fluorination of thionocarbonates and acetals 30 10. Experimental section. 31 11. Conclusion. 63 12

  9. Measurement of diffusion of fluorescent compounds and autofluorescence in skin in vivo using a confocal instrument

    NASA Astrophysics Data System (ADS)

    Buttenschoen, K. K.; Sutton, E. E.; Daly, D.; Girkin, J. M.

    2016-02-01

    Using compact and affordable instrumentation based upon fluorescent confocal imaging we have tracked the movement of autofluorescent compounds through skin in near real time with high temporal and spatial resolution and sensitivity. The ability to measure the diffusion of compounds through skin with such resolution plays an important role for applications such as monitoring the penetration of pharmaceuticals applied to skin and assessing the integrity of the skin barrier. Several measurement methods exist, but they suffer from a number of problems such as being slow, expensive, non-portable and lacking sensitivity. To address these issues, we adapted a technique that we previously developed for tracking fluorescent compounds in the eye to measure the autofluorescence and the diffusion of externally applied fluorescent compounds in skin in vivo. Results are presented that show the change in autofluorescence of the volar forearm over the course of a week. We furthermore demonstrate the ability of the instrument to measure the diffusion speed and depth of externally applied fluorescent compounds both in healthy skin and after the skin barrier function has been perturbed. The instrument is currently being developed further for increased sensitivity and multi-wavelength excitation. We believe that the presented instrument is suitable for a large number of applications in fields such as assessment of damage to the skin barrier, development of topical and systemic medication and tracking the diffusion of fluorescent compounds through skin constructs as well as monitoring effects of skin products and general consumer products which may come into contact with the skin.

  10. Enhancing muconic acid production from glucose and lignin-derived aromatic compounds via increased protocatechuate decarboxylase activity

    SciTech Connect

    Johnson, Christopher W.; Salvachua, Davinia; Khanna, Payal; Smith, Holly; Peterson, Darren J.; Beckham, Gregg T.

    2016-04-22

    The conversion of biomass-derived sugars and aromatic molecules to cis,cis-muconic acid (referred to hereafter as muconic acid or muconate) has been of recent interest owing to its facile conversion to adipic acid, an important commodity chemical. Metabolic routes to produce muconate from both sugars and many lignin-derived aromatic compounds require the use of a decarboxylase to convert protocatechuate (PCA, 3,4-dihydroxybenzoate) to catechol (1,2-dihydroxybenzene), two central aromatic intermediates in this pathway. Several studies have identified the PCA decarboxylase as a metabolic bottleneck, causing an accumulation of PCA that subsequently reduces muconate production. A recent study showed that activity of the PCA decarboxylase is enhanced by co-expression of two genetically associated proteins, one of which likely produces a flavin-derived cofactor utilized by the decarboxylase. Using entirely genome-integrated gene expression, we have engineered Pseudomonas putida KT2440-derived strains to produce muconate from either aromatic molecules or sugars and demonstrate in both cases that co-expression of these decarboxylase associated proteins reduces PCA accumulation and enhances muconate production relative to strains expressing the PCA decarboxylase alone. In bioreactor experiments, co-expression increased the specific productivity (mg/g cells/h) of muconate from the aromatic lignin monomer p-coumarate by 50% and resulted in a titer of >15 g/L. In strains engineered to produce muconate from glucose, co-expression more than tripled the titer, yield, productivity, and specific productivity, with the best strain producing 4.92+/-0.48 g/L muconate. Furthermore, this study demonstrates that overcoming the PCA decarboxylase bottleneck can increase muconate yields from biomass-derived sugars and aromatic molecules in industrially relevant strains and cultivation conditions.

  11. Enhancing muconic acid production from glucose and lignin-derived aromatic compounds via increased protocatechuate decarboxylase activity

    DOE PAGES

    Johnson, Christopher W.; Salvachua, Davinia; Khanna, Payal; ...

    2016-04-22

    The conversion of biomass-derived sugars and aromatic molecules to cis,cis-muconic acid (referred to hereafter as muconic acid or muconate) has been of recent interest owing to its facile conversion to adipic acid, an important commodity chemical. Metabolic routes to produce muconate from both sugars and many lignin-derived aromatic compounds require the use of a decarboxylase to convert protocatechuate (PCA, 3,4-dihydroxybenzoate) to catechol (1,2-dihydroxybenzene), two central aromatic intermediates in this pathway. Several studies have identified the PCA decarboxylase as a metabolic bottleneck, causing an accumulation of PCA that subsequently reduces muconate production. A recent study showed that activity of the PCAmore » decarboxylase is enhanced by co-expression of two genetically associated proteins, one of which likely produces a flavin-derived cofactor utilized by the decarboxylase. Using entirely genome-integrated gene expression, we have engineered Pseudomonas putida KT2440-derived strains to produce muconate from either aromatic molecules or sugars and demonstrate in both cases that co-expression of these decarboxylase associated proteins reduces PCA accumulation and enhances muconate production relative to strains expressing the PCA decarboxylase alone. In bioreactor experiments, co-expression increased the specific productivity (mg/g cells/h) of muconate from the aromatic lignin monomer p-coumarate by 50% and resulted in a titer of >15 g/L. In strains engineered to produce muconate from glucose, co-expression more than tripled the titer, yield, productivity, and specific productivity, with the best strain producing 4.92+/-0.48 g/L muconate. Furthermore, this study demonstrates that overcoming the PCA decarboxylase bottleneck can increase muconate yields from biomass-derived sugars and aromatic molecules in industrially relevant strains and cultivation conditions.« less

  12. The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

    2015-10-01

    This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the

  13. Oil sands development contributes polycyclic aromatic compounds to the Athabasca River and its tributaries

    PubMed Central

    Kelly, Erin N.; Short, Jeffrey W.; Schindler, David W.; Hodson, Peter V.; Ma, Mingsheng; Kwan, Alvin K.; Fortin, Barbra L.

    2009-01-01

    For over a decade, the contribution of oil sands mining and processing to the pollution of the Athabasca River has been controversial. We show that the oil sands development is a greater source of contamination than previously realized. In 2008, within 50 km of oil sands upgrading facilities, the loading to the snowpack of airborne particulates was 11,400 T over 4 months and included 391 kg of polycyclic aromatic compounds (PAC), equivalent to 600 T of bitumen, while 168 kg of dissolved PAC was also deposited. Dissolved PAC concentrations in tributaries to the Athabasca increased from 0.009 μg/L upstream of oil sands development to 0.023 μg/L in winter and to 0.202 μg/L in summer downstream. In the Athabasca, dissolved PAC concentrations were mostly <0.025 μg/L in winter and 0.030 μg/L in summer, except near oil sands upgrading facilities and tailings ponds in winter (0.031–0.083 μg/L) and downstream of new development in summer (0.063–0.135 μg/L). In the Athabasca and its tributaries, development within the past 2 years was related to elevated dissolved PAC concentrations that were likely toxic to fish embryos. In melted snow, dissolved PAC concentrations were up to 4.8 μg/L, thus, spring snowmelt and washout during rain events are important unknowns. These results indicate that major changes are needed to the way that environmental impacts of oil sands development are monitored and managed. PMID:19995964

  14. Paternò-Büchi reaction between aromatic carbonyl compounds and 1-(3-furyl)alkanols.

    PubMed

    D'Auria, Maurizio; Emanuele, Lucia; Racioppi, Rocco; Valente, Anna

    2008-01-01

    The photochemical reaction between aromatic carbonyl compounds and 3-furylmethanol derivatives occurs with high regioselectivity. In most of the experiments formation of oxetanes occurs at the hydroxyalkylated double bond. With chiral 1-(3-furyl)alkanols the reaction occurs with good-high stereoselectivity. In the case of 1-(3-furyl)-benzyl alcohol the stereoselectivity can be explained on the basis of the conformers of the reagent, assuming the formation of a complex between the carbonyl compound and the hydroxyl group.

  15. Solid-matrix fluorescence and phosphorescence and solid-phase microextraction of polycyclic aromatic hydrocarbons with hydrophobic paper

    SciTech Connect

    Ackerman, A.H.; Hurtubise, R.J.

    1999-07-01

    Solid-matrix fluorescence (SMF) and solid-matrix phosphorescence (SMP) have been used in conjunction with solid-phase microextraction to characterize mixtures of polycyclic aromatic hydrocarbons (PAHs) isolated from water. Whatman 1PS paper was used to extract the PAH from water, and then the isolated PAHs were directly identified on the paper by obtaining SMF and SMP spectra. The SMF and SMP properties of 10 PAH were obtained, and the PAHs in a two-component mixture, a three-component mixture, and a four-component mixture were easily identified by a combination of SMF and SMP. No external heavy atom was needed to acquire the SMP data. Benzo[{ital e}]pyrene gave a limit of detection of 6.2 pg/mL with SMP, and with SMF benzo[{ital a}]pyrene gave a limit of detection of 19 pg/mL. {copyright} {ital 1999} {ital Society for Applied Spectroscopy}

  16. PHOTOACTIVATION AND TOXICITY OF MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN MARINE SEDIMENT

    EPA Science Inventory

    The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration se...

  17. Polycyclic aromatic compounds as anticancer agents: synthesis and biological evaluation of methoxy dibenzofluorene derivatives

    PubMed Central

    Becker, Frederick F.; Banik, Bimal K.

    2014-01-01

    Synthesis of a new methoxy dibenzofluorene through alkylation, cyclodehydration and aromatization in a one-pot operation is achieved for the first time. Using this hydrocarbon, a few derivatives are prepared through aromatic nitration, catalytic hydrogenation, coupling reaction with a side chain and reduction. The benzylic position of this hydrocarbon with the side chain is oxidized and reduced. Some of these derivatives have demonstrated excellent antitumor activities in vitro. This study confirms antitumor activity depends on the structures of the molecules. PMID:25136549

  18. Determination of the aromatic compounds in plant cuticular waxes using FT-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Dubis, Eligiusz N.; Dubis, Alina T.; Popławski, J.

    2001-09-01

    The infrared study of the aromatic components of hops ( Humulus lupulus) cuticular wax was performed. HATR FT-IR technique for fresh leaves and their extract analysis was applied. Phenylmethyl myristate, 2-phenylethyl myristate and docosyl benzoate were synthesized and used as reference standards. An absorption band in the range of 709-966 cm -1 indicates the presence of aromatic esters in plant cuticular waxes.

  19. Long wave fluorophore sensor compounds and other fluorescent sensor compounds in polymers

    DOEpatents

    Walsh, Joseph C.; Heiss, Aaron M.; Noronha, Glenn; Vachon, David J.; Lane, Stephen M.; Satcher, Jr., Joe H.; Peyser, Thomas A.; Van Antwerp, William Peter; Mastrototaro, John Joseph

    2004-07-20

    Fluorescent biosensor molecules, fluorescent biosensors and systems, as well as methods of making and using these biosensor molecules and systems are described. Embodiments of these biosensor molecules exhibit fluorescence emission at wavelengths greater than about 650 nm. Typical biosensor molecules include a fluorophore that includes an iminium ion, a linker moiety that includes a group that is an anilinic type of relationship to the fluorophore and a boronate substrate recognition/binding moiety, which binds glucose. The fluorescence molecules modulated by the presence or absence of polyhydroxylated analytes such as glucose. This property of these molecules of the invention, as well as their ability to emit fluorescent light at greater than about 650 nm, renders these biosensor molecules particularly well-suited for detecting and measuring in-vivo glucose concentrations.

  20. Scavenging ratio of polycyclic aromatic compounds in rain and snow at the Athabasca oil sands region

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Cheng, I.; Muir, D.; Charland, J.-P.

    2014-07-01

    Athabasca oil sands industry in northern Alberta, Canada is a possible source of polycyclic aromatic compounds (PACs). Monitored PACs, including polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes, in precipitation and in air at three near-source sites in the Fort MacKay and Fort McMurray area during May 2011 to August 2012 were analyzed to generate a database of scavenging (or washout) ratios (Wt) for PACs scavenged by both snow and rain. Median precipitation and air concentrations of parent PAHs over the May 2011 to August 2012 period ranged from 0.3-184.9 (chrysene) ng L-1 and 0.01-3.9 (naphthalene) ng m-3, respectively, which were comparable to literature values. Higher concentrations in precipitation and air were observed for alkylated PAHs and dibenzothiophenes. The median precipitation and air concentrations were 11.3-646.7 (C3-fluoranthene/pyrene) ng L-1 and 0.21-16.9 (C3-naphthalene) ng m-3, respectively, for alkylated PAHs, and 8.5-530.5 (C4-dibenzothiophene) ng L-1 and 0.13-6.6 (C2-dibenzothiophene) ng m-3 for dibenzothiophenes and their alkylated derivatives. Median Wt over the measurement period were 6100-1.1 × 106 from snow scavenging and 350-2.3 × 105 from rain scavenging depending on the PAC species. Median Wt for parent PAHs were within the range of those observed at other urban and suburban locations. But Wt for acenaphthylene in snow samples was 2-7 times higher. Some individual snow and rain samples exceeded literature values by a factor of 10. Wt for benzo(a)pyrene, dibenz(a,h)anthracene, and benzo(g,h,i)perylene in snow samples had reached 107, which is the maximum for PAH snow scavenging ratios reported in literature. From the analysis of data subsets, Wt for particulate-phase dominant PACs were 14-20 times greater than gas-phase dominant PACs in snow samples and 7-20 times greater than gas-phase dominant PACs in rain samples. Wt from snow scavenging was ∼9 times greater than rain scavenging for particulate

  1. Scavenging ratios of polycyclic aromatic compounds in rain and snow in the Athabasca oil sands region

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Cheng, I.; Muir, D.; Charland, J.-P.

    2015-02-01

    The Athabasca oil sands industry in northern Alberta, Canada, is a possible source of polycyclic aromatic compounds (PACs). Monitored PACs, including polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes (DBTs), in precipitation and in air at three near-source sites in the Fort MacKay and Fort McMurray area during January 2011 to May 2012, were used to generate a database of scavenging ratios (Wt) for PACs scavenged by both snow and rain. Higher concentrations in precipitation and air were observed for alkylated PAHs and DBTs compared to the other PACs. The sums of the median precipitation concentrations over the period of data analyzed were 0.48 μ g L-1 for the 18 PAHs, 3.38 μ g L-1 for the 20 alkylated PAHs, and 0.94 μ g L-1 for the 5 DBTs. The sums of the median air concentrations for parent PAHs, alkylated PAHs, and DBTs were 8.37, 67.26, and 11.83 ng m-3, respectively. Median Wt over the measurement period were 6100 - 1.1 × 106 from snow scavenging and 350 - 2.3 × 105 from rain scavenging depending on the PAC species. Median Wt for parent PAHs were within the range of those observed at other urban and suburban locations, but Wt for acenaphthylene in snow samples were 2-7 times higher compared to other urban and suburban locations. Wt for some individual snow and rain samples exceeded literature values by a factor of 10. Wt for benzo(a)pyrene, dibenz(a,h)anthracene, and benzo(g,h,i)perylene in snow samples had reached 107, which is the maximum for PAH snow scavenging ratios reported in the literature. From the analysis of data subsets, Wt for particulate-phase dominant PACs were 14-20 times greater than gas-phase dominant PACs in snow samples and 7-20 times greater than gas-phase dominant PACs in rain samples. Wt from snow scavenging were ~ 9 times greater than from rain scavenging for particulate-phase dominant PACs and 4-9.6 times greater than from rain scavenging for gas-phase dominant PACs. Gas-particle fractions of each PAC

  2. Penicillium chrysogenum var. halophenolicum, a new halotolerant strain with potential in the remediation of aromatic compounds in high salt environments.

    PubMed

    Leitão, Ana Lúcia; García-Estrada, Carlos; Ullán, Ricardo Vicente; Guedes, Sumaya Ferreira; Martín-Jiménez, Patricia; Mendes, Benilde; Martín, Juan Francisco

    2012-01-20

    A halotolerant phenylacetate-degrading fungus Penicillium CLONA2, previously isolated from a salt mine at Algarve (Portugal), was identified as a variant of P. chrysogenum using the ITS-5,8S rDNA and the D1/D2 domain of 28S rDNA sequences. The metabolic features and genetic characteristics suggest that this strain belongs to a subgroup of P. chrysogenum, named var. halophenolicum. The presence of the penicillin biosynthetic cluster was proven by Southern hybridizations using probes internal to the pcbAB and penDE genes and sequencing of the pcbAB-pcbC intergenic region. However the pcbAB-pcbC divergent promoter region contained 20 point modifications with respect to that of the wild type P. chrysogenum NRRL1951. The CLONA2 strain produced non-aromatic natural penicillins rather than benzylpenicillin in a medium containing potassium phenylacetate (the precursor of benzylpenicillin) and was able to grow well on phenylacetatic acid using it as sole carbon source. Due to the ability of P. chrysogenum CLONA2 to degrade aromatic compounds, this strain may be an interesting organism for aromatic compounds remediation in high salinity environments.

  3. Acid-promoted chemoselective introduction of amide functionality onto aromatic compounds mediated by an isocyanate cation generated from carbamate.

    PubMed

    Sumita, Akinari; Kurouchi, Hiroaki; Otani, Yuko; Ohwada, Tomohiko

    2014-10-01

    Carbamates have been used as precursors of isocyanates, but heating in the presence of strong acids is required because cleavage of the C-O bond in carbamates is energy-demanding even in acid media. Direct amidation of aromatic compounds by isocyanate cations generated at room temperature from carbamoyl salicylates in trifluoromethanesulfonic acid (TfOH) was examined. Carbamates with ortho-salicylate as an ether group (carbamoyl salicylates) showed dramatically accelerated O-C bond dissociation in TfOH, which resulted in facile generation of the isocyanate cation. These chemoselective intermolecular aromatic amidation reactions proceeded even at room temperature and showed good compatibility with other electrophilic functionalities and high discrimination between N-monosubstituted carbamate and N,N-disubstituted carbamate. The reaction rates of secondary and tertiary amide formation were markedly different, and this difference was utilized to achieve successive (tandem) amidation reactions of molecules with an N-monosubstituted carbamate and an N,N-disubstituted carbamate with two kinds of aromatic compounds.

  4. Laser desorption studies using laser-induced fluorescence of large aromatic molecules

    NASA Astrophysics Data System (ADS)

    Smith, G. P.; Krancevic, B.; Huestis, D. L.; Oser, H.

    2009-01-01

    Pulsed laser desorption of non-volatile organic dye molecules paraterphenyl and tetra-t-butyl-p-quinquephenyl (QUI) was studied using gas phase ultraviolet laser induced fluorescence, following heating of a steel substrate by a pulsed 1.06- µm Nd:YAG laser. The fluorescence signal intensity is linear in concentration up to at least 30 monolayers and shows infrared power threshold behavior, as expected for evaporation, at ˜0.2 J/cm2. Similar signal levels were also observed in air, with 532-nm heating, and using other metallic or dark black surfaces.

  5. Lone pair ... pi interactions between water oxygens and aromatic residues: quantum chemical studies based on high-resolution protein structures and model compounds.

    PubMed

    Jain, Alok; Ramanathan, Venkatnarayan; Sankararamakrishnan, Ramasubbu

    2009-03-01

    The pi electron cloud of aromatic centers is known to be involved in several noncovalent interactions such as C--H...pi, O--H...pi, and pi...pi interactions in biomolecules. Lone-pair (lp) ... pi interactions have gained attention recently and their role in biomolecular structures is being recognized. In this article, we have carried out systematic analysis of high-resolution protein structures and identified more than 400 examples in which water oxygen atoms are in close contact (distance < 3.5 A) with the aromatic centers of aromatic residues. Three different methods were used to build hydrogen atoms and we used a consensus approach to find out potential candidates for lp...pi interactions between water oxygen and aromatic residues. Quantum mechanical calculations at MP2/6-311++G(d,p) level on model systems based on protein structures indicate that majority of the identified examples have energetically favorable interactions. The influence of water hydrogen atoms was investigated by sampling water orientations as a function of two parameters: distance from the aromatic center and the angle between the aromatic plane and the plane formed by the three water atoms. Intermolecular potential surfaces were constructed using six model compounds representing the four aromatic amino acids and 510 different water orientations for each model compound. Ab initio molecular orbital calculations at MP2/6-311++G(d,p) level show that the interaction energy is favorable even when hydrogen atoms are farthest from the aromatic plane while water oxygen is pointing toward the aromatic center. The strength of such interaction depends upon the distance of water hydrogen atoms from the aromatic substituents. Our calculations clearly show that the lp...pi interactions due to the close approach of water oxygen and aromatic center are influenced by the positions of water hydrogen atoms and the aromatic substituents.

  6. Differential effects of topically applied formalin and aromatic compounds on neurogenic-mediated microvascular leakage in rat skin.

    PubMed

    Futamura, Masaki; Goto, Shiho; Kimura, Ryoko; Kimoto, Izumi; Miyake, Mio; Ito, Komei; Sakamoto, Tatsuo

    2009-01-08

    Various volatile organic compounds (VOCs) act as a causative agent of skin inflammation. We investigated the effect of topical application of several VOCs and formalin on microvascular leakage in rat skin. We tested capsaicin, which is a reagent that specifically causes the skin response via endogenously released tachykinins. Evans blue dye extravasation served as an index of the increase in skin vascular permeability. After shaving the abdomen, we applied formalin, m-xylene, toluene, styrene, benzene, ethylbenzene, acetone, diethyl ether, hexane, heptane, cyclohexane and capsaicin to the skin. At 40min after application, skin samples were collected. Among all of the VOCs tested, all of the aromatic compounds significantly produced skin microvascular leakage that was similar to formalin and capsaicin. We also investigated the skin responses seen after the intravenous administration of CP-99,994 (1.5 or 5mg/kg), which is a tachykinin NK1 receptor antagonist, ketotifen (1 or 3mg/kg), which is a histamine H1 receptor antagonist that stabilizes the mast cells, and the topical application of capsazepine (22.5 or 50mM), which is the transient receptor potential vanilloid 1 (TRPV1) antagonist. The response induced by formalin and capsaicin was completely inhibited by CP-99,994. On the other hand, the antagonist partially reduced the response induced by m-xylene, toluene and styrene by 39%, 50% and 46%, respectively. Capsazepine and ketotifen did not alter the response induced by formalin or any of the aromatic compounds. Like capsaicin, formalin and the aromatic compounds at least partially caused skin microvascular leakage, which was due to tachykinin NK1 receptor activation related to the release of tachykinins from the sensory nerve endings. However, it is unlikely that mast cells and TRPV1 play an important role in the skin response.

  7. Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods.

    PubMed

    Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

    2015-01-01

    In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g(-1) lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced.

  8. Use of Time-Resolved Fluorescence to Monitor Bioactive Compounds in Plant Based Foodstuffs.

    PubMed

    Lemos, M Adília; Sárniková, Katarína; Bot, Francesca; Anese, Monica; Hungerford, Graham

    2015-06-26

    The study of compounds that exhibit antioxidant activity has recently received much interest in the food industry because of their potential health benefits. Most of these compounds are plant based, such as polyphenolics and carotenoids, and there is a need to monitor them from the field through processing and into the body. Ideally, a monitoring technique should be non-invasive with the potential for remote capabilities. The application of the phenomenon of fluorescence has proved to be well suited, as many plant associated compounds exhibit fluorescence. The photophysical behaviour of fluorescent molecules is also highly dependent on their microenvironment, making them suitable probes to monitor changes in pH, viscosity and polarity, for example. Time-resolved fluorescence techniques have recently come to the fore, as they offer the ability to obtain more information, coupled with the fact that the fluorescence lifetime is an absolute measure, while steady state just provides relative and average information. In this work, we will present illustrative time-resolved measurements, rather than a comprehensive review, to show the potential of time-resolved fluorescence applied to the study of bioactive substances. The aim is to help assess if any changes occur in their form, going from extraction via storage and cooking to the interaction with serum albumin, a principal blood transport protein.

  9. Use of Time-Resolved Fluorescence to Monitor Bioactive Compounds in Plant Based Foodstuffs

    PubMed Central

    Lemos, M. Adília; Sárniková, Katarína; Bot, Francesca; Anese, Monica; Hungerford, Graham

    2015-01-01

    The study of compounds that exhibit antioxidant activity has recently received much interest in the food industry because of their potential health benefits. Most of these compounds are plant based, such as polyphenolics and carotenoids, and there is a need to monitor them from the field through processing and into the body. Ideally, a monitoring technique should be non-invasive with the potential for remote capabilities. The application of the phenomenon of fluorescence has proved to be well suited, as many plant associated compounds exhibit fluorescence. The photophysical behaviour of fluorescent molecules is also highly dependent on their microenvironment, making them suitable probes to monitor changes in pH, viscosity and polarity, for example. Time-resolved fluorescence techniques have recently come to the fore, as they offer the ability to obtain more information, coupled with the fact that the fluorescence lifetime is an absolute measure, while steady state just provides relative and average information. In this work, we will present illustrative time-resolved measurements, rather than a comprehensive review, to show the potential of time-resolved fluorescence applied to the study of bioactive substances. The aim is to help assess if any changes occur in their form, going from extraction via storage and cooking to the interaction with serum albumin, a principal blood transport protein. PMID:26132136

  10. Chemometrics-assisted excitation-emission fluorescence spectroscopy on nylon-attached rotating disks. Simultaneous determination of polycyclic aromatic hydrocarbons in the presence of interferences.

    PubMed

    Cañas, Alejandro; Richter, Pablo; Escandar, Graciela M

    2014-12-10

    This work presents a green and very simple approach which enables the accurate and simultaneous determination of benzo[a]pyrene, dibenz[a,h]anthracene, benz[a]anthracene, and chrysene, concerned and potentially carcinogenic heavy-polycyclic aromatic hydrocarbons (PAHs) in interfering samples. The compounds are extracted from water samples onto a device composed of a small rotating Teflon disk, with a nylon membrane attached to one of its surfaces. After extraction, the nylon membrane containing the concentrated analytes is separated from the Teflon disk, and fluorescence excitation-emission matrices are directly measured on the nylon surface, and processed by applying parallel factor analysis (PARAFAC), without the necessity of a desorption step. Under optimum conditions and for a sample volume of 25 mL, the PAHs extraction was carried out in 20 min. Detection limits based on the IUPAC recommended criterion and relative errors of prediction were in the ranges 20-100 ng L(-1) and 5-7%, respectively. Thanks to the combination of the ability of nylon to strongly retain PAHs, the easy rotating disk extraction approach, and the selectivity of second-order calibration, which greatly simplifies sample treatment avoiding the use of toxic solvents, the developed method follows most green analytical chemistry principles.

  11. Dual-emitting nanocomposites derived from rare-earth compound nanotubes for ratiometric fluorescence sensing applications

    NASA Astrophysics Data System (ADS)

    Sun, Tian-Ying; Zhang, Da-Quan; Yu, Xue-Feng; Xiang, Yang; Luo, Min; Wang, Jia-Hong; Tan, Guo-Long; Wang, Qu-Quan; Chu, Paul K.

    2013-01-01

    A new class of ratiometric fluorescence sensors composed of rare-earth (RE) compound nanotubes is described. Polyethylenimine-coated yttrium hydroxide fluoride nanotubes (YHF NTs) that were synthesized hydrothermally exhibit highly efficient fluorescence when doped with RE ions. The polyethylenimine on the NTs facilitates the incorporation of phosphors such as quantum dots or organic dyes onto the NT surface to produce dual-emitting nanocomposites which are excellent ratiometric fluorescence sensors. The phosphor layer and underlying tubes in the nanocomposites act as the indicator and reference probes, respectively. This ratiometric fluorescence method which can be applied to the detection of heavy metals in solutions, temperature sensing, and pH sensing boasts high sensitivity and selectivity as well as better accuracy than traditional intensity-based fluorescence methods.A new class of ratiometric fluorescence sensors composed of rare-earth (RE) compound nanotubes is described. Polyethylenimine-coated yttrium hydroxide fluoride nanotubes (YHF NTs) that were synthesized hydrothermally exhibit highly efficient fluorescence when doped with RE ions. The polyethylenimine on the NTs facilitates the incorporation of phosphors such as quantum dots or organic dyes onto the NT surface to produce dual-emitting nanocomposites which are excellent ratiometric fluorescence sensors. The phosphor layer and underlying tubes in the nanocomposites act as the indicator and reference probes, respectively. This ratiometric fluorescence method which can be applied to the detection of heavy metals in solutions, temperature sensing, and pH sensing boasts high sensitivity and selectivity as well as better accuracy than traditional intensity-based fluorescence methods. Electronic supplementary information (ESI) available: EA and TGA profiles, emission spectra of YHF:Eu NTs. See DOI: 10.1039/c2nr33217e

  12. Rapid determination of hazardous compounds in food based on a competitive fluorescence microsphere immunoassay.

    PubMed

    Zou, Mingqiang; Gao, Haixia; Li, Jinfeng; Xu, Fang; Wang, Ling; Jiang, Jizhi

    2008-03-15

    Development of a microsphere-based competitive fluorescence immunoassay for the determination of hazardous low-molecular-weight compounds in food is described. In this method, antigens are covalently bound to carboxy-modified microspheres to compete monoclonal antibody with low-molecular-weight compounds in food samples; mouse IgG/fluorescein isothiocyanate conjugate is used as the fluorescent molecular probe. Thus, the hazardous low-molecular-weight compounds are quantified using a multiparameter flow cytometer. This method has been evaluated using clenbuterol as a model compound. It has a sensitivity of 0.01 ng/mL with dynamic range of 0.01-100 ng/mL, and the concentration of clenbuterol providing 50% inhibition (IC(50)) is 1.1 ng/mL. The main advantages of this method are its high efficiency, biocompatibility, and selectivity, as well as ultralow trace sample consumption and low cost.

  13. Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

    PubMed

    Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

    2015-11-15

    Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution

  14. Application of FT-IR spectroscopy for control of the medium composition during the biodegradation of nitro aromatic compounds.

    PubMed

    Grube, Mara; Muter, Olga; Strikauska, Silvija; Gavare, Marita; Limane, Baiba

    2008-11-01

    Previous studies showed that cabbage leaf extract (CLE) added to the growth medium can noticeably promote the degradation of nitro aromatic compounds by specific consortium of bacteria upon their growth. For further development of the approach for contaminated soil remediation it was necessary to evaluate the qualitative and/or quantitative composition of different origin CLE and their relevance on the growth of explosives-degrading bacteria. Six CLE (different by species, cultivars and harvesting time) were tested and used as additives to the growth medium. It was shown that nitro aromatic compounds can be identified in the FT-IR absorption spectra by the characteristic band at 1,527 cm(-1), and in CLE by the characteristic band at 1,602 cm(-1). The intensity of the CLE band at 1,602 cm(-1) correlated with the concentration of total nitrogen (R2=0.87) and decreased upon the growth of bacteria. The content of nitrogen in CLE differed (0.22-1.00 vol.%) and significantly influenced the content of total carbohydrates (9.50-16.00% DW) and lipids [3.90-9.90% dry weight (DW)] accumulated in bacterial cells while the content of proteins was similar in all samples. Though this study showed quantitative differences in the composition of the studied CLE and the response of bacterial cells to the composition of the growth media, and proved the potential of this additive for remediation of contaminated soil. It was shown that analysis of CLE and monitoring of the conversion of nitro aromatic compounds can be investigated by FT-IR spectroscopy as well as by conventional chemical methods.

  15. SiRNAs conjugated with aromatic compounds induce RISC-mediated antisense strand selection and strong gene-silencing activity

    SciTech Connect

    Kubo, Takanori; Yanagihara, Kazuyoshi; Takei, Yoshifumi; Mihara, Keichiro; Sato, Yuichiro; Seyama, Toshio

    2012-10-05

    Highlights: Black-Right-Pointing-Pointer SiRNAs conjugated with aromatic compounds (Ar-siRNAs) at 5 Prime -sense strand were synthesized. Black-Right-Pointing-Pointer Ar-siRNAs increased resistance against nuclease degradation. Black-Right-Pointing-Pointer Ar-siRNAs were thermodynamically stable compared with the unmodified siRNA. Black-Right-Pointing-Pointer High levels of cellular uptake and cytoplasmic localization were found. Black-Right-Pointing-Pointer Strong gene-silencing efficacy was exhibited in the Ar-siRNAs. -- Abstract: Short interference RNA (siRNA) is a powerful tool for suppressing gene expression in mammalian cells. In this study, we focused on the development of siRNAs conjugated with aromatic compounds in order to improve the potency of RNAi and thus to overcome several problems with siRNAs, such as cellular delivery and nuclease stability. The siRNAs conjugated with phenyl, hydroxyphenyl, naphthyl, and pyrenyl derivatives showed strong resistance to nuclease degradation, and were thermodynamically stable compared with unmodified siRNA. A high level of membrane permeability in HeLa cells was also observed. Moreover, these siRNAs exhibited enhanced RNAi efficacy, which exceeded that of locked nucleic acid (LNA)-modified siRNAs, against exogenous Renilla luciferase in HeLa cells. In particular, abundant cytoplasmic localization and strong gene-silencing efficacy were found in the siRNAs conjugated with phenyl and hydroxyphenyl derivatives. The novel siRNAs conjugated with aromatic compounds are promising candidates for a new generation of modified siRNAs that can solve many of the problems associated with RNAi technology.

  16. Comparative study of aromatic compounds in fruit wines from raspberry, strawberry, and mulberry in central Shaanxi area

    PubMed Central

    Feng, Yiming; Liu, Min; Ouyang, Yanan; Zhao, Xianfang; Ju, Yanlun; Fang, Yulin

    2015-01-01

    Background Although grape wines have firmly dominated the production and consumption markets of fruit wines, raspberry, strawberry, and mulberry have been utilized to make wines because of their joyful aroma and high contents of polyphenolic phytochemicals and essential fatty acids. However, little is known about aromatic compounds of the wines produced from these three fruits. Methods The aromatic composition of fruit wines produced from raspberry, strawberry, mulberry, and red grape was analyzed by GC-MS. Odor activity values (OAVs) and relative odor contributions (ROCs) were used to estimate the sensory contribution of the aromatic compounds to the overall flavor of the wines. Results In strawberry, raspberry, and mulberry wines, 27, 30, and 31 odorants were detected, respectively. Alcohols formed the most abundant group, followed by esters and acids. The grape wine contained a wider variety (16 types) of alcohols, and 4-methyl-2-pentanol and 2,3-butanediol were not present in the three fruit wines. The quantity of esters in raspberry (1.54%) and mulberry wines (2.08%) were higher than those of strawberry wine (0.78%), and mulberry wine contained more types of esters. There were no significant differences of acids between the three fruit wines and the control wine. In addition, 2-heptanone, 2-octanone, 2-nonanone, and 2-undecanone were unique to raspberry wine, and nonanal was present only in mulberry wine. The indistinguishable aroma of the three fruit wines was attributed to the dominance of fruity and floral odor components derived from ethyl esters of fatty acids and their contributions to the global aroma of the three fruit wines. Conclusion The present study demonstrated that there were significant differences in the volatile components of fruit wines made from raspberry, strawberry, and mulberry. The aroma compounds were more abundant in the raspberry and mulberry wines than in the strawberry wine, but the quality of strawberry wine was superior to

  17. Characterization of polycyclic aromatic compounds in diesel exhaust particulate extract responsible for aryl hydrocarbon receptor activity

    NASA Astrophysics Data System (ADS)

    Soontjens, Carol D.; Holmberg, Kristina; Westerholm, Roger N.; Rafter, Joseph J.

    Chemical fractions of a model diesel exhaust particulate extract, notably the fraction containing polycyclic aromatic hydrocarbons (PAH) (Fraction II), mono-nitro PAH (Fraction III), and dinitro-PAH (Fraction IV) have been shown to displace binding of 2,3,7,8-tetrachloro[1,6-[ 3H

  18. Immunological disorders associated with polychlorinated biphenyls and related halogenated aromatic hydrocarbon compounds

    USGS Publications Warehouse

    Noguchi, G.E.; Leatherland, J.F.; Woo, P.T.K.

    1998-01-01

    This review characterizes immunological disorders in fish associated with the widespread environmental contaminants, polychlorinated biphenyls (PCBs), and related halogenated aromatic hydrocarbons (HAHs). Special attention is devoted to comparing the sensitivity of fish species, identifying sensitive immunological endpoints and postulating mechanisms of action.

  19. Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds

    PubMed Central

    Kameda, Takayuki; Azumi, Eri; Fukushima, Aki; Tang, Ning; Matsuki, Atsushi; Kamiya, Yuta; Toriba, Akira; Hayakawa, Kazuichi

    2016-01-01

    Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments. PMID:27075250

  20. Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds

    NASA Astrophysics Data System (ADS)

    Kameda, Takayuki; Azumi, Eri; Fukushima, Aki; Tang, Ning; Matsuki, Atsushi; Kamiya, Yuta; Toriba, Akira; Hayakawa, Kazuichi

    2016-04-01

    Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments.

  1. Modeling the toxicity of aromatic compounds to tetrahymena pyriformis: the response surface methodology with nonlinear methods.

    PubMed

    Ren, Shijin

    2003-01-01

    Response surface models based on multiple linear regression had previously been developed for the toxicity of aromatic chemicals to Tetrahymena pyriformis. However, a nonlinear relationship between toxicity and one of the molecular descriptors in the response surface model was observed. In this study, response surface models were established using six nonlinear modeling methods to handle the nonlinearity exhibited in the aromatic chemicals data set. All models were validated using the method of cross-validation, and prediction accuracy was tested on an external data set. Results showed that response surface models based on locally weighted regression scatter plot smoothing (LOESS), multivariate adaptive regression splines (MARS), neural networks (NN), and projection pursuit regression (PPR) provided satisfactory power of model fitting and prediction and had similar applicabilities. The response surface models based on nonlinear methods were difficult to interpret and conservative in discriminating toxicity mechanisms.

  2. Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds.

    PubMed

    Kameda, Takayuki; Azumi, Eri; Fukushima, Aki; Tang, Ning; Matsuki, Atsushi; Kamiya, Yuta; Toriba, Akira; Hayakawa, Kazuichi

    2016-04-14

    Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments.

  3. Chemical characterization and mutagenic properties of polycyclic aromatic compounds in sediment from tributaries of the Great Lakes

    USGS Publications Warehouse

    Fabacher, David L.; Schmitt, Christopher J.; Besser, John M.; Mac, Michael J.

    1988-01-01

    Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with solvents and characterized chemically for polycyclic aromatic compounds (PACs). An aqueous phase and a crude organic extract were obtained. The crude organic extract was further resolved into fractions A-2 (polycyclic aromatic hydrocarbons) and A-3 (nitrogen-containing polycyclic aromatic compounds), which were analyzed for PACs by gas chromatography and gas chromatography-mass spectrometry. The extracts and fractions were tested for mutagenicity in three assays: Ames, rat hepatocyte unscheduled DNA synthesis, and Chinese hamster ovary hypoxanthine-guanine phosphoribosyl transferase (CHO/HGPRT). Sediments from the industrial sites contained 27 to 363 μg/g total PACs; the reference site, less than 1 μg/g. Qualitative differences in the residue profiles among the sites were attributable to the probable sources of the PACs (petroleum versus combustion). Only one industrial site yielded measurable (0.1 μg/g or more) concentrations of individual nitrogen-containing PACs. In the Ames assay, only the highest doses of the A-2 fractions from two sites approached positive results. Conversely, the crude organic extract and A-2 and A-3 fractions from all sites induced unscheduled DNA synthesis. Crude organic extracts and the A-2 and A-3 fractions from all industrial sites gave well-defined dose-response relations in the CHO/HGPRT assay. We established the presence of chemical mutagens in sediment that could be correlated with neoplasms in fish from many of the sites; however, the mutagenicity of the sediment extracts was not completely related to the degree of contamination by PACs. We also discuss the utility of mutagenicity assays in the evaluation of complex chemical mixtures and recommend the use of a CHO/HGPRT-type assay in which cells are not required to proliferate in the presence of potential interfering chemicals.

  4. Hazardous components and health effects of atmospheric aerosol particles: reactive oxygen species, soot, polycyclic aromatic compounds and allergenic proteins.

    PubMed

    Shiraiwa, Manabu; Selzle, Kathrin; Pöschl, Ulrich

    2012-08-01

    This review outlines recent advances in the investigation of the chemical properties, molecular interactions and health effects of hazardous compounds in atmospheric aerosols, in particular reactive oxygen species (ROS), soot, polycyclic aromatic compounds (PACs) and allergenic proteins. Epidemiological studies show correlations between air particulate matter and adverse health effects of air pollution including allergy, asthma, cardiovascular and respiratory diseases, but the causative relations and mechanisms of interaction on the molecular level are still unclear. ROS generated by photochemical and heterogeneous reactions in the atmosphere seem to play a key role in aerosol health effects and provide a direct link between atmospheric and physiological multiphase processes. Soot and PACs can trigger formation of ROS in vivo, leading to inflammation and cellular damage. PACs as well as allergenic proteins are efficiently oxygenated and nitrated upon exposure to ozone and nitrogen dioxide, which leads to an enhancement of their toxicity and allergenicity.

  5. Laccase Production and Differential Transcription of Laccase Genes in Cerrena sp. in Response to Metal Ions, Aromatic Compounds, and Nutrients

    PubMed Central

    Yang, Jie; Wang, Guozeng; Ng, Tzi Bun; Lin, Juan; Ye, Xiuyun

    2016-01-01

    Laccases can oxidize a wide range of aromatic compounds and are industrially valuable. Laccases often exist in gene families and may differ from each other in expression and function. Quantitative real-time polymerase chain reaction (qPCR) was used for transcription profiling of eight laccase genes in Cerrena sp. strain HYB07 with validated reference genes. A high laccase activity of 280.0 U/mL was obtained after submerged fermentation for 5 days. Laccase production and laccase gene transcription at different fermentation stages and in response to various environmental cues were revealed. HYB07 laccase activity correlated with transcription levels of its predominantly expressed laccase gene, Lac7. Cu2+ ions were indispensable for efficient laccase production by HYB07, mainly through Lac7 transcription induction, and no aromatic compounds were needed. HYB07 laccase synthesis and biomass accumulation were highest with non-limiting carbon and nitrogen. Glycerol and inorganic nitrogen sources adversely impacted Lac7 transcription, laccase yields, and fungal growth. The present study would further our understanding of transcription regulation of laccase genes, which may in turn facilitate laccase production as well as elucidation of their physiological roles. PMID:26793186

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

    SciTech Connect

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

    2010-01-01

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

  7. Determination of aromatic compounds in eluates of pyrolysis solid residues using HS-GC-MS and DLLME-GC-MS.

    PubMed

    Bernardo, Maria S; Gonçalves, M; Lapa, N; Barbosa, R; Mendes, B; Pinto, F; Gulyurtlu, Ibrahim

    2009-11-15

    A method for the determination of 15 aromatic hydrocarbons in eluates from solid residues produced during the co-pyrolysis of plastics and pine biomass was developed. In a first step, several sampling techniques (headspace solid phase microextraction (HS-SPME), static headspace sampling (HS), and dispersive liquid-liquid microextraction (DLLME) were compared in order to evaluate their sensitivity towards these analytes. HS-SPME and HS sampling had the better performance, but DLLME was itself as a technique able to extract volatiles with a significant enrichment factor. HS sampling coupled with GC-MS was chosen for method validation for the analytes tested. Calibration curves were constructed for each analyte with correlation coefficients higher than 0.999. The limits of detection were in the range of 0.66-37.85 ng/L. The precision of the HS method was evaluated and good repeatability was achieved with relative standard deviations of 4.8-13.2%. The recoveries of the analytes were evaluated by analysing fortified real eluate samples and were in the range of 60.6-113.9%. The validated method was applied in real eluate samples. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the compounds in higher concentrations. The DLLME technique coupled with GC-MS was used to investigate the presence of less volatile contaminants in eluate samples. This analysis revealed the presence of significant amounts of alkyl phenols and other aromatic compounds with appreciable water solubility.

  8. Solvothermal synthesis of CdIn2S4 photocatalyst for selective photosynthesis of organic aromatic compounds under visible light.

    PubMed

    Ling, Cancan; Ye, Xiangju; Zhang, Jinghu; Zhang, Jinfeng; Zhang, Sujuan; Meng, Sugang; Fu, Xianliang; Chen, Shifu

    2017-12-01

    Ternary chalcogenide semiconductor, cadmium indium sulfide (CdIn2S4), was prepared by a simple solvothermal method using ethylene glycol as a solvent, as well as indium chloride tetrahydrate (InCl3(.)4H2O), cadmium nitrate tetrahydrate [Cd(NO3)2(.)4H2O], and thiacetamide (TAA) as precursors. The resulted sample was subject to a series of characterizations. It is the first time to use CdIn2S4 sample as a visible light-driven photocatalyst for simultaneous selective redox transformation of organic aromatic compounds. The results indicate that the as-synthesized CdIn2S4 photocatalyst not only has excellent photocatalytic performance compared with pure In2S3 and CdS for the selective oxidation of aromatic alcohols in an oxygen environment, but also shows high photocatalytic redox activities under nitrogen atmosphere. A possible mechanism for the photocatalytic redox reaction in the coupled system was proposed. It is hoped that our current work could extend the applications of CdIn2S4 photocatalyst and provide new insights for selective transformations of organic compounds.

  9. Effect of surfactants at low concentrations on the desorption and biodegradation of sorbed aromatic compounds in soil

    SciTech Connect

    Aronstein, B.N.; Calvillo, Y.M.; Alexander, M. )

    1991-10-01

    A study was conducted to determine the effect of low concentrations of surfactants on the biodegradation of sorbed aromatic compounds in soil. The nonionic alcohol ethoxylate surfactants Alfonic 810-60 and Novel II 1412-56 increased the extent of desorption of phenanthrene from a mineral soil. Alfonic 810-60 enhanced desorption of biphenyl from this soil at one concentration tested, but Novel II 1412-56 did not. Less than 0.01{per thousand} of the added phenanthrene and biphenyl was present in solution after their introduction into an organic soil, and the surfactants did not promote desorption. The two surfactants at 10 {mu}g/g of soil markedly increased the extent of biodegradation of phenanthrene in both the mineral and the organic soil; the stimulation was greater in the organic soil. Biphenyl mineralization in the mineral soil was not affected by either surfactant, but biodegradation in the organic soil was enhanced by Alfonic 810-60 at 100 {mu}g/g. The authors suggest that surfactants at low concentrations may promote the mineralization of sorbed aromatic compounds in polluted soils, even when surfactant-induced desorption is not appreciable.

  10. Inhibition of heterocyclic aromatic amine formation in fried ground beef patties by garlic and selected garlic-related sulfur compounds.

    PubMed

    Shin, Inn-Seung; Rodgers, W John; Gomaa, Enayat A; Strasburg, Gale M; Gray, J Ian

    2002-11-01

    The effects of garlic and selected organosulfur compounds (diallyl disulfide, dipropyl disulfide, diallyl sulfide, allyl methyl sulfide, allyl mercaptan, cysteine, and cystine) on the formation of heterocyclic aromatic amines (HAAs) in fried ground beef patties were evaluated. Minced garlic cloves (ca. 4.8 to 16.7%, wt/wt) or organosulfur compounds (0.67 mmol) were added directly to ground beef. Patties (100 g) were fried at 225 degrees C (surface temperature) for 10 min per side. Two patties were fried for each replication, and five replicates were analyzed for each treatment. For each replicate, four subsamples were analyzed (two unspiked subsamples for concentration and two spiked subsamples for the recovery of HAA standards). The volatile sulfur compounds significantly (P < 0.05) reduced concentrations of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine by reductions of 46 to 81%, while average reductions of 35, 22, and 71%, were achieved with cystine, cysteine, and whole garlic, respectively. The volatile sulfur compounds reduced concentrations of 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline by 34 to 67%, while reductions of 25, 19, and 63% (P < 0.05) were achieved with cystine, cysteine, and whole garlic, respectively. These studies confirm that garlic and some organosulfur compounds have the potential to reduce HAA formation incooked beef patties.

  11. Determination of polycyclic aromatic hydrocarbons in milk samples by high-performance liquid chromatography with fluorescence detection.

    PubMed

    Kishikawa, Naoya; Wada, Mitsuhiro; Kuroda, Naotaka; Akiyama, Syuzo; Nakashima, Kenichiro

    2003-06-15

    This paper describes a high-performance liquid chromatographic (HPLC) method for the determination of polycyclic aromatic hydrocarbons (PAHs) in milk samples. The method involves a liquid-liquid extraction procedure after saponification of milk samples with sodium hydroxide. Reproducible determination with highly sensitive detection was attained by HPLC with fluorescence detection using 1,2-bis(9-anthryl)ethane as an internal standard. The detection limits of 12 kinds of PAHs ranged from 1.3 to 76 ng/kg milk at a signal/noise ratio of 3. By the proposed method, the presence of 12 and 11 kinds of PAHs could be confirmed in commercial milk and human milk samples, respectively. The average concentrations of total PAHs (mean+/-SD, micro g/kg) were found to be 0.99+/-0.37 for commercial milk (n=14), 2.01+/-0.30 for infant formula (n=3) and 0.75+/-0.47 for human milk (n=51). High correlation coefficients between the concentrations of total PAHs and triglyceride were observed for commercial milk (r=0.659) and human milk (r=0.645).

  12. Synthesis of a fluorescently labeled compound for the detection of arsenic-induced apoptotic HL60 cells.

    PubMed

    Femia, A Lis; Temprana, C Facundo; Amor, M Silvia; Grasselli, Mariano; Alonso, Silvia Del V

    2012-03-01

    Arsenic compounds have shown medical usefulness since they proved to be effective in causing complete remission of acute promyelocytic leukemia. In this work we obtained a fluorescently labeled arsenic compound that can be used with current fluorescence techniques for basic and applied research, focused on arsenic-induced apoptosis studies. This compound is an arsanilic acid bearing a covalently linked FITC that was chemically synthesized and characterized by fluorescence, UV-Vis, mass and FTIR spectrometry. In addition, we assessed its apoptotic activity as well as its fluorescent labeling properties in HL60 cell line as a leukemia cell model through flow cytometry. We obtained a compound with a 1:1 FITC:arsenic ratio and a 595 m/z, confirming its structure by FTIR. This compound proved to be useful at inducing apoptosis in the leukemia cell model and labeling this apoptotic cell population, in such a way that the highest FITC fluorescence correlated with the highest arsenic amount.

  13. Tracking Biological Organic Compounds In Atmospheric Deposition In Alpine Environments With Fluorescence Spectroscopy

    NASA Astrophysics Data System (ADS)

    Mladenov, N.; Oldani, K. M.; Williams, M. W.; Schmidt, S. K.; Darcy, J.; Lemons, S.; Reche, I.

    2013-12-01

    Alpine environments, such as those of the Colorado Rocky Mountains, USA and the Sierra Nevada Mountains, Spain, contain undeveloped, barren soils that are carbon-limited. Atmospheric wet and dry deposition of organic carbon (OC) represents a substantial fraction of the OC load available to alpine soils, and includes contributions from atmospheric pollutants, dust, and biological aerosols, such as bacteria, algae, fungi, and plant debris. To evaluate the seasonal variability and sources of atmospheric deposition at these alpine sites, we measured the chemical characteristics of weekly wet and dry deposition and snowpack samples, including characterization of dissolved organic matter (DOM) and water soluble organic matter (WSOM) with fluorescence spectroscopy. The excitation-emission matrix (EEM) spectra we acquired show the presence of recurring peaks at low excitation and emission wavelengths typically associated with highly biodegradable organic carbon, presumably derived from the aromatic amino acids, tyrosine and tryptophan. Solar simulation experiments demonstrated that amino acid-like fluorescent components were more resistant to photo-degradation than humic- and fulvic-like fluorescent components. Our results also reveal the presence of a unique fluorophore, not previously described, that is found in both Rocky Mountains and the Sierra Nevada snowpack, wet deposition, and dry deposition and may be attributed to fluorescent pigments in bacteria. Biological aerosols may represent a labile source of carbon for alpine soil microbes, and consequently their deposition has important consequences for biogeochemical processes occurring in barren, alpine soils. Excitation emission matrix image of 24 Aug 2010 wet deposition sample from the Soddie site at Niwot Ridge, Colorado showing a unique fluorescent component with dual excitation peaks (285 nm and 340 nm) at 410 nm emission.

  14. Hydrogen and carbon isotopic ratios of polycyclic aromatic compounds in two CM2 carbonaceous chondrites and implications for prebiotic organic synthesis

    NASA Astrophysics Data System (ADS)

    Huang, Yongsong; Aponte, José C.; Zhao, Jiaju; Tarozo, Rafael; Hallmann, Christian

    2015-09-01

    Study of meteoritic organic compounds offers a unique opportunity to understand the origins of the organic matter in the early Solar System. Meteoritic polycyclic aromatic hydrocarbons (PAHs) and heteropolycyclic aromatic compounds (HACs) have been studied for over fifty years, however; their hydrogen stable isotopic ratios (δD) have never been reported. Compound-specific δD measurements of PAHs and HACs are important, in part because the carbon isotopic ratios (δ13C) of various meteoritic PAHs cannot be readily distinguished from their terrestrial counterparts and it is difficult to rule out terrestrial contamination based on carbon isotopic ratios alone. In this study, we have extracted and identified more than sixty PAHs and HACs present in two CM2 carbonaceous chondrites Murchison and LON 94101. Their carbon and hydrogen stable isotopic ratios (δ13C and δD) were measured and used to discuss about their synthetic environments and formation mechanisms. The concentration of aromatic compounds is ∼30% higher in Murchison than in the Antarctic meteorite LON 94101, but both samples contained similar suites of PAHs and HACs. All PAHs and HACs found exhibited positive δD values (up to 1100‰) consistent with an extraterrestrial origin, indicating the relatively low δ13C values are indeed an inherent feature of the meteoritic aromatic compounds. The hydrogen isotopic data suggest aromatic compounds in carbonaceous chondrites were mainly formed in the cold interstellar environments. Molecular level variations in hydrogen and carbon isotopic values offer new insights to the formation pathways for the aromatic compounds in carbonaceous chondrites.

  15. Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods

    PubMed Central

    Tang, Pei-Ling; Hassan, Osman; Maskat, Mohamad Yusof; Badri, Khairiah

    2015-01-01

    In this study, oil palm empty fruit bunch (OPEFBF) was pretreated with alkali, and lignin was extracted for further degradation into lower molecular weight phenolic compounds using enzymes and chemical means. Efficiency of monomeric aromatic compounds production from OPEFBF lignin via chemical (nitrobenzene versus oxygen) and enzymatic [cutinase versus manganese peroxidase (MnP)] approaches was investigated. The effects of sodium hydroxide concentration (2, 5, and 10% wt.) and reaction time (30, 90, and 180 minutes) on the yield of aromatic compounds were studied. The results obtained indicated that nitrobenzene oxidation produced the highest yield (333.17 ± 49.44 ppm hydroxybenzoic acid, 5.67 ± 0.25 ppm p-hydroxybenzaldehyde, 25.57 ± 1.64 ppm vanillic acid, 168.68 ± 23.23 ppm vanillin, 75.44 ± 6.71 ppm syringic acid, 815.26 ± 41.77 ppm syringaldehyde, 15.21 ± 2.19 ppm p-coumaric acid, and 44.75 ± 3.40 ppm ferulic acid), among the tested methods. High sodium hydroxide concentration (10% wt.) was needed to promote efficient nitrobenzene oxidation. However, less severe oxidation condition was preferred to preserve the hydroxycinnamic acids (p-coumaric acid and ferulic acid). Cutinase-catalyzed hydrolysis was found to be more efficient than MnP-catalyzed oxidation in the production of aromatic compounds. By hydrolyzed 8% wt. of lignin with 0.625 mL cutinase g−1 lignin at pH 8 and 55°C for 24 hours, about 642.83 ± 14.45 ppm hydroxybenzoic acid, 70.19 ± 3.31 ppm syringaldehyde, 22.80 ± 1.04 ppm vanillin, 27.06 ± 1.20 ppm p-coumaric acid, and 50.19 ± 2.23 ppm ferulic acid were produced. PMID:26798644

  16. Angular distribution of light emission from compound-eye cornea with conformal fluorescent coating

    NASA Astrophysics Data System (ADS)

    Martín-Palma, Raúl J.; Miller, Amy E.; Pulsifer, Drew P.; Lakhtakia, Akhlesh

    2014-09-01

    The complex morphology of the apposition compound eyes of insects of many species provides them a wide angular field of view. This characteristic makes these eyes attractive for bioreplication as artificial sources of light. The cornea of a blowfly eye was conformally coated with a fluorescent thin film with the aim of achieving wide field-of-view emission. On illumination by shortwave-ultraviolet light, the conformally coated eye emitted visible light whose intensity showed a weaker angular dependence than a fluorescent thin film deposited on a flat surface.

  17. Transferable potentials for phase equilibria. 10. Explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds.

    PubMed

    Rai, Neeraj; Siepmann, J Ilja

    2013-01-10

    The explicit-hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to various substituted benzenes through the parametrization of the exocyclic groups -F, -Cl, -Br, -C≡N, and -OH and to polycyclic aromatic hydrocarbons through the parametrization of the aromatic linker carbon atom for multiple rings. The linker carbon together with the TraPPE-EH parameters for aromatic heterocycles constitutes a force field for fused-ring heterocycles. Configurational-bias Monte Carlo simulations in the Gibbs ensemble were carried out to compute vapor-liquid coexistence curves for fluorobenzene; chlorobenzene; bromobenzene; di-, tri-, and hexachlorobenzene isomers; 2-chlorofuran; 2-chlorothiophene; benzonitrile; phenol; dihydroxybenzene isomers; 1,4-benzoquinone; naphthalene; naphthalene-2-carbonitrile; naphthalen-2-ol; quinoline; benzo[b]thiophene; benzo[c]thiophene; benzoxazole; benzisoxazole; benzimidazole; benzothiazole; indole; isoindole; indazole; purine; anthracene; and phenanthrene. The agreement with the limited experimental data is very satisfactory, with saturated liquid densities and vapor pressures reproduced to within 1.5% and 15%, respectively. The mean unsigned percentage errors in the normal boiling points, critical temperatures, and critical densities are 0.9%, 1.2%, and 1.4%, respectively. Additional simulations were carried out for binary systems of benzene/benzonitrile, benzene/phenol, and naphthalene/methanol to illustrate the transferability of the developed potentials to binary systems containing compounds of different polarity and hydrogen-bonding ability. A detailed analysis of the liquid-phase structures is provided for selected neat systems and binary mixtures.

  18. Tunable ultraviolet laser-induced fluorescence detection of trace plastics and dissolved organic compounds in water.

    PubMed

    Sivaprakasam, Vasanthi; Killinger, Dennis K

    2003-11-20

    We developed a tunable (220-285-nm) UV and fixed 266-nm laser-induced fluorescence (LIF) system using a spectrometer and a cooled CCD imaging detector to measure the excitation-emission matrix spectra of various compounds in water, including quinine sulfate and plastic compound bisphenol-A. The LIF instrument was used for the fast, nonspecific determination of trace amounts of dissolved organic compounds present in natural water supplies and various brand name bottled distilled water and bottled drinking water. Plastic-related compounds that leached out of plastic utensils and containers were also detected with this instrument. The sensitivity of the system was approximately 1-2 orders of magnitude better than that for a commercial system.

  19. Tunable ultraviolet laser-induced fluorescence detection of trace plastics and dissolved organic compounds in water

    NASA Astrophysics Data System (ADS)

    Sivaprakasam, Vasanthi; Killinger, Dennis K.

    2003-11-01

    We developed a tunable (220-285-nm) UV and fixed 266-nm laser-induced fluorescence (LIF) system using a spectrometer and a cooled CCD imaging detector to measure the excitation-emission matrix spectra of various compounds in water, including quinine sulfate and plastic compound bisphenol-A. The LIF instrument was used for the fast, nonspecific determination of trace amounts of dissolved organic compounds present in natural water supplies and various brand name bottled distilled water and bottled drinking water. Plastic-related compounds that leached out of plastic utensils and containers were also detected with this instrument. The sensitivity of the system was approximately 1-2 orders of magnitude better than that for a commercial system.

  20. Thin layer chromatography/fluorescence detection of 3,4-methylenedioxy-methamphetamine and related compounds.

    PubMed

    Kato, Noriyuki; Fujita, Susumu; Ohta, Hikoto; Fukuba, Makoto; Toriba, Akira; Hayakawa, Kazuichi

    2008-11-01

    A rapid and sensitive method for the detection of six methylenedioxylatedphenethylamines, 3,4-methylenedioxymethamphetamine (MDMA); 3,4-methylenedioxyamphetamine; 3,4-methylenedioxyethylamphetamine; N-methyl-1-(3,4-methylenedioxyphenyl)-2-butamine; N-methyl-1-(3,4-methylenedioxyphenyl)-3-butamine; and 3,4-methylenedioxydimethylamphetamine, by thin-layer chromatography with fluorescence detection is proposed. These compounds form fluorophores on the developing plate following spraying with a reagent consisting of sodium hypochlorite, potassium hexacyanoferrate (III), and sodium hydroxide, and heating for 3 min at 100 degrees C. Blue fluorescent spots were observed under ultraviolet light in a wavelength range of 250-400 nm. The detection limits for MDMA and the above related compounds were 50 ng. The proposed method was effectively applied to the detection of MDMA in urine samples.

  1. Anti-prion activity of a panel of aromatic chemical compounds: in vitro and in silico approaches.

    PubMed

    Ferreira, Natalia C; Marques, Icaro A; Conceição, Wesley A; Macedo, Bruno; Machado, Clarice S; Mascarello, Alessandra; Chiaradia-Delatorre, Louise Domeneghini; Yunes, Rosendo Augusto; Nunes, Ricardo José; Hughson, Andrew G; Raymond, Lynne D; Pascutti, Pedro G; Caughey, Byron; Cordeiro, Yraima

    2014-01-01

    The prion protein (PrP) is implicated in the Transmissible Spongiform Encephalopathies (TSEs), which comprise a group of fatal neurodegenerative diseases affecting humans and other mammals. Conversion of cellular PrP (PrP(C)) into the scrapie form (PrP(Sc)) is the hallmark of TSEs. Once formed, PrP(Sc) aggregates and catalyzes PrP(C) misfolding into new PrP(Sc) molecules. Although many compounds have been shown to inhibit the conversion process, so far there is no effective therapy for TSEs. Besides, most of the previously evaluated compounds failed in vivo due to poor pharmacokinetic profiles. In this work we propose a combined in vitro/in silico approach to screen for active anti-prion compounds presenting acceptable drugability and pharmacokinetic parameters. A diverse panel of aromatic compounds was screened in neuroblastoma cells persistently infected with PrP(Sc) (ScN2a) for their ability to inhibit PK-resistant PrP (PrP(Res)) accumulation. From ∼200 compounds, 47 were effective in decreasing the accumulation of PrP(Res) in ScN2a cells. Pharmacokinetic and physicochemical properties were predicted in silico, allowing us to obtain estimates of relative blood brain barrier permeation and mutagenicity. MTT reduction assays showed that most of the active compounds were non cytotoxic. Compounds that cleared PrP(Res) from ScN2a cells, were non-toxic in the MTT assay, and presented a good pharmacokinetic profile were investigated for their ability to inhibit aggregation of an amyloidogenic PrP peptide fragment (PrP(109-149)). Molecular docking results provided structural models and binding affinities for the interaction between PrP and the most promising compounds. In summary, using this combined in vitro/in silico approach we have identified new small organic anti-scrapie compounds that decrease the accumulation of PrP(Res) in ScN2a cells, inhibit the aggregation of a PrP peptide, and possess pharmacokinetic characteristics that support their drugability. These

  2. Anti-Prion Activity of a Panel of Aromatic Chemical Compounds: In Vitro and In Silico Approaches

    PubMed Central

    Ferreira, Natalia C.; Marques, Icaro A.; Conceição, Wesley A.; Macedo, Bruno; Machado, Clarice S.; Mascarello, Alessandra; Chiaradia-Delatorre, Louise Domeneghini; Yunes, Rosendo Augusto; Nunes, Ricardo José; Hughson, Andrew G.; Raymond, Lynne D.; Pascutti, Pedro G.; Caughey, Byron; Cordeiro, Yraima

    2014-01-01

    The prion protein (PrP) is implicated in the Transmissible Spongiform Encephalopathies (TSEs), which comprise a group of fatal neurodegenerative diseases affecting humans and other mammals. Conversion of cellular PrP (PrPC) into the scrapie form (PrPSc) is the hallmark of TSEs. Once formed, PrPSc aggregates and catalyzes PrPC misfolding into new PrPSc molecules. Although many compounds have been shown to inhibit the conversion process, so far there is no effective therapy for TSEs. Besides, most of the previously evaluated compounds failed in vivo due to poor pharmacokinetic profiles. In this work we propose a combined in vitro/in silico approach to screen for active anti-prion compounds presenting acceptable drugability and pharmacokinetic parameters. A diverse panel of aromatic compounds was screened in neuroblastoma cells persistently infected with PrPSc (ScN2a) for their ability to inhibit PK-resistant PrP (PrPRes) accumulation. From ∼200 compounds, 47 were effective in decreasing the accumulation of PrPRes in ScN2a cells. Pharmacokinetic and physicochemical properties were predicted in silico, allowing us to obtain estimates of relative blood brain barrier permeation and mutagenicity. MTT reduction assays showed that most of the active compounds were non cytotoxic. Compounds that cleared PrPRes from ScN2a cells, were non-toxic in the MTT assay, and presented a good pharmacokinetic profile were investigated for their ability to inhibit aggregation of an amyloidogenic PrP peptide fragment (PrP109–149). Molecular docking results provided structural models and binding affinities for the interaction between PrP and the most promising compounds. In summary, using this combined in vitro/in silico approach we have identified new small organic anti-scrapie compounds that decrease the accumulation of PrPRes in ScN2a cells, inhibit the aggregation of a PrP peptide, and possess pharmacokinetic characteristics that support their drugability. These compounds are

  3. Synthesis and fluorescence properties of six fluorescein-nitroxide radical hybrid-compounds.

    PubMed

    Sato, Shingo; Endo, Susumu; Kurokawa, Yusuke; Yamaguchi, Masaki; Nagai, Akio; Ito, Tomohiro; Ogata, Tateaki

    2016-12-05

    Six fluorescein-nitroxide radical hybrid-compounds (2ab, 3ab, 4, and 5) were synthesized by the condensation of 5- or 6-carboxy-fluorescein and 4-amino-TEMPO (2ab), 5- or 6-aminofluorescein and 4-carboxy-TEMPO (3ab), and fluorescein and 4-carboxy-TEMPO (4), or by reaction of the 3-hydroxyl group of fluorescein with DPROXYL-3-ylmethyl methanesulfonate (5). Fluorescence intensities (around 520nm) after reduction of the radical increased to 1.43-, 1.38-, and 1.61-folds for 2a, 2b and 3b respectively; 3a alone exhibited a decrease in intensity on reduction. Since 4 was readily solvolyzed in PBS or even methanol to afford fluorescein and 4-carboxy-TEMPO, its fluorescence change could not be measured. Hybrid compound 5 containing an ether-linkage between the fluorescein phenol and 3-hydroxymethyl-DPROXYL hydroxyl centers, was stable and on reduction, showed a maximum increase (3.21-fold) in relative fluorescence intensity in PBS (pH5.0), despite its remarkably low absolute fluorescence intensity.

  4. Synthesis and fluorescence properties of six fluorescein-nitroxide radical hybrid-compounds

    NASA Astrophysics Data System (ADS)

    Sato, Shingo; Endo, Susumu; Kurokawa, Yusuke; Yamaguchi, Masaki; Nagai, Akio; Ito, Tomohiro; Ogata, Tateaki

    2016-12-01

    Six fluorescein-nitroxide radical hybrid-compounds (2ab, 3ab, 4, and 5) were synthesized by the condensation of 5- or 6-carboxy-fluorescein and 4-amino-TEMPO (2ab), 5- or 6-aminofluorescein and 4-carboxy-TEMPO (3ab), and fluorescein and 4-carboxy-TEMPO (4), or by reaction of the 3-hydroxyl group of fluorescein with DPROXYL-3-ylmethyl methanesulfonate (5). Fluorescence intensities (around 520 nm) after reduction of the radical increased to 1.43-, 1.38-, and 1.61-folds for 2a, 2b and 3b respectively; 3a alone exhibited a decrease in intensity on reduction. Since 4 was readily solvolyzed in PBS or even methanol to afford fluorescein and 4-carboxy-TEMPO, its fluorescence change could not be measured. Hybrid compound 5 containing an ether-linkage between the fluorescein phenol and 3-hydroxymethyl-DPROXYL hydroxyl centers, was stable and on reduction, showed a maximum increase (3.21-fold) in relative fluorescence intensity in PBS (pH 5.0), despite its remarkably low absolute fluorescence intensity.

  5. Chitosan-based film supported copper nanoparticles: A potential and reusable catalyst for the reduction of aromatic nitro compounds.

    PubMed

    de Souza, Jaqueline F; da Silva, Gabriela T; Fajardo, André R

    2017-04-01

    In this study, copper nanoparticles (CuNPs) were synthesized and stabilized into a chitosan/poly(vinyl alcohol) (CP) based film using a simple protocol under mild conditions. The polymeric matrix utilized in this study allows synthesizing stable nanoparticle with narrow size distribution within the film matrix. Further, this system showed very attractive properties, such as good mechanical properties, chemical resistance, easy handling during use and recovery, relatively low-cost as compared to other similar systems, among others. The catalytic performance of CP-Cu film was tested in the reduction reaction of nitrobenzene (NB) to aniline (AN). Our findings reveal that CP-Cu film catalyzes the reaction efficiently and also decreases the energy of activation (Ea) as compared to other catalysts. The catalytic efficiency of CP-Cu regarding this reaction was kept even after 6 consecutive reuse cycles. All these results rank this novel system as a promising catalyst in the reduction of aromatic nitro compounds to aromatic amines.

  6. Vehicle occupants' exposure to aromatic volatile organic compounds while commuting on an urban-suburban route in Korea.

    PubMed

    Jo, W K; Choi, S J

    1996-08-01

    This study identified in-auto and in-bus exposures to six selected aromatic volatile organic compounds (VOCs) for commutes on an urban-suburban route in Korea. A bus-service route was selected to include three segments of Taegu and one suburban segment (Hayang) to satisfy the criteria specified for this study. This study indicates that motor vehicle exhaust and evaporative emissions are major sources of both auto and bus occupants' exposures to aromatic VOCs in both Taegu and Hayang. A nonparametric statistical test (Wilcoxon test) showed that in-auto benzene levels were significantly different from in-bus benzene levels for both urban-segment and suburban-segment commutes. The test also showed that the benzene-level difference between urban-segment and suburban-segment commutes was significant for both autos and buses. An F-test showed the same statistical results for the comparison of the summed in-vehicle concentration of the six target VOCs (benzene, toluene, ethylbenzene, and o,m,p-xylenes) as those for the comparison of the in-vehicle benzene concentration. On the other hand, the in-vehicle benzene level only and the sum were not significantly different among the three urban-segment commutes and between the morning and evening commutes. The in-auto VOC concentrations were intermediate between the results for the Los Angeles and Boston. The in-bus VOC concentrations were about one-tenth of the Taipei, Taiwan results.

  7. Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase.

    PubMed

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

    2015-01-01

    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.

  8. A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.

    PubMed

    Melissen, Sigismund T A G; Tognetti, Vincent; Dupas, Georges; Jouanneau, Julien; Lê, Guillaume; Joubert, Laurent

    2013-11-01

    The reaction pathways of several Friedel-Crafts acylations involving phenyl aromatic compounds were studied using density functional theory. The reactions were related to the Friedel-Crafts polycondensation of polyaryletherketones. In particular, the acylation of benzene with benzoyl chloride to form benzophenone and variations on this reaction were investigated. The acylation of benzene by one molecule of terephthaloyl chloride or isophthaloyl chloride as well as acylations at the m-, o-, and p-positions of diphenyl ether with one molecule of benzoyl chloride were studied. Adding an additional acyl chloride group to the electrophile appeared to have little influence on the reaction pathway, although the activation energy for the C-C bond-forming steps that occurred when isophthaloyl choride was used was different to the activation energy observed when terephthaloyl chloride was used. Upon changing the nucleophile to diphenyl ether, the reactivity changed according to the trend predicted on based on the o-, p-directing effects of the ether group. The deprotonation step that restored aromaticity varied widely according to the reaction. The rate-determining step in all of the studied reactions was the formation of the acylium ion, followed in importance by either the formation of the Wheland intermediate or the abstraction of hydrogen, depending on the reactivity of the nucleophile.

  9. Toxicity of eight polycyclic aromatic compounds to red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba).

    PubMed

    Sverdrup, Line E; Krogh, Paul Henning; Nielsen, Torben; Kjaer, Christian; Stenersen, Jørgen

    2003-12-01

    The effect of eight polycyclic aromatic compounds (PACs) on the seed emergence and early life-stage growth of three terrestrial plants (Sinapsis alba, Trifolium pratense and Lolium perenne) were studied in a greenhouse, using a Danish agricultural soil with an organic carbon content of 1.6%. After three weeks of exposure, seed emergence and seedling weight (fresh weight and dry weight) were determined. Exposure concentrations were verified with chemical analysis. The substances tested were four polycyclic aromatic hydrocarbons (fluoranthene, pyrene, phenanthrene and fluorene), the N-, S-, and O-substituted analogues of fluorene (carbazole, dibenzothiophene and dibenzofuran, respectively), and the quinoline representative acridine. Seedling growth was a far more sensitive endpoint than seed emergence for all substances. Concentrations estimated to give a 20% reduction of seedling fresh weight (EC20-values) ranged from 36 to 290 mgkg(-1) for carbazole, 43 to 93 mgkg(-1) for dibenzofuran, 37 to 110 mgkg(-1) for dibenzothiophene, 140 to 650 mgkg(-1) for fluoranthene, 55 to 380 mgkg(-1) for fluorene, 37 to 300 mgkg(-1) for phenanthrene, and 49 to 1300 mgkg(-1) for pyrene. For acridine, no toxicity was observed within the concentration range tested (1-1000 mgkg(-1)). As illustrated by the EC20-values, there was a rather large difference in sensitivity between the species, and T. pratense was the most sensitive of the species tested.

  10. Degradation of specific aromatic compounds migrating from PEX pipes into drinking water.

    PubMed

    Ryssel, Sune Thyge; Arvin, Erik; Lützhøft, Hans-Christian Holten; Olsson, Mikael Emil; Procházková, Zuzana; Albrechtsen, Hans-Jørgen

    2015-09-15

    Nine specific compounds identified to migrate from polyethylene (PE) and cross-linked polyethylene (PEX) to drinking water were investigated for their degradation in drinking water. Three sample types were studied: field samples (collected at consumer taps), PEX pipe water extractions, and water samples spiked with target compounds. Four compounds were quantified in field samples at concentrations of 0.15-8.0 μg/L. During PEX pipe water extraction 0.42 ± 0.20 mg NVOC/L was released and five compounds quantified (0.5-6.1 μg/L). The degradation of these compounds was evaluated in PEX-pipe water extractions and spiked samples. 4-ethylphenol was degraded within 22 days. Eight compounds were, however, only partially degradable under abiotic and biotic conditions within the timeframe of the experiments (2-4 weeks). Neither inhibition nor co-metabolism was observed in the presence of acetate or PEX pipe derived NVOC. Furthermore, the degradation in drinking water from four different locations with three different water works was similar. In conclusion, eight out of the nine compounds studied would - if being released from the pipes - reach consumers with only minor concentration decrease during water distribution.

  11. The synthesis of new fluorescent bichromophoric compounds as ratiometric pH probes for intracellular measurements.

    PubMed

    Saura, A Vanessa; Marín, María J; Burguete, M Isabel; Russell, David A; Galindo, Francisco; Luis, Santiago V

    2015-07-28

    Three different bichromophoric compounds (1-3) containing an aminomethyl anthracene moiety linked to a second chromophore (pyrene, 4-nitrobenzo-2-oxa-1,3-diazole (NBD) and dansyl) through a valine-derived pseudopeptidic spacer have been prepared and their fluorescent properties studied. The results obtained show that upon irradiation the photophysical behavior of these probes involves electronic energy transfer from the excited anthracene to the second chromophore and also intramolecular photoinduced electron transfer. The X-ray structure obtained for 3 reveals that the folding associated with the pseudopeptidic spacer favours a close proximity of the two chromophores. The emissive response of 3 is clearly dependent on the pH of the medium, hence this bichromophoric compound was shown to be an excellent ratiometric pH fluorescent sensor. The emission intensity due to the anthracene moiety exhibits a decrease at neutral-basic pH values that is concomitant with an increase in the intensity arising from the dansyl fluorophore. These properties make this compound a good candidate for biological pH sensing as has been confirmed by preliminary studies with RAW 264.7 macrophage cells imaged by means of confocal fluorescence microscopy with an average pH estimation of 5.4-5.8 for acidic organelles.

  12. Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

    PubMed Central

    Wang, Hai Ming

    2013-01-01

    Summary The formation of soluble 1:2 complexes within hydrophilic γ-cyclodextrin (γ-CD) thioethers allows to perform photodimerizations of aromatic guests under controlled, homogenous reaction conditions. The quantum yields for unsubstituted anthracene, acenaphthylene, and coumarin complexed in these γ-CD thioethers were found to be up to 10 times higher than in the non-complexed state. The configuration of the photoproduct reflected the configuration of the dimeric inclusion complex of the guest. Anti-parallel orientation of acenaphthylene within the CD cavity led to the exclusive formation of the anti photo-dimer in quantitative yield. Parallel orientation of coumarin within the complex of a CD thioether led to the formation of the syn head-to-head dimer. The degree of complexation of coumarin could be increased by employing the salting out effect. PMID:24062853

  13. Persistence of polycyclic aromatic compounds of different molecular size and water solubility in surficial sediment of an intertidal sandflat

    SciTech Connect

    Wilcock, R.J.; Northcott, G.L.; Corban, G.A.; Wilkins, A.L.; Langdon, A.G.

    1996-05-01

    The persistence of 13 polycyclic aromatic hydrocarbons (PAHs), ranging from two- to six-ring compounds, in an intertidal sandflat was studied by applying uniform amounts (0.10 g) of each to the surface of the sandflat and then monitoring concentrations over time. The mass of total PAH, after initial losses, declined slowly, so that after 256 d 12% of the applied material remained. Vertical concentration profiles indicated that little downward movement occurred and that most of the mass was concentrated in the top 2 cm, where most losses also occurred. The study has shown that anthropogenic PAHs have persistences comparable with organochlorine pesticides in aerobic sediments of intertidal sandflats. Rank correlations showed that the order of persistence may be predicted on the basis of molecular size parameters, such as molecular weight, molecular volume, and area. Persistence of PAHs in intertidal sandflats appears to be regulated by simple, physical processes.

  14. Function and the biosynthesis of unusual corrinoids by a novel activation mechanism of aromatic compounds in anaerobic bacteria

    NASA Astrophysics Data System (ADS)

    Stupperich, E.; Eisinger, H. J.

    A corrinoid screening of several phylogenetically diverse ``archaebacteria'' revealed vitamin B12-like corrinoids. This indicates an optimized structure and function relationship of the corrinoids under different bacterial growth conditions during the early evolution of live. Some of these corrinoids have been substituted by modified corrinoids in growing cells without affecting the generation times of the bacteria. In this respect, the discovery of the unique para-cresolyl cobamide from the eubacterium Sporomusa ovata attracted attention. The unusual structure of this corrinoid was achieved by a biosynthesis proceeding via a novel and stereospecific activation mechanism of aromatic compounds. The corrinoid was detected both in the membrane fraction and in the soluble fraction of the cells. Methyltransfer is one of the probable functions of the para-cresolyl cobamide in Sporomusa.

  15. [Studies by means of 1H NMR spectroscopy of complex formation of aromatic biologically active compounds with antibiotic topotecan].

    PubMed

    Mosunov, A A; Kostiukov, V V; Evstigneev, M P

    2012-01-01

    The analysis of heteroassociation of antibiotic topotecan (TPT) with aromatic biologically active compounds (BAC): caffeine, mutagens ethidium bromide and proflavine, antibiotic daunomycin, vitamins flavin-mononucleotide and nicotinamide, has been carried out in the work using 1H NMR spectroscopy data. The equilibrium constants of heteroassociation and induced chemical shifts of the protons have been obtained in the complexes with BAC. It is found that the complex formation TPT-BAC has the nature of stacking of the chromophores, additionally stabilized in the case of proflavine by intermolecular hydrogen bond. Calculation of the basic components of the Gibbs free energy of the complexation reactions is carried out, and the factors which stabilize and destabilize the heterocomplexes of molecules are revealed.

  16. Description of Sphingomonas xenophaga sp. nov. for strains BN6T and N,N which degrade xenobiotic aromatic compounds.

    PubMed

    Stolz, A; Schmidt-Maag, C; Denner, E B; Busse, H J; Egli, T; Kämpfer, P

    2000-01-01

    The taxonomic position of two bacterial strains, BN6T and N,N, with the ability to degrade xenobiotic aromatic compounds (naphthalenesulfonates or N,N-dimethylaniline) was investigated. The 165 rRNA gene sequence, the G+C content of the DNA (62-63 mol%) and the detection of ubiquinone Q-10, 2-hydroxymyristic acid and the sphingoglycolipid present clearly placed the two strains into the genus Sphingomonas. Both strains are representatives of one species according to the level of DNA relatedness (70.7%). The strains could be separated from all validly described taxa of the genus Sphingomonas, according to the 16S rRNA gene sequence (the highest sequence similarity observed was 96 % to Sphingomonas yanoikuyae), the pattern of the polar lipids and physiological characteristics. Therefore, the new species Sphingomonas xenophaga is proposed to accommodate strains BN6T (= DSM 6383T) and N,N (= DSM 8566).

  17. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds

    PubMed Central

    2016-01-01

    The stereospecific cross-coupling of secondary boronic esters with sp2 electrophiles (Suzuki–Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel–Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C–C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp2)–C(sp3) and an adjacent C–B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations. PMID:27384259

  18. Development of Enantiospecific Coupling of Secondary and Tertiary Boronic Esters with Aromatic Compounds.

    PubMed

    Odachowski, Marcin; Bonet, Amadeu; Essafi, Stephanie; Conti-Ramsden, Philip; Harvey, Jeremy N; Leonori, Daniele; Aggarwal, Varinder K

    2016-08-03

    The stereospecific cross-coupling of secondary boronic esters with sp(2) electrophiles (Suzuki-Miyaura reaction) is a long-standing problem in synthesis, but progress has been achieved in specific cases using palladium catalysis. However, related couplings with tertiary boronic esters are not currently achievable. To address this general problem, we have focused on an alternative method exploiting the reactivity of a boronate complex formed between an aryl lithium and a boronic ester. We reasoned that subsequent addition of an oxidant or an electrophile would remove an electron from the aromatic ring or react in a Friedel-Crafts-type manner, respectively, generating a cationic species, which would trigger 1,2-migration of the boron substituent, creating the new C-C bond. Elimination (preceded by further oxidation in the former case) would result in rearomatization giving the coupled product stereospecifically. Initial work was examined with 2-furyllithium. Although the oxidants tested were unsuccessful, electrophiles, particularly NBS, enabled the coupling reaction to occur in good yield with a broad range of secondary and tertiary boronic esters, bearing different steric demands and functional groups (esters, azides, nitriles, alcohols, and ethers). The reaction also worked well with other electron-rich heteroaromatics and 6-membered ring aromatics provided they had donor groups in the meta position. Conditions were also found under which the B(pin)- moiety could be retained in the product, ortho to the boron substituent. This protocol, which created a new C(sp(2))-C(sp(3)) and an adjacent C-B bond, was again applicable to a range of secondary and tertiary boronic esters. In all cases, the coupling reaction occurred with complete stereospecificity. Computational studies verified the competing processes involved and were in close agreement with the experimental observations.

  19. Threshold detection of aromatic compounds in wine with an electronic nose and a human sensory panel

    NASA Astrophysics Data System (ADS)

    Santos, José Pedro; Lozano, Jesús; Aleixandre, Manuel; Arroyo, Teresa; Cabellos, Juan Mariano; Gil, Mar; del Carmen Horrillo, Maria

    2009-05-01

    An electronic nose (e-nose) based on thin film semiconductor sensors has been developed in order to compare the performance with a trained human sensory panel. The panel had 25 members and was trained to detect concentration thresholds of some compounds of interest present in wine. Typical red wine compounds such as whiskylactone and white wine compounds such as 3-methyl butanol were measured at different concentrations starting from the detection threshold found in literature (in the micrograms to milligrams per liter range). Pattern recognition methods (principal component analisys and neural networks) were used to process the data. The results showed that the performance of the e-nose for threshold detection was much better than the human panel. The compounds were detected by the e-nose at concentrations up to ten times lower than the panel. Moreover the e-nose was able to identify correctly each concentration level therefore quantitative applications are devised for this system.

  20. Obligate sulfide-dependent degradation of methoxylated aromatic compounds and formation of methanethiol and dimethyl sulfide by a freshwater sediment isolate, Parasporobacterium paucivorans gen. nov., sp. nov.

    PubMed

    Lomans, B P; Leijdekkers, P; Wesselink, J J; Bakkes, P; Pol, A; van der Drift, C; den Camp, H J

    2001-09-01

    Methanethiol (MT) and dimethyl sulfide (DMS) have been shown to be the dominant volatile organic sulfur compounds in freshwater sediments. Previous research demonstrated that in these habitats MT and DMS are derived mainly from the methylation of sulfide. In order to identify the microorganisms that are responsible for this type of MT and DMS formation, several sulfide-rich freshwater sediments were amended with two potential methyl group-donating compounds, syringate and 3,4,5-trimethoxybenzoate (0.5 mM). The addition of these methoxylated aromatic compounds resulted in excess accumulation of MT and DMS in all sediment slurries even though methanogenic consumption of MT and DMS occurred. From one of the sediment slurries tested, a novel anaerobic bacterium was isolated with syringate as the sole carbon source. The strain, designated Parasporobacterium paucivorans, produced MT and DMS from the methoxy groups of syringate. The hydroxylated aromatic residue (gallate) was converted to acetate and butyrate. Like Sporobacterium olearium, another methoxylated aromatic compound-degrading bacterium, the isolate is a member of the XIVa cluster of the low-GC-content Clostridiales group. However, the new isolate differs from all other known methoxylated aromatic compound-degrading bacteria because it was able to degrade syringate in significant amounts only in the presence of sulfide.

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

    PubMed

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

    2016-03-01

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

  2. Activation of Ca2+ uptake and inhibition of reversal of the sarcoplasmic reticulum Ca2+ pump by aromatic compounds.

    PubMed

    Petretski, J H; Wolosker, H; de Meis, L

    1989-12-05

    The effects of aromatic compounds in sarcoplasmic reticulum Ca2+-ATPase were investigated. The solubility of the drugs in various organic solvents and water was measured. The ratio between the solubility in organic solvents and that in water (distribution coefficient) was used as an index of their hydrophobicity. The order found was triphenylphosphine greater than diphenylamine greater than 3-nitrophenol greater than 4-nitrophenol greater than 1,3-dihydroxybenzene. The effects observed on the Ca2+-ATPase were correlated with hydrophobicity of the drugs, activation and inhibition being obtained at a lower concentration the greater the distribution coefficient of the drug into organic solvent. In leaky vesicles, the effects of each compound on the ATPase activity varied depending on the Ca2+ concentration in the medium: it inhibited in the presence of 5 microM Ca2+ and activated when the Ca2+ concentration was raised to 2 mM. In intact vesicles, 3- and 4-nitrophenol, diphenylamine, and triphenylphosphine enhanced both the rate of ATP hydrolysis and the amount of Ca2+ accumulated by the vesicles. These four drugs inhibited Ca2+ uptake when ITP was used as substrate. 1,3-Dihydroxybenzene enhanced the amount of Ca2+ accumulated by the vesicles regardless of whether ATP or ITP was the substrate. All five compounds inhibited the phosphorylation of the enzyme by Pi, the efflux of Ca2+, and the synthesis of ATP measured during the reversal of the Ca2+ pump. The results indicate that the hydrophobic character of various organic compounds determines their access to sensitive domains of the membrane-bound calcium pump. Additional specific effects are then produced, depending on the structure of each compound.

  3. The characterization of polycyclic aromatic hydrocarbons produced in combustion and pyrolysis environments: Laboratory-generated products of model compounds

    NASA Astrophysics Data System (ADS)

    Marsh, Nathan Douglas

    Laboratory and computational techniques have been developed to characterize polycyclic aromatic hydrocarbons (PAH), presumed soot precursors and potentially harmful by-products of a variety of pyrolysis and combustion processes. Newly synthesized reference standards and the application of high-pressure liquid chromatography (HPLC) with ultraviolet-visible (UV) absorption spectroscopy have led to the unequivocal identification, among combustion and pyrolysis products, of several new PAH, many of which belong to the two newly recognized PAH classes, ethynyl-PAH and cyclopenta-fused PAH (CP-PAH). Empirical rules have also been formulated for the UV spectra of ethynyl- and CP-PAH; these rules allow preliminary identification of candidate compounds in combustion products, prior to labor-intensive synthetic procedures necessary for identity confirmation. Pyrolysis products have been analyzed in two sets of experiments: benzene droplet combustion and gas-phase catechol (ortho-dihydroxybenzene) pyrolysis. In the first, benzene droplets are ignited and then captured by a phase-discriminating sampling probe; gas-phase pyrolysis products transported into the liquid phase of the droplet are identified and quantified. In the second set of experiments, catechol is pyrolysed in a laminar-flow reactor, at 700--1000°C and 0.4--1 sec, producing a range of aromatic products; the 30 most abundant are quantified. Compositional analysis of the pyrolysis products by HPLC reveals a wide variety of PAH which have never before been identified as products of these fuels. In general, most products appear to be the result of multiple ring-buildup steps. The data reported here for catechol products represent one of the most extensive quantifications of aromatic products from any fuel, and the only one for catechol. Semiempirical quantum chemical computations have been performed in order to examine the potential energy surfaces and equilibrium distributions of several compounds. The observed

  4. Investigation of chlorinated aromatic compounds in the environment: Methods development and data interpretation

    SciTech Connect

    Ding, Wanghsien.

    1989-01-01

    Detection of low levels of chlorinated benzene compounds (CLBZ) and polychlorinated biphenyls (PCBs) in soil samples has been investigated with respect to potential sources in an industrial area of western New York state. The extract obtained by steam distillation was used directly with minimal additional cleanup steps for high resolution gas chromatography/mass spectrometry (HRGC/MS) and high resolution gas chromatography with electron capture detection (HRGC/ECD) analysis. The Nielson-Kryger steam distillation technique was used to extract CLBZ compounds and PCB congeners from soil samples. The recoveries of the CLBZ compounds in soil samples were monitored by comparison of the response for the {sup 13}C-labelled analogues in each isomeric group. The mean recoveries from field samples ranged from 63% to 76%. The recoveries of PCB congeners were measured using four air-dried subsurface soils which were spiked with Aroclors standard mixture. The mean recoveries of most PCB congeners ranged from 80% to 99%. Using HRGC/MS in the selected ion monitoring mode (SIM), a detection limit below 10 pg/g (10 pptr, parts per trillion) of the CLBZ compounds was achieved. For GC/ECD, an Apiezon L-coated glass capillary column was used to determine PCB congeners at background levels. More than 69 PCB congeners were separated on this column. The detection limit for an individual congener was about 0.01 ng/g. Application of SIMCA (SImple Modeling by Chemical Analogy) pattern recognition and multiple discriminant analysis showed that the pattern of CLBZ compounds in soil samples collected near Love Canal was similar to the patterns from the other areas in the Niagara Falls area. The highest concentrations of CLBZ compounds were detected in the area which is near and downwind from an industrial center with many potential sources of airborne emissions.

  5. Solid compounds of europium and terbium with some aromatic carboxylic acids

    SciTech Connect

    Chupakhina, R.A.; Biryulina, V.N.; Kasimova, L.V.; Balakhonov, V.G.

    1986-10-20

    By the reactions of europium and terbium hydroxides with aqueous solutions of benzoic, salicylic, phthalic, and phthalaldehydic acids, compounds were obtained with the compositions: for phthalic acid M/sub 2/L/sub 3/ x 3H/sub 2/O, and for the other acids ML/sub 3/ x 3H/sub 2/O, in which M = Eu/sup 3 +/, Tb/sup 3 +/; L is the anion of the corresponding acid. The compounds of europium and terbium with phthalaldehydric acid were prepared for the first time.

  6. Influence of extraction methodologies on the analysis of five major volatile aromatic compounds of citronella grass (Cymbopogon nardus) and lemongrass (Cymbopogon citratus) grown in Thailand

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Infusions of citronella grass (Cymbopogon nardus) and lemongrass (Cymbopogon citratus) have been commonly used in folk medicine in Thailand and other Asian countries. This study focuses on a systematic comparison of two extraction methods for major volatile aromatic compounds (VACs) of citronella g...

  7. Treatment of sludge containing nitro-aromatic compounds in reed-bed mesocosms - Water, BOD, carbon and nutrient removal

    SciTech Connect

    Gustavsson, L.; Engwall, M.

    2012-01-15

    Highlights: Black-Right-Pointing-Pointer It is necessary to improve existing and develop new sludge management techniques. Black-Right-Pointing-Pointer One method is dewatering and biodegradation of compounds in constructed wetlands. Black-Right-Pointing-Pointer The result showed high reduction of all tested parameters after treatment. Black-Right-Pointing-Pointer Plants improve degradation and Phragmites australis is tolerant to xenobiotics. Black-Right-Pointing-Pointer The amount of sludge could be reduced by 50-70%. - Abstract: Since the mid-1970s, Sweden has been depositing 1 million ton d.w sludge/year, produced at waste water treatment plants. Due to recent legislation this practice is no longer a viable method of waste management. It is necessary to improve existing and develop new sludge management techniques and one promising alternative is the dewatering and treatment of sludge in constructed wetlands. The aim of this study was to follow reduction of organic carbon, BOD and nutrients in an industrial sludge containing nitro-aromatic compounds passing through constructed small-scale wetlands, and to investigate any toxic effect such as growth inhibition of the common reed Phragmites australis. The result showed high reduction of all tested parameters in all the outgoing water samples, which shows that constructed wetlands are suitable for carbon and nutrient removal. The results also showed that P. australis is tolerant to xenobiotics and did not appear to be affected by the toxic compounds in the sludge. The sludge residual on the top of the beds contained low levels of organic carbon and is considered non-organic and could therefore be landfilled. Using this type of secondary treatment method, the amount of sludge could be reduced by 50-70%, mainly by dewatering and biodegradation of organic compounds.

  8. Terpenoids and aromatic compounds from the New Zealand liverworts Plagiochila, Schistochila, and Heteroscyphus species.

    PubMed

    Nagashima, Fumihiro; Sekiguchi, Takashi; Takaoka, Shigeru; Asakawa, Yoshinori

    2004-05-01

    A new clerodane- and two new ent-rosane-type diterpenoids have been isolated from the New Zealand liverworts Heteroscyphus billardierii and Plagiochila deltoidea, respectively. The known bisbibenzyl compounds and acetophenones have also been isolated from Schistochila glaucescens and Plagiochila fasciculata. Their structures were established by extensive NMR techniques. Chemosystematics of the Plagiochila species have been discussed.

  9. Fluorescence decrease of conjugated polymers by the catalytic activity of horseradish peroxidase and its application in phenolic compounds detection.

    PubMed

    González-Sánchez, M I; Laurenti, M; Rubio-Retama, J; Valero, E; Lopez-Cabarcos, E

    2011-04-11

    We report the fluorescence decrease of the water-soluble π-π-conjugated polymer poly(2-methoxy-5-propyloxy sulfonate phenylene vinylene, MPS-PPV) by the catalytic activity of horseradish peroxidase in the presence of H(2)O(2). MPS-PPV acts as a donor substrate in the catalytic cycle of horseradish peroxidase where the electron-deficient enzymatic intermediates compounds I and II can subtract electrons from the polymer leading to its fluorescence decrease. The addition of phenolic drug acetaminophen to the former solution favors the decrease of the polymer fluorescence, which indicates the peroxidase-catalyzed co-oxidation of MPS-PPV and acetaminophen. The encapsulation of horseradish peroxidase within polyacrylamide microgels allows the isolation of intermediates compound I and compound II from the polymer, leading to a fluorescence decrease that is only due to the product of biocatalytic acetaminophen oxidation. This system could be used to develop a new device for phenolic compounds detection.

  10. Effect of Biofilm Formation by Oenococcus oeni on Malolactic Fermentation and the Release of Aromatic Compounds in Wine

    PubMed Central

    Bastard, Alexandre; Coelho, Christian; Briandet, Romain; Canette, Alexis; Gougeon, Régis; Alexandre, Hervé; Guzzo, Jean; Weidmann, Stéphanie

    2016-01-01

    The winemaking process involves the alcoholic fermentation of must, often followed by malolactic fermentation (MLF). The latter, mainly carried out by the lactic acid bacterium Oenococcus oeni, is used to improve wine quality when acidity reduction is required. Moreover, it prevents microbial spoilage and improves the wine’s organoleptic profile. Prior observations showed that O. oeni is able to resist several months in harsh wine conditions when adhered on oak barrels. Since biofilm is a prevailing microbial lifestyle in natural environments, the capacity of O. oeni to form biofilms was investigated on winemaking material such as stainless steel and oak chips. Scanning Electron Microscopy and Confocal Laser Scanning Microscopy showed that O. oeni was able to adhere to these surfaces and form spatially organized microcolonies embedded in extracellular substances. To assess the competitive advantage of this mode of life in wine, the properties of biofilm and planktonic cells were compared after inoculation in a fermented must (pH 3.5 or 3.2 and 12% ethanol) The results indicated that the biofilm culture of O. oeni conferred (i) increased tolerance to wine stress, and (ii) functional performance with effective malolactic activities. Relative gene expression focusing on stress genes and genes involved in EPS synthesis was investigated in a mature biofilm and emphasized the role of the matrix in increased biofilm resistance. As oak is commonly used in wine aging, we focused on the O. oeni biofilm on this material and its contribution to the development of wine color and the release of aromatic compounds. Analytical chromatography was used to target the main oak aging compounds such as vanillin, gaiacol, eugenol, whisky-lactones, and furfural. The results reveal that O. oeni biofilm developed on oak can modulate the wood-wine transfer of volatile aromatic compounds during MLF and aging by decreasing furfural, gaiacol, and eugenol in particular. This work showed that O

  11. Toward a Molecular Understanding of the Typicality of Chardonnay Wines: Identification of Powerful Aromatic Compounds Reminiscent of Hazelnut.

    PubMed

    Gros, Jacques; Lavigne, Valérie; Thibaud, Fannie; Gammacurta, Marine; Moine, Virginie; Dubourdieu, Denis; Darriet, Philippe; Marchal, Axel

    2017-02-08

    Chardonnay wines impart a unique complex aroma characterized by its buttery, yellow stone fruit, melon, bready, and woody notes. Among the terms used in the sensory analysis of these wines, this study investigated hazelnut-like attributes. Multidimensional gas chromatography coupled to olfactometry identified five pyrroles reminiscent of hazelnut: 1-ethylpyrrole-2-carboxaldehyde, 1H-pyrrole, 2-acetyl-1H-pyrrole (first identification in wine), 1-methylpyrrole-2-carboxaldehyde, and 1H-pyrrole-2-carboxaldehyde. Quantitative analyses demonstrated their significantly higher abundance in Chardonnay wines. However, they proved irrelevant in sensory terms, given the low amounts measured in wine compared to their olfactory detection threshold. Nevertheless, the presence of methanethiol derivatives from these pyrroles was investigated in wine. 1-Methylpyrrole-2-methanethiol and 1-ethylpyrrole-2-methanethiol were identified and exhibited hazelnut-like aroma. These compounds, which have not been observed in natural products to date, are potent volatile compounds with detection thresholds of 0.7 and 1.4 ng/L, respectively, in model wine. These findings open up promising perspectives concerning the interpretation of the typical aromatic nuances of some Chardonnay wines.

  12. Combining cryogenic fiber optic probes with commercial spectrofluorimeters for the synchronous fluorescence Shpol'skii spectroscopy of high molecular weight polycyclic aromatic hydrocarbons.

    PubMed

    Moore, Anthony F T; Barbosa, Fernando; Campiglia, Andres D

    2014-01-01

    Cryogenic fiber optic probes are combined for the first time with a commercial spectrofluorometer for Shpol'skii spectroscopy measurements at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. Accurate and reproducible acquisition of fluorescence spectra and signal intensities is demonstrated with three well known Shpol'skii systems, namely, anthracene/heptane, pyrene/hexane, and benzo[a]pyrene/octane. The ability to adjust the excitation and emission bandpass of the spectrofluorimeter to reach both site-resolution and analytically valuable signal-to-noise ratios was illustrated with benzo[a]pyrene in n-octane. The analytical potential of 4.2 K synchronous fluorescence Shpol'skii spectroscopy for the analysis of high molecular weight-polycyclic aromatic hydrocarbons was then explored for the first time. The judicious optimization of wavelength offsets permitted the successful determination of dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,i]pyrene, and naphtho[2,3-a]pyrene without previous chromatographic separation from a soil extract with complex matrix composition. The simplicity of the experimental procedure, the competitive analytical figures of merit, and the selectivity of analysis turn 4.2 K synchronous fluorescence Shpol'skii spectroscopy into a valuable alternative for screening isomers of high molecular weight polycyclic aromatic hydrocarbons in environmental samples.

  13. Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Zaugg, Steven D.; Burkhardt, Mark R.; Burbank, Teresa L.; Olson, Mary C.; Iverson, Jana L.; Schroeder, Michael P.

    2006-01-01

    A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces

  14. Mechanism of hydrostimulated displacement of aromatic compounds from cellulose triacetate films

    NASA Astrophysics Data System (ADS)

    Mikheev, Yu. A.; Guseva, L. N.; Ershov, Yu. A.

    2010-02-01

    The effect of temperature on the rate of desorption into water of naphthalene, diphenyl, benzophenone, para-terphenyl, α-naphthol, stilbene, anthracene, and dibutyl phthalate introduced into cellulose triacetate films was studied. It was shown that in water, the removal rate of these compounds from the films increases sharply as compared to desorption into air. The relation between the activation energies and pre-exponential factors characterizing the desorption rate was found in the form of a compensatory effect. The nature of the compensatory effect is explained by osmotic phenomena due to hydrophobic hydration of the polymer. We conclude that mobile polymeric chains of non-crystalline polymer are structured around water and Ar-compound molecules as sponge-like structures forming fringed nanoporous capsules. The simultaneous presence of molecules of different compounds in the polymer was found to cause osmotic competition for a place in the sponge; water absorbed by the chain sponge enhances the volume pulsations of nanocapsules. It was revealed that diffusion occurs because of thermal fluctuations inducing the reorganization of nanoporous capsules and their movement together with Ar-molecules in the matrix by the principle of peristalsis.

  15. Identification and quantification of known polycyclic aromatic hydrocarbons and pesticides in complex mixtures using fluorescence excitation-emission matrices and parallel factor analysis.

    PubMed

    Ferretto, Nicolas; Tedetti, Marc; Guigue, Catherine; Mounier, Stéphane; Redon, Roland; Goutx, Madeleine

    2014-07-01

    Polycyclic aromatic hydrocarbons (PAHs) and pesticides are among the most widespread organic contaminants in aquatic environments. Because of their aromatic structure, PAHs and pesticides have intrinsic fluorescence properties in the ultraviolet/blue spectral range. In this study, excitation-emission matrix (EEM) fluorescence spectroscopy and parallel factor (PARAFAC) analysis were used to characterise and discriminate fluorescence signatures of nine PAHs and three pesticides at the μg L(-1) level in the presence of humic substances (0.1-10 mgCL(-1)). These contaminants displayed a diversity of fluorescence signatures regarding spectral position (λEx: 220-335 nm, λEm: 310-414 nm), Stokes shift (39-169 nm) and number of peaks (1-8), with detection limits ranging from 0.02 to 1.29μgL(-1). The EEM/PARAFAC method applied to mixtures of PAHs with humic substances validated a seven-component model that included one humic-like fluorophore and six PAH-like fluorophores. The EEM/PARAFAC method applied to mixtures of pesticides with humic substances validated a six-component model that included one humic-like fluorophore and three pesticide-like fluorophores. The EEM/PARAFAC method adequately quantified most of the contaminants for humic substance concentrations not exceeding 2.5 mg CL(-1). The application of this method to natural (marine) samples was demonstrated through (1) the match between the Ex and Em spectra of PARAFAC components and the Ex and Em spectra of standard PAHs, and (2) the good linear correlations between the fluorescence intensities of PARAFAC components and the PAH concentrations determined by GC-MS.

  16. Enhancing the Photostability of Arylvinylenebipyridyl Compounds as Fluorescent Indicators for Intracellular Zinc(II) Ions

    PubMed Central

    Yuan, Zhao; Younes, Ali H.; Allen, John R.; Davidson, Michael W.; Zhu, Lei

    2015-01-01

    Arylvinylenebipyridyl (AVB) ligands are bright, zinc(II)-sensitive fluoroionophores. The applicability of AVBs as fluorescent indicators for imaging cellular zinc(II), however, is limited by low photostability, partially attributable to the photoisomerization of the vinylene functionality. Two configurationally immobilized (i.e., “locked”) AVB analogues are prepared in this work. The zinc(II)-sensitive photophysical properties and zinc(II) affinities of both AVBs and their locked analogues are characterized in organic and aqueous media. The zinc(II) sensitivity of the emission is attributed to the zinc(II)-dependent energies of the charge transfer excited states of these compounds. The configurationally locked ligands have improved photostability, while maintaining the brightness and zinc(II) sensibility of their AVB progenitors. The feasibility of the “locked” AVB analogues with improved photostability for imaging intracellular Zn(II) of eukaryotic cells using laser confocal fluorescence microscopy is demonstrated. PMID:25942357

  17. Stability of polycyclic aromatic compounds in polyurethane foam-type passive air samplers upon O3 exposure

    NASA Astrophysics Data System (ADS)

    Jariyasopit, Narumol; Liu, Yongchun; Liggio, John; Harner, Tom

    2015-11-01

    Stability of polycyclic aromatic compounds (PACs) in polyurethane foam (PUF) disks upon O3 exposure was studied in a flow tube. A wide range of PACs was evaluated by spiking PUF disks with PACs and exposing to O3 at concentrations that were equivalent to two months exposure, a typical deployment period for these passive air samplers. Ambient concentrations of O3 (∼50 ppb) at 0% and 50% relative humidity (RH) were applied. At 0% RH, 23 of 68 PACs yielded more than 50% loss after exposure. The mean percent loss was 30% with perylene and 9,10-dimethylanthracene the most reactive polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs, respectively. At 50% RH, 77% of the studied PACs was stable upon O3 exposure (PACexposed/PACunexposed > 0.7). The mean percent loss was 17% and only 7 of 68 PACs yielded greater than 50% loss. In general, the reactivity of most of the PACs decreased at higher RH, except for the reactive PAHs (acenaphthylene, 2,3-dimethylanthracene, 9,10-dimethylanthracene, dibenzothiophene, and 2-methyldibenzothiophene) which demonstrated lower RH dependence. The experimental conditions in this study represent a worst case scenario for the stability of PACs sorbed to PUF. In reality, the sampling of PACs in ambient air represents an 'aged' component of PACs where the most reactive species have already partially been removed. Also, PACs in ambient air will be associated with the particle phase to varying extents that will help to enhance their stability. Therefore, under regular operating conditions, over a 2-month exposure, we expect a minimal error in the measurement of total concentration of PACs in air using the PUF disk passive sampler.

  18. Polar polycyclic aromatic compounds from different coal types show varying mutagenic potential, EROD induction and bioavailability depending on coal rank.

    PubMed

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

    2014-10-01

    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.

  19. Comparative studies on sulfhydryl determination of soy protein using two aromatic disulfide reagents and two fluorescent reagents.

    PubMed

    Ruan, Qijun; Chen, Yeming; Kong, Xiangzhen; Hua, Yufei

    2013-03-20

    In this study, the sulfhydryl (SH) contents of unheated and heated (90 °C, 5 min) soy protein were detected under different conditions (pH, reagent addition order, SDS/GuHCl concentration, EDTA) using two aromatic disulfide reagents: 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) and 4,4'-dithiodipyridine (DPS). Two fluorescent alkylating reagents, monobromobimane (mBBr) and N-(1-pyrenyl)maleimide (NPM), were chosen due to their high sensitivity and were also used. Amino acid analysis was used to detect the SH (cysteine) contents of unheated (7.51 ± 0.45 μmol SH/g protein) and heated (1.47 ± 0.10 μmol SH/g protein) soy protein, and similar results were obtained using enzymatic hydrolysis-assisted DPS. The SH content detected by DTNB was affected by pH, denaturant species, and denaturant concentration, and the best results were obtained at pH 7.0 when 6 M GuHCl was added after DTNB. These results were lower than that of the amino acid analysis, however. The SH detected by DPS was not as affected as that of DTNB by pH, denaturant species, and denaturant concentration. Additionally, the results of the amino acid analysis were similar to that of DPS at pH 7.0 in 2% SDS and 4-6 M GuHCl when SDS and GuHCl were added after DPS. EDTA did not have a significant effect on SH detection when DTNB and DPS were added before SDS and GuHCl. Finally, although mBBr and NPM can detect SH in low protein concentrations ((1)/10 of that required for DTNB and DPS), mBBr and NPM overestimated the SH content of soy protein. Therefore, using DPS at pH 7.0 when it is added before SDS and GuHCl is the most reliable method for detecting the SH content of soy protein.

  20. Development and application of fluorescent, green light-activatable caged compound

    NASA Astrophysics Data System (ADS)

    Umeda, Nobuhiro; Urano, Yasuteru; Nagano, Tetsuo

    2011-03-01

    Caged compound is one of the most powerful tools for spatiotemporal control of biomolecules in cells, which can be activated by irradiation of light. However, ultra violet light, which is required for activation of caged compounds, can damage cells and has poor permeability into tissues. In addition, invisibility of caged compounds makes it difficult to tell distribution of released small molecules. At the conference, we will describe the development of novel caging group and new caged compounds which are fluorescently visible and efficiently activatable with green light. We have found that boron dipyrromethene (BODIPY), known as a widely used fluorophore, is a potential caging group for phenol, carboxyl acid and amine, which can be photolized with irradiation of green light at around 500 nm wavelength. Based on the novel photo-reaction of 4-phenoxy BODIPY derivatives, we have developed caged histamine and applied it to HeLa cells. Photo-irradiation to cells in the presence of caged histamine induced transient increase of calcium ion in cytosol, which was specifically inhibited with pyrilamine, a H1 blocker. Also, we showed that BODIPY-caged compound can be utilized in vivo with tissue-permeable 500 nm green light.

  1. Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids

    NASA Astrophysics Data System (ADS)

    Dutka, V. S.; Matsyuk, N. V.; Dutka, Yu. V.

    2011-01-01

    The influence of different solvents on the oxidation reaction rate of pyridine (Py), quinoline (QN), acridine (AN), α-oxyquinoline (OQN) and α-picolinic acid (APA) by peroxydecanoic acid (PDA) was studied. It was found that the oxidation rate grows in the series Py < QN < AN, and the rate of the oxidation reaction of compounds containing a substituent in the α position from a reactive center is significantly lower than for unsubstituted analogues. The effective energies of activation of the oxidation reaction were found. It was shown that in the first stage, the reaction mechanism includes the rapid formation of an intermediate complex nitrogen-containing compound, peroxyacid, which forms products upon decomposing in the second stage. A kinetic equation that describes the studied process is offered. The constants of equilibrium of the intermediate complex formation ( K eq) and its decomposition constant ( k 2) in acetone and benzene were calculated. It was shown that the nature of the solvent influences the numerical values of both K p and k 2. It was established that introduction of acetic acid (which is able to form compounds with Py) into the reaction medium slows the rate of the oxidation process drastically. Correlation equations linking the polarity, polarizability, electrophilicity, and basicity of solvents with the constant of the PDA oxidation reaction rate for Py were found. It was concluded that the basicity and polarity of the solvent have a decisive influence on the oxidation reaction rate, while the polarizability and electrophilicity of the reaction medium do not influence the oxidation reaction rate.

  2. Gadolinium(III)-sensitized fluorescence of europium in its mixed-metal compounds with trifluroacetate

    NASA Astrophysics Data System (ADS)

    Kalinovskaya, I. V.; Zadorozhnaya, A. N.

    2017-04-01

    The fluorescence properties of mixed-metal compounds of Eu(III) and Gd(III) with trifluoroacetic acid, Eu1-xGdx(C2F3O2)3·yD·zH2O, where D - 1,10-phenanthroline, 2,2-dipyridil, diphenylguanidine, x = 0, 0.25, 0.5, or 0.7, were studied. Luminescence spectroscopic evidence and the examination of excitation spectra indicate the occurrence of efficient energy transfer from the gadolinium to the europium ion. The greatest promotion of Eu3+ photoluminescence at 615 nm is observed when Eu:Gd = 1:1.

  3. Dibasic Ammonium Phosphate Application Enhances Aromatic Compound Concentration in Bog Bilberry Syrup Wine.

    PubMed

    Wang, Shao-Yang; Li, Yi-Qing; Li, Teng; Yang, Hang-Yu; Ren, Jie; Zhang, Bo-Lin; Zhu, Bao-Qing

    2016-12-29

    A nitrogen deficiency always causes bog bilberry syrup wine to have a poor sensory feature. This study investigated the effect of nitrogen source addition on volatile compounds during bog bilberry syrup wine fermentation. The syrup was supplemented with 60, 90, 120 or 150 mg/L dibasic ammonium phosphate (DAP) before fermentation. Results showed that an increase of DAP amounts accelerated fermentation rate, increased alcohol content, and decreased sugar level. Total phenol and total flavonoid content were also enhanced with the increase of DAP amounts. A total of 91 volatile compounds were detected in the wine and their concentrations were significantly enhanced with the increase of DAP. Ethyl acetate, isoamyl acetate, phenethyl acetate, ethyl butanoate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, isobutanol, isoamyl alcohol, levo-2,3-butanediol, 2-phenylethanol, meso-2,3-butanediol, isobutyric acid, hexanoic acid, and octanoic acid exhibited a significant increase of their odor activity value (OAV) with the increase of DAP amounts. Bog bilberry syrup wine possessed fruity, fatty, and caramel flavors as its major aroma, whereas a balsamic note was the least present. The increase of DAP amounts significantly improved the global aroma attributes, thereby indicating that DAP supplementation could promote wine fermentation performance and enhance the sensory quality of bog bilberry syrup wine.

  4. [Development of novel fluorescence-derivatization-HPLC methods enabling highly sensitive and selective analysis of biological compounds].

    PubMed

    Todoroki, Kenichiro

    2011-01-01

    Fluorescence-derivatization-HPLC methods are powerful tools for performing the analysis of bioactive compounds with high sensitivity and selectivity. In this paper, the author reviews the development of the following four types of novel fluorescence-derivatization-HPLC analytical systems: (1) simultaneous HPLC analysis of melatonin and its related compounds through post-column electrochemical demethylation and fluorescence derivatization, (2) HPLC analysis of 5-hydroxyindoles based on fluorescence derivatization by online pre-column photocatalytic oxidation with benzylamine, (3) reagent peak-free HPLC analysis for aliphatic amines and amino acids using F-trap pyrene as a fluorous tag-bound fluorescence derivatization reagent, and (4) reagent peak-free HPLC analysis for carboxylic acids using a fluorous scavenging-derivatization method. The authors have also successfully applied these systems to biological and pharmaceutical analyses.

  5. Aromatic fluorine compounds. X. The 2,3- and 2,6-difluoropyridines

    USGS Publications Warehouse

    Finger, G.C.; Starr, L.D.; Roe, A.; Link, W.J.

    1962-01-01

    The preparation of difluoropyridines by the Schiemann reaction was investigated. 2-Amino-6-fluoropyridine (IIIa), necessary for the synthesis of 2,6-difluoropyridine (IVa) by the Schiemann reaction, was conveniently prepared by the Curtius degradation of 6-fluoropicolinic hydrazide (IIa) and by the Hofmann reaction on 6-fluoropicolinamide (IId). Since an ??-fluorine on a pyridine nucleus is preferentially replaced by hydrazine when it is either adjacent to or opposite a carbomethoxy group, the hydrazides necessary for the synthesis of 3-amino-2- and 6-fluoropyridine could not be prepared. These amines were prepared from the appropriate 2-fluoropyridinecarboxamide by the Hofmann reaction. The preparation of difluoropyridines was successful with two of the aminofluoropyridines and led to the following new compounds: 2,3-difluoro(IVb) and 2,6-difluoropyridine (IVa).

  6. Bringing bioactive compounds into membranes: the UbiA superfamily of intramembrane aromatic prenyltransferases

    PubMed Central

    Li, Weikai

    2016-01-01

    The UbiA superfamily of intramembrane prenyltransferases catalyzes a key biosynthetic step in the production of ubiquinones, menaquinones, plastoquinones, hemes, chlorophylls, vitamin E, and structural lipids. These lipophilic compounds serve as electron and proton carriers for cellular respiration and photosynthesis, as antioxidants to reduce cell damage, and as structural components of microbial cell walls and membranes. This article reviews the biological functions and enzymatic activities of representative members of the superfamily, focusing on the remarkable recent research progress revealing that the UbiA superfamily is centrally implicated in several important physiological processes and human diseases. Because prenyltransferases in this superfamily have distinctive substrate preferences, two recent crystal structures are compared to illuminate the general mechanism for substrate recognition. PMID:26922674

  7. Spectral Response and Diagnostics of Biological Activity of Hydroxyl-Containing Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Mayer, G. V.; Bel'kov, M. V.; Shadyro, O. I.

    2016-08-01

    Using IR Fourier spectra and employing quantum-chemical calculations of electronic structure, spectra, and proton-acceptor properties, synthetic derivatives of aminophenol exhibiting biological activity in the suppression of herpes, influenza, and HIV viruses have been investigated from a new perspective, with the aim of establishing the spectral response of biological activity of the molecules. It has been experimentally established that the participation of the aminophenol hydroxyl group in intramolecular hydrogen bonds is characteristic of structures with antiviral properties. A quantum-chemical calculation of the proton-acceptor ability of the investigated aminophenol derivatives has shown that biologically active structures are characterized by a high proton-acceptor ability of oxygen of the hydroxyl group. A correlation that has been obtained among the formation of an intramolecular hydrogen bond, high proton-acceptor ability, and antiviral activity of substituted aminophenols enables us to predict the pharmacological properties of new medical preparations of the given class of compounds.

  8. Aromatic-hydroxyl interaction of an alpha-aryl ether lignin model-compound on SBA-15, present at pyrolysis temperatures.

    PubMed

    Kandziolka, M V; Kidder, M K; Gill, L; Wu, Z; Savara, A

    2014-11-28

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic-hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C-H stretches, as well as a red-shift and broadening of the surface hydroxyl O-H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ∼400 °C whereupon the ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.

  9. An arsenic fluorescent compound as a novel probe to study arsenic-binding proteins.

    PubMed

    Femia, A Lis; Temprana, C Facundo; Santos, Javier; Carbajal, María Laura; Amor, María Silvia; Grasselli, Mariano; Alonso, Silvia Del V

    2012-12-01

    Arsenic-binding proteins are under continuous research. Their identification and the elucidation of arsenic/protein interaction mechanisms are important because the biological effects of these complexes may be related not only to arsenic but also to the arsenic/protein structure. Although many proteins bearing a CXXC motif have been found to bind arsenic in vivo, new tools are necessary to identify new arsenic targets and allow research on protein/arsenic complexes. In this work, we analyzed the performance of the fluorescent compound APAO-FITC (synthesized from p-aminophenylarsenoxide, APAO, and fluorescein isothiocyanate, FITC) in arsenic/protein binding assays using thioredoxin 1 (Trx) as an arsenic-binding protein model. The Trx-APAO-FITC complex was studied through different spectroscopic techniques involving UV-Vis, fluorescence, atomic absorption, infrared and circular dichroism. Our results show that APAO-FITC binds efficiently and specifically to the Trx binding site, labeling the protein fluorescently, without altering its structure and activity. In summary, we were able to study a protein/arsenic complex model, using APAO-FITC as a labeling probe. The use of APAO-FITC in the identification of different protein and cell targets, as well as in in vivo biodistribution studies, conformational studies of arsenic-binding proteins, and studies for the design of drug delivery systems for arsenic anti-cancer therapies, is highly promising.

  10. Comparing Urinary Biomarkers of Airborne and Dermal Exposure to Polycyclic Aromatic Compounds in Asphalt-Exposed Workers

    PubMed Central

    Sobus, Jon R.; McClean, Michael D.; Herrick, Robert F.; Waidyanatha, Suramya; Nylander-French, Leena A.; Kupper, Lawrence L.; Rappaport, Stephen M.

    2009-01-01

    When working with hot mix asphalt, road pavers are exposed to polycyclic aromatic hydrocarbons (PAHs) through the inhalation of vapors and particulate matter (PM) and through dermal contact with PM and contaminated surfaces. Several PAHs with four to six rings are potent carcinogens which reside in these particulate emissions. Since urinary biomarkers of large PAHs are rarely detectable in asphalt workers, attention has focused upon urinary levels of the more volatile and abundant two-ring and three-ring PAHs as potential biomarkers of PAH exposure. Here, we compare levels of particulate polycyclic aromatic compounds (P-PACs, a group of aromatic hydrocarbons containing PAHs and heterocyclic compounds with four or more rings) in air and dermal patch samples from 20 road pavers to the corresponding urinary levels of naphthalene (U-Nap) (two rings), phenanthrene (U-Phe) (three rings), monohydroxylated metabolites of naphthalene (OH-Nap) and phenanthrene (OH-Phe), and 1-hydroxypyrene (OH-Pyr) (four rings), the most widely used biomarker of PAH exposure. For each worker, daily breathing-zone air (n = 55) and dermal patch samples (n = 56) were collected on three consecutive workdays along with postshift, bedtime, and morning urine samples (n = 149). Measured levels of P-PACs and the urinary analytes were used to statistically model exposure–biomarker relationships while controlling for urinary creatinine, smoking status, age, body mass index, and the timing of urine sampling. Levels of OH-Phe in urine collected postshift, at bedtime, and the following morning were all significantly associated with levels of P-PACs in air and dermal patch samples. For U-Nap, U-Phe, and OH-Pyr, both air and dermal patch measurements of P-PACs were significant predictors of postshift urine levels, and dermal patch measurements were significant predictors of bedtime urine levels (all three analytes) and morning urine levels (U-Nap and OH-Pyr only). Significant effects of

  11. Spectroscopic Evidence of Anthropogenic Compounds Extraction from Polymers by Fluorescent Dissolved Organic Matter in Natural Water

    NASA Astrophysics Data System (ADS)

    Miranda, M.; Trojzuck, A.; Voss, D.; Gassmann, S.; Zielinski, O.

    2016-04-01

    FDOM is one of the most important carriers of anthropogenic compounds in natural waters. It can combine with environmental contaminants and polymers to form diverse chemical structures. To this end, here a microfluidic chip was designed for the analysis of these changes in fluorescent dissolved organic matter (FDOM) fingerprints due to thermal treatment and varying time intervals of exposure. Excitation Emission Matrix Spectroscopy (EEMS) approach was utilized to detect and identify the inherent compounds in sampled FDOM. Strong direct correlations were founded, Spearman rank correlation values (ρ = 0.85 at α = 0.1, n = 4) and linear correlation R2 = 0.8359 were noted between thermal treatment pattern 2 and fluorescence intensity of samples. Materials, acrylic based glue and cyclic olefin copolymer (COC) polymer, used to design the microfluidic sensor were determined to possess unique spectral features in the ultraviolet to green spectrum using EEMS. The study therefore provides an insight on methods to identify contaminants in natural waters. This underlines the potential of optical sensors providing measurements at fast intervals, enabling environmental monitoring.

  12. Comparative study on catalytic hydrodehalogenation of halogenated aromatic compounds over Pd/C and Raney Ni catalysts

    NASA Astrophysics Data System (ADS)

    Ma, Xuanxuan; Liu, Sujing; Liu, Ying; Gu, Guodong; Xia, Chuanhai

    2016-04-01

    Catalytic hydrodehalogenation (HDH) has proved to be an efficient approach to dispose halogenated aromatic compounds (HACs). Liquid-phase HDH of single and mixed halobenzenes/4-halophenols with H2 over 5% Pd/C and Raney Ni catalyst are investigated and compared. For liquid-phase HDH of single HACs, hydrogenolytic scission reactivity of C-X bonds decreases in order of C-Br > C-Cl > C-I > C-F over Pd/C catalyst, and in order of C-I > C-Br > C-Cl > C-F over Raney Ni catalyst. To clarify the reason why hydrogenolytic scission reactivity of C-X bonds over Pd/C and Raney Ni catalysts exhibits different trends, liquid-phase HDH of mixed HACs over Pd/C and Raney Ni catalysts were studied, and catalysts are characterized by SEM, EDX, and XRD techniques. It was found that the high adsorption of iodoarenes on Pd/C catalyst caused the HDH reactivity of iodoarenes to be lower than that of chloroarenes and bromoarenes in the HDH of single HACs. Moreover, the adsorption of in situ produced iodine ion (I‑) to catalyst surface would result in the decline of catalytic activity, which might be the main reason why the HDH reactivity of HACs in the presence of NaI is rather low.

  13. Comparative study on catalytic hydrodehalogenation of halogenated aromatic compounds over Pd/C and Raney Ni catalysts

    PubMed Central

    Ma, Xuanxuan; Liu, Sujing; Liu, Ying; Gu, Guodong; Xia, Chuanhai

    2016-01-01

    Catalytic hydrodehalogenation (HDH) has proved to be an efficient approach to dispose halogenated aromatic compounds (HACs). Liquid-phase HDH of single and mixed halobenzenes/4-halophenols with H2 over 5% Pd/C and Raney Ni catalyst are investigated and compared. For liquid-phase HDH of single HACs, hydrogenolytic scission reactivity of C-X bonds decreases in order of C-Br > C-Cl > C-I > C-F over Pd/C catalyst, and in order of C-I > C-Br > C-Cl > C-F over Raney Ni catalyst. To clarify the reason why hydrogenolytic scission reactivity of C-X bonds over Pd/C and Raney Ni catalysts exhibits different trends, liquid-phase HDH of mixed HACs over Pd/C and Raney Ni catalysts were studied, and catalysts are characterized by SEM, EDX, and XRD techniques. It was found that the high adsorption of iodoarenes on Pd/C catalyst caused the HDH reactivity of iodoarenes to be lower than that of chloroarenes and bromoarenes in the HDH of single HACs. Moreover, the adsorption of in situ produced iodine ion (I−) to catalyst surface would result in the decline of catalytic activity, which might be the main reason why the HDH reactivity of HACs in the presence of NaI is rather low. PMID:27113406

  14. Diversity of culturable nocardioform actinomycetes from wastewater treatment plants in Spain and their role in the biodegradability of aromatic compounds.

    PubMed

    Soler, Albert; García-Hernández, Jorge; Zornoza, Andrés; Alonso, José Luis

    2017-03-06

    Currently, municipal and industrial wastewater treatment plants (WWTPs) are mainly focusing on reduction of biological oxygen demand and on the removal of nutrients. However, there are microorganisms that interfere with the process. In this environment, there is a large diversity of microorganisms that have not been studied in detail and that could provide real and practical solutions to the foaming problems. Among such microorganisms, Gram-positive actinomycete bacteria are of special interest because they are known for producing secondary metabolites as well as chemically diverse compounds and for their capacity to degrade recalcitrant pollutants. Three different media were chosen to isolate actinomycetes from 28 WWTPs in Spain. A total of 189 activated sludge samples were collected; 126 strains were isolated and identified to belong to 1 suborder, i.e. Corynebacterineae, and 7 genera, i.e. Corynebacterium, Dietzia, Gordonia, Mycobacterium, Rhodococcus, Tsukamurella and Williamsia. Furthermore, 71 strains were capable of biodegrading at least 1 aromatic product, and that 27 of them amplified for catA gene. The results of this research help us understand the complexity of the foam-forming microbial populations in Spain and it shows that WWTPs can be a good source of microorganisms that can degrade phenol or naphthalene.

  15. Metagenomic Analysis of the Pygmy Loris Fecal Microbiome Reveals Unique Functional Capacity Related to Metabolism of Aromatic Compounds

    PubMed Central

    Xu, Bo; Xu, Weijiang; Yang, Fuya; Li, Junjun; Yang, Yunjuan; Tang, Xianghua; Mu, Yuelin; Zhou, Junpei; Huang, Zunxi

    2013-01-01

    The animal gastrointestinal tract contains a complex community of microbes, whose composition ultimately reflects the co-evolution of microorganisms with their animal host. An analysis of 78,619 pyrosequencing reads generated from pygmy loris fecal DNA extracts was performed to help better understand the microbial diversity and functional capacity of the pygmy loris gut microbiome. The taxonomic analysis of the metagenomic reads indicated that pygmy loris fecal microbiomes were dominated by Bacteroidetes and Proteobacteria phyla. The hierarchical clustering of several gastrointestinal metagenomes demonstrated the similarities of the microbial community structures of pygmy loris and mouse gut systems despite their differences in functional capacity. The comparative analysis of function classification revealed that the metagenome of the pygmy loris was characterized by an overrepresentation of those sequences involved in aromatic compound metabolism compared with humans and other animals. The key enzymes related to the benzoate degradation pathway were identified based on the Kyoto Encyclopedia of Genes and Genomes pathway assignment. These results would contribute to the limited body of primate metagenome studies and provide a framework for comparative metagenomic analysis between human and non-human primates, as well as a comparative understanding of the evolution of humans and their microbiome. However, future studies on the metagenome sequencing of pygmy loris and other prosimians regarding the effects of age, genetics, and environment on the composition and activity of the metagenomes are required. PMID:23457582

  16. Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

    PubMed

    Willis, Alison M; Oris, James T

    2014-09-01

    The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms.

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

    PubMed

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

    2010-08-15

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

  18. Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

    PubMed

    Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

    2013-02-05

    Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

  19. Limiting activity coefficients of some aromatic and aliphatic nitro compounds in water

    SciTech Connect

    Benes, M.; Dohnal, V.

    1999-09-01

    Limiting activity coefficients of nine nitroaromatic compounds and four nitroalkanes in water were determined in the range of environmentally related temperatures by measuring suitable phase equilibria. For liquid and solid nitroaromatics (nitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 1-chloro-2-nitrobenzene, and 1-chloro-4-nitrobenzene) the aqueous solubilities were measured by a conventional batch contacting method with UV spectrophotometric analysis, while for nitroalkanes (nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane) the air-water partitioning (Henry`s law constant H{sub 12} or air-water partition coefficient K{sub aw}) was determined by the inert gas stripping method employing gas chromatography. Whenever possible, results were compared to literature values. Calculation of H{sub 12} or K{sub aw} for nitroaromatics from the measured solubilities is hindered by the lack of reliable vapor pressure data. On the basis of the temperature dependences of the solubilities measured, the enthalpies of solution at infinite dilution for the nitroaromatics in water were evaluated.

  20. Headspace in-tube microextraction coupled with micellar electrokinetic chromatography of neutral aromatic compounds.

    PubMed

    Cho, Sung Min; Park, Bum Su; Jung, Woo Sung; Lee, Sang Won; Jung, Yunhwan; Chung, Doo Soo

    2016-02-01

    Headspace (HS) extraction can be carried out easily and aptly via single drop microextraction coupled with capillary electrophoresis (CE). However, one drawback is the difficulty of keeping the single drop stably at the capillary tip. To solve this problem, we have recently demonstrated HS in-tube microextraction (ITME) of acidic compounds such as chlrophenols in an acidic sample using a basic run buffer plug in the separation capillary for CE as an acceptor phase. In this report, an organic acceptor plug in a capillary was used to extract neutral organic volatile pollutants such as BTEX (benzene, toluene, ethylbenzene, and m-xylene). After extraction, the analytes enriched in the organic acceptor plug were analyzed with micellar electrokinetic chromatography (MEKC). The enrichment factors for BTEX in a standard solution were up to 350 under an optimal condition of 25°C for 20 min. As an application, BTEX spiked into bottled water were analyzed with HS-ITME-MEKC, and the enrichment factors for BTEX were up to 320. The limits of detections were 1-4 ppb, which are at least 200 times lower than the US Environmental Protection Agency guidelines for drinking water, except benzene. The entire procedure of HS-ITME-MEKC was carried out automatically using a commercial CE instrument.

  1. Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

    NASA Astrophysics Data System (ADS)

    Ziegelgruber, Kate L.; Knope, Karah E.; Frisch, Mark; Cahill, Christopher L.

    2008-02-01

    A novel thorium (IV) coordination polymer, Th(C 5H 2N 2O 4) 2(H 2O) 2 ( 1), has been prepared under the hydrothermal reaction of thorium nitrate tetrahydrate and 3,5-pyrazoledicarboxylic acid (H 3pdc). Compound 1 (orthorhombic, P2 12 12 1, a=6.9362(5) Å, b=10.7806(8) Å, c=17.9915(14) Å, Z=2, R1=0.0210, w R2=0.0470) consists of thorium metal centers connected via H 3pdc linkages to form an overall three-dimensional structure containing π- π interactions between the pyrazole rings. 2,3-Pyrazinedicarboxylic acid (H 2pzdc) was explored as well to (1) study the effect of the location of the carboxylic groups around the aromatic ring and (2) produce heterometallic compounds. Thorium (IV) and copper (II) were combined with H 2pzdc, resulting in an interesting decomposition reaction characterized though the isolation of Th(C 2O 4) 2(H 2O) 2·2H 2O ( 2) (monoclinic, C2/ c, a=13.8507(12) Å, b=7.8719(7) Å, c=10.7961(16) Å, β=118.0310(10)°, Z=2, R1=0.0160, w R2=0.0349), Cu(C 6H 2N 2O 4) ( 3) (monoclinic, C2/ c, a=11.499(3) Å, b=7.502(2) Å, c=7.402(2) Å, β=93.892(5)°, Z=4, R1=0.0472, w R2=0.0745) and Cu(C 5H 3N 2O 2)(NO 3)(H 2O) ( 4). The capture of these species provides mechanistic evidence for the formation of the oxalate anions observed in 2 via the decarboxylation of H 2pzdc to yield the linker in 4: 2-pyrazinecarboxylate anions.

  2. Fragmentation pathways and mechanisms of aromatic compounds in atmospheric pressure studied by GC-DMS and DMS-MS

    NASA Astrophysics Data System (ADS)

    Kendler, Shai; Lambertus, Gordon R.; Dunietz, Barry D.; Coy, Stephen L.; Nazarov, Erkinjon G.; Miller, Raanan A.; Sacks, Richard D.

    2007-06-01

    Differential mobility spectrometry (DMS) is a highly sensitive sensing technology capable of selecting and detecting ions based on the difference between ion mobility at high and low electric field. The combination of a micro-fabricated DMS with gas chromatography (GC) has allowed extensive investigation of the ion chemistry and collisionally induced dissociation (CID) of diaryl molecules on a millisecond timescale at temperatures up to 130 °C. DMS-pre-filtered time-of-flight mass spectrometry (DMS-MS) has been used to verify the chemical composition of the ion species resolved by GC-DMS. This work focuses on the fragmentation of diaryl compounds, including diphenyl methane (DPM) and bibenzyl (BB), using information from the DMS and DMS-MS spectra of a series of aromatic compounds. Density functional theory calculations have been used to investigate the geometry and the energy along the reaction coordinate for the loss of benzene from DPM·H+ and BB·H+ for comparison with GC-DMS and DMS-MS experimental results and with previously reported chemical ionization MS. DPM-H+ is observed to undergo field-induced fragmentation in the DMS to produce C7H7+(Bz+) and unobserved neutral benzene with a low energy barrier. In contrast, BB·H+ fragments to C8H9+ and benzene with a higher energy barrier. Calculated barriers and experimental results are in qualitative agreement. Depletion of the ionized fragments in favor of ion-neutral clusters was also observed at higher concentrations. It is suggested that CID in DMS can further enhance DMS analytical performance.

  3. Effect of community structure on the kinetics of anaerobic degradation of aromatic compounds

    SciTech Connect

    McInerney, M.J.

    1989-11-01

    The kinetics of benzoate degradation by Syntrophus buswellii grown in coculture with Desulfovibrio strain G-11 was determined. At low benzoate concentrations the rate of degradation deviated from that predicted by a first-order decay process and reached a threshold of 2 to 3 {mu}M benzoate. S. buswellii was adapted to grow with crotonate and experiments are in progress to isolate this bacterium. An anaerobic bacterium was isolated that catalyzed the cleavage of an aryl ether bond of phenoxyacetate and its chlorinated derivatives forming the respective phenol. The anaerobic fatty acid-degrading bacterium, Syntrophomonas wolfei, catalyzed a rapid formate-bicarbonate exchange reaction and slowly degraded formate. Enzymatic studies showed that the levels of hydrogenase in cell-free extracts of S. wolfei grown in pure culture or in coculture with Methanospirillum hungatei contained very high specific activities of hydrogenase. Formate dehydrogenase activity was present, but the activity was 700 to 900-fold less than hydrogenase activity. S. wolfei was adapted to grow with mono and di-unsaturated fatty acids 5 to 6 carbons in length. Analysis of the fermentation products showed that part of the substrate was {beta}-oxidized while remainder was reduced to the corresponding saturated fatty acid. Propionate was produced from a hexadienoate suggesting that another pathway in addition to {beta}-oxidation exists for the degradation of this compound. Labeling studies and analysis of the monomeric composition of poly-{beta}-hydroxyalkanoate in S. wolfei showed that early in growth PHA was made by the incorporation of an intermediate without cleavage of a C-C bond. Later, PHA was made by a pathway in equilibrium with the acetate pool.

  4. Analysis of Plant Growth-Promoting Effects of Fluorescent Pseudomonas Strains Isolated from Mentha piperita Rhizosphere and Effects of Their Volatile Organic Compounds on Essential Oil Composition.

    PubMed

    Santoro, Maricel V; Bogino, Pablo C; Nocelli, Natalia; Cappellari, Lorena Del Rosario; Giordano, Walter F; Banchio, Erika

    2016-01-01

    Many species or strains of the genus Pseudomonas have been characterized as plant growth promoting rhizobacteria (PGPR). We used a combination of phenotypic and genotypic techniques to analyze the community of fluorescent Pseudomonas strains in the rhizosphere of commercially grown Mentha piperita (peppermint). Biochemical techniques, Amplified rDNA Restriction Analysis (ARDRA), and 16S rRNA gene sequence analysis revealed that the majority of the isolated native fluorescent strains were P. putida. Use of two Repetitive Sequence-based PCR (rep-PCR) techniques, BOX-PCR and ERIC-PCR, allowed us to evaluate diversity among the native strains and to more effectively distinguish among them. PGPR activity was tested for the native strains and reference strain P. fluorescens WCS417r. Micropropagated M. piperita plantlets were exposed to microbial volatile organic compounds (mVOCs) emitted by the bacterial strains, and plant biomass parameters and production of essential oils (EOs) were measured. mVOCs from 11 of the native strains caused an increase in shoot fresh weight. mVOCs from three native strains (SJ04, SJ25, SJ48) induced changes in M. pierita EO composition. The mVOCs caused a reduction of metabolites in the monoterpene pathway, for example menthofuran, and an increase in menthol production. Menthol production is the primary indicator of EO quality. The mVOCs produced by native strains SJ04, SJ25, SJ48, and strain WCS417r were analyzed. The obtained mVOC chromatographic profiles were unique for each of the three native strains analyzed, containing varying hydrocarbon, aromatic, and alogenic compounds. The differential effects of the strains were most likely due to the specific mixtures of mVOCs emitted by each strain, suggesting a synergistic effect occurs among the compounds present.

  5. Analysis of Plant Growth-Promoting Effects of Fluorescent Pseudomonas Strains Isolated from Mentha piperita Rhizosphere and Effects of Their Volatile Organic Compounds on Essential Oil Composition

    PubMed Central

    Santoro, Maricel V.; Bogino, Pablo C.; Nocelli, Natalia; Cappellari, Lorena del Rosario; Giordano, Walter F.; Banchio, Erika

    2016-01-01

    Many species or strains of the genus Pseudomonas have been characterized as plant growth promoting rhizobacteria (PGPR). We used a combination of phenotypic and genotypic techniques to analyze the community of fluorescent Pseudomonas strains in the rhizosphere of commercially grown Mentha piperita (peppermint). Biochemical techniques, Amplified rDNA Restriction Analysis (ARDRA), and 16S rRNA gene sequence analysis revealed that the majority of the isolated native fluorescent strains were P. putida. Use of two Repetitive Sequence-based PCR (rep-PCR) techniques, BOX-PCR and ERIC-PCR, allowed us to evaluate diversity among the native strains and to more effectively distinguish among them. PGPR activity was tested for the native strains and reference strain P. fluorescens WCS417r. Micropropagated M. piperita plantlets were exposed to microbial volatile organic compounds (mVOCs) emitted by the bacterial strains, and plant biomass parameters and production of essential oils (EOs) were measured. mVOCs from 11 of the native strains caused an increase in shoot fresh weight. mVOCs from three native strains (SJ04, SJ25, SJ48) induced changes in M. pierita EO composition. The mVOCs caused a reduction of metabolites in the monoterpene pathway, for example menthofuran, and an increase in menthol production. Menthol production is the primary indicator of EO quality. The mVOCs produced by native strains SJ04, SJ25, SJ48, and strain WCS417r were analyzed. The obtained mVOC chromatographic profiles were unique for each of the three native strains analyzed, containing varying hydrocarbon, aromatic, and alogenic compounds. The differential effects of the strains were most likely due to the specific mixtures of mVOCs emitted by each strain, suggesting a synergistic effect occurs among the compounds present. PMID:27486441

  6. Regulation of glutathione S-transferase Ya subunit gene expression: Identification of a unique xenobiotic-responsive element controlling inducible expression by planar aromatic compounds

    SciTech Connect

    Rushmore, T.H.; King, R.G.; Pickett, C.B. ); Paulson, K.E. )

    1990-05-01

    The authors have identified a region in the 5{prime} flanking sequence of the glutathione S-transferase Ya subunit gene that contains a unique xenobiotic-responsive element (XRE). The regulatory region spans nucleotides {minus}722 to {minus}682 of the 5{prime} flanking sequence and is responsible for part of the basal level as well as inducible expression of the Ya subunit gene by planar aromatic compounds such as {beta}-naphthoflavone ({beta}-NF) and 3-methylcholanthrene. The DNA sequence of this region ({beta}-NF-responsive element) is distinct from the DNA sequence of the XRE found in the cytochrome P-450 IA1 gene. In addition to the region containing the {beta}-NF-responsive element, two other regulatory regions of the Ya subunit gene have been identified. The data suggest that regulation of gene expression by planar aromatic compounds can be mediated by a DNA sequence this is distinct from the XRE sequence.

  7. In situ growth of monodispersed Fe3O4 nanoparticles on graphene for the removal of heavy metals and aromatic compounds.

    PubMed

    Wu, Hai-Xia; Wu, Jia-Wei; Niu, Zhi-Gang; Shang, Xiu-Li; Jin, Jun

    2013-01-01

    We report on the efficient removal of heavy metal ions and aromatic compounds from simulated wastewater with a nanocomposite. The nanocomposite was obtained via thermal decomposition of the precursor Fe(acac)3 onto the surface of graphene, modified by diethylenetriamine pentaacetic anhydride through dopamine. It was found that the maximum adsorption capacity of the nanocomposite toward Cu(2+) and naphthalene was 207.9 and 72.2 mg g(-1) respectively, displaying a high efficiency for the removal of heavy metal ions as well as aromatic compounds at pH 7.0 and 293 K. The Langmuir for naphthalene and the Freundlich for the Cu(2+) adsorption isotherms were applicable for describing the removal processes. Furthermore, the nanocomposite was carefully examined by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectra, and UV-vis spectroscopy. This work provides a very efficient, fast and convenient approach to exploring a promising nanocomposite for water treatment.

  8. Direct detection of the hydrolysis of nerve agent model compounds using a fluorescent probe.

    PubMed

    Zheng, Xueying; Okolotowicz, Karl; Wang, Beilin; Macdonald, Mary; Cashman, John R; Zhang, Jun

    2010-09-06

    Nerve agents are highly toxic organophosphorus compounds (OPs) that are used as chemical warfare agents. Developing a catalytic bioscavenger to efficiently detoxify nerve agents in the bloodstream of affected individuals has been recognized as an attractive approach to prevent nerve agent toxicity. However, the search for nerve agent catalysts has been hindered by the lack of efficient direct assays for nerve agent hydrolysis. In addition, authentic nerve agents are restricted and access to use for experiments by the general research community is prohibited. Herein we report development of a method that combines use of novel nerve agent model compounds possessing a thiocholine leaving group that reacts with the fluorescent thio-detection probe, BES-Thio, to afford detection of sub-micromolar amounts of nerve agent model compounds hydrolysis products. The detection sensitivity of BES-Thio assay was approximately 10 times better than the Ellman assay. This developed method is useful as a direct, sensitive screening method for evaluating OP hydrolysis efficiency from catalytic cholinesterases. When the assay was assembled in the presence of oxime, OP-inhibited cholinesterases that were able to be reactivated by specific oxime showed oxime-assisted enzyme-mediated OP hydrolysis. Therefore, this method is also useful to screen oxime analogs to identify novel agents that can reactivate OP-inhibited cholinesterases or to screen various enzymes to identify pseudo-catalytic bioscavengers that can be readily reactivated by clinically approved oximes.

  9. The influence of the eluent composition on the retention of derivatives of some aromatic heterocyclic compounds in reversed-phase high-performance liquid chromatography

    NASA Astrophysics Data System (ADS)

    Kurbatova, S. V.; Saifutdinov, B. R.

    2009-07-01

    The influence of the composition of water-acetonitrile eluents on the retention of derivatives of aromatic heterocyclic compounds in reversed-phase high-performance liquid chromatography was studied. The coefficients of the displacement of acetonitrile molecules from the adsorption layer and equilibrium constants of quasi-chemical reactions of sorption and solvation of sorbate molecules were determined. For the investigated chromatographic systems, the applicability scope of the basic adsorption retention models are discussed.

  10. The Aspergillus niger faeB gene encodes a second feruloyl esterase involved in pectin and xylan degradation and is specifically induced in the presence of aromatic compounds.

    PubMed Central

    de Vries, Ronald P; vanKuyk, Patricia A; Kester, Harry C M; Visser, Jaap

    2002-01-01

    The faeB gene encoding a second feruloyl esterase from Aspergillus niger has been cloned and characterized. It consists of an open reading frame of 1644 bp containing one intron. The gene encodes a protein of 521 amino acids that has sequence similarity to that of an Aspergillus oryzae tannase. However, the encoded enzyme, feruloyl esterase B (FAEB), does not have tannase activity. Comparison of the physical characteristics and substrate specificity of FAEB with those of a cinnamoyl esterase from A. niger [Kroon, Faulds and Williamson (1996) Biotechnol. Appl. Biochem. 23, 255-262] suggests that they are in fact the same enzyme. The expression of faeB is specifically induced in the presence of certain aromatic compounds, but not in the presence of other constituents present in plant-cell-wall polysaccharides such as arabinoxylan or pectin. The expression profile of faeB in the presence of aromatic compounds was compared with the expression of A. niger faeA, encoding feruloyl esterase A (FAEA), and A. niger bphA, the gene encoding a benzoate-p-hydroxylase. All three genes have different subsets of aromatic compounds that induce their expression, indicating the presence of different transcription activating systems in A. niger that respond to aromatic compounds. Comparison of the activity of FAEA and FAEB on sugar-beet pectin and wheat arabinoxylan demonstrated that they are both involved in the degradation of both polysaccharides, but have opposite preferences for these substrates. FAEA is more active than FAEB towards wheat arabinoxylan, whereas FAEB is more active than FAEA towards sugar-beet pectin. PMID:11931668

  11. Sporobacterium olearium gen. nov., sp. nov., a new methanethiol-producing bacterium that degrades aromatic compounds, isolated from an olive mill wastewater treatment digester.

    PubMed

    Mechichi, T; Labat, M; Garcia, J L; Thomas, P; Patel, B K

    1999-10-01

    A strictly chemo-organotrophic, anaerobic bacterium was isolated from an olive mill wastewater treatment digester on syringate and designated strain SR1T. The cells were slightly curved rods, stained Gram-positive and possessed terminal spores. Strain SR1T utilized crotonate, methanol and a wide range of aromatic compounds including 3,4,5-trimethoxybenzoate (TMB), 3,4,5-trimethoxycinnamate (TMC), syringate, 3,4,5-trimethoxyphenylacetate (TMPA), 3,4,5-trimethoxyphenylpropionate (TMPP), ferulate, sinapate, vanillate, 3,4-dimethoxybenzoate, 2,3-dimethoxybenzoate, gallate, 2,4,6-trihydroxybenzoate (THB), pyrogallol, phloroglucinol and quercetin as carbon and energy sources. Acetate and butyrate were produced from aromatic compounds, methanol and crotonate whereas methanethiol (MT) was produced from methoxylated aromatic compounds and methanol. Strain SR1T had a G + C content of 38 mol% and grew optimally between 37 and 40 degrees C at pH 7.2 on a crotonate-containing medium. Phylogenetically, strain SR1T was a member of cluster XIVa of the Clostridiales group and shared a sequence similarity of 90% with Clostridum aminovalericum and Eubacterium fissicatena. Consequently, its precise neighbourliness to any one of them depended on the selection of strains of the cluster. On the basis of the phylogenetic and phenotypic evidence presented in this paper, the designation of strain SR1T as Sporobacterium olearium gen. nov., sp. nov. is proposed. The type strain is SR1T (= DSM 12504T).

  12. Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model.

    PubMed

    Galano, Annia

    2007-03-08

    Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.

  13. Enumeration of human colonic bacteria producing phenolic and indolic compounds: effects of pH, carbohydrate availability and retention time on dissimilatory aromatic amino acid metabolism.

    PubMed

    Smith, E A; Macfarlane, G T

    1996-09-01

    Concentrations of phenolic compounds in human gut contents were more than fourfold higher in the distal colon (6.2 mmol kg-1) compared to the proximal bowel (1.4 mmol kg-1). Tryptophan metabolites were never found in more than trace amounts in large intestinal contents and phenol substituted fatty acids were the major products of aromatic amino acid fermentation that accumulated in the proximal colon, whereas phenol and p-cresol were more important in the distal gut, accounting for 70% of all products of dissimilatory aromatic amino acid metabolism. In vitro incubations of colonic material showed that phenol was produced most rapidly (1.0 mumol g-1 h-1), whereas indole was formed comparatively slowly (0.06 mumol g-1 h-1). Most probable number (MPN) estimations demonstrated that large populations of phenol and indole producing bacteria occur in the large intestine (range log10 9.8-11.5 (g dry wt faeces)-1, mean 10.6, N = 7). With respect to phenolic compounds, phenylacetate and phenylpropionate producers predominated, while indoleacetate-forming bacteria were the major tryptophan-utilizing organisms. Quantitation of products of dissimilatory aromatic amino acid metabolism in MPN tubes showed that phenol and phenylpropionate mainly accumulated at low sample dilutions, whereas phenylacetate, p-cresol, indoleacetate and indolepropionate were formed in greatest amounts at high sample dilutions. The significance of pH and carbohydrate availability with respect to aromatic amino acid metabolism was shown in batch culture fermentation studies, where net production of phenolic compounds by mixed populations of intestinal bacteria was reduced by approximately 33% during growth at pH 5.5 compared to pH 6.8, and by 60% in the presence of a fermentable carbohydrate. Experiments with 16 species of intestinal bacteria belonging to six different genera showed that environmental factors such as low pH and high carbohydrate availability markedly reduced dissimilatory aromatic amino

  14. Polymer optical fiber compound parabolic concentrator tip for enhanced coupling efficiency for fluorescence based glucose sensors.

    PubMed

    Hassan, Hafeez Ul; Nielsen, Kristian; Aasmul, Soren; Bang, Ole

    2015-12-01

    We demonstrate that the light excitation and capturing efficiency of fluorescence based fiber-optical sensors can be significantly increased by using a CPC (Compound Parabolic Concentrator) tip instead of the standard plane-cut tip. We use Zemax modelling to find the optimum CPC tip profile and fiber length of a polymer optical fiber diabetes sensor for continuous monitoring of glucose levels. We experimentally verify the improved performance of the CPC tipped sensor and the predicted production tolerances. Due to physical size requirements when the sensor has to be inserted into the body a non-optimal fiber length of 35 mm is chosen. For this length an average improvement in efficiency of a factor of 1.7 is experimentally demonstrated and critically compared to the predicted ideal factor of 3 in terms of parameters that should be improved through production optimization.

  15. Temporal variation in the deposition of polycyclic aromatic compounds in snow in the Athabasca Oil Sands area of Alberta.

    PubMed

    Manzano, Carlos A; Muir, Derek; Kirk, Jane; Teixeira, Camilla; Siu, May; Wang, Xiaowa; Charland, Jean-Pierre; Schindler, David; Kelly, Erin

    2016-09-01

    Atmospheric deposition of polycyclic aromatic compounds (PACs) via and onto snow, and their releasing during spring snowmelt has been a concern in the Athabasca Oil Sands Region of Alberta. This study was designed to evaluate the concentrations, loadings, and distribution of PACs in springtime snowpack and how they have changed since the first study in 2008. Snowpack samples were collected in late winters 2011-2014 at varying distances from the main developments. PAC concentration and deposition declined exponentially with distance, with pyrenes, chrysenes, and dibenzothiophenes dominating the distribution within the first 50 km. The distribution of PACs was different between sites located close to upgraders and others located close to mining facilities. Overall, PAC loadings were correlated with priority pollutant elements and water chemistry parameters, while wind direction and speed were not strong contributors to the variability observed. Total PAC mass deposition during winter months and within the first 50 km was initially estimated by integrating the exponential decay function fitted through the data using a limited number of sites from 2011 to 2014: 1236 kg (2011), 1800 kg (2012), 814 kg (2013), and 1367 (2014). Total loadings were estimated to have a twofold increase between 2008 and 2014, although the increase observed was not constant. Finally, kriging interpolation is presented as an alternative and more robust approach to estimate PAC mass deposition in the area. After a more intensive sampling campaign in 2014, the PAC mass deposition was estimated to be 1968 kg.

  16. Characterization of trace organic compounds associated with aged and diluted sidestream tobacco smoke in a controlled atmosphere—volatile organic compounds and polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Baek, Sung-Ok; Jenkins, Roger A.

    In this study, a wide range of volatile organic constituents of aged and diluted sidestream tobacco smoke (ADSS) were determined in a controlled atmosphere, where ADSS is the sole source of target compounds. The ADSS was generated in a 30 m 3 environmental test chamber using a variety of cigarettes, including the Kentucky 1R4F reference cigarette and eight commercial brands, and a total of 24 experimental runs were conducted. Target analytes were divided into three groups, i.e. vapor and particulate phase markers for environmental tobacco smoke (ETS), volatile organic compounds (VOC) including carbonyls, and polycyclic aromatic hydrocarbons (PAH). The VOC samples were collected on triple sorbent traps, and then analyzed by thermal desorption coupled with gas chromatography/mass spectrometry (GC/MS), while the carbonyl compounds were sampled on DNPH cartridges, being analyzed by HPLC. ETS particles in the chamber were collected by high volume sampling, and then used for the determination of PAHs by GC/MS. Among more than 30 target VOCs, acetaldehyde appeared to be the most abundant compound, followed by 2-methyl-1,3-butadiene, and formaldehyde. The results from the chamber study were further used to generate characterized ratios of selected VOCs to 3-ethenyl pyridine (3-EP), a vapor phase ETS marker. The ratios appeared to be in generally good agreement with published values in the literature. This suggests that the characteristic ratios may be useful for quantifying the impact of ETS on the VOC concentrations in 'real world' indoor environments, which are affected by a complex mixture of components from multiple sources. The yields of ETS markers from this study are all slightly lower than those estimated by other studies, while VOC yields are in reasonable agreement in many cases with values in the literature. Among 16 target PAHs, chrysene appeared to be most abundant, followed by benzo(a)anthracene (BaA) and benzo(a)pyrene (BaP). The average contents of BaP and

  17. Coutilization of glucose and glycerol enhances the production of aromatic compounds in an Escherichia coli strain lacking the phosphoenolpyruvate: carbohydrate phosphotransferase system

    PubMed Central

    Martínez, Karla; de Anda, Ramón; Hernández, Georgina; Escalante, Adelfo; Gosset, Guillermo; Ramírez, Octavio T; Bolívar, Francisco G

    2008-01-01

    Background Escherichia coli strains lacking the phosphoenolpyruvate: carbohydrate phosphotransferase system (PTS) are capable of coutilizing glucose and other carbon sources due to the absence of catabolite repression by glucose. In these strains, the lack of this important regulatory and transport system allows the coexistence of glycolytic and gluconeogenic pathways. Strains lacking PTS have been constructed with the goal of canalizing part of the phosphoenolpyruvate (PEP) not consumed in glucose transport to the aromatic pathway. The deletion of the ptsHIcrr operon inactivates PTS causing poor growth on this sugar; nonetheless, fast growing mutants on glucose have been isolated (PB12 strain). However, there are no reported studies concerning the growth potential of a PTS- strain in mixtures of different carbon sources to enhance the production of aromatics compounds. Results PB12 strain is capable of coutilizing mixtures of glucose-arabinose, glucose-gluconate and glucose-glycerol. This capacity increases its specific growth rate (μ) given that this strain metabolizes more moles of carbon source per unit time. The presence of plasmids pRW300aroGfbr and pCLtktA reduces the μ of strain PB12 in all mixtures of carbon sources, but enhances the productivity and yield of aromatic compounds, especially in the glucose-glycerol mixture, as compared to glucose or glycerol cultures. No acetate was detected in the glycerol and the glucose-glycerol batch fermentations. Conclusion Due to the lack of catabolite repression, PB12 strain carrying multicopy plasmids containing tktA and aroGfbr genes is capable of coutilizing glucose and other carbon sources; this capacity, reduces its μ but increases the production of aromatic compounds. PMID:18211716

  18. Ab initio and sup 17 O NMR study of aromatic compounds with dicoordinate oxygen atoms. (1) Methoxy- and (methylenedioxy)benzene derivatives

    SciTech Connect

    Biekofsky, R.R.; Pomilio, A.B.; Contreras, R.H. ); Orendt, A.M.; Facelli, J.C. )

    1990-09-20

    {sup 17}O NMR data at natural abundance in toluene-d{sub 8} at 74{degree}C were obtained for aromatic compounds containing methoxy and methylenedioxy groups as side-chains substituents. {sup 17}O chemical shifts of this series of compounds are significantly influenced by both electronic and steric effects. Ortho electronic and steric substituent chemical shift effects for methoxy and methylenedioxy groups were estimated. Ab initio calculations at the 4-31G level were used to determine geometries of the compounds to gain insight into the structural aspects of these compounds. A correlation between the calculated bond orders, P{sub C{sub Ar}P{minus}O}, and the {sup 17}O chemical shift was found.

  19. Application of a quantitative structure retention relationship approach for the prediction of the two-dimensional gas chromatography retention times of polycyclic aromatic sulfur heterocycle compounds.

    PubMed

    Gieleciak, Rafal; Hager, Darcy; Heshka, Nicole E

    2016-03-11

    Information on the sulfur classes present in petroleum is a key factor in determining the value of refined products and processing behavior in the refinery. A large part of the sulfur present is included in polycyclic aromatic sulfur heterocycles (PASHs), which in turn are difficult to desulfurize. Furthermore, some PASHs are potentially more mutagenic and carcinogenic than polycyclic aromatic hydrocarbons, PAHs. All of this calls for improved methods for the identification and quantification of individual sulfur species. Recent advances in analytical techniques such as comprehensive two-dimensional gas chromatography (GC×GC) have enabled the identification of many individual sulfur species. However, full identification of individual components, particularly in virgin oil fractions, is still out of reach as standards for numerous compounds are unavailable. In this work, a method for accurately predicting retention times in GC×GC using a QSRR (quantitative structure retention relationship) method was very helpful for the identification of individual sulfur compounds. Retention times for 89 saturated, aromatic, and polyaromatic sulfur-containing heterocyclic compounds were determined using two-dimensional gas chromatography. These retention data were correlated with molecular descriptors generated with CODESSA software. Two independent QSRR relationships were derived for the primary as well as the secondary retention characteristics. The predictive ability of the relationships was tested by using both independent sets of compounds and a cross-validation technique. When the corresponding chemical standards are unavailable, the equations developed for predicting retention times can be used to identify unknown chromatographic peaks by matching their retention times with those of sulfur compounds of known molecular structure.

  20. Stir bar sorptive extraction approaches with a home-made portable electric stirrer for the analysis of polycyclic aromatic hydrocarbon compounds in environmental water.

    PubMed

    Mao, Xiangju; Hu, Bin; He, Man; Fan, Wenying

    2012-10-19

    In this study, novel off/on-site stir bar sorptive extraction (SBSE) approaches with a home-made portable electric stirrer have been developed for the analysis of polycyclic aromatic hydrocarbon compounds (PAHs). In these approaches, a miniature battery-operated electric stirrer was employed to provide agitation of sample solutions instead of the commonly used large size magnetic stirrer powered by alternating current in conventional SBSE process, which could extend the SBSE technique from the conventional off-site analysis to the on-site sampling. The applicability of the designed off/on-site SBSE sampling approaches was evaluated by polydimethylsiloxane (PDMS) coating SBSE-high performance liquid chromatography-fluorescence detection (HPLC-FLD) analysis of six target PAHs in environmental water. The home-made portable electric stirrer is simple, easy-to-operate, user friendly, low cost, easy-to-be-commercialized, and can be processed in direct immersion SBSE, headspace sorptive extraction (HSSE) and continuous flow (CF)-SBSE modes. Since the stir bar was fixed onto the portable device by magnetic force, it is very convenient to install, remove and replace the stir bar, and the coating friction loss which occurred frequently in conventional SBSE process could be avoided. The parameters affecting the extraction of six target PAHs by the home-made portable SBSE sampling device with different sampling modes were studied. Under the optimum extraction conditions, good linearity was obtained by all of three SBSE extraction modes with correlation coefficient (R) higher than 0.9971. The limits of detection (LODs, S/N=3) were 0.05-3.41 ng L(-1) for direct immersion SBSE, 0.03-2.23 ng L(-1) for HSSE and 0.09-3.75 ng L(-1) for CF-SBSE, respectively. The proposed portable PDMS-SBSE-HPLC-FLD method was applied for the analysis of six target PAHs in East Lake water, and the analytical results obtained by on-site SBSE sampling were in good agreement with that obtained by off

  1. Fluorination of aromatic compounds by cleavage of aryl-tin bonds with F-18 F/sub 2/ and CH/sub 3/COOF

    SciTech Connect

    Adam, M.J.; Abeysekera, B.F.; Ruth, T.J.; Jivan, S.; Pate, B.D.

    1984-01-01

    Direct fluorination of aromatic nuclei is difficult since the reaction is usually accompanied by unselective, partial, or total replacement of hydrogen. By attaching the tri-n-butyltin moiety to one position of the ring one can achieve an enhanced reactivity and site selectivity toward electrophilic fluorination. The intent of this study was to demonstrate the utility of the fluorodestannylation reaction for fluorine labelling of aromatic compounds and to compare F/sub 2/ and acetyl hypofluorite as the fluorinating agents. Thus, eight stannylated aromatic compounds (1-8) were synthesized via lithium halogen exchange of the bromo precursor and subsequent transmetallation using tri-n-butyltin chloride. The stannylated substrates were treated with F-18 F/sub 2/ and -78/sup 0/C and CH/sub 3/COOF at room temperature. Both reagents gave good yields of labelled aryl fluorides. Overall, acetyl hypofluorite gave more consistent yields (approx. =70%), while F/sub 2/ gave more variable yields (54-95%). This method is currently being extended to label more complex systems such as L-Dopa with F-18 for brain studies with positron emission tomography. The authors have successfully stannylated Dopa on the ring and fluorination studies of this substrate are underway.

  2. Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

    SciTech Connect

    Ziegelgruber, Kate L.; Knope, Karah E.; Frisch, Mark; Cahill, Christopher L.

    2008-02-15

    A novel thorium (IV) coordination polymer, Th(C{sub 5}H{sub 2}N{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2} (1), has been prepared under the hydrothermal reaction of thorium nitrate tetrahydrate and 3,5-pyrazoledicarboxylic acid (H{sub 3}pdc). Compound 1 (orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.9362(5) A, b=10.7806(8) A, c=17.9915(14) A, Z=2, R{sub 1}=0.0210, wR{sub 2}=0.0470) consists of thorium metal centers connected via H{sub 3}pdc linkages to form an overall three-dimensional structure containing {pi}-{pi} interactions between the pyrazole rings. 2,3-Pyrazinedicarboxylic acid (H{sub 2}pzdc) was explored as well to (1) study the effect of the location of the carboxylic groups around the aromatic ring and (2) produce heterometallic compounds. Thorium (IV) and copper (II) were combined with H{sub 2}pzdc, resulting in an interesting decomposition reaction characterized though the isolation of Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) (monoclinic, C2/c, a=13.8507(12) A, b=7.8719(7) A, c=10.7961(16) A, {beta}=118.0310(10){sup o}, Z=2, R{sub 1}=0.0160, wR{sub 2}=0.0349), Cu(C{sub 6}H{sub 2}N{sub 2}O{sub 4}) (3) (monoclinic, C2/c, a=11.499(3) A, b=7.502(2) A, c=7.402(2) A, {beta}=93.892(5){sup o}, Z=4, R{sub 1}=0.0472, wR{sub 2}=0.0745) and Cu(C{sub 5}H{sub 3}N{sub 2}O{sub 2})(NO{sub 3})(H{sub 2}O) (4). The capture of these species provides mechanistic evidence for the formation of the oxalate anions observed in 2 via the decarboxylation of H{sub 2}pzdc to yield the linker in 4: 2-pyrazinecarboxylate anions. - Graphical abstract: 3,5-Pyrazoledicarboxylic and 2,3-pyridinedicarboxylic acid were utilized in synthesizing two novel thorium (IV) coordination polymers. Attempts to synthesize a Th-Cu bimetallic compound with 2,3-pyridinedicarboxylic acid resulted in a triphasic mixture (2, 3 and 4, respectively). The oxalate anion observed in Th(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}.2H{sub 2}O (2) is theorized to result from decarboxylation of 2

  3. Measurement of aromatic compounds in automobile exhaust gases with membrane inlet mass spectrometry equipped with an on-line-probe and an automatic Tenax-Sampler

    SciTech Connect

    Matz, G.; Walte, A.; Muenchmeyer, W.; Rikeit, H.E.

    1996-09-01

    A novel membrane inlet mass spectrometer is used to monitor organic compounds in combustion emissions. Different gas probes, which can be changed in minutes, have been developed for use in combination with the mobile mass spectrometer. With the On-Line-Probe, volatile organic compounds (BTXE) can be measured down to the ppm range with a cycle rate of one analysis per second. Time resolved measurements of aromatic compounds together with other exhaust gases can be done. By sampling with a polymer adsorbent, analysis with thermal desorption and GC/MS down to the ppb concentration range can be achieved. A six-fold Tenax-Sampler, connected to the mobile GC/MS system, is capable of taking and transferring the samples automatically. Because sampling with this device is independent from the analysis, measurements of narrow time windows in a dynamical process can be done easily. The whole analytical equipment was evaluated on-site through measurements on an engine test stand, a dynamometer and on the road during real traffic. It is shown, that time resolved quantitative measurements give information on the influence of special driving conditions (warm up, congestion) on the amount of aromatic compounds emitted by automobile exhausts.

  4. Simultaneous metabolism of chloro- and methyl-aromatic compounds by selected bacterial strains. Final report, 20 August 1991-19 August 1992

    SciTech Connect

    Focht, D.D.

    1993-05-27

    Microorganisms are frequently able to degrade anthropogenic materials using pathways that evolved for the assimilation of related naturally-occurring compounds. Complications can arise, however, during the metabolism of mixtures when incompatible intermediates are formed from different components. The breakdown of chloro- and methyl-aromatics, for example, produces catechols which are oxidized differently: chlorocatechols are normally cleaved by ortho fission and methylcatechols by meta fission. If both systems act simultaneously, suicide substrates or dead-end metabolites are usually formed. Nevertheless, bacteria differ in their, ability to cope with such mixtures. A unique bacterium, Pseudomonas cepacia MB2 was isolated by selective enrichment on 2-methylbenzoate, yet was also able to fortuitously utilize 3-chloro-2-methylbenzoate as a sole carbon source. This strain is unique in its ability to utilize an aromatic acid containing both a methyl and chloro substituent via the metafission pathway without the production of suicidal products.

  5. Kinetic solvent isotope effect in steady-state turnover by CYP19A1 suggests involvement of Compound 1 for both hydroxylation and aromatization steps

    PubMed Central

    Khatri, Yogan; Luthra, Abhinav; Duggal, Ruchia; Sligar(s), Stephen G.

    2014-01-01

    CYP19A1, or human aromatase catalyzes the conversion of androgens to estrogens in a three-step reaction through the formation of 19-hydroxy and 19-aldehyde intermediates. While the first two steps of hydroxylation are thought to proceed through a high-valent iron-oxo species, controversy exists surrounding the identity of the reaction intermediate that catalyzes the lyase and aromatization reaction. We investigated the kinetic isotope effect on the steady-state turnover of Nanodisc-incorporated human CYP19A1 to explore the mechanisms of this reaction. Our experiments reveal a significant (∼2.5) kinetic solvent isotope effect for the C10-C19 lyase reaction, similar to that of the first two hydroxylation steps (2.7 and 1.2). These data implicate the involvement of Compound 1 as a reactive intermediate in the final aromatization step of CYP19A1. PMID:24997347

  6. Creating and virtually screening databases of fluorescently-labelled compounds for the discovery of target-specific molecular probes

    NASA Astrophysics Data System (ADS)

    Kamstra, Rhiannon L.; Dadgar, Saedeh; Wigg, John; Chowdhury, Morshed A.; Phenix, Christopher P.; Floriano, Wely B.

    2014-11-01

    Our group has recently demonstrated that virtual screening is a useful technique for the identification of target-specific molecular probes. In this paper, we discuss some of our proof-of-concept results involving two biologically relevant target proteins, and report the development of a computational script to generate large databases of fluorescence-labelled compounds for computer-assisted molecular design. The virtual screening of a small library of 1,153 fluorescently-labelled compounds against two targets, and the experimental testing of selected hits reveal that this approach is efficient at identifying molecular probes, and that the screening of a labelled library is preferred over the screening of base compounds followed by conjugation of confirmed hits. The automated script for library generation explores the known reactivity of commercially available dyes, such as NHS-esters, to create large virtual databases of fluorescence-tagged small molecules that can be easily synthesized in a laboratory. A database of 14,862 compounds, each tagged with the ATTO680 fluorophore was generated with the automated script reported here. This library is available for downloading and it is suitable for virtual ligand screening aiming at the identification of target-specific fluorescent molecular probes.

  7. Comparison of aryl hydrocarbon hydroxylase and acetanilide 4-hydroxylase induction by polycyclic aromatic compounds in human and mouse cell lines.

    PubMed

    Jaiswal, A K; Nebert, D W; Eisen, H W

    1985-08-01

    The human MCF-7 and the mouse Hepa-1 cell culture lines were compared for aryl hydrocarbon hydroxylase and acetanilide 4-hydroxylase inducibility by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and benzo[a]anthracene (BA) and TCDD- and BA-specific binding in the cytosol and nucleus. The effective concentration of BA in the growth medium required to induce either enzyme to 50% of its maximally inducible activity (EC50) was the same (5-11 microM) in both MCF-7 and Hepa-1 cells. On the other hand, the EC50 for TCDD in MCF-7 cells (5-25 nM) was more than 40-fold greater than that in Hepa-1 cells (0.4 to 0.6 nM). P1-450- and P3-450-specific mouse cDNA probes were used to quantitate mRNA induction in the Hepa-1 cell line. P1-450 mRNA was induced markedly by TCDD and benzo[a] anthracene, whereas P3-450 mRNA was induced negligibly. A P1-450-specific human cDNA probe was used to quantitate P1-450 mRNA induction in the MCF-7 cell line. Aryl hydrocarbon hydroxylase inducibility by TCDD or BA always paralleled P1-450 mRNA inducibility in either the mouse or human line. Although the cytosolic Ah receptor in Hepa-1 cells was easily detected by sucrose density gradient centrifugation, gel permeation chromatography, and anion-exchange high-performance liquid chromatography, the cytosolic receptor cannot be detected in MCF-7 cells. Following in vivo exposure of cultures to radiolabeled TCDD, the intranuclear concentration of inducer-receptor complex was at least fifty times greater in Hepa-1 than MCF-7 cultures. The complete lack of measurable cytosolic receptor and almost totally absent inducer-receptor complex in the nucleus of MCF-7 cells was, therefore, out of proportion to its capacity for aryl hydrocarbon hydroxylase and acetanilide 4-hydroxylase inducibility. This MCF-7 line should provide an interesting model for a better understanding of the mechanisms of drug-metabolizing enzyme induction by polycyclic aromatic compounds, including the Ah receptor-mediated mechanism.

  8. Antigenicity of sulfanilamide and its metabolites using fluorescent-labelled compounds.

    PubMed

    Eyanagi, R; Toda, A; Ishii, Y; Saito, H; Soeda, S; Shimeno, H; Shigematsu, H

    2005-09-01

    In order to clarify the onset mechanisms of drug-induced allergies, three fluorescent-labelled compounds were synthesized by subjecting sulfanilamide (SA), a base compound for sulfonamides, and its active metabolites, i.e. sulfanilamide hydroxylamine and sulfanilamide nitroso, to dansylation using dansylchloride. In other words, 5-dimethylamino-N-(4-aminobenzyl)-naphthalenesulfonamide (DNS-4ABA), 5-dimethylamino-N-(4-hydroxylaminobenzyl)-1-naphthalenesulfonamide (DNS-4HABA) and 5-dimethylamino-N-(4-nitrosobenzyl)-1-naphthalenesulfonamide (DNS-4NSBA) were synthesized as model haptens. When analysed by HPLC, a conjugate of DNS-4HABA and glutathione (GSH) with nucleophilic amino acids had two peaks (P-1 and P-2). FAB-MS and 1H-NMR revealed that the DNS-4HABA-GSH conjugate consisted of sulphinamide and semimercaptal. The reactivity of GSH to DNS-4ABA, DNS-4HABA and DNS-4NSBA was quantified by HPLC using an oxidization system (horseradish peroxidase/H2O2). The results show that production of DNS-4NSBA-GSH-conjugate was four to eight times higher than that of DNS-4HABA-GSH conjugate, but that DNS-4ABA did not bind with GSH. Skin reactions were assessed using guinea pigs, and strong delayed erythema was seen with DNS-4NSBA, which bound most strongly with GSH, whereas weak delayed erythema was seen with DNS-4ABA, which did not bind with GSH. This suggests a correlation between GSH conjugate production and skin reactions. DNS-4HABA enzymatically bound with proteins in rat and guinea pig liver cytosol and microsomal fractions. The proteins that bound to DNS-4HABA were purified by HPLC and then subjected to N-terminal amino acid analysis. Ubiquitin (10 kDa) and fatty acid binding protein (30 kDa) were detected in the rat liver cytosol fraction; retinol-dehydrogenase (35 kDa) in the rat microsomal fraction; and glutathione-S-transferase B (mmu) (25 kDa) in the guinea pig liver cytosol fraction. When DNS-4HABA or DNS-4NSBA binds to proteins that play important roles in the body

  9. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Compounds and Their Ions. 7; Phenazine, a Dual Substituted Polycyclic Aromatic Nitrogen Heterocycle

    NASA Technical Reports Server (NTRS)

    Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W., Jr.; Allamandola, L. J.

    2004-01-01

    The matrix-isolation technique has been employed to measure the mid-infrared spectra of phenazine (C12H8N2), a dual substituted Polycyclic Aromatic Nitrogen Heterocycle (PANH), in the neutral, cationic and anionic forms. The experimentally measured band frequencies and intensities are tabulated and compared with their calculated values as well as those of the non-substituted parent molecule, anthracene. The theoretical band positions and intensities were calculated using both the 3-31 G as well as the larger 6-3lG* Basis Sets. A comparison of the results can be found in the tables. The spectroscopic properties of phenazine and its cation are similar to those observed in mono-substituted PANHs, with one exception. The presence of a second nitrogen atom results in an additional enhancement of the cation's total integrated intensity, for the 1500-1000 cm(sup -1) (6.7 to 10 micron) region, over that observed for a mono-substituted PANH cation. The significance of this enhancement and the astrobiological implications of these results are discussed.

  10. USE OF FLUORESCENT POLYCYLIC AROMATIC HYDROCARBON PROBES IN STUDYING THE IMPACT OF COLLOIDS ON POLLUTANT TRANSPORT IN GROUNDWATER

    EPA Science Inventory

    A fluorescence-quenching method was developed to assess the hydrophobic organic pollutant binding potential of organic colloids (OC) in unaltered natural waters. This method allows (1) direct assessment of the importance of OC-enhanced pollutant transport for environmental sam- p...

  11. Analysis of EU priority polycyclic aromatic hydrocarbons in food supplements using high performance liquid chromatography coupled to an ultraviolet, diode array or fluorescence detector.

    PubMed

    Danyi, Sophie; Brose, François; Brasseur, Catherine; Schneider, Yves-Jacques; Larondelle, Yvan; Pussemier, Luc; Robbens, Johan; De Saeger, Sarah; Maghuin-Rogister, Guy; Scippo, Marie-Louise

    2009-02-09

    High performance liquid chromatography coupled to an ultraviolet, diode array or fluorescence detector (HPLC/UV-FLD) has been used to set up a method to detect the 15(+1) EU priority polycyclic aromatic hydrocarbons (PAHs) in food supplements covering the categories of dried plants and plant extracts excluding oily products. A mini validation was performed and the following parameters have been determined: limit of detection, limit of quantification, precision, recovery and linearity. They were in close agreement with quality criteria described in the Commission Regulation (EC) No 333/2007 concerning the PAH benzo[a]pyrene in foodstuffs, except the not fluorescent cyclopenta[c,d]pyrene for which the UV detection leads to a higher limit of detection. Analysis of twenty commercial food supplements covering mainly the class of dried plants was performed to evaluate their PAHs contamination levels and to test the applicability of the method to various plant matrices. Fifty percent of analyzed samples showed concentration exceeding 2 microgkg(-1) for one or more PAHs.

  12. Application of p-toluidine in chromogenic detection of catechol and protocatechuate, diphenolic intermediates in catabolism of aromatic compounds

    SciTech Connect

    Parke, D. )

    1992-08-01

    In the presence of p-toluidine and iron, protocatechuate and catechols yield color. Inclusion of p-toluidine in media facilities the screening of microbial strains for alterations affecting aromatic catabolism. Such strains include mutants affected in the expression of oxygenases and Escherichia coli colonies carrying cloned or subcloned aromatic catabolic genes which encode enzymes giving rise to protocatechuate or catechol. The diphenolic detection system can also be applied to the creation of vectors relying on insertion of cloned DNA into one of the latter marker genes.

  13. Steady-state and time resolved fluorescence analysis on tyrosine-histidine model compounds.

    PubMed

    Voicescu, Mariana; Heinrich, Martine; Hellwig, Petra

    2009-03-01

    Four model compounds, for a tyrosine-histidine covalent bonding, 2-(5-imidazolyl)-4-methylphenol (C-C bonding in ortho-position at the phenyl group); 2'-(1-imidazolyl)-4-methylphenol (C-N bonding in ortho'-position at the phenyl group); 2-(5-imidazolyl)-4-H-phenol and 2-(5-imidazolyl)-4-H-phenol, at physiological pH have been studied by UV-Vis absorption, steady-state and time resolved fluorescence spectroscopy. Their absorption and emission properties are presented and discussed. The photophysical properties depend on the para-substituted phenyl group as well as on C-C/C-N bonding in the Phenol-Imidazole linkage. The N position, N1-N3/N1-N4, in the imidazole group was found to be relevant. The results are discussed with relevance to the redox processes of tyrosine and to better understand the role of a tyrosine-histidine covalent linkage as found in cytochrome c oxidase.

  14. Diterpenoids and aromatic compounds from the three New Zealand liverworts Jamesoniella kirkii, Balantiopsis rosea, and Radula species.

    PubMed

    Nagashima, Fumihiro; Kuba, Yoshiyuki; Asakawa, Yoshinori

    2006-06-01

    Three new aromatics were isolated from the New Zealand liverwort Balantiopsis rosea. A new bibenzyl was isolated from an unidentified Radula species, together with known bibenzyls. Jamesoniella kirkii yielded three known ent-isopimarane and two ent-kaurane diterpenoids. Their structures were confirmed by NMR techniques, chemical reaction, and X-ray crystallographic analysis.

  15. Technical description of candidate fluorescence compounds and radioisotopes for a nuclear smuggling deterrence tag (IL500E)

    SciTech Connect

    Hartenstein, S.D.; Aryaeinejad, R.

    1996-03-01

    This report summarizes the efforts completed in identifying candidate fluorescence compounds and radioisotopes for a developing tagging system. The tagging system is being developed as a deterrent to nuclear smuggling, by providing a means of: (1) tracing materials and pilferers to the facility of origin for any recovered special nuclear materials; (2) inventory control of long-term stored items containing special nuclear materials; and (3) tracking materials transferred between facilities. The tagging system uses four types of tagging materials to cover a range of applications intended to prevent the pilfering of special nuclear materials. One material, fluorescent compounds which are invisible without ultraviolet or near-infrared detection systems, is marked on controlled items with a tracking pattern that corresponds to a specified item in a specified location in the data control system. The tagging system uses an invisible, fluorescent dusting powder to mark equipment and personnel who inappropriately handle the tagged material. The tagging system also uses unique combinations of radionuclides to identify the facility of origin for any special nuclear material. Currently, 18 long-lived radioisotopes, 38 short-live radioisotopes and 10 fluorescent compounds have been selected as candidate materials for the tagging system.

  16. Graphene stabilized ultra-small CuNi nanocomposite with high activity and recyclability toward catalysing the reduction of aromatic nitro-compounds

    NASA Astrophysics Data System (ADS)

    Fang, Hao; Wen, Ming; Chen, Hanxing; Wu, Qingsheng; Li, Weiying

    2015-12-01

    Nowadays, it is of great significance and a challenge to design a noble-metal-free catalyst with high activity and a long lifetime for the reduction of aromatic nitro-compounds. Here, a 2D structured nanocomposite catalyst with graphene supported CuNi alloy nanoparticles (NPs) is prepared, and is promising for meeting the requirements of green chemistry. In this graphene/CuNi nanocomposite, the ultra-small CuNi nanoparticles (~2 nm) are evenly anchored on graphene sheets, which is not only a breakthrough in the structures, but also brings about an outstanding performance in activity and stability. Combined with a precise optimization of the alloy ratios, the reaction rate constant of graphene/Cu61Ni39 reached a high level of 0.13685 s-1, with a desirable selectivity as high as 99% for various aromatic nitro-compounds. What's more, the catalyst exhibited a unprecedented long lifetime because it could be recycled over 25 times without obvious performance decay or even a morphology change. This work showed the promise and great potential of noble-metal-free catalysts in green chemistry.Nowadays, it is of great significance and a challenge to design a noble-metal-free catalyst with high activity and a long lifetime for the reduction of aromatic nitro-compounds. Here, a 2D structured nanocomposite catalyst with graphene supported CuNi alloy nanoparticles (NPs) is prepared, and is promising for meeting the requirements of green chemistry. In this graphene/CuNi nanocomposite, the ultra-small CuNi nanoparticles (~2 nm) are evenly anchored on graphene sheets, which is not only a breakthrough in the structures, but also brings about an outstanding performance in activity and stability. Combined with a precise optimization of the alloy ratios, the reaction rate constant of graphene/Cu61Ni39 reached a high level of 0.13685 s-1, with a desirable selectivity as high as 99% for various aromatic nitro-compounds. What's more, the catalyst exhibited a unprecedented long lifetime

  17. Far infrared (terahertz) spectroscopy of a series of polycyclic aromatic hydrocarbons and application to structure interpretation of asphaltenes and related compounds

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco; Angelini, Giancarlo; García-Hernández, D. A.; Manchado, Arturo

    2013-07-01

    A series of 33 different polycyclic aromatic hydrocarbons (PAHs) were studied by far infrared spectroscopy (terahertz spectroscopy) in the spectral range comprised between 600 and 50 cm-1. In addition to common PAHs like naphthalene, anthracene, phenanthrene, fluoranthene, picene, pyrene, benzo[α]pyrene, and perylene, also quite unusual PAHs were studied like tetracene, pentacene, acenaphtene, acenaphtylene, triphenylene, and decacyclene. A series of alkylated naphthalenes and anthracenes were studied as well as methypyrene. Partially or totally hydrogenated PAHs were also object of the present investigation, ranging from tetrahydronaphthalene (tetralin) to decahydronaphthalene (decalin), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, hexahydropyrene, and dodecahydrotriphenylene. Finally, the large and quite rare PAHs coronene, quaterrylene, hexabenzocoronene, and dicoronylene were studied by far infrared spectroscopy. The resulting reference spectra were used in the interpretation of the chemical structure of asphaltenes (as extracted from a heavy petroleum fraction and from bitumen), the chemical structures of other petroleum fractions known as DAE (distillate aromatic extract) and RAE (residual aromatic extract), and a possible interpretation of components of the chemical structure of anthracite coal. Asphaltenes, heavy petroleum fractions, and coal were proposed as model compounds for the interpretation of the emission spectra of certain proto-planetary nebulae (PPNe) with a good matching in the mid infrared between the band pattern of the PPNe emission spectra and the spectra of these oil fractions or coal. Although this study was finalized in an astrochemical context, it may find application also in the petroleum and coal chemistry.

  18. Far infrared (terahertz) spectroscopy of a series of polycyclic aromatic hydrocarbons and application to structure interpretation of asphaltenes and related compounds.

    PubMed

    Cataldo, Franco; Angelini, Giancarlo; García-Hernández, D Aníbal; Manchado, Arturo

    2013-07-01

    A series of 33 different polycyclic aromatic hydrocarbons (PAHs) were studied by far infrared spectroscopy (terahertz spectroscopy) in the spectral range comprised between 600 and 50 cm(-1). In addition to common PAHs like naphthalene, anthracene, phenanthrene, fluoranthene, picene, pyrene, benzo[α]pyrene, and perylene, also quite unusual PAHs were studied like tetracene, pentacene, acenaphtene, acenaphtylene, triphenylene, and decacyclene. A series of alkylated naphthalenes and anthracenes were studied as well as methypyrene. Partially or totally hydrogenated PAHs were also object of the present investigation, ranging from tetrahydronaphthalene (tetralin) to decahydronaphthalene (decalin), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, hexahydropyrene, and dodecahydrotriphenylene. Finally, the large and quite rare PAHs coronene, quaterrylene, hexabenzocoronene, and dicoronylene were studied by far infrared spectroscopy. The resulting reference spectra were used in the interpretation of the chemical structure of asphaltenes (as extracted from a heavy petroleum fraction and from bitumen), the chemical structures of other petroleum fractions known as DAE (distillate aromatic extract) and RAE (residual aromatic extract), and a possible interpretation of components of the chemical structure of anthracite coal. Asphaltenes, heavy petroleum fractions, and coal were proposed as model compounds for the interpretation of the emission spectra of certain proto-planetary nebulae (PPNe) with a good matching in the mid infrared between the band pattern of the PPNe emission spectra and the spectra of these oil fractions or coal. Although this study was finalized in an astrochemical context, it may find application also in the petroleum and coal chemistry.

  19. Detection of Non-aromatic Organic Compounds in Meteorites using Imaging Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Scott, J. R.; Hinman, N. W.; Richardson, C. D.; Mahon, R. C.; McJunkin, T. R.

    2009-12-01

    Our most extensive understanding of extraterrestrial organic matter is based on what has been learned from meteorites that have been delivered naturally to Earth. Meteorites have been analyzed by a variety of techniques ranging from extensive sample preparation with extraction and subsequent chromatography to direct laser desorption mass spectrometry (LDMS). While extraction studies have reported a variety of organics (e.g., aliphatic and aromatic hydrocarbons, ketones, aldehydes, and amino acids), LDMS studies have only reported polycyclic aromatic hydrocarbons (PAHs). This is rather surprising considering that Yan et al. (Talanta 2007, 72, 634-641) reported that even a small amount of PAH enables the detection of organics that are not otherwise ionized during the desorption event from minerals. Therefore, we have begun re-investigating meteorites because, regardless of the source of the organic compounds, the presences of PAHs should allow other organic molecules to be observed using imaging laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (LD-FTICR-MS). Indeed, we have mapped meteorites (e.g., EETA 79001) and found many mass-to-charge peaks that are non-aromatic as determined by analysis of their mass defects. Mapping also revealed that the distribution of organics is heterogeneous, which necessitates the collection of a mass spectrum from a single laser shot so that minor peaks of interest are not lost in signal averaging. These studies have implications for analyzing future returned samples from Mars or elsewhere with minimal preparation or damage.

  20. Validated analytical strategy for the determination of polycyclic aromatic compounds in marine sediments by liquid chromatography coupled with diode-array detection and mass spectrometry.

    PubMed

    González-Piñuela, Cristina; Alonso-Salces, Rosa M; Andrés, Ana; Ortiz, Inmaculada; Viguri, Javier R

    2006-10-06

    The aim of this work was to optimise and validate the experimental conditions for the analysis of 20 polycyclic aromatic compounds (PACs) [19 polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophene as polycyclic aromatic sulphur heterocycle (PASH)] in marine sediments by reversed-phase high-performance liquid chromatography (LC) coupled to photodiode array detection (DAD) and to mass spectrometry (MS). The LC-MS interface used was atmospheric pressure chemical ionization (APCI) in the positive ion mode. The operational parameters of the APCI interface and MS detection, such as organic modifier, fragmentation voltage, gain, vaporizer temperature, corona current, capillary voltage, drying gas (N2) and nebulizer pressure, were studied. The sediments were subjected to microwave-assisted solvent extraction (MAE) and clean-up by solid-phase extraction (SPE). The relevance of the selected PACs lies in the fact that 16 PACs are classified by the US Environmental Protection Agency as priority pollutants; 17 PACs are detected in the Prestige oil spill; and 8 PACs are included in the priority substance list of the EU water policy. Recoveries from 47% to 102% were obtained for SRM 1944 certified reference sediment. The limits of quantitation were lower than 100 ngg(-1) dry weight for most PACs, and good precision was achieved.

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

    PubMed

    Ariyasena, Thiloka C; Poole, Colin F

    2014-09-26

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

  2. Surfactants, Aromatic and Isoprenoid Compounds, and Fatty Acid Biosynthesis Inhibitors Suppress Staphylococcus aureus Production of Toxic Shock Syndrome Toxin 1▿

    PubMed Central

    McNamara, Peter J.; Syverson, Rae Ellen; Milligan-Myhre, Kathy; Frolova, Olga; Schroeder, Sarah; Kidder, Joshua; Hoang, Thanh; Proctor, Richard A.

    2009-01-01

    Menstrual toxic shock syndrome is a rare but potentially life-threatening illness manifest through the actions of Staphylococcus aureus toxic shock syndrome toxin 1 (TSST-1). Previous studies have shown that tampon additives can influence staphylococcal TSST-1 production. We report here on the TSST-1-suppressing activity of 34 compounds that are commonly used additives in the pharmaceutical, food, and perfume industries. Many of the tested chemicals had a minimal impact on the growth of S. aureus and yet were potent inhibitors of TSST-1 production. The TSST-1-reducing compounds included surfactants with an ether, amide, or amine linkage to their fatty acid moiety (e.g., myreth-3-myristate, Laureth-3, disodium lauroamphodiacetate, disodium lauramido monoethanolamido, sodium lauriminodipropionic acid, and triethanolamine laureth sulfate); aromatic compounds (e.g. phenylethyl and benzyl alcohols); and several isoprenoids and related compounds (e.g., terpineol and menthol). The membrane-targeting and -altering effects of the TSST-1-suppressing compounds led us to assess the activity of molecules that are known to inhibit fatty acid biosynthesis (e.g., cerulenin, triclosan, and hexachlorophene). These compounds also reduced S. aureus TSST-1 production. This study suggests that more additives than previously recognized inhibit the production of TSST-1. PMID:19223628

  3. Development of analytical method for catechol compounds in mouse urine using hydrophilic interaction liquid chromatography with fluorescence detection.

    PubMed

    Kanamori, Takahiro; Isokawa, Muneki; Funatsu, Takashi; Tsunoda, Makoto

    2015-03-15

    An analytical method for catecholamines and related compounds using hydrophilic interaction liquid chromatography (HILIC) with native fluorescence detection has been developed. We found that ZIC-cHILIC with phosphorylcholine was suitable for the separation of catechol compounds with good peak shapes among six different HILIC columns (Inertsil SIL, Inertsil Amide, Inertsil Diol, TSKgel NH2-100, ZIC-HILIC, and ZIC-cHILIC). Using ZIC-cHILIC, eight catechol compounds (dopamine, epinephrine, norepinephrine, 3,4-dihydroxyphenylalanine, 3,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylglycol, 3,4-dihydroxymandelic acid, and internal standard 3,4-dihydroxybenzylamine) were separated within 15min. The limit of detection at a signal to noise ratio of 3 was 3-28nM. An improved sensitivity was obtained as compared to that of reversed-phase liquid chromatography. This was partly attributed to the increase in the fluorescence intensity of the catechol compounds in the acetonitrile-rich mobile phase. Solid phase extraction using a monolithic silica disk-packed spin column with phenylboronate moieties, which have affinity to catechol compounds, was performed for the selective extraction of catechol compounds from mouse urine. Dopamine, epinephrine, norepinephrine, 3,4-dihydroxyphenylalanine, and 3,4-dihydroxyphenylglycol were successfully quantified in mouse urine.

  4. Magnetic microsphere-confined graphene for the extraction of polycyclic aromatic hydrocarbons from environmental water samples coupled with high performance liquid chromatography-fluorescence analysis.

    PubMed

    Wang, Weina; Ma, Ruiyang; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2013-06-07

    In this paper, a magnetic microsphere-confined graphene adsorbent (Fe3O4@SiO2-G) was fabricated and used for the extraction of five polycyclic aromatic hydrocarbons (fluorene, anthracene, phenanthrene, fluoranthene and pyrene) from environmental water samples prior to high performance liquid chromatography with fluorescence detection. The Fe3O4@SiO2-G was characterized by various instrumental methods. Various experimental parameters that could affect the extraction efficiencies, such as the amount of Fe3O4@SiO2-G, the pH and ionic strength of sample solution, the extraction time and the desorption conditions, were investigated. Due to the high surface area and excellent adsorption capacity of the Fe3O4@SiO2-G, satisfactory extraction can be achieved with only 15mg of the adsorbent per 250mL solution and 5min extraction. Under the optimum conditions, a linear response was observed in the concentration range of 5-1500ngL(-1) for fluorene, 2.5-1500ngL(-1) for anthracene and 15-1500ngL(-1) for phenanthrene, fluoranthene and pyrene, with the correlation coefficients (r) ranging from 0.9897 to 0.9961. The limits of detection (S/N=3) of the method were between 0.5 and 5.0ngL(-1). The relative standard deviations (RSDs) were less than 5.6%. The recoveries of the method were in the range between 83.2% and 108.2%. The results indicated that this graphene-based magnetic nanocomposite had a great adsorptive ability toward the five polycyclic aromatic hydrocarbons from environmental water samples.

  5. Heterolytic Activation of Hydrogen Promoted by Ruthenium Nanoparticles immobilized on Basic Supports and Hydrogenation of Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Fang, Minfeng

    Despite the aggressive development and deployment of new renewable and nuclear technologies, petroleum-derived transportation fuels---gasoline, diesel and jet fuels---will continue to dominate the markets for decades. Environmental legislation imposes severe limits on the tolerable proportion of aromatics, sulfur and nitrogen contents in transportation fuels, which is difficult to achieve with current refining technologies. Catalytic hydrogenation plays an important role in the production of cleaner fuels, both as a direct means to reduce the aromatics and as a key step in the hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) processes. However, conventional catalysts require drastic conditions and/or are easily poisoned by S or N aromatics. Therefore, there is still a need for new efficient catalysts for hydrogenation reactions relevant to the production of cleaner fossil fuels. Our catalyst design involves metallic nanoparticles intimately associated with a basic support, with the aim of creating a nanostructure capable of promoting the heterolytic activation of hydrogen and ionic hydrogenation mechanisms, as a strategy to avoid catalyst poisoning and enhance catalytic activity. We have designed and prepared a new nanostructured catalytic material composed of RuNPs immobilized on the basic polymer P4VPy. We have demonstrated that the Ru/P4VPy catalyst can promote heterolytic hydrogen activation and a unique surface ionic hydrogenation mechanism for the efficient hydrogenation of N-aromatics. This is the first time these ionic hydrogenation pathways have been demonstrated on solid surfaces. For the RuNPs surfaces without basic sites in close proximity, the conventional homolytic H2 splitting is otherwise involved. Using the mechanistic concepts from Ru/P4VPy, we have designed and prepared the Ru/MgO catalyst, with the aim to improve the catalytic efficiency for the hydrogenation of heteroatom aromatics operating by the ionic hydrogenation mechanism. The Ru

  6. Optimization of H3O+/O2+ Dual-mode Ionization in PTR-MS for Simultaneous Detection of Alkanes, Olefins and Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Amador-Muñoz, O.; Misztal, P. K.; Weber, R.; Drozd, G.; Worton, D. R.; Goldstein, A. H.

    2014-12-01

    Measurements of VOC composition from fossil fuels are analytically challenging because of the complex mixture of hydrocarbons (saturated, unsaturated, aromatics, etc). Speciated chemical measurements typically rely on relatively slow GC separation. Proton transfer reaction mass spectrometry (PTR-MS) is advantageous due to its fast response and high sensitivity. The most common ionization mechanism applied to VOC detection by PTR-MS is proton transfer from hydronium ion (H3O+). However, alkanes cannot be detected using H3O+ ionization chemistry because their proton affinities are too low. Ionization of alkanes is possible via electron transfer and/or hydride abstraction using O2+ or NO+. We used PTR-MS to analyze aromatic, alkene and alkane (linear, branched and cyclic) compounds simultaneously not by switching the ionization agents, but by adjusting the drift tube voltage and optimizing the ratio of H3O+/O2+ produced in the instrument's ion source. The highest detection sensitivity for aromatic and alkene compounds was produced by proton transfer from H3O+, while hydride abstraction by O2+ allowed detection of alkanes. For alkanes, sensitivities ranged from 1.1±0.01 cps/ppbv for n-decane to 74.7±0.25 cps/ppbv for decalin. Sensitivities in O2+ mode were from 6 (Adamantane) to 146 (4-Methyl nonane) times higher than those obtained in H3O+ mode under the same ion source and drift tube voltage conditions. Sensitivities for butyl benzene and 1-decene were 157±0.57 and 66.8±0.21 cps/ppbv, respectively. Sensitivity differences among C10 hydrocarbons are related to their structure, which affects their ionization energies (IE) and hence ease of hydride abstraction. Sensitivities at the parent ion mass were inversely correlated with IE (142 cps/ppbv/eV). This suggests higher electronic stability for cyclic non substituted compounds, followed by cyclic substituted, branch linear and linear C10 hydrocarbons. Although selectivity is a known shortcoming of quadrupole

  7. Laser-induced fluorescence detection strategies for sodium atoms and compounds in high-pressure combustors

    NASA Technical Reports Server (NTRS)

    Weiland, Karen J. R.; Wise, Michael L.; Smith, Gregory P.

    1993-01-01

    A variety of laser-induced fluorescence schemes were examined experimentally in atmospheric pressure flames to determine their use for sodium atom and salt detection in high-pressure, optically thick environments. Collisional energy transfer plays a large role in fluorescence detection. Optimum sensitivity, at the parts in 10 exp 9 level for a single laser pulse, was obtained with the excitation of the 4p-3s transition at 330 nm and the detection of the 3d-3p fluorescence at 818 nm. Fluorescence loss processes, such as ionization and amplified spontaneous emission, were examined. A new laser-induced atomization/laser-induced fluorescence detection technique was demonstrated for NaOH and NaCl. A 248-nm excimer laser photodissociates the salt molecules present in the seeded flames prior to atom detection by laser-induced fluorescence.

  8. A Lewis acid-promoted cyclization of ethenetricarboxylate derivative aromatic compounds. Novel syntheses of oxindoles and benzofuranones via Friedel-Crafts intramolecular Michael addition.

    PubMed

    Yamazaki, Shoko; Morikawa, Satoshi; Iwata, Yuko; Yamamoto, Machiko; Kuramoto, Kaori

    2004-11-07

    A novel cyclization reaction of ethenetricarboxylate derivative aromatic compounds in the presence of various Lewis acids gave benzo-annulated cyclic compounds such as oxindole and benzofuran derivatives via Friedel-Crafts intramolecular Michael addition in high yields. For example, the reaction of diethyl 2-[(N-methyl-N-phenylcarbamoyl)methylene]malonate (1a) in the presence of ZnCl2 at room temperature gave diethyl 2-(1-methyl-2-oxoindolin-3-yl)malonate (2a) in 98% yield. The reactions also proceeded with a catalytic amount of a Lewis acid such as AlCl3, ZnCl2, ZnBr2, Sc(OTf)3, or InBr3.

  9. Use of green fluorescent protein labeled non-tuberculous mycobacteria to evaluate the activity quaternary ammonium compound disinfectants and antibiotics.

    PubMed

    Cortesia, Claudia; Bello, Teresita; Lopez, Gustavo; Franzblau, Scott; de Waard, Jacobus; Takiff, Howard

    Although infections with NonTuberculous Mycobacteria have become less common in AIDS patients, they are important opportunistic infections after surgical procedures, likely because they are ubiquitous and not efficiently killed by many commonly used disinfectants. In Venezuela there have recently been many non-tuberculous mycobacteria soft tissue infections after minor surgical procedures, some apparently related to the use of a commercial disinfectant based on a Quaternary Ammonium Compound. We studied the activity of this and other quaternary ammonium compounds on different non-tuberculous mycobacteria by transforming the mycobacteria with a dnaA-gfp fusion and then monitoring fluorescence to gauge the capacity of different quaternary ammonium compounds to inhibit bacterial growth. The minimum inhibitory concentration varied for the different quaternary ammonium compounds, but M. chelonae and M. abscessus were consistently more resistant than M. smegmatis, and M. terrae more resistant than M. bovis BCG.

  10. Preparation of an aminopropyl imidazole-modified silica gel as a sorbent for solid-phase extraction of carboxylic acid compounds and polycyclic aromatic hydrocarbons.

    PubMed

    Wang, Na; Guo, Yong; Wang, Licheng; Liang, Xiaojing; Liu, Shujuan; Jiang, Shengxiang

    2014-05-21

    In this paper, a kind of aminopropyl imidazole-modified silica sorbent was synthesized and used as a solid-phase extraction (SPE) sorbent for the determination of carboxylic acid compounds and polycyclic aromatic hydrocarbons (PAHs). The resultant aminopropyl imidazole-modified silica sorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA) to ensure the successful binding of aminopropyl imidazole on the surface of silica gel. Then the aminopropyl imidazole-modified silica sorbent served as a SPE sorbent for the enrichment of carboxylic acid compounds and PAHs. The new sorbent exhibited high extraction efficiency towards the tested compounds and the results show that such a sorbent can offer multiple intermolecular interactions: electrostatic, π-π, and hydrophobic interactions. Several parameters affecting the extraction recovery, such as the pH of sample solution, the pH of eluent, the solubility of eluent, the volume of eluent, and sample loading, were also investigated. Under the optimized conditions, the proposed method was applied to the analysis of four carboxylic acid compounds and four PAHs in environmental water samples. Good linearities were obtained for all the tested compounds with R(2) larger than 0.9903. The limits of detection were found to be in the range of 0.0065-0.5 μg L(-1). The recovery values of spiked river water samples were from 63.2% to 112.3% with relative standard deviations (RSDs) less than 10.1% (n = 4).

  11. Investigation of the distribution of organochlorine and polycyclic aromatic hydrocarbon compounds in the Lower Columbia River using semipermeable-membrane devices

    USGS Publications Warehouse

    McCarthy, Kathleen A.; Gale, Robert W.

    1999-01-01

    Organochlorine and polycyclic aromatic hydrocarbon compounds are of concern in the Columbia River Basin because of their adverse effects on fish and wildlife. Because these compounds can have important biological consequences at concentrations well below the detection limits associated with conventional water-sampling techniques, we used semipermeable membrane devices (SPMDs) to sample water, and achieved sub-parts-per-quintillion detection limits. We deployed SPMDs during 1997 low-flow conditions and 1998 high-flow conditions at nine main-stem sites and seven tributary sites, spanning approximately 700 miles of the Columbia River. We also collected streambed sediment from three sites. SPMD extracts and sediments were analyzed for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, polychlorinated biphenyls, organochlorine pesticides and related transformation products, and polycyclic aromatic hydrocarbons. Our data indicate that (1) in the absence of additional sources, mechanisms such as volatilization, dilution, and settling of suspended particles can act to significantly reduce concentrations of contaminants along the river's flow path, (2) elevated concentrations of contaminants in the Portland-Vancouver area are primarily from local rather than upstream sources, (3) elevated concentrations of many compounds tend to be diluted during periods of high discharge, (4) much higher discharge in the main stem considerably dilutes elevated concentrations entering from tributaries, (5) the distribution of hydrophobic organic compounds in streambed sediment is not necessarily indicative of their distribution in the dissolved-phase, and (6) SPMDs can reveal patterns of contaminant occurrence at environmentally relevant concentrations that are undetectable by conventional water-sampling techniques.

  12. Polybenzimidazole via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  13. Fluorescent Molecular Rotors of Organoboron Compounds from Schiff Bases: Synthesis, Viscosity, Reversible Thermochromism, Cytotoxicity, and Bioimaging Cells.

    PubMed

    Ibarra-Rodrı Guez, Marisol; Muñoz-Flores, Blanca M; Dias, H V Rasika; Sánchez, Mario; Gomez-Treviño, Alberto; Santillan, Rosa; Farfán, Norberto; Jiménez-Pérez, Víctor M

    2017-03-03

    We report the design, synthesis, and characterization of two new fluorescent molecular rotors of boron derived from Schiff bases: (2,4,8,10-tetra-tert-butyl-6-phenyldibenzo[d,h][1,3,6,2]dioxazaboronine (3) and 1,4-bis(2,4,8,10-tetra-tert-butyldibenzo[d,h][1,3,6,2]dioxazaboronin-6-yl)benzene (4), as well as the free ligand 2-[[(3,5-di-tert-butyl-2-hydroxyphenyl)imino]methyl]-4,6-di-tert-butylphenol 1. All compounds were fully characterized by NMR ((1)H, (11)B, and (13)C), IR, UV/vis, fluorescence spectroscopy, and high-resolution mass spectrometry. The crystal structures of 3 and 4 showed tetracoordinated boron atoms with semiplanar skeleton ligands. The free rotation of the fluorescent molecular rotor, only observed in the binuclear compound, was decreased with increasing viscosity, while the quantum yield was increased. Interestingly, the property of reversible thermochromism was found in organoboron 4 in the solid state. DFT calculations to determine the both complexes have free rotation around the CPh-B1 bond. The boron compounds 3 and 4 have shown low cytotoxicity activity in cell line A-431 and low green staining in cells.

  14. Quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair by HPLC with fluorescence detection: a biological monitoring method to evaluate the exposure to PAHs.

    PubMed

    Toriba, Akira; Kuramae, Yayoi; Chetiyanukornkul, Thaneeya; Kizu, Ryoichi; Makino, Tsunehisa; Nakazawa, Hiroyuki; Hayakawa, Kazuichi

    2003-01-01

    A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

  15. Pyrolysis of simple coal model compounds containing aromatic carboxylic acids: Does decarboxylation lead to cross-linking?

    SciTech Connect

    Eskay, T.P.; Britt, P.F.; Buchanan, A.C. III

    1996-02-01

    The thermolysis of two aromatic carboxylic acids 1,2-(3,3`-dicarboxyphenyl)ethane (2) have been investigated at 400{degree} C as models of carboxylic acids in low rank coals. The major decomposition pathway observed is decarboxylation, which mainly occurs by an ionic pathway. This decarboxylation route does not lead to any significant amount of coupling or high molecular weight products that would be indicative of cross-linking products in coal. The pyrolysis of 1 and 2 will be investigated under a variety of conditions that better mimic the enviromment found in coal to further delineate the role that decarboxylation plays in coal cross-linking chemistry.

  16. Investigation of the distribution of organochlorine and polycyclic aromatic hydrocarbon compounds in the lower Columbia River using semipermeable membrane devices

    SciTech Connect

    McCarthy, K.A.; Gale, R.W.

    1999-01-01

    The authors used semipermeable membrane devices (SPMDs) to sample water, and achieved sub-parts-per-quintillion detection limits. They deployed SPMDs during 1997 low-flow conditions and 1998 high-flow conditions at nine main-stem sites and seven tributary sites, spanning approximately 700 miles of the Columbia River. They also collected streambed sediment from three sites. SPMD extracts and sediments were analyzed for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzo-furans, polychlorinated biphenyls, organochlorine pesticides and related transformation products, and polycyclic aromatic hydrocarbons.

  17. Generation of standard gas mixtures of halogenated, aliphatic, and aromatic compounds and prediction of the individual output rates based on molecular formula and boiling point.

    PubMed

    Thorenz, Ute R; Kundel, Michael; Müller, Lars; Hoffmann, Thorsten

    2012-11-01

    In this work, we describe a simple diffusion capillary device for the generation of various organic test gases. Using a set of basic equations the output rate of the test gas devices can easily be predicted only based on the molecular formula and the boiling point of the compounds of interest. Since these parameters are easily accessible for a large number of potential analytes, even for those compounds which are typically not listed in physico-chemical handbooks or internet databases, the adjustment of the test gas source to the concentration range required for the individual analytical application is straightforward. The agreement of the predicted and measured values is shown to be valid for different groups of chemicals, such as halocarbons, alkanes, alkenes, and aromatic compounds and for different dimensions of the diffusion capillaries. The limits of the predictability of the output rates are explored and observed to result in an underprediction of the output rates when very thin capillaries are used. It is demonstrated that pressure variations are responsible for the observed deviation of the output rates. To overcome the influence of pressure variations and at the same time to establish a suitable test gas source for highly volatile compounds, also the usability of permeation sources is explored, for example for the generation of molecular bromine test gases.

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

    PubMed

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

    2017-05-05

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

  19. The Geoglobus acetivorans Genome: Fe(III) Reduction, Acetate Utilization, Autotrophic Growth, and Degradation of Aromatic Compounds in a Hyperthermophilic Archaeon

    PubMed Central

    Mardanov, Andrey V.; Slododkina, Galina B.; Slobodkin, Alexander I.; Beletsky, Alexey V.; Gavrilov, Sergey N.; Kublanov, Ilya V.; Bonch-Osmolovskaya, Elizaveta A.; Skryabin, Konstantin G.

    2014-01-01

    Geoglobus acetivorans is a hyperthermophilic anaerobic euryarchaeon of the order Archaeoglobales isolated from deep-sea hydrothermal vents. A unique physiological feature of the members of the genus Geoglobus is their obligate dependence on Fe(III) reduction, which plays an important role in the geochemistry of hydrothermal systems. The features of this organism and its complete 1,860,815-bp genome sequence are described in this report. Genome analysis revealed pathways enabling oxidation of molecular hydrogen, proteinaceous substrates, fatty acids, aromatic compounds, n-alkanes, and organic acids, including acetate, through anaerobic respiration linked to Fe(III) reduction. Consistent with the inability of G. acetivorans to grow on carbohydrates, the modified Embden-Meyerhof pathway encoded by the genome is incomplete. Autotrophic CO2 fixation is enabled by the Wood-Ljungdahl pathway. Reduction of insoluble poorly crystalline Fe(III) oxide depends on the transfer of electrons from the quinone pool to multiheme c-type cytochromes exposed on the cell surface. Direct contact of the cells and Fe(III) oxide particles could be facilitated by pilus-like appendages. Genome analysis indicated the presence of metabolic pathways for anaerobic degradation of aromatic compounds and n-alkanes, although an ability of G. acetivorans to grow on these substrates was not observed in laboratory experiments. Overall, our results suggest that Geoglobus species could play an important role in microbial communities of deep-sea hydrothermal vents as lithoautotrophic producers. An additional role as decomposers would close the biogeochemical cycle of carbon through complete mineralization of various organic compounds via Fe(III) respiration. PMID:25416759

  20. Estimating the physicochemical properties of polyhalogenated aromatic and aliphatic compounds using UPPER: part 1. Boiling point and melting point.

    PubMed

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

    2015-01-01

    The UPPER (Unified Physicochemical Property Estimation Relationships) model uses enthalpic and entropic parameters to estimate 20 biologically relevant properties of organic compounds. The model has been validated by Lian and Yalkowsky on a data set of 700 hydrocarbons. The aim of this work is to expand the UPPER model to estimate the boiling and melting points of polyhalogenated compounds. In this work, 19 new group descriptors are defined and used to predict the transition temperatures of an additional 1288 compounds. The boiling points of 808 and the melting points of 742 polyhalogenated compounds are predicted with average absolute errors of 13.56 K and 25.85 K, respectively.

  1. Synthesis, crystal structures and magnetic properties of dinuclear copper(II) compounds with NNO tridentate Schiff base ligands and bridging aliphatic diamine and aromatic diimine linkers.

    PubMed

    Rigamonti, Luca; Forni, Alessandra; Pievo, Roberta; Reedijk, Jan; Pasini, Alessandro

    2011-04-07

    The synthesis and the characterization of new dinuclear copper(II) compounds of general formula [(L(a-d))(2)Cu(2)(μ-N-N)](ClO(4))(2) (1-6) with either neutral aliphatic diamine (N-N = piperazine, pip) or aromatic diimine (N-N = 4,4'-bipyridine, 4,4'-bipy) linker are reported. The copper ligands L(-) (L(a-) = (E)-2-((2-aminoethylimino)methyl)phenolate, L(b-) = (E)-2-((2-aminopropylimino)methyl)-phenolate, L(c-) = (E)-2-((2-aminoethylimino)methyl)4-nitrophenolate, L(d-) = (E)-2-((2-aminoethylimino)methyl)4-methoxyphenolate) are NNO tridentate Schiff bases derived from the monocondensation of a substituted salicylaldehyde 5-G-salH (G = NO(2), H, OMe) with ethylenediamine, en, or 1,3-propylenediamine, tn. The crystal structures of compounds [(L(a))(2)Cu(2)(MeOH)(2)(μ-4,4'-bipy)](ClO(4))(2) (1·2MeOH), [(L(b))(2)Cu(2)(MeOH)(2)(μ-4,4'-bipy)](ClO(4))(2) (2·2MeOH), [(L(d))(2)Cu(2)(μ-4,4'-bipy)](ClO(4))(2) (4), [(L(a))(2)Cu(2)(μ-pip)](ClO(4))(2) (5) and [(L(b))(2)Cu(2)(μ-pip)](ClO(4))(2) (6) have been determined, revealing the preferred (e-e)-chair conformation of the bridging piperazine in compounds 5 and 6. The presence of hydrogen-bond-mediated intermolecular interactions, that involve the methanol molecules, yields dimers of dinuclear units for 1·2MeOH, and infinite zig-zag chains for 2·2MeOH. The temperature dependences of the magnetic susceptibilities χ(M)(T) for all compounds were measured, indicating the presence of antiferromagnetic Cu-Cu exchange. For the compounds 2-4 with 4,4'-bipy, the coupling constants J are around -1 cm(-1), while in compound 1 no interaction could be detected. The compounds 5 and 6 with piperazine display higher Cu-Cu magnetic interactions through the σ-bonding backbone of the bridging molecule, with J around -8 cm(-1), and the coupling is favoured by the (e-e)-chair conformation of the diamine ring. The non-aromatic, but shorter, linker piperazine gives rise to stronger Cu-Cu antiferromagnetic couplings than the aromatic, but

  2. Nonplanar aromatic compounds. 3. A proposed new strategy for the synthesis of Buckybowls. Synthesis, structure and reactions of

    PubMed

    Bodwell; Fleming; Mannion; Miller

    2000-08-25

    A new strategy for the synthesis of Buckybowls is presented and initial attempts to implement it are reported. This involves annulation of further rings onto polycyclic aromatic systems that prefer to be planar but have been "pre-bent" by the installation of a tether. Pyrenophane 2b reacts with TCNE and PTAD to give 1:1 and 1:2 adducts, respectively. The less strained pyrenophane 2c is unreactive toward TCNE but gives a 1:2 adduct with PTAD. Attempted electrophilic aromatic brominations of pyrenophane 2e under a variety of conditions were unsuccessful, as were attempts to brominate cyclophanediene 1c, the direct synthetic precursor of 2c. Tether cleavage and addition reactions occurred rather than substitution. In an effort to circumvent tether cleavage problems, [7]-, [8]- and [9](2,7)pyrenophanes 22b-d were prepared. However, attempted bromination and Friedel-Crafts acylations failed. Evidence for the fleeting existence of [6](2,7)pyrenophane 22a was also obtained. Comparison of structural data (X-ray and AM1 calculations) for the pyrenophanes 22a-d with their 1,n-dioxa analogues 2a-d indicates that the nature of the tether has a strong effect on the degree of bend in the pyrene moiety and this led to the identification of trioxapyrenophane 28 as the next target in the quest for increasingly bent pyrenes.

  3. Towards habitat-oriented systems biology of "Aromatoleum aromaticum" EbN1: chemical sensing, catabolic network modulation and growth control in anaerobic aromatic compound degradation.

    PubMed

    Rabus, Ralf; Trautwein, Kathleen; Wöhlbrand, Lars

    2014-04-01

    The denitrifying betaproteobacterium "Aromatoleum aromaticum" EbN1 is a well-studied model organism for anaerobic degradation of aromatic compounds. Following publication of its genome in 2005, comprehensive physiological-proteomic studies were conducted to deduce functional understanding from the genomic blueprint. A catabolic network (85 predicted, 65 identified proteins) for anaerobic degradation of 24 aromatic growth substrates (including 11 newly recognized) was established. Newly elucidated pathways include those for 4-ethylphenol and plant-derived 3-phenylpropanoids, involving functional assignment of several paralogous genes. The substrate-specific regulation of individual peripheral degradation pathways is probably initiated by highly specific chemical sensing via dedicated sensory/regulatory proteins, e.g. three different σ⁵⁴-dependent one-component sensory/regulatory proteins are predicted to discriminate between three phenolic substrates (phenol, p-cresol and 4-ethylphenol) and two different two-component systems are assumed to differentiate between two alkylbenzenes (toluene, ethylbenzene). Investigations under in situ relevant growth conditions revealed (a) preferred utilization of benzoate from a mixture with succinate results from repressed synthesis of a C₄-dicarboxylate TRAP transporter; (b) response to alkylbenzene-induced solvent stress comprises metabolic re-routing of acetyl-CoA and reducing equivalents to poly(3-hydroxybutyrate) synthesis, alteration of cellular membrane composition and formation of putative solvent efflux systems; and (c) multifaceted adaptation to slow growth includes adjustment of energy demand for maintenance and preparedness for future nutritional opportunities, i.e. provision of uptake systems and catabolic enzymes for multiple aromatic substrates despite their absence. This broad knowledge base taken together with the recent development of a genetic system will facilitate future functional, biotechnological

  4. An anaerobic field injection experiment in a landfill leachate plume, Grindsted, Denmark: 1. Experimental setup, tracer movement, and fate of aromatic and chlorinated compounds

    NASA Astrophysics Data System (ADS)

    Rügge, Kirsten; Bjerg, Poul L.; Pedersen, JøRn K.; MosbæK, Hans; Christensen, Thomas H.

    1999-04-01

    A continuous, natural-gradient field injection experiment, involving 18 xenobiotic compounds and bromide as tracers, was performed in the anaerobic region of a leachate plume downgradient from the Grindsted Landfill, Denmark. The injection lasted for 195 days, and within this period a continuous cloud was established. Over a period of 924 days the cloud movement was monitored in approximately 70 discrete sampling points in the central part of the cloud, and the spatial distribution was described by seven cloud snapshots involving 400-700 sampling points. The bromide cloud movement closely followed the varying flow direction predicted by the water table measurements. Moment analysis showed decreasing tracer flow velocities and reduced capture of bromide mass with time, which may be explained by varying flow conditions (direction, hydraulic gradient) and the heterogeneous geological conditions in the sandy aquifer. Naphthalene, having the highest log Kow value, was the most retarded compound, with a retardation of less than 10%. Therefore sorption was not considered to be a significant attenuation process for any of the compounds studied. Transformation under iron-reducing conditions was observed for toluene, o-xylene, TeCM, 1,1,1-TCA, PCE, and TCE, while transformation of benzene and napthalene was not detected in the aquifer within the time frame of this study. First-order transformation rates were in the range of 0.028-0.039 d-1 and 0.0014-0.0028 d-1 for the aromatic compounds toluene and o-xylene, respectively. The rates for the chlorinated aliphatic compounds, tetrachloromethane, 1,1,1- trichloroethane, tetrachloroethylene, and trichloroethylene, were >0.7 d-1, 0.0044-0.0054 d-1, 0.0012-0.0038 d-1, and 0.0003-0.001 d-1, respectively. Long lag periods and slow transformation rates were observed for some of the compounds, suggesting that lack of transformation reported in the literature may be attributable to short experimental periods in those studies.

  5. Development of a novel neodymium compound for in vivo fluorescence imaging.

    PubMed

    Aita, Kazuki; Temma, Takashi; Kuge, Yuji; Saji, Hideo

    2007-01-01

    We developed a novel fluorescent probe that contains the neodymium(III) complex moiety and fluorescein moiety. This probe can emit long-lived near-infrared luminescence derived from a Nd ion through excitation of the fluorescein moiety with visible light (lambda(ex) = 488 nm, lambda(em) = 880 nm, lifetime = 2.3 micros). These results indicate the possibility of the probe as a candidate for in vivo fluorescence molecular imaging.

  6. Health risk impacts analysis of fugitive aromatic compounds emissions from the working face of a municipal solid waste landfill in China.

    PubMed

    Liu, Yanjun; Liu, Yanting; Li, Hao; Fu, Xindi; Guo, Hanwen; Meng, Ruihong; Lu, Wenjing; Zhao, Ming; Wang, Hongtao

    2016-12-01

    Aromatic compounds (ACs) emitted from landfills have attracted a lot of attention of the public due to their adverse impacts on the environment and human health. This study assessed the health risk impacts of the fugitive ACs emitted from the working face of a municipal solid waste (MSW) landfill in China. The emission data was acquired by long-term in-situ samplings using a modified wind tunnel system. The uncertainty of aromatic emissions is determined by means of statistics and the emission factors were thus developed. Two scenarios, i.e. 'normal-case' and 'worst-case', were presented to evaluate the potential health risk in different weather conditions. For this typical large anaerobic landfill, toluene was the dominant species owing to its highest releasing rate (3.40±3.79g·m(-2)·d(-1)). Despite being of negligible non-carcinogenic risk, the ACs might bring carcinogenic risks to human in the nearby area. Ethylbenzene was the major health threat substance. The cumulative carcinogenic risk impact area is as far as ~1.5km at downwind direction for the normal-case scenario, and even nearly 4km for the worst-case scenario. Health risks of fugitive ACs emissions from active landfills should be concerned, especially for landfills which still receiving mixed MSW.

  7. Compound specific radiocarbon analysis as a tool to quantitatively apportion modern and fossil sources of polycyclic aromatic hydrocarbons in environmental matrices

    SciTech Connect

    Eglinton, T.I.: Pearson, A.; McNichol, A.P.

    1996-12-31

    The quantitative apportionment of multiple sources of toxic compounds in natural systems has been of substantial interest in recent years. Polycyclic aromatic hydrocarbons (PAHs), which represent one of the largest classes of suspected chemical carcinogens/mutagens, are one such example. The biogeochemistry of PAHs in the environment is extremely complex as a result of the multitude of potential sources (both anthropogenic and natural), differing reactivities and solubilities, and transport and depositional processes that control their provenance. PAHs sources can be broadly divided into two categories: (a) {open_quotes}Pyrogenic{close_quotes} PAHs from high-temperature processes (i.e., incomplete combustion (pyrolysis) of organic materials); (b) PAHs from lower temperature processes (i.e. uncombusted petroleum contamination). Pyrogenic PAHs can be further separated into fossil fuel (coal and petroleum) combustion sources, and biomass combustion sources (charcoal burning; cigarette smoking, forest/grass fires, barbeques etc.). Although a variety of criteria may be used to distinguish petroleum from combustion sources of polycyclic aromatic hydrocarbons (PAHs) in environmental samples, it is much more difficult to distinguish PAHs derived from modem (e.g. residential wood combustion) versus fossil fuel (e.g. coal combustion) pyrogenic sources. This paper describes results of isotope dating of a coal tar extract and and air particulate sample.

  8. Pollution characteristics of volatile organic compounds, polycyclic aromatic hydrocarbons and phthalate esters emitted from plastic wastes recycling granulation plants in Xingtan Town, South China

    NASA Astrophysics Data System (ADS)

    Huang, De-Yin; Zhou, Shun-Gui; Hong, Wei; Feng, Wei-Feng; Tao, Liang

    2013-06-01

    With the aim to investigate the main pollution characteristics of exhaust gases emitted from plastic waste recycling granulation plants, mainly volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs) were analyzed in Xingtan Town, the largest distribution center of plastic waste recycling in China. Both inside and outside the plants, the total concentrations of volatile monocyclic aromatic hydrocarbons (MAHs), PAHs and PAEs ranged from 2000 to 3000 μg m-3, 450 to 1200 ng m-3, and 200 to 1200 ng m-3, respectively. Their concentration levels inside the plants were higher than those outside the plants, and PAHs and PAEs were mainly distributed in the gas-phase. Notably, highly toxic benzo[a]pyrene (BaP) could be detected inside the plants, and harmful PAEs could be detected not only inside but also outside the plants, although PAEs are non-volatile. The exhaust gas composition and concentration were related to the plastic feedstock and granulation temperature.

  9. Adsorbed States of phosphonate derivatives of N-heterocyclic aromatic compounds, imidazole, thiazole, and pyridine on colloidal silver: comparison with a silver electrode.

    PubMed

    Podstawka, Edyta; Olszewski, Tomasz K; Boduszek, Bogdan; Proniewicz, Leonard M

    2009-09-03

    Here, we report a systematic surface-enhanced Raman spectroscopy (SERS) study of the structures of phosphonate derivatives of the N-heterocyclic aromatic compounds imidazole (ImMeP ([hydroxy(1H-imidazol-5-yl)methyl]phosphonic acid) and (ImMe)(2)P (bis[hydroxy-(1H-imidazol-4-yl)-methyl]phosphinic acid)), thiazole (BAThMeP (butylaminothiazol-2-yl-methyl)phosphonic acid) and BzAThMeP (benzylaminothiazol-2-yl-methyl)phosphonic acid)), and pyridine ((PyMe)(2)P (bis[(hydroxypyridin-3-yl-methyl)]phosphinic acid)) adsorbed on nanometer-sized colloidal particles. We compared these structures to those on a roughened silver electrode surface to determine the relationship between the adsorption strength and the geometry. For example, we showed that all of these biomolecules interact with the colloidal surface through aromatic rings. However, for BzAThMeP, a preferential interaction between the benzene ring and the colloidal silver surface is observed more so than that between the thiazole ring and this substrate. The PC(OH)C fragment does not take part in the adsorption process, and the phosphonate moiety of ImMeP and (ImMe)(2)P, being removed from the surface, only assists in this process.

  10. First approach to nitrogen-containing fused aromatic hydrocarbons as targets for organoelectronics utilizing a new transformation of O-protected diaryl methanols.

    PubMed

    Bałczewski, Piotr; Bodzioch, Agnieszka; Rózycka-Sokołowska, Ewa; Marciniak, Bernard; Uznański, Paweł

    2010-02-22

    A new concise approach for the construction of heteroatom analogues of polycyclic aromatic benzo[g]quinoline, benzo[b]carbazole, and pyrido[b]carbazole systems via diaryl methanols is described. This transformation involves formation of a central benzene ring fused to two aromatic 5- or 6-membered rings of pyrrole and/or pyridine by using a combination of two aromatic aldehydes, of which at least one contains a ring nitrogen. Analysis of the UV and fluorescent properties, Stokes shifts, quantum yields in solution, and pi-stacking interactions in the crystal structures of the new materials was performed. These polycyclic aromatic compounds show potential as small-molecule organoelectronic materials.

  11. Fluorescence spectroscopy as a specific tool for the interaction study of two surfactants with natural and synthetic organic compounds

    NASA Astrophysics Data System (ADS)

    Jung, Aude-Valérie; Frochot, Céline; Bersillon, Jean-Luc

    2016-04-01

    Four different techniques were used to study the binding of cationic cetyltrimethylammonium bromide (CTAB) and non-ionic nonylphenylethoxyl (NPE) surfactants to three synthetic organic components that mimic humic-like aggregates and to two natural aggregated humic substances (HS) extracted from aquatic suspended matter. The composition of synthetic organic components were chosen to be similar to high molecular weight highly processed terrigenous HS and low and high molecular weight less processed terrigenous (or aquatic terrigenous) HS. The natural HS were extracted under two different meteorological conditions (rainy and dry periods). No significant interaction between the non-ionic surfactant and any of the studied compounds was found. Concerning CTAB; pH, conductivity and turbidity measurements, along with fluorescence spectroscopy were combined to provide a better understanding of interactions between organic aggregates and the surfactant. The spectroscopic data show that a "highly processed terrigenous HS" fluorophore interacts in a different way with the cationic surfactant than an "aquatic terrigenous (or less processed terrigenous) HS" fluorophore does. Under similar conditions, some spectral changes in the fluorescence signal are correlated to changes in non-specific physical-chemical parameters (pH, turbidity, conductivity) for the organic compounds tested. The complexation mechanism is essentially governed by charge neutralization, which can be monitored specifically by the fluorescence of the organic moieties.

  12. Separation and identification of highly fluorescent compounds derived from trans-resveratrol in the leaves of Vitis vinifera infected by Plasmopara viticola.

    PubMed

    Tříska, Jan; Vrchotová, Naděžda; Olejníčková, Julie; Jílek, Rudolf; Sotolář, Radek

    2012-03-06

    A method for identification of highly fluorescent compounds in vine leaves infected by Plasmopara viticola was developed using reversed phase liquid chromatography with simultaneous diode array and fluorometric detection. Fluorescent compounds were extracted from leaves with a methanol-water mixture (70:30). Separation by HPLC was performed using a C(18) column and gradient elution with water-acetonitrile mixtures (20-80% of acetonitrile). The main unknown fluorescent compound was identified by line spectral comparison with a standard obtained by UV photoisomerization of trans-resveratrol glucoside, and its structure was confirmed by liquid chromatography-mass spectrometry. Identification and structural elucidation of the fluorescent compound in the leaves of Vitis vinifera allows early detection of Plasmopara viticola invasion.

  13. Is Gamma Radiation Suitable to Preserve Phenolic Compounds and to Decontaminate Mycotoxins in Aromatic Plants? A Case-Study with Aloysia citrodora Paláu.

    PubMed

    Pereira, Eliana; Barros, Lillian; Antonio, Amilcar L; Cabo Verde, Sandra; Santos-Buelga, Celestino; Ferreira, Isabel C F R; Rodrigues, Paula

    2017-02-23

    This study aimed to determine the effect of gamma radiation on the preservation of phenolic compounds and on decontamination of dry herbs in terms of ochratoxin A (OTA) and aflatoxin B1 (AFB1), using Aloysia citrodora Paláu as a case study. For this purpose, artificially contaminated dry leaves were submitted to gamma radiation at different doses (1, 5, and 10 kGy; at dose rate of 1.7 kGy/h). Phenolic compounds were analysed by HPLC-DAD-ESI/MS and mycotoxin levels were determined by HPLC-fluorescence. Eleven phenolic compounds were identified in the samples and despite the apparent degradation of some compounds (namely verbasoside), 1 and 10 kGy doses point to a preservation of the majority of the compounds. The mean mycotoxin reduction varied between 5.3% and 9.6% for OTA and from 4.9% to 5.2% for AFB1. It was not observed a significant effect of the irradiation treatments on mycotoxin levels, and a slight degradation of the phenolic compounds in the irradiated samples was observed.

  14. Fluorescence properties of flavonoid compounds. Quantification in paprika samples using spectrofluorimetry coupled to second order chemometric tools.

    PubMed

    Monago-Maraña, Olga; Durán-Merás, Isabel; Galeano-Díaz, Teresa; Muñoz de la Peña, Arsenio

    2016-04-01

    The influence of pH on the fluorescence of flavonoid compounds was investigated and the highest fluorescence emission was obtained in basic medium. Selected conditions to improve this signal were: pH 9.5, 0.14 M Britton Robinson buffer and methanol between 5% and 10%. The excitation-emission fluorescence matrices of a set of 36 samples of Spanish paprika were analyzed by means of parallel factor analysis (PARAFAC). Thus, the profiles of possible fluorescence components (PARAFAC loadings) were obtained. One of these profiles was identified by matching PARAFAC scores with LC analysis on the same samples. Two clusters of samples were obtained when score values were plotted against each other. Spectrofluorimetry coupled to second order multivariate calibration methods, as unfolded-partial least squares with residual bilinearization (U-PLS/RBL) and multidimensional-partial least-squares with residual bilinearization (N-PLS/RBL), was investigated to quantify quercetin and kaempferol in those samples. Good results were obtained for quercetin by this approach.

  15. Pilot study of sampling and analysis for polynuclear aromatic compounds in indoor air. Report for 1 February-30 September 1984

    SciTech Connect

    Chuang, J.C.; Mack, G.A.; Koetz, J.R.; Petersen, B.A.

    1986-12-01

    The report presents the results of a nine-home indoor-air study that the authors performed in Columbus, Ohio in the winter of 1984. The main objective of the study was the field evaluation of sampling and analysis methodology. However, several additional results of the study are interesting and useful, including the finding of polynuclear aromatic hydrocarbons (PAH) at levels from 0.000 to 143 ng/cu m in residences, strong correlations of these levels with smoking by occupants, little influence of fireplace use on the PAH levels, the identification of quinoline as a potential marker for cigarette smoking, and measurement of 2- and 3-nitrofluoranthene, which are potent mutagens, at significant levels from 0.000 to 0.185 ng/cu m, also correlated with smoking.

  16. Poly cyclic aromatic hydrocarbons in Recent lake sediments—II. Compounds derived from biogenic precursors during early diagenesis

    NASA Astrophysics Data System (ADS)

    Wakeham, Stuart G.; Schaffner, Christian; Giger, Walter

    1980-03-01

    Five groups of polycyclic aromatic hydrocarbons (PAH) thought to be derived by early-diagenetic transformations of biogenic precursors are apparently present in Recent sediments of four lakes (Lake Lucerne. Lake Zürich, and Greifensee. Switzerland, and Lake Washington, northwest U.S.A.) These natural PAH include: (1) perylene. (2) an extended series of phenanthrene homologs. (3) retene and pimanthrene derived from diterpenes. (4) a series of tetra- and pentacyclic PAH derived from pentacyclic triterpenes of the amyrin-type. (5) tetra- and pentacyclic PAH formed from pentacyclic triterpenes with five-membered E-rings. Since these PAH are abundant in very young sediment layers, the transformation reactions involved appear to be faster than previously thought and may be microbially mediated. There is no evidence that anthropogenic or petrogenic sources can account for the distributions of these groups of PAH in cores of Recent lake sediments.

  17. Occurrence and accumulation features of polycyclic aromatic hydrocarbons and synthetic musk compounds in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters.

    PubMed

    Moon, Hyo-Bang; An, Yong-Rock; Park, Kyum Joon; Choi, Seok-Gwan; Moon, Dae-Yeon; Choi, Minkyu; Choi, Hee-Gu

    2011-09-01

    Reports of the occurrence and accumulation patterns of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in marine mammals are scarce. In this study, the concentrations and accumulation profiles of PAHs and SMCs were determined in blubber from finless porpoises in Korean coastal waters. Total concentrations of PAHs and SMCs ranged from 6.0 to 432 (mean: 160) ng/g lipid weight and from 17 to 144 (mean: 52) ng/g lipid weight, respectively. Residue levels of PAHs were lower than those reported from other studies, while residue levels of SMCs were relatively higher than those reported in other studies. Naphthalene was the most abundant PAH and HHCB was the dominant SMC observed in finless porpoises. The concentrations of PAHs and SMCs were not correlated with each other, but were significantly correlated within the same chemical groups. No correlations were found between body size and residue levels of PAHs and SMCs.

  18. Non-covalent interactions of nitrous oxide with aromatic compounds: Spectroscopic and computational evidence for the formation of 1:1 complexes

    SciTech Connect

    Cao, Qian; Gor, Gennady Y.; Krogh-Jespersen, Karsten; Khriachtchev, Leonid

    2014-04-14

    We present the first study of intermolecular interactions between nitrous oxide (N{sub 2}O) and three representative aromatic compounds (ACs): phenol, cresol, and toluene. The infrared spectroscopic experiments were performed in a Ne matrix and were supported by high-level quantum chemical calculations. Comparisons of the calculated and experimental vibrational spectra provide direct identification and characterization of the 1:1 N{sub 2}O-AC complexes. Our results show that N{sub 2}O is capable of forming non-covalently bonded complexes with ACs. Complex formation is dominated by dispersion forces, and the interaction energies are relatively low (about −3 kcal mol{sup −1}); however, the complexes are clearly detected by frequency shifts of the characteristic bands. These results suggest that N{sub 2}O can be bound to the amino-acid residues tyrosine or phenylalanine in the form of π complexes.

  19. Induction of aromatic amino acids and phenylpropanoid compounds in Scrophularia striata Boiss. cell culture in response to chitosan-induced oxidative stress.

    PubMed

    Kamalipourazad, Maryam; Sharifi, Mohsen; Maivan, Hassan Zare; Behmanesh, Mehrdad; Chashmi, Najmeh Ahmadian

    2016-10-01

    Manipulation of cell culture media by elicitors is one of most important strategies to inducing secondary metabolism for the production of valuable metabolites. In this investigation, inducing effect of chitosan on physiological, biochemical, and molecular parameters were investigated in cell suspension cultures of Scrophularia striata Boiss. The results showed that chitosan concentration and time of elicitation are determinants of the effectiveness of the elicitor. Accumulation of aromatic amino acids (phenylalanine [Phe] and tyrosine [Tyr]), phenylpropanoid compounds (phenolic acids [PAs] and echinacoside [ECH]), hydrogen peroxide (H2O2) production, phenylalanine ammonia-lyase (PAL) activity and gene expression, and antioxidant enzymes (superoxide dismutase [SOD], peroxidase [POX], catalase [CAT]) activities were altered by changing the exposure time of elicitation. Results showed that, upon elicitation with chitosan, oxidative events were induced, antioxidant responses of S. striata cells were boosted through enhanced activity of an effective series of scavenging enzymes (SOD, CAT, and POX), and biosynthesis of non-enzymatic antioxidants (ECH and PAs [cinnamic, p-coumaric and, caffeic acids]). The increase in amino acid content and PAL activity at early days of exposure to chitosan was related with rises in phenolic compounds. These results provide evidence that chitosan by up-regulation of PAL gene differentially improves the production of phenylpropanoid compounds, which are of medical commercial value with good biotechnological prospects.

  20. [Bayesian regularized BP neural network model for quantitative relationship between the electrochemical reduction potential and molecular structures of chlorinated aromatic compounds].

    PubMed

    Sun, Wei; Zeng, Guang-ming; Wei, Wan-zhi; Huang, Guo-he

    2005-03-01

    Bayesian regularized BP neural network (BRBPNN) technique was applied in QSPR model in environmental field. The BRBPNN model for quantitative relationship between the electrochemical reduction potential (ERP) and chemical structures of 87 chlorinated aromatic compounds was established. The structure descriptor pool is consisted of Cl number (Cl), molecular weight (MW) and 6 quantum chemistry parameters which are calculated by MOPAC2000 built in ChemOffice2004, including energy of the highest occupied molecular orbital (E(HOMO)), energy of the lowest occupied molecular orbital (E(LUMO)), heat of formation(HF), dipole(DIP), electronic energy(EE), core-core repulsion(CCR). The achieved optimal network structure was 6-20-1, which possessed stronger fitting and prediction capacity than that of the stepwise linear regression and with the correlation coefficients square and the mean square error for the training set and the test set as 0.999 and 0.000105, 0.965 and 0.00159 respectively. The sum of square weights between each input neuron and the hidden layer of BRBPNN(6-20-1) indicate the effect of descriptor on the electric potential declining in the order of ELUMO > EHOMO > HF> CCR > EE > DIP. The scatter diagrams show that the EE descriptors had positive effect on ERP, and ELUMO, HF, DIP had negative effects, and EHOMO and CCR showed ambiguous effects. Results show that Bayesian regularized BP neural network is of automated regularization parameter selection capability and thus may ensure the excellent generation ability and robustness. This study threw more light on the applicability of electrochemical treatment for the chlorinated aromatic compounds and the analysis on electrochemical reduction mechanism.

  1. Activation of Ca sup 2+ uptake and inhibition of reversal of the sarcoplasmic reticulum Ca sup 2+ pump by aromatic compounds

    SciTech Connect

    Petretski, J.H.; Wolosker, H.; de Meis, L. )

    1989-12-05

    The effects of aromatic compounds in sarcoplasmic reticulum Ca2+-ATPase were investigated. The solubility of the drugs in various organic solvents and water was measured. The ratio between the solubility in organic solvents and that in water (distribution coefficient) was used as an index of their hydrophobicity. The order found was triphenylphosphine greater than diphenylamine greater than 3-nitrophenol greater than 4-nitrophenol greater than 1,3-dihydroxybenzene. The effects observed on the Ca2+-ATPase were correlated with hydrophobicity of the drugs, activation and inhibition being obtained at a lower concentration the greater the distribution coefficient of the drug into organic solvent. In leaky vesicles, the effects of each compound on the ATPase activity varied depending on the Ca2+ concentration in the medium: it inhibited in the presence of 5 microM Ca2+ and activated when the Ca2+ concentration was raised to 2 mM. In intact vesicles, 3- and 4-nitrophenol, diphenylamine, and triphenylphosphine enhanced both the rate of ATP hydrolysis and the amount of Ca2+ accumulated by the vesicles. These four drugs inhibited Ca2+ uptake when ITP was used as substrate. 1,3-Dihydroxybenzene enhanced the amount of Ca2+ accumulated by the vesicles regardless of whether ATP or ITP was the substrate. All five compounds inhibited the phosphorylation of the enzyme by Pi, the efflux of Ca2+, and the synthesis of ATP measured during the reversal of the Ca2+ pump. The results indicate that the hydrophobic character of various organic compounds determines their access to sensitive domains of the membrane-bound calcium pump. Additional specific effects are then produced, depending on the structure of each compound.

  2. Contributions of Selected Biogenic and Aromatic Compounds to the Formation of Tropospheric Secondary Organic Aerosol over Several Sites in the United States

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Kleindienst, T. E.; Lewandowski, M.; Offenberg, J. H.; Corse, E. W.; Gerald, T.; Edney, E.

    2009-12-01

    The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory and field research effort to better understand the contribution of biogenic and aromatic hydrocarbons to the formation of submicron ambient secondary organic aerosol (SOA). In the laboratory, isoprene, α-pinene, β-caryophyllene, 1,3-butadiene, 2-methyl-3-buten-2-ol, benzene, and toluene were individually irradiated under a wide range of conditions in a photochemical reaction chamber in the presence of nitrogen oxide (NOx). These hydrocarbons are thought to contribute to ambient SOA formation. In field studies conducted in Research Triangle Park, NC; Duke Forest in Chapel Hill, NC; Atlanta, GA; Pensacola, FL; Birmingham and Centerville, AL; Riverside, CA; Detroit, MI; Northbrook, East St. Louis and Bondville, IL; and Cincinnati, OH, ambient PM2.5 samples were collected for various periods between 2003 and 2006. The SOA collected from these laboratory experiments and the ambient PM2.5 samples were analyzed for organic carbon (OC) concentration and for organic tracer compounds by GC-MS using BSTFA derivatization for their identification and quantification. An organic tracer-based method was developed for estimating ambient SOA concentrations from individual SOA precursors to allow an assessment of SOA model predictions with ambient data. The results show that several major reaction products detected in SOA formed in the laboratory photooxidations were among the major compounds detected in field samples, effectively connecting laboratory and field results. Using the tracer-based method, the contributions of isoprene and monoterpenes to SOA formation show strong seasonal dependencies. However, no clear seasonal variations were observed for sesquiterpenes and aromatic hydrocarbons. The contribution of 2-methyl-3-buten-2-ol to ambient SOA was found to be not only season dependent but also higher in locations dominated by conifers, which are

  3. Dissolution of biological samples in deep eutectic solvents: an approach for extraction of polycyclic aromatic hydrocarbons followed by liquid chromatography-fluorescence detection.

    PubMed

    Helalat-Nezhad, Zahra; Ghanemi, Kamal; Fallah-Mehrjardi, Mehdi

    2015-05-15

    A novel sample preparation method based on the complete dissolution of marine biological samples in choline chloride-oxalic acid (ChCl-Ox) deep eutectic solvent was developed for fast and efficient extraction of eight polycyclic aromatic hydrocarbons (PAHs) using minimum volumes of cyclohexane. The extracted PAHs were purified and then measured by high-performance liquid chromatography-fluorescence detection (HPLC-FL). The effect of key parameters on extraction recoveries and precision was investigated. At optimized conditions, the studied samples were dissolved under atmospheric pressure in ChCl-Ox (1:2) at 55°C for 30min, which is considerably lower than the temperature used in the classical and current methods. After dissolution, it took approximately 20min to quantitatively extract the PAHs from ChCl-Ox using 5mL cyclohexane. Depending on the analyte, the developed method was linear over the calibration range 1.0-250, 2.0-250, and 5.0-250ngg(-1), with r(2)>0.996. The detection limits of the method were between 0.50 and 3.08ngg(-1). The intra-day and inter-day precisions (based on the relative standard deviation, n=5) of the spiked PAHs at a concentration level of 50ngg(-1) were better than 12.6% and 13.3%, respectively. Individual PAH recoveries from spiked marine fish and macroalgae samples were in the range of 71.6% to 109.6%. For comparison, the spiked samples were also subjected to the Soxhlet extraction method. The simplicity of the procedure, high extraction efficiency, short analysis time, and use of safe and inexpensive components suggest the proposed method has a high potential for utilization in routine trace PAH analysis in biological samples.

  4. Detection of organophosphorus compound based on a sol-gel silica planar waveguide doped with a green fluorescent protein and an organophosphorus hydrolase

    NASA Astrophysics Data System (ADS)

    Enami, Y.; Tsuchiya, K.; Suye, S.

    2011-06-01

    In this letter, the authors report the real-time detection of an organophosphorus compound using a sol-gel silica planar waveguide doped with a green fluorescent protein and an organophosphorus hydrolase on a yeast-cell surface display. The waveguide was pumped at 488 nm, and it emitted green fluorescence at the far field. The green fluorescent light at 550 nm changed by 50% from the original power 1 min after application of the organophosphorus compound. The results enable the real-time detection of sarin and other biochemicals by using an in-line fiber sensor network.

  5. Trimerization of aromatic nitriles

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1977-01-01

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

  6. Correlation Of Balkan Endemic Nephropathy With Fluorescent Organic Compounds In Shallow Groundwater

    NASA Astrophysics Data System (ADS)

    Goldberg, Marvin C.; Feder, Gerald L.; Radovanovic, Zoran

    1994-04-01

    Balkan endemic nephropathy (BEN) is a disease of intersitial nephropathy leading to end-stage renal failure. The disease occurs in persons living in villages on alluvial valleys of streams tributary to the Danube River in Rumania, Bulgaria and former Yugoslavia. The etiologic agent is not known, but a contaminant in shallow groundwater has become suspect. In this study, samples of drinking water from endemic and non-endemic village water supplies were analyzed by excitation/emission matrix (EEM) fluorescence spectroscopy. Spectra characteristic of groundwater from BEN households show elongated teardrop shapes in the fluorescence excitation/emission matrix. A sharp rise occurs in fluorescence emission between 380 and 400 nanometers (nm) and a trailing emission intensity from 400 to 550 nm. Spectra of groundwater samples from some BEN households have an additional excitation maxima at 300 nm, which further contributes to the emission intensity at 400 nm. Spectra of water samples from non-BEN households located in endemic villages show characteristics of BEN household waters, exhibiting the 250-nm excitation peak, even though the fluorophoric intensity is much less than that in samples from BEN household waters. Samples from non-endemic villages do not show the characteristic EEM spectra described as "teardrop shaped". The non-BEN households have lower concentrations of these fluorophores in the drinking water than the endemic households; hence, one of the factors in contracting the disease may be the concentration of these fluorescent materials in drinking water.

  7. Cancer risk from polycyclic aromatic compounds in fine particulate matter generated from household coal combustion in Xuanwei, China.

    PubMed

    Lui, K H; Bandowe, Benjamin A Musa; Tian, Linwei; Chan, Chi-Sing; Cao, Jun-Ji; Ning, Zhi; Lee, S C; Ho, K F

    2017-02-01

    Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs: OPAHs and azaarenes: AZAs) were characterized in fine particulates (PM2.5) emitted from indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. A sample from the community with the highest mortality contained the highest total concentration of PAHs, OPAHs and AZAs and posed the highest excess cancer risk from a lifetime of inhaling fine particulates. Positive correlations between total carbonyl-OPAHs, total AZAs and total PAHs implied that the emissions were dependent on similar factors, regardless of sample location and type. The calculated cancer risk ranged from 5.23-10.7 × 10(-3), which is higher than the national average. The risk in each sample was ∼1-2 orders of magnitude higher than that deemed high risk, suggesting that the safety of these households is in jeopardy. The lack of potency equivalency factors for the PAH derivatives could possibly have underestimated the overall cancer risk.

  8. Matrix assisted ionization: new aromatic and nonaromatic matrix compounds producing multiply charged lipid, peptide, and protein ions in the positive and negative mode observed directly from surfaces.

    PubMed

    Li, Jing; Inutan, Ellen D; Wang, Beixi; Lietz, Christopher B; Green, Daniel R; Manly, Cory D; Richards, Alicia L; Marshall, Darrell D; Lingenfelter, Steven; Ren, Yue; Trimpin, Sarah

    2012-10-01

    Matrix assisted inlet ionization (MAII) is a method in which a matrix:analyte mixture produces mass spectra nearly identical to electrospray ionization without the application of a voltage or the use of a laser as is required in laserspray ionization (LSI), a subset of MAII. In MAII, the sample is introduced by, for example, tapping particles of dried matrix:analyte into the inlet of the mass spectrometer and, therefore, permits the study of conditions pertinent to the formation of multiply charged ions without the need of absorption at a laser wavelength. Crucial for the production of highly charged ions are desolvation conditions to remove matrix molecules from charged matrix:analyte clusters. Important factors affecting desolvation include heat, vacuum, collisions with gases and surfaces, and even radio frequency fields. Other parameters affecting multiply charged ion production is sample preparation, including pH and solvent composition. Here, findings from over 100 compounds found to produce multiply charged analyte ions using MAII with the inlet tube set at 450 °C are presented. Of the compounds tested, many have -OH or -NH(2) functionality, but several have neither (e.g., anthracene), nor aromaticity or conjugation. Binary matrices are shown to be applicable for LSI and solvent-free sample preparation can be applied to solubility restricted compounds, and matrix compounds too volatile to allow drying from common solvents. Our findings suggest that the physical properties of the matrix such as its morphology after evaporation of the solvent, its propensity to evaporate/sublime, and its acidity are more important than its structure and functional groups.

  9. Investigation of the Interaction between 1,3-Diazaheterocyclic Compounds and the Fat Mass and Obesity-Associated Protein by Fluorescence Spectroscopy and Molecular Modeling.

    PubMed

    Zhang, Lijiao; Ren, Ting; Tian, Xianhai; Wang, Zechun; Yu, Wenquan; Wang, Ruiyong; Chang, Junbiao

    2017-01-01

    In this paper, The binding of twelve 1,3-diazaheterocyclic compounds (1a-1 l) to the fat mass and obesity-associated (FTO) protein was investigated by fluorescence, UV-vis absorption spectroscopy and molecular modeling. Results indicated that the intrinsic fluorescence of FTO is quenched by the nine compounds (1a-1i) with a static quenching procedure. No interaction was observed between FTO protein and compounds (1j-1 l). The thermodynamic parameters obtained from the fluorescence data showed that the hydrophobic force played a major role in stabilizing the complex. The results of synchronous and three-dimensional fluorescence spectra showed that the conformation of FTO was changed. In addition, the influence of molecular structure on the quenching effect has been investigated.

  10. A fluorescent microplate assay quantifies bacterial efflux and demonstrates two distinct compound binding sites in AcrB.

    PubMed

    Iyer, Ramkumar; Ferrari, Annette; Rijnbrand, R; Erwin, Alice L

    2015-04-01

    A direct assay of efflux by Escherichia coli AcrAB-TolC and related multidrug pumps would have great value in discovery of new Gram-negative antibiotics. The current understanding of how efflux is affected by the chemical structure and physical properties of molecules is extremely limited, derived from antibacterial data for compounds that inhibit growth of wild-type E. coli. We adapted a previously described fluorescent efflux assay to a 96-well microplate format that measured the ability of test compounds to compete for efflux with Nile Red (an environment-sensitive fluor), independent of antibacterial activity. We show that Nile Red and the lipid-sensitive probe DiBAC4-(3) [bis-(1,3-dibutylbarbituric acid)-trimethine oxonol] can quantify efflux competition in E. coli. We extend the previous findings that the tetracyclines compete with Nile Red and show that DiBAC4-(3) competes with macrolides. The extent of the competition shows a modest correlation with the effect of the acrB deletion on MICs within the compound sets for both dyes. Crystallographic studies identified at least two substrate binding sites in AcrB, the proximal and distal pockets. High-molecular-mass substrates bound the proximal pocket, while low-mass substrates occupied the distal pocket. As DiBAC4-(3) competes with macrolides but not with Nile Red, we propose that DiBAC4-(3) binds the proximal pocket and Nile Red likely binds the distal site. In conclusion, competition with fluorescent probes can be used to study the efflux process for diverse chemical structures and may provide information as to the site of binding and, in some cases, enable rank-ordering a series of related compounds by efflux.

  11. A Fluorescent Microplate Assay Quantifies Bacterial Efflux and Demonstrates Two Distinct Compound Binding Sites in AcrB

    PubMed Central

    Ferrari, Annette; Rijnbrand, R.; Erwin, Alice L.

    2015-01-01

    A direct assay of efflux by Escherichia coli AcrAB-TolC and related multidrug pumps would have great value in discovery of new Gram-negative antibiotics. The current understanding of how efflux is affected by the chemical structure and physical properties of molecules is extremely limited, derived from antibacterial data for compounds that inhibit growth of wild-type E. coli. We adapted a previously described fluorescent efflux assay to a 96-well microplate format that measured the ability of test compounds to compete for efflux with Nile Red (an environment-sensitive fluor), independent of antibacterial activity. We show that Nile Red and the lipid-sensitive probe DiBAC4-(3) [bis-(1,3-dibutylbarbituric acid)-trimethine oxonol] can quantify efflux competition in E. coli. We extend the previous findings that the tetracyclines compete with Nile Red and show that DiBAC4-(3) competes with macrolides. The extent of the competition shows a modest correlation with the effect of the acrB deletion on MICs within the compound sets for both dyes. Crystallographic studies identified at least two substrate binding sites in AcrB, the proximal and distal pockets. High-molecular-mass substrates bound the proximal pocket, while low-mass substrates occupied the distal pocket. As DiBAC4-(3) competes with macrolides but not with Nile Red, we propose that DiBAC4-(3) binds the proximal pocket and Nile Red likely binds the distal site. In conclusion, competition with fluorescent probes can be used to study the efflux process for diverse chemical structures and may provide information as to the site of binding and, in some cases, enable rank-ordering a series of related compounds by efflux. PMID:25645845

  12. Achieving second order advantage with multi-way partial least squares and residual bi-linearization with total synchronous fluorescence data of monohydroxy-polycyclic aromatic hydrocarbons in urine samples.

    PubMed

    Calimag-Williams, Korina; Knobel, Gaston; Goicoechea, H C; Campiglia, A D

    2014-02-06

    An attractive approach to handle matrix interference in samples of unknown composition is to generate second- or higher-order data formats and process them with appropriate chemometric algorithms. Several strategies exist to generate high-order data in fluorescence spectroscopy, including wavelength time matrices, excitation-emission matrices and time-resolved excitation-emission matrices. This article tackles a different aspect of generating high-order fluorescence data as it focuses on total synchronous fluorescence spectroscopy. This approach refers to recording synchronous fluorescence spectra at various wavelength offsets. Analogous to the concept of an excitation-emission data format, total synchronous data arrays fit into the category of second-order data. The main difference between them is the non-bilinear behavior of synchronous fluorescence data. Synchronous spectral profiles change with the wavelength offset used for sample excitation. The work presented here reports the first application of total synchronous fluorescence spectroscopy to the analysis of monohydroxy-polycyclic aromatic hydrocarbons in urine samples of unknown composition. Matrix interference is appropriately handled by processing the data either with unfolded-partial least squares and multi-way partial least squares, both followed by residual bi-linearization.

  13. Determination of aromatic sulphur compounds in heavy gas oil by using (low-)flow modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry.

    PubMed

    Franchina, Flavio Antonio; Machado, Maria Elisabete; Tranchida, Peter Quinto; Zini, Cláudia Alcaraz; Caramão, Elina Bastos; Mondello, Luigi

    2015-03-27

    The present research is focused on the development of a flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry (FM GC × GC-MS/MS) method for the determination of classes of aromatic organic sulphur compounds (benzothiophenes, dibenzothiophenes, and benzonaphthothiophene) in heavy gas oil (HGO). The MS/MS instrument was used to provide both full-scan and multiple-reaction-monitoring (MRM) data. Linear retention index (LRI) ranges were used to define the MRM windows for each chemical class. Calibration solutions (internal standard: 1-fluoronaphthalene) were prepared by using an HGO sample, depleted of S compounds. Calibration information was also derived for the thiophene class (along with MRM and LRI data), even though such constituents were not present in the HGO. Linearity was satisfactory over the analyzed concentration range (1-100 mg/L); intra-day precision for the lowest calibration point was always below 17%. Accuracy was also satisfactory, with a maximum percentage error of 3.5% (absolute value) found among the S classes subjected to (semi-)quantification. The highest limit of quantification was calculated to be 299 μg/L (for the C1-benzothiophene class), while the lowest was 21 μg/L (for the C4-benzothiophene class).

  14. Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia)

    USGS Publications Warehouse

    Kannan, K.; Moon, H.-B.; Yun, S.-H.; Agusa, T.; Thomas, N.J.; Tanabe, S.

    2008-01-01

    Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations. ?? The Royal Society of Chemistry.

  15. Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia).

    PubMed

    Kannan, Kurunthachalam; Moon, Hyo-Bang; Yun, Se Hun; Agusa, Tetsuro; Thomas, Nancy J; Tanabe, Shinsuke

    2008-04-01

    Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.

  16. The soluble methane mono-oxygenase of Methylococcus capsulatus (Bath). Its ability to oxygenate n-alkanes, n-alkenes, ethers, and alicyclic, aromatic and heterocyclic compounds.

    PubMed

    Colby, J; Stirling, D I; Dalton, H

    1977-08-01

    1. Methane mono-oxygenase of Methylococcus capsulatus (Bath) catalyses the oxidation of various substituted methane derivatives including methanol. 2. It is a very non-specific oxygenase and, in some of its catalytic properties, apparently resembles the analogous enzyme from Methylomonas methanica but differs from those found in Methylosinus trichosporium and Methylomonas albus. 3. CO is oxidized to CO2. 4. C1-C8 n-alkanes are hydroxylated, yielding mixtures of the corresponding 1- and 2-alcohols; no 3- or 4-alcohols are formed. 5. Terminal alkenes yield the corresponding 1,2-epoxides. cis- or trans-but-2-ene are each oxidized to a mixture of 2,3-epoxybutane and but-2-en-1-ol with retention of the cis or trans configuration in both products; 2-butanone is also formed from cis-but-2-ene only. 6. Dimethyl ether is oxidized. Diethyl ether undergoes sub-terminal oxidation, yielding ethanol and ethanal in equimolar amounts. 7. Methane mono-oxygenase also hydroxylates cyclic alkanes and aromatic compounds. However, styrene yields only styrene epoxide and pyridine yields only pyridine N-oxide. 8. Of those compounds tested, only NADPH can replace NADH as electron donor.

  17. The soluble methane mono-oxygenase of Methylococcus capsulatus (Bath). Its ability to oxygenate n-alkanes, n-alkenes, ethers, and alicyclic, aromatic and heterocyclic compounds.

    PubMed Central

    Colby, J; Stirling, D I; Dalton, H

    1977-01-01

    1. Methane mono-oxygenase of Methylococcus capsulatus (Bath) catalyses the oxidation of various substituted methane derivatives including methanol. 2. It is a very non-specific oxygenase and, in some of its catalytic properties, apparently resembles the analogous enzyme from Methylomonas methanica but differs from those found in Methylosinus trichosporium and Methylomonas albus. 3. CO is oxidized to CO2. 4. C1-C8 n-alkanes are hydroxylated, yielding mixtures of the corresponding 1- and 2-alcohols; no 3- or 4-alcohols are formed. 5. Terminal alkenes yield the corresponding 1,2-epoxides. cis- or trans-but-2-ene are each oxidized to a mixture of 2,3-epoxybutane and but-2-en-1-ol with retention of the cis or trans configuration in both products; 2-butanone is also formed from cis-but-2-ene only. 6. Dimethyl ether is oxidized. Diethyl ether undergoes sub-terminal oxidation, yielding ethanol and ethanal in equimolar amounts. 7. Methane mono-oxygenase also hydroxylates cyclic alkanes and aromatic compounds. However, styrene yields only styrene epoxide and pyridine yields only pyridine N-oxide. 8. Of those compounds tested, only NADPH can replace NADH as electron donor. PMID:411486

  18. Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

    NASA Astrophysics Data System (ADS)

    Sato, Shingo; Tsunoda, Minoru; Suzuki, Minoru; Kutsuna, Masahiro; Takido-uchi, Kiyomi; Shindo, Mitsuru; Mizuguchi, Hitoshi; Obara, Heitaro; Ohya, Hiroaki

    2009-01-01

    Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe 2+ and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths—661 (Cy5) or 568 (Cy3) nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.

  19. Two rhodamine 6G derivative compounds: a structural and fluorescence single-crystal study.

    PubMed

    Di Paolo, Matias; Bossi, Mariano L; Baggio, Ricardo; Suarez, Sebastián A

    2016-10-01

    The synthesis, characterization, structural analysis and fluorescence properties of two rhodamine 6G derivatives are described, namely a propargylamine derivative, 3',6'-bis(ethylamino)-2',7'-dimethyl-2-(methylcyanide)spiro[isoindole-1,9'-xanthen]-3(2H)-one (I), and a γ-aminobutyric acid (GABA) derivative, 3',6'-bis(ethylamino)-2',7'-dimethyl-3-oxospiro[isoindole-1,9'-xanthen]-2(3H)-yl)butyricacid (II). Both structures are compared with four similar ones from the Cambridge Structural Database (CSD), and the interactions involved in the stabilization are analyzed using the atoms in molecules (AIM) theory. Finally, a single-crystal in-situ reaction study is presented, carried out by fluorescence methods, which enabled the `opening' of the spirolactam ring in the solid phase.

  20. Potential of LC Coupled to Fluorescence Detection in Food Metabolomics: Determination of Phenolic Compounds in Virgin Olive Oil.

    PubMed

    Monasterio, Romina P; Olmo-García, Lucía; Bajoub, Aadil; Fernández-Gutiérrez, Alberto; Carrasco-Pancorbo, Alegría

    2016-09-24

    A powerful chromatographic method coupled to a fluorescence detector was developed to determine the phenolic compounds present in virgin olive oil (VOO), with the aim to propose an appropriate alternative to liquid chromatography-mass spectrometry. An excitation wavelength of 285 nm was selected and four different emission wavelengths (316, 328, 350 and 450 nm) were simultaneously recorded, working therefore on "multi-emission" detection mode. With the use of commercially available standards and other standards obtained by semipreparative high performance liquid chromatography, it was possible to identify simple phenols, lignans, several complex phenols, and other phenolic compounds present in the matrix under study. A total of 26 phenolic compounds belonging to different chemical families were identified (23 of them were susceptible of being quantified). The proposed methodology provided detection and quantification limits within the ranges of 0.004-7.143 μg·mL(-1) and 0.013-23.810 μg·mL(-1), respectively. As far as the repeatability is concerned, the relative standard deviation values were below 0.43% for retention time, and 9.05% for peak area. The developed methodology was applied for the determination of phenolic compounds in ten VOOs, both monovarietals and blends. Secoiridoids were the most abundant fraction in all the samples, followed by simple phenolic alcohols, lignans, flavonoids, and phenolic acids (being the abundance order of the latter chemical classes logically depending on the variety and origin of the VOOs).

  1. Potential of LC Coupled to Fluorescence Detection in Food Metabolomics: Determination of Phenolic Compounds in Virgin Olive Oil

    PubMed Central

    Monasterio, Romina P.; Olmo-García, Lucía; Bajoub, Aadil; Fernández-Gutiérrez, Alberto; Carrasco-Pancorbo, Alegría

    2016-01-01

    A powerful chromatographic method coupled to a fluorescence detector was developed to determine the phenolic compounds present in virgin olive oil (VOO), with the aim to propose an appropriate alternative to liquid chromatography-mass spectrometry. An excitation wavelength of 285 nm was selected and four different emission wavelengths (316, 328, 350 and 450 nm) were simultaneously recorded, working therefore on “multi-emission” detection mode. With the use of commercially available standards and other standards obtained by semipre