Sample records for heterocyclic aromatic compounds

  1. Physicochemical Mechanisms of Synergistic Biological Action of Combinations of Aromatic Heterocyclic Compounds

    Directory of Open Access Journals (Sweden)

    Maxim P. Evstigneev


    Full Text Available The mechanisms of synergistic biological effects observed in the simultaneous use of aromatic heterocyclic compounds in combination are reviewed, and the specific biological role of heteroassociation of aromatic molecules is discussed.

  2. Theoretical investigation of the second- and third-order nonlinear optical properties of some fused heterocyclic aromatic compounds (United States)

    Bader, Mamoun M.


    The results of coupled perturbed Hartree-Fock (CPHF) ab initio extended basis set calculations on the gepmetric structures, dipole moments, static first-order ((alpha) ), second-order ((beta) ), and third-order polarizabilities ((gamma) ) of a series of fused heterocyclic aromatic compounds based on quinoline are reported. The effects of the presence/absence of the nitrogen atom as well as the introduction of other substituents (OH, NH2, NO2) at various positions in the ring system on these molecular properties are described. The effect of the presence of N-oxide is also examined. Suggestions for the design of heterocyclic systems with enhanced polarizabilities are made.

  3. Stereoselective synthesis of organosulfur compounds incorporating N-aromatic heterocyclic motifs and quaternary carbon centers via a sulfa-Michael triggered tandem reaction. (United States)

    Qin, Tianyou; Cheng, Lu; Zhang, Sean Xiao-An; Liao, Weiwei


    A novel sulfa-Michael addition (SMA)-triggered tandem reaction was developed by combining a SMA reaction with a simultaneous rearomatization process utilizing a less reactive carbonyl group as an intramolecular electrophile partner, which provided a unique synthetic route to access various organosulfur compounds incorporating an N-aromatic heterocyclic motif and quaternary carbon centers.

  4. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li


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

  5. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions

    NARCIS (Netherlands)

    León Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.


    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  6. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions.

    NARCIS (Netherlands)

    Leon Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.


    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  7. Adsorbed States of phosphonate derivatives of N-heterocyclic aromatic compounds, imidazole, thiazole, and pyridine on colloidal silver: comparison with a silver electrode. (United States)

    Podstawka, Edyta; Olszewski, Tomasz K; Boduszek, Bogdan; Proniewicz, Leonard M


    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.

  8. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications (United States)

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.


    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  9. Composite glycerol/graphite/aromatic acid matrices for thin-layer chromatography/matrix-assisted laser desorption/ionization mass spectrometry of heterocyclic compounds. (United States)

    Esparza, Cesar; Borisov, R S; Varlamov, A V; Zaikin, V G


    New composite matrices have been suggested for the analysis of mixtures of different synthetic organic compounds (N-containing heterocycles and erectile dysfunction drugs) by thin layer chromatography/matrix-assisted laser desorption ionization time-of-flight mass spectrometry (TLC/MALDI-TOF). Different mixtures of classical MALDI matrices and graphite particles dispersed in glycerol were used for the registration of MALDI mass spectra directly from TLC plates after analytes separation. In most of cases, the mass spectra possessed [M+H](+) ions; however, for some analytes only [M+Na](+) and [M+K](+) ions were observed. These ions have been used to generate visualized TLC chromatograms. The described approach increases the desorption/ionization efficiencies of analytes separated by TLC, prevent spot blurring, simplifies and decrease time for sample preparation. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Synthesis and spectroscopic identification of a new series of 2-iminothia-zolidin-4-one compounds from aromatic heterocyclic primary amines (United States)

    Azeez, Hashim J.; Bahram, Roshna


    The present work describes the synthesis and spectroscopic characterization some new 2-imino-thiazolidin-4-one derivatives along with study of their antibacterial activities. The synthesis steps have been classified into three main parts as follows: The first part of this work included preparation of the starting material 2-amino-4-(substitutedphenyl)- 1,3-thiazole during the reaction of thiourea with substituted acetophenone in the presence of iodine. The second part was the synthesis of 2-chloroacetamido-4-(substitutedphenyl)-1,3-thiazole, which has been achieved by the reaction of heterocyclic amine which readily underwent nucleophilic substitution reaction with chloroacetyl chloride in benzene. The third part involved synthesized intermediate compounds, which easily undergo cyclization reaction and result in the formation of a new series of desired products 2-imino-3-[4-(substitutedphenyl)-1,3-thiazol-2-yl] thiazolidin-4-ones. The structures of the synthesized compounds were assigned on the basis of the spectral data such as IR, 1H-NMR, 13C-NMR and 13C-DEPT-135 spectra, which showed the expected frequencies and signals. Finally, the synthesized compounds were screened against two types of bacteria both Escherichia coli G (-ve) and Staphylococcus aureus G (+ve) microorganisms. The results revealed that most tested compounds were showed medium to high activity against both types of test organisms of bacteria especially against E-coli.

  11. Coupling Reactions of α-Bromocarboxylate with Non-Aromatic N-Heterocycles

    Directory of Open Access Journals (Sweden)

    Jozef Csollei


    Full Text Available The conditions for the C-N bond forming reaction (C-N coupling reaction between α-bromocarboxylate and nitrogen-containing non-aromatic heterocyclic rings under heterogeneous copper(I oxide catalysis are investigated in this paper. All the generated compounds were fully characterized by IR, NMR and MS spectroscopy. Ab initio/DFT calculations of partial charges on nitrogen atoms in all the discussed heterocycles and on C(2 of carboxylate under applied conditions were predicted. These in silico results correlate relatively with the experimental observations.

  12. Overview of Polycyclic Aromatic Compounds (PAC) (United States)

    Achten, Christine; Andersson, Jan T.


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

  13. Alkynylation of heterocyclic compounds using hypervalent iodine reagent. (United States)

    Kamlar, M; Císařová, I; Veselý, J


    The alkynylation of various nitrogen- and/or sulphur-containing heterocyclic compounds using hypervalent iodine TMS-EBX by utilization of tertiary amines under mild conditions is described. The developed metal-free methodology furnishes the corresponding alkynylated heterocycles bearing quaternary carbon in high yields.

  14. Design, synthesis and evaluation of aromatic heterocyclic derivatives as potent antifungal agents. (United States)

    Zhao, Shizhen; Zhang, Xiangqian; Wei, Peng; Su, Xin; Zhao, Liyu; Wu, Mengya; Hao, Chenzhou; Liu, Chunchi; Zhao, Dongmei; Cheng, Maosheng


    To further enhance the anti-Aspergillus efficacy of our previously discovered antifungal lead compounds (1), a series of aromatic heterocyclic derivatives were designed, synthesized and evaluated for in vitro antifungal activity. Many of the target compounds showed good inhibitory activity against Candida albicans and Cryptococcus neoformans. In particular, the isoxazole nuclei were more suited for improving the activity against Aspergillus spp. Among these compounds, 2-F substituted analogues 23g and 23h displayed the most remarkable in vitro activity against Candida spp., C. neoformans, A. fumigatus and fluconazole-resistant C.alb. strains, which is superior or comparable to the activity of the reference drugs fluconazole and voriconazole. Notably, the compounds 23g and 23h exhibited low inhibition profiles for various isoforms of human cytochrome P450 and excellent blood plasma stability. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  15. [Development of novel methods for synthesis of heterocyclic compounds catalyzed by transition metals in fluorinated alcohols]. (United States)

    Saito, Akio


    New possibilities for catalytic syntheses of lactone derivatives and nitrogen-containing heterocyclic compounds in fluorinated alcohols are described. The cationic Rh(I) catalyst in fluorinated alcohol solvents (hexafluoroisopropanol: HFIP, trifluoroethanol: TFE) brought about not only mild cycloaddition reactions of ester-tethered compounds but also a facile formation of indole derivatives by the aromatic amino-Claisen rearrangement of N-propargyl aniline derivatives. The use of HFIP as an additive exerted a remarkable effect on the Pictet-Spengler reaction catalyzed by the fluorinated surfactant-combined Brønsted acid catalyst in water.

  16. Alkylation of organic aromatic compounds (United States)

    Smith, L.A. Jr.


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

  17. Heterocyclic Aromatics in Petroleum Coke, Snow, Lake Sediments, and Air Samples from the Athabasca Oil Sands Region. (United States)

    Manzano, Carlos A; Marvin, Chris; Muir, Derek; Harner, Tom; Martin, Jonathan; Zhang, Yifeng


    The aromatic fractions of snow, lake sediment, and air samples collected during 2011-2014 in the Athabasca oil sands region were analyzed using two-dimensional gas chromatography following a nontargeted approach. Commonly monitored aromatics (parent and alkylated-polycyclic aromatic hydrocarbons and dibenzothiophenes) were excluded from the analysis, focusing mainly on other heterocyclic aromatics. The unknowns detected were classified into isomeric groups and tentatively identified using mass spectral libraries. Relative concentrations of heterocyclic aromatics were estimated and were found to decrease with distance from a reference site near the center of the developments and with increasing depth of sediments. The same heterocyclic aromatics identified in snow, lake sediments, and air were observed in extracts of delayed petroleum coke, with similar distributions. This suggests that petroleum coke particles are a potential source of heterocyclic aromatics to the local environment, but other oil sands sources must also be considered. Although the signals of these heterocyclic aromatics diminished with distance, some were detected at large distances (>100 km) in snow and surface lake sediments, suggesting that the impact of industry can extend >50 km. The list of heterocyclic aromatics and the mass spectral library generated in this study can be used for future source apportionment studies.

  18. Aromatic character of nanographene model compounds. (United States)

    Sakamoto, Kenkichi; Nishina, Naoko; Enoki, Toshiaki; Aihara, Jun-ichi


    Superaromatic stabilization energy (SSE) defined to estimate the degree of macrocyclic aromaticity can be used as a local aromaticity index for individual benzene rings in very large polycyclic aromatic hydrocarbons (PAHs) and finite-length graphene nanoribbons. Aromaticity patterns estimated using SSEs indicate that the locations of both highly aromatic and reactive rings in such carbon materials are determined primarily by the edge structures. Aromatic sextets are first placed on the jutting benzene rings on armchair edges, if any, and then on inner nonadjacent benzene rings. In all types of nanographene model compounds, the degree of local aromaticity varies markedly near the edges.

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

    Samokhvalov, Alexander


    Sulfur aromatic compounds, such as mono-, di-, tri-, and tetraalkyl-substituted thiophene, benzothiophenes, dibenzothiophenes, are the molecular components of many fossils (petroleum, oil shale, tar sands, bitumen). Structural units of natural, cross-linked heteroaromatic polymers present in brown coals, turf, and soil are similar to those of sulfur aromatic compounds. Many sulfur aromatic compounds are found in the streams of petroleum refining and upgrading (naphthas, gas oils) and in the consumer products (gasoline, diesel, jet fuels, heating fuels). Besides fossils, the structural fragments of sulfur aromatic compounds are present in molecules of certain organic semiconductors, pesticides, small molecule drugs, and in certain biomolecules present in human body (pheomelanin pigments). Photocatalysis is the frontier area of physical chemistry that studies chemical reactions initiated by absorption of photons by photocatalysts, that is, upon electronic rather than thermal activation, under "green" ambient conditions. This review provides systematization and critical review of the fundamental chemical and physicochemical information on heterogeneous photocatalysis of sulfur aromatic compounds accumulated in the last 20-30 years. Specifically, the following topics are covered: physicochemical properties of sulfur aromatic compounds, major classes of heterogeneous photocatalysts, mechanisms and reactive intermediates of photocatalytic reactions of sulfur aromatic compounds, and the selectivity of these reactions. Quantum chemical calculations of properties and structures of sulfur aromatic compounds, their reactive intermediates, and the structure of adsorption complexes formed on the surface of the photocatalysts are also discussed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Compositions comprising a polypeptide having cellulolytic enhancing activity and a heterocyclic compound and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Feng; Sweeney, Matthew; Quinlan, Jason


    The present invention relates to compositions comprising: a polypeptide having cellulolytic enhancing activity and a heterocyclic compound. The present invention also relates to methods of using the compositions.

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

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


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

  2. Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst (United States)

    Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.


    Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

  3. Synthesis and Broad-Spectrum Antiviral Activity of Some Novel Benzo-Heterocyclic Amine Compounds

    Directory of Open Access Journals (Sweden)

    Da-Jun Zhang


    Full Text Available A series of novel unsaturated five-membered benzo-heterocyclic amine derivatives were synthesized and assayed to determine their in vitro broad-spectrum antiviral activities. The biological results showed that most of our synthesized compounds exhibited potent broad-spectrum antiviral activity. Notably, compounds 3f (IC50 = 3.21–5.06 μM and 3g (IC50 = 0.71–34.87 μM showed potent activity towards both RNA viruses (influenza A, HCV and Cox B3 virus and a DNA virus (HBV at low micromolar concentrations. An SAR study showed that electron-withdrawing substituents located on the aromatic or heteroaromatic ring favored antiviral activity towards RNA viruses.

  4. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    KAUST Repository

    Hussain, Tanveer


    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory calculations. Binding energy range for nucleobases, amino acids and heterocyclic molecules with both the sheets have been found to be (0.43-1.16eV), (0.70-1.58eV) and (0.22-0.96eV) respectively, which along with the binding distances show that these molecules bind to both sheets by physisorption and chemisorption process. The exchange of electric charges between the monolayers and the incident molecules has been examined by means of Bader charge analysis. It has been observed that the introduction of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules alters the electronic properties of both silicene and germanene nano sheets as studied by plotting the total (TDOS) and partial (PDOS) density of states. The DOS plots reveal the variation in the band gaps of both silicene and germanene caused by the introduction of studied molecules. Based on the obtained results we suggest that both silicene and germanene monolayers in their pristine form could be useful for sensing of biomolecules.

  5. Screening of molecular cell targets for carcinogenic heterocyclic aromatic amines by using CALUX® reporter gene assays. (United States)

    Steinberg, Pablo; Behnisch, Peter A; Besselink, Harrie; Brouwer, Abraham A


    Heterocyclic aromatic amines (HCAs) are compounds formed when meat or fish are cooked at high temperatures for a long time or over an open fire. To determine which pathways of toxicity are activated by HCAs, nine out of the ten HCAs known to be carcinogenic in rodents (2-amino-9H-pyrido[2,3-b]indole (AαC), 2-aminodipyrido[1,2-a:3',2-d]imidazole (Glu-P-2), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC), 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2)) were tested in the estrogen receptor α (ERα), androgen receptor (AR), glucocorticoid receptor (GR), peroxisome proliferator-activated receptor γ2 (PPARγ2), polycyclic aromatic hydrocarbons (PAH), Nrf2, and p53 CALUX® reporter gene assays. Trp-P-1 was the only HCA that led to a positive response in the ERα, PPARγ2, and Nrf2 CALUX® assays. In the PAH CALUX® assay, Trp-P-2, MeAαC, and AαC induced luciferase activity to a greater extent than MeIQ and PhIP. In the p53 CALUX® assay without a coupled metabolic activation, only Trp-P-1 and Trp-P-2 enhanced luciferase expression; when a metabolic activation step was coupled to the p53 CALUX® assay, Trp-P-1, Glu-P-2, MeIQ, MeIQx, and PhIP induced a positive response. No HCA was positive in the AR and GR CALUX® assays. Taken together, the results obtained show that the battery of CALUX® assays performed in the present study can successfully be used to screen for molecular cell targets of carcinogenic compounds such as HCAs.

  6. Protonation energies of 1-5-ring polycyclic aromatic nitrogen heterocyclics: comparing experiment and theory. (United States)

    Wiseman, Alexander; Sims, Lacey A; Snead, Russell; Gronert, Scott; Maclagan, Robert G A R; Meot-Ner Mautner, Michael


    Polycyclic nitrogen heterocyclic compounds (PANHs) can be protonated in the gas phase in mass spectrometry, in solution in acidic and biological environments, and if present, in interstellar clouds. Intrinsic molecular effects on PANH basicities can be observed by their gas phase protonation thermochemistry. We determined the gas phase basicities/proton affinities (GBs/PAs) of prototype one-nitrogen, 3-5-ring PANH compounds of increasing sizes and polarizabilities by kinetic bracketing, using proton transfer reactions to reference bases. The experimental proton affinities increase from 1-ring (pyridine, 222.2); to 2-ring (quinoline, 227.8); to 3-5-ring compounds, 227-234 kcal mol(-1). We also calculated the GB/PA values at the M06-2X/6-311+G**//B3LYP/6-31g* level. The computed PAs agree, within the experimental uncertainty, with the experimental values anchored to the upper range of the NIST GB/PA database. Specifically, the computed PAs are smaller than the experimental values by 1.4 ± 0.9 kcal/mol for nonaromatic nitrogen reference bases and for 1-5-ring PANHs, independently of the number of rings, aromaticity, and molecular size. Therefore, a useful method to calculate proton affinities of PANH compounds can use M06-2X/6-311+G**//B3LYP/6-31g* computational PAs + 1.4 ± 0.9 kcal mol(-1). The agreement with experiment supports the NIST database within this accuracy, in the upper range up to 235 kcal mol(-1), even though there are no direct absolute experimental anchor points in this range. For astrochemical applications, the measured PAs allow calculating the energies of the (PANH)(+•) + H2 → (PANH)H(+) + H(•) reactions that may convert the radical ions to less reactive 11-electron ions. The reactions are endothermic or nearly thermoneutral for the 3-5-ring ions and would be very slow at low temperatures, allowing reactive (PANH)(+•) radical ions to persist in interstellar clouds.

  7. Model Compound Studies of Rigid Rod Aromatic Heterocyclic Polymer Systems. Part 1. The Crystal and Molecular Structures of 2,6-Diphenylbenzo (1,2- d:4,5-d’) Bisthiazole & 2,6-Diphenylbenzo (1,2-d:5,4-d’) Bisoxazole (United States)


    to date, the paraconfigured aromatic heterocyclic class of polymers, such as the polybenzoxazoles (PBO) and the polybenz- thiazoles (PBT), are...especially promising, since precipitated films and fibers of these materials exhibit high tensile strengths and good thermal oxidative stabilities. These...The molecular order present in fibers and precipitated films of PBO is believed to exist to some degree in solution just prior to fiber formation and

  8. Synthesis, characterization and in vitro anti-invasive activity screening of polyphenolic and heterocyclic compounds. (United States)

    Parmar, Virinder S; Sharma, Nawal K; Husain, Mofazzal; Watterson, Arthur C; Kumar, Jayant; Samuelson, Lynne A; Cholli, Ashok L; Prasad, Ashok K; Kumar, Ajay; Malhotra, Sanjay; Kumar, Naresh; Jha, Amitabh; Singh, Amarjit; Singh, Ishwar; Himanshu; Vats, Archana; Shakil, Najam A; Trikha, Smriti; Mukherjee, Shubasish; Sharma, Sunil K; Singh, Sanjay K; Kumar, Ajay; Jha, Hriday N; Olsen, Carl E; Stove, Christophe P; Bracke, Marc E; Mareel, Marc M


    Invasion is the hallmark of malignant tumors, and is responsible for the bad prognosis of the untreated cancer patients. The search for anti-invasive treatments led us to screen compounds of different classes for their effect in an assay for invasion. Thirty-nine new compounds synthesized in the present study along with 56 already reported compounds belonging mainly to the classes of lactones, pyrazoles, isoxazoles, coumarins, desoxybenzoins, aromatic ketones, chalcones, chromans, isoflavanones have been tested against organotypic confronting cultures of invasive human MCF-7/6 mammary carcinoma cells with embryonic chick heart fragments in vitro. Three of them (a pyrazole derivative, an isoxazolylcoumarin and a prenylated desoxybenzoin) inhibited invasion at concentrations as low as 1 microM; instead of occupying and replacing the heart tissue within 8 days, the MCF-7/6 cells grew around the heart fragments and left it intact, when treated with these compounds. At the anti-invasive concentration of 1 microM, the three compounds did not affect the growth of the MCF-7/6 cells, as shown in the sulforhodamine B assay. Aggregate formation on agar was not stimulated by any of the three anti-invasive compounds, making an effect on the E-cadherin/catenin complex improbable. This is an invasion suppressor that can be activated in MCF-7/6 cells by a number of other molecules. Our data indicate that some polyphenolic and heterocyclic compounds are anti-invasive without being cytotoxic for the cancer cells.

  9. Normal-phase liquid chromatography retention behavior of polycyclic aromatic sulfur heterocycles and alkyl-substituted polycyclic aromatic sulfur heterocycle isomers on an aminopropyl stationary phase. (United States)

    Wilson, Walter B; Hayes, Hugh V; Sander, Lane C; Campiglia, Andres D; Wise, Stephen A


    Retention indices for 67 polycyclic aromatic sulfur heterocycles (PASHs) and 80 alkyl-substituted PASHs were determined using normal-phase liquid chromatography (NPLC) on an aminopropyl (NH 2 ) stationary phase. The retention behavior of PASH on the NH 2 phase is correlated with the number of aromatic carbon atoms and two structural characteristics have a significant influence on their retention: non-planarity (thickness, T) and the position of the sulfur atom in the bay-region of the structure. Correlations between solute retention on the NH 2 phase and T of PASHs were investigated for three cata-condensed (cata-) PASH isomer groups: (a) 13 four-ring molecular mass (MM) 234 Da cata-PASHs, (b) 20 five-ring MM 284 Da cata-PASHs, and (c) 12 six-ring MM 334 Da cata-PASHs. Correlation coefficients ranged from r = -0.49 (MM 234 Da) to r = -0.65 (MM 334 Da), which were significantly lower than structurally similar PAH isomer groups (r = -0.70 to r = -0.99). The NPLC retention behavior of the PASHs are compared to similar results for PAHs.


    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, Wren; Sephton, Mark A., E-mail: [Impacts and Astromaterials Research Centre, Department of Earth Science and Engineering, Imperial College London SW7 2AZ (United Kingdom)


    The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responses of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.

  11. Bacterial formation of hydroxylated aromatic compounds

    NARCIS (Netherlands)

    Tweel, van den W.J.J.


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

  12. The effect of perfluorination on the aromaticity of benzene and heterocyclic six-membered rings. (United States)

    Wu, Judy I; Pühlhofer, Frank G; Schleyer, Paul von Ragué; Puchta, Ralph; Kiran, Boggavarapu; Mauksch, Michael; Hommes, Nico J R van Eikema; Alkorta, Ibon; Elguero, José


    Despite having six highly electronegative F's, perfluorobenzene C(6)F(6) is as aromatic as benzene. Ab initio block-localized wave function (BLW) computations reveal that both C(6)F(6) and benzene have essentially the same extra cyclic resonance energies (ECREs). Localized molecular orbital (LMO)-nucleus-independent chemical shifts (NICS) grids demonstrates that the F's induce only local paratropic contributions that are not related to aromaticity. Thus, all of the fluorinated benzenes (C(6)F(n)H((6-n)), n = 1-6) have similar ring-LMO-NICS(pi zz) values. However, 1,3-difluorobenzene 2b and 1,3,5-trifluorobenzene 3c are slightly less aromatic than their isomers due to a greater degree of ring charge alternation. Isoelectronic C(5)H(5)Y heterocycles (Y = BH(-), N, NH(+)) are as aromatic as benzene, based on their ring-LMO-NICS(pi zz) and ECRE values, unless extremely electronegative heteroatoms (e.g., Y = O(+)) are involved.

  13. Process for the preparation of aromatic compounds

    NARCIS (Netherlands)

    Schenk, N.J.; Biesbroek, Arnold; Heeres, André; Heeres, Hero


    Aromatic compounds are prepared from a feed stream comprising biomass or a mixture of biomass and synthetic polymer in a process, comprising: a) subjecting the feed stream to a pyrolysis treatment in the presence of a cracking catalyst to yield a vaporous fraction comprising hydrocarbons with

  14. Degradation and formation of polycyclic aromatic compounds during bioslurry treatment of an aged gasworks soil. (United States)

    Lundstedt, Staffan; Haglund, Peter; Oberg, Lars


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

  15. Facile Synthesis and Antimicrobial Evaluation of Some New Heterocyclic Compounds Incorporating a Biologically Active Sulfamoyl Moiety (United States)

    Darwish, Elham S.


    A facile and convenient synthesis of new heterocyclic compounds containing a sulfamoyl moiety suitable for use as antimicrobial agents was reported. The precursor 3-oxo-3-phenyl-N-(4-sulfamoylphenyl)propionamide was coupled smoothly with arenediazonium salt producing hydrazones which reacted with malononitrile or triethylorthoformate affording pyridazine and triazine derivatives, respectively. Also, the reactivity of the same precursor with DMF-DMA was followed by aminotriazole; aromatic aldehydes was followed by hydrazine hydrate, triethylorthoformate, or thiourea affording triazolo[1,5-a]pyrimidine, pyrazole, acrylamide, and dihydropyrimidine derivatives, respectively. On the other hand, treatment of the precursor propionamide with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt which was treated with dilute HCl followed by 2-bromo-1-phenylethanone affording carboxamide derivative. While the same intermediate salt reacted in situ with chloroacetone, ethyl 2-chloroacetate, 3-(2-bromoacetyl)-2H-chromen-2-one, methyl iodide, or 2-oxo-N-phenylpropane hydrazonoyl chloride afforded the thiophene, ketene N,S-acetal, and thiadiazole derivatives, respectively. The structure of the new products was established based on elemental and spectral analysis. Antimicrobial evaluation of some selected examples from the synthesized products was carried out whereby four compounds were found to have moderate activities and one compound showed the highest activity. PMID:25215312

  16. Quantitative correlation of mutagenic and carcinogenic potencies for heterocyclic amines from cooked foods and additional aromatic amines. (United States)

    Hatch, F T; Knize, M G; Moore, D H; Felton, J S


    Aromatic amines have long been recognized as animal and human carcinogens. Recently heterocyclic aromatic amines (thermic amines) have been found in small amounts in cooked foods, primarily meats, and have proven to be potent mutagens and rodent carcinogens. Availability of quantitative databases for mutagenic potency in Salmonella and for carcinogenic potency in rodents has made possible a study of ten heterocyclic thermic amines and 24 aromatic amines. Potencies on mutagenic and carcinogenic scales were significantly correlated. By multiple linear regression analysis and multivariate analysis of variance, two descriptive structural factors were found to modulate the two modes of biological response. These factors were number of rings and methyl substitution at carbon atoms. The quantitative correlation between mutagenic and carcinogenic potencies and the modulating structural factors suggest a significant similarity of molecular mechanisms and support the utility of the short-term bacterial assay in evaluating hazard levels.

  17. Simultaneous determination of 9 heterocyclic aromatic amines in pork products by liquid chromatography coupled with triple quadrupole tandem mass spectrometry (United States)

    Shen, X. C.; Zhang, Y. L.; Cui, Y. Q.; Xu, L. Y.; Li, X.; Qi, J. H.


    Heterocyclic aromatic amines (HAAs) are potent mutagens that formed at high temperature in cooked, protein-rich food. Owing to their frequent intake, an accurate method is essential to access human health risk of HAAs exposure through detecting these compounds in various heat-treated meat products. In this study, a liquid chromatography-electrospray tandem mass spectrometry (LC--ESI-MS/MS) method was developed to perform the determination of 9 mutagenic heterocyclic amines (HAAs) in meat samples with multiple reaction monitoring (MRM) mode. Ultrasound assisted extraction and diatomaceous earth was employed to extract HAAs from food samples, and the analytes were purified and enriched using tandem solid phase extraction, with propyl sulfonic acid coupled to a C18 cartridge. Two parameters, extraction time and eluent, were carefully optimized to improve the extraction and purification efficiency. The LC separation was carried out using a Zorbax SB-C18 (3.5 μm particle size, 2.1 × 150 mm i.d.) column and optimized some parameters, such as pH, concentration and volume. Under the optimal experimental conditions, recoveries ranged from 52.97% to 97.11% with good quality parameters: limit of detection values between 0.02 and 0.24 ng mL-1, linearity (R2>0.998), and run-to-run and day-to-day precisions lower than 9.81% achieved. To evaluate the performance of the method in high throughput analysis of complex meat samples, the LC-MS/MS method was applied to the analysis of HAAs in three food samples, and the results demonstrated that the method can be used for the trace determination of HAAs in pork samples.

  18. On the Extraction of Aromatic Compounds from Hydrocarbons by Imidazolium Ionic Liquids (United States)

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


    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.

  19. Aromatic compounds from three Brazilian Lauraceae species

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Molecular complexes of MoO/sub 2/Cl/sub 2/ with aromatic and heterocyclic azomethines

    Energy Technology Data Exchange (ETDEWEB)

    Abramenko, V.L.; Garnovskij, A.D.; Surpina, L.V. (Voroshilovgradskij Mashinostroitel' nyj Inst. (Ukrainian SSR); Rostovskij-na-Donu Inst. Sel' skokhozyajstvennogo Mashinostroeniya (USSR))


    Earlier unknown MoO/sub 2/Cl/sub 2/xnL(2) molecular complexes (n=0.5, 1, 2; L=Schitt bases (SB) from banzoic (L/sup 1/), Si cylic, ..beta..-oxynaphthoic aldehydes and aromatic, aliphatic, heterocyclic mono- and diamines) are prepared by MoO/sub 2/Cl/sub 2/ (1) interaction with SB in organic solvents. Complex composition is determined by ligand nature. The prepared compounds are finely crystalline substances easily hydrolized in water, unsoluble in most solvents. Increase of frequency of C=N-bond valent oscillations by 10-40 cm/sup -1/ as compared with its position in L spectrum is observed in IR spectra 2 that points out molybdenum coordination by azomethine atom of nitrogen. Bands of Ph-O valent oscillations (1280-1300 cm/sup -1/) and OH/sup -/ (2800-3200 cm/sup -1/) under complexing are not practically shifted that testifies to conservation of intramolecular hydrogen bond in coordinated molecules of the ligands. The mentioned peculiarities in IR spectra permitted to attribute 2 to molecular type complexes with donor-acceptor bond N ..-->.. Mo(6). According to conductometric measurements 2 are 1:2 electrolytes in MeOH and dimethylformamide solutions and they are subjected to the reaction of the main solvolysis.

  1. Development and understanding of new membranes based on aromatic polymers and heterocycles for fuel cells (United States)

    Li, Wen

    Direct methanol fuel cells (DMFC) are appealing as a power source for portable devices as they do not require recharging with an electrical outlet. However, the DMFC technology is confronted with the high crossover of methanol fuel from the anode to the cathode through the currently used Nafion membrane, which not only wastes the fuel but also poisons the cathode platinum catalyst. With an aim to overcome the problems encountered with the Nafion membrane, this dissertation focuses on the design and development of new polymeric membrane materials for DMFC and a fundamental understanding of their structure-property-performance relationships. Several polymeric blend membranes based on acid-base interactions between an aromatic acidic polymer such as sulfonated ploy(ether ether ketone) (SPEEK) and an aromatic basic polymer such as heterocycle tethered poly(sulfone) (PSf) have been explored. Various heterochylces like nitro-benzimidazole (NBIm), 1H-Perimidine (PImd), and 5-amino-benzotriazole (BTraz) have been tethered to PSf to understand the influence of pKa values and the size of the hetrocycles. The blend membranes show lower methanol crossover and better performance in DMFC than plain SPEEK due to an enhancement in proton conductivity through acid-base interactions and an insertion of the heterocycle side groups into the ionic clusters of SPEEK as indicated by small angle X-ray scattering and TEM data. The SPEEK/PSf-PImd blend membrane shows the lowest methanol crossover due to the larger size of the side groups, while the SPEEK/PSf-BTraz blend membrane shows the highest proton conductivity and maximum power density. To further investigate the methanol-blocking effect of the heterocycles, N,N'-Bis-(1H-benzimidazol-2-yl)-isophthalamide (BBImIP) having two amino-benzimidazole groups bonded to a phenyl ring has been incorporated into sulfonated polysulfone (SPSf) and SPEEK membranes. With two 2-amino-benzimidazole groups, which could greatly increase the proton

  2. Degradation of phenolics, nitrogen-heterocyclics and polynuclear aromatic hydrocarbons in a rotating biological contactor. (United States)

    Jeswani, Hansa; Mukherji, Suparna


    The degradation of phenolics, heterocyclics and polynuclear aromatic hydrocarbons (PAHs) in a synthetic biomass gasifier wastewater with average COD of 1388 mg/L was studied in a three stage rotating biological contactor (RBC) using the pyrene degrader, Exiguobacterium aurantiacum and activated sludge consortia (1:3 v/v). As the organic loading rate (OLR) was varied from 3.3 to 14 g/m(2)/d, the COD removal ranged from 63.3% to 92.6%. Complete removal of all the constituents was observed at the lowest OLR of 3.3g/m(2)/d. At 24h hydraulic retention time (HRT) and OLR of 6.6g/m(2)/d complete removal of pyridine, quinoline and benzene and 85-96% removal of phenol, naphthalene, phenanthrene, fluoranthene and pyrene was observed. E. aurantiacum was found to be the dominant bacteria in the biofilm. Clark's model provided good fits to data for all the three stages of the RBC. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Inhibitory effect of liposomal solutions of grape seed extract on the formation of heterocyclic aromatic amines. (United States)

    Natale, Daniela; Gibis, Monika; Rodriguez-Estrada, Maria Teresa; Weiss, Jochen


    The effectiveness of grape seed extract (GSE) encapsulated in liposomes to inhibit the formation of heterocyclic aromatic amines (HAA) during frying of beef patties was assessed. All liposomal systems were prepared by high pressure homogenization at 22 500 psi. A total of six samples (rapeseed oil (control), GSE at 0.1% and 0.2%, and GSE-containing liposomes with 1%, 2%, and 5% soy lecithin) were investigated. MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5b]pyridine), Norharman, and Harman were found after the marinade application and frying. PhIP concentrations decreased upon marination with GSE (0.1%) and GSE-containing liposomes (1% and 5%) (p oil control (p < 0.01) while no effect on β-carboline formation was observed. Results are in contrast to previous studies that had shown that liposomal encapsulation may enhance effectiveness of polyphenols to inhibit radical reactions. A mechanistic model was proposed to explain the observed differences.

  4. Chitosan Film Containing an Iron Complex: Synthesis and Prospects for Heterocyclic Aromatic Amines (HAAs) Recognition. (United States)

    da Silva, Maria Aparecida S; Abreu, Dieric S; Costa, Leandro A; Aguiar, Natanna de A; Paulo, Tércio F; Longhinotti, Elisane; Diógenes, Izaura C N


    Hybrid organic-inorganic materials have been seen as a promising approach to produce sensors for the detection and/or recognition of heterocyclic aromatic amines (HAAs). This work shows the synthesis of a hybrid film as a result of the incorporation of [Fe(CN)5(NH3)]3- into chitosan (CS); CS-[(CN)5Fe(NH3)]3-. The sensitivity of CS-[(CN)5Fe(NH3)]3- toward HAA-like species was evaluated by using pyrazine (pz) as probe molecule in vapor phase by means of electrochemistry and spectroscopic techniques. The crystallinity (SEM-EDS and XRD) decrease of CS-[(CN)5Fe(NH3)]3- in comparison to CS was assigned to the disturbance of the hydrogen bond network within the polymer. Such conclusion was reinforced by the water contact angle measurements. The results presented in this work indicate physical and intermolecular interactions, mostly hydrogen bond, between [Fe(CN)5(NH3)]3- and CS, where the complex is likely trapped in the polymer with its sixth coordination site available for substitution reactions.

  5. Stereochemical Basis for a Unified Structure Activity Theory of Aromatic and Heterocyclic Rings in Selected Opioids and Opioid Peptides

    Directory of Open Access Journals (Sweden)

    Joel S. Goldberg


    Full Text Available This paper presents a novel unified theory of the structure activity relationship of opioids and opioid peptides. It is hypothesized that a virtual or known heterocyclic ring exists in all opioids which have activity in humans, and this ring occupies relative to the aromatic ring of the drug, approximately the same plane in space as the piperidine ring of morphine. Since the rings of morphine are rigid, and the aromatic and piperidine rings are critical structural components for morphine’s analgesic properties, the rigid morphine molecule allows for approximations of the aromatic and heterocyclic relationships in subsequent drug models where bond rotations are common. This hypothesis and five propositions are supported by stereochemistry and experimental observations. Proposition #1 The structure of morphine provides a template. Proposition #2 Steric hindrance of some centric portion of the piperidine ring explains antagonist properties of naloxone, naltrexone and alvimopam. Proposition #3 Methadone has an active conformation which contains a virtual heterocyclic ring which explains its analgesic activity and racemic properties. Proposition #4 The piperidine ring of fentanyl can assume the morphine position under conditions of nitrogen inversion. Proposition #5 The first 3 amino acid sequences of beta endorphin (l-try-gly-gly and the active opioid dipeptide, l-tyr-pro, (as a result of a peptide turn and zwitterion bonding form a virtual piperazine-like ring which is similar in size, shape and location to the heterocyclic rings of morphine, meperidine, and methadone. Potential flaws in this theory are discussed. This theory could be important for future analgesic drug design.

  6. Stereochemical basis for a unified structure activity theory of aromatic and heterocyclic rings in selected opioids and opioid peptides. (United States)

    Goldberg, Joel S


    This paper presents a novel unified theory of the structure activity relationship of opioids and opioid peptides. It is hypothesized that a virtual or known heterocyclic ring exists in all opioids which have activity in humans, and this ring occupies relative to the aromatic ring of the drug, approximately the same plane in space as the piperidine ring of morphine. Since the rings of morphine are rigid, and the aromatic and piperidine rings are critical structural components for morphine's analgesic properties, the rigid morphine molecule allows for approximations of the aromatic and heterocyclic relationships in subsequent drug models where bond rotations are common. This hypothesis and five propositions are supported by stereochemistry and experimental observations.Proposition #1 The structure of morphine provides a template. Proposition #2 Steric hindrance of some centric portion of the piperidine ring explains antagonist properties of naloxone, naltrexone and alvimopam. Proposition #3 Methadone has an active conformation which contains a virtual heterocyclic ring which explains its analgesic activity and racemic properties. Proposition #4 The piperidine ring of fentanyl can assume the morphine position under conditions of nitrogen inversion. Proposition #5 The first 3 amino acid sequences of beta endorphin (l-try-gly-gly) and the active opioid dipeptide, l-tyr-pro, (as a result of a peptide turn and zwitterion bonding) form a virtual piperazine-like ring which is similar in size, shape and location to the heterocyclic rings of morphine, meperidine, and methadone. Potential flaws in this theory are discussed.This theory could be important for future analgesic drug design.

  7. Componentes voláteis do café torrado. Parte I: compostos heterocíclicos Volatile components in roasted coffee. Part I: heterocyclic compounds

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Bastos De Maria


    Full Text Available A review of heterocyclic compounds in roasted coffee is presented. The contents, precursors and sensorial properties of furans, pyrroles, oxazoles, thiazoles, thiophenes, pyrazines and pyridines are discussed. The impact heterocyclic compounds of coffee aroma are described.

  8. Influence of fused aromatic ring on the stability of charge transfer complex between iodine and some five membered heterocyclic molecules through ultrasonic and spectral studies (United States)

    Ulagendran, V.; Balu, P.; Kannappan, V.; Kumar, R.; Jayakumar, S.


    The charge transfer (CT) interaction between two fused heterocyclic compounds with basic pyrrole group as donors, viz., indole (IND) and carbazole (CAR), and iodine (acceptor) in DMSO medium is investigated by ultrasonic and UV-visible spectral methods at 303 K. The formation of CT complex in these systems is established from the trend in acoustical and excess thermo acoustical properties with molar concentration. The frequency acoustic spectra (FAS) is also carried out on these two systems for two fixed concentrations 0.002 M and 0.02 M, and in the frequency range 1 MHz-10 MHz to justify the frequency chosen for ultrasonic study. The absorption coefficient values in solution are computed and discussed. The formation constants of these complexes are determined using Kannappan equation in ultrasonic method. The formation of 1:1 complexes between iodine and IND, CAR was established by the theory of Benesi - Hildebrand in the UV-visible spectroscopic method. The stability constants of the CT complexes determined by spectroscopic and ultrasonic methods show a similar trend. These values also indicate that the presence of fused aromatic ring influences significantly when compared with K values of similar CT complexes of parent five membered heterocyclic compound (pyrrole) reported by us earlier.

  9. Separation of nitrogen heterocyclic compounds contained in coal tar absorption oil fraction by solvent extraction; Yobai chushutsuho ni yoru korutaru kyushuyu ryubun ni fukumareru ganchisso fukuso kanshiki kagobutsu no bunri

    Energy Technology Data Exchange (ETDEWEB)

    Egashira, R.; Nagai, M. [Tokyo Inst. of Tech., Tokyo (Japan). Graduate School of Science and Engineering


    The liquid-liquid equilibrium properties (distribution coefficient and separation selectivity) between the feed of coal tar absorption oil fraction and the solvent (aqueous solution of methanol or that of tetrahydrothiophene-1,1-dioxide (sulfolane)) were experimentally measured with changing various conditions (water content in the solvent, etc.) in order to study the performance of operation and of separation. Nitrogen heterocyclic compounds (2,3-benzopyridine (quinoline), 3,4-benzopyridine (isoquinoline), and 2,3-benzopyrrole (benzo[b]pyrrole, indole)) were extracted preferentially to aromatic hydrocarbon (2-methylnaphthalene) in all case. The distribution coefficients of heterocyclic compounds and aromatic hydrocarbon decreased, and the separation selectivities of the heterocyclic compounds relative to the aromatic hydrocarbon increased with the water content in the extract. The aqueous solution of methanol was superior as a solvent to that of sulfolane in terms of both operation and separation performances. The above distribution coefficients were used to carry out the simple process simulation of extraction operation where the solvent was the aqueous solution of methanol. The multi-stage structure of equilibrium stage and counter-current contact between the feed and solvent improved the concentrations and yield of the heterocyclic compounds in the product that indicated process feasibility of the separation technique. (author)

  10. Effects of Electron Acceptors, Reducing Agents, and Toxic Metabolites on Anaerobic Degradation of Heterocyclic Compounds

    DEFF Research Database (Denmark)

    Licht, Dorthe; Ahring, Birgitte Kiær; Arvin, Erik


    Degradation of four heterocyclic compounds was examined under nitrate-reducing, sulphate-reducing and methanogenic conditions. Soil samples from a creosote-polluted site in Denmark were used as inoculum. Indole and quinoline were degraded under all redox conditions with the highest degradation...

  11. The C-H bond dissociation enthalpies in fused N-heterocyclic compounds (United States)

    Wang, Ying-Xing; Zheng, Wen-Rui; Ding, Lan-Lan


    The C-H bond dissociation enthalpies (BDEs) of the 26 N, O, S-containing mono-heterocyclic compounds were evaluated using the composite high-level ab initio methods G3 and G4. The C-H BDEs for 32 heterocyclic compounds were calculated using 8 types of density functional theory (DFT) methods. Comparing with the experimental values, the BMK method gave the lowest root mean square error (RMSE) of 7.2 kJ/mol. Therefore, the C-H BDEs of N-fused-heterocyclic compounds at different positions were investigated by the BMK method. By NBO analysis two linear relationships between the C-H BDEs of quinoline and isoquinoline with natural charges qC/ e in molecules and with natural charges qC/ e in radicals were found. The substituent effects on C(α)-H BDEs in N-fused-heterocyclic compounds were also discussed. It was found that there are two linear relationships between the C(α)-H BDEs of quinoline and isoquinoline derivatives with natural charges qC(α)/ e for the EDGs and CEGs substituents.

  12. Spectroscopic Characterization of Key Aromatic and Heterocyclic Molecules: A Route toward the Origin of Life (United States)

    Puzzarini, Cristina; Baiardi, Alberto; Bloino, Julien; Barone, Vincenzo; Murphy, Thomas E.; Drew, H. Dennis; Ali, Ashraf


    To gain information on the abiotic synthesis of the building blocks of life from simple molecules, and their subsequent chemical evolution to biological systems, the starting point is the identification of target species in Titan-like planets; I.e., planets that resemble the primitive Earth, as well as in Earth-like planets in the habitable zone of their star, namely planets where life can be already originated. In this scenario, molecular spectroscopy plays a crucial role because spectroscopic signatures are at the basis of an unequivocal proof for the presence of these target molecules. Thanks to advances in many different techniques and NASA’s successful Kepler exoplanet transit mission, thousands of diverse planets outside of our solar system have been discovered. The James Webb Space Telescope (JWST), scheduled to be launched in 2018, will be very helpful in the identification of biosignature gases in Earth-like planets’ atmospheres and prebiotic molecule signatures in Titan-like atmospheres, by observing their absorption during transits. Although the search for key-target molecules in exoplanet atmospheres can be carried out by the JWST Transit Spectroscopy in the infrared (IR) region (0.6-29 μm wavelength range), opportunities for their detection in protostellar cores, protoplanetary disks, and on Titan are also offered by interferometric high spectral and spatial resolution observations using the Atacama Large Millimeter/submillimeter Array. In the present work, target molecules have been selected, and their spectroscopic characterization presented in view of supporting their infrared and complementary millimeter/submillimeter-wave spectral observations. In detail, the selected target molecules include: (1) the three-membered oxygen-containing heterocycles, oxirane and protonated oxirane; (2) the cyclopropenyl cation and its methyl derivative; (3) two examples of ortho- and peri-fused tri-cyclic aromatic rings, I.e., the phenalenyl cation ({{{C}}}13

  13. [Determination of 10 heterocyclic aromatic amines in beef jerky by high performance liquid chromatography]. (United States)

    Wan, Kehui; Peng, Zengqi; Shao, Bin; Yao, Yao; Shi, Jinming


    An analytical method was developed for the simultaneous determination of 10 heterocyclic aromatic amines (HAAs) in beef jerky by solid phase extraction-high performance liquid chromatography (SPE-HPLC). The HAAs were eluted from an Extrelut NT 20 SPE column with 60 mL dichlormethane (containing 5% toluene), and then the extract was purified with a propylsulfonic acid silica (PRS) column and a C18 SPE column, and finally, the HAAs were stored in a methanol-ammonia solution. The separation was achieved by using a TSK-gel ODS-80 column and a gradient elution with the mobile phases of acetonitrile and 0.05 mol/L acetic acid-ammonium acetate buffer (pH 3.5). The identification and quantitative analysis of the HAAs fraction were carried out using an HPLC system with ultraviolet-fluorescence detectors. The results showed that the correlation coefficients of the 10 HAAs were all above 0.999 and the limits of detection were in the range from 0.02 to 2.46 ng/g. The recoveries of the 10 HAAs spiked in beef samples were 61.69% - 101.81% with the relative standard deviations (RSDs) between 0.28% and 7.81%. 1-Methyl-9H-pyrido[4,3-b] indole (Harman) and 9H-pyrido [4,3-b]indole (Norharman) were detected in all beef jerky, and the total HAAs content of beef jerky were between 16.65 and 60.38 ng/g. This method is with wide linear range and high sensitivity, and is enough for the analysis of the HAAs in actual meat samples.

  14. Physiologically active substances from marine sponges IV: Heterocyclic compounds. (United States)

    Chib, J S; Stempien, M F; Cecil, J T; Ruggieri, G D; Nigrelli, R F


    Several guanidine compounds were synthesized by the reaction of acid chlorides of thiophene and furan with guanidines. Some of these compounds showed antibiotic and cytotoxic activities. Series of pyrrole compounds were synthesized and found to have significant antibiotic activity.

  15. Content of heterocyclic amines and polycyclic aromatic hydrocarbons in pork, beef and chicken barbecued at home by Danish consumers

    DEFF Research Database (Denmark)

    Aaslyng, Margit D.; Duedahl-Olesen, Lene; Jensen, Kirsten


    It is a well-known fact that, when meat is barbecued, several harmful components, including heterocyclic amines (HCA) and polycyclic aromatic hydrocarbons (PAH), may be formed. The aim of this study was to determine the HCA and PAH content in meat (pork, chicken and beef) when barbecued at home...... of PAH showed a markedly higher concentration of PAH in beef compared with pork and chicken. In general, a correlation between the HCA content and the surface colour of the meat was found, the darker the colour the higher the HCA concentrations....

  16. Heterocyclic compounds: toxic effects using algae, daphnids, and the Salmonella/microsome test taking methodical quantitative aspects into account. (United States)

    Eisentraeger, Adolf; Brinkmann, Corinna; Hollert, Henner; Sagner, Anne; Tiehm, Andreas; Neuwoehner, Judith


    Heterocyclic aromatic hydrocarbons containing nitrogen, sulfur, or oxygen (NSO-HET), have been detected in air, soil, sewage sludge, marine environments, and freshwater sediments. Since toxicity data on this class of substances are scarce, the present study focuses on possible implications NSO-HET have for ecotoxicity (algae and daphnids) and mutagenicity (Salmonella/microsome test). A combination of bioassays and chemical-analytical quantification of the test compounds during toxicity assays should aid in determination of the hazard potential. Samples of the test concentrations of 14 NSO-HET were taken at the beginning and end of the bioassays; these samples were then quantified by high-performance liquid chromatography. The toxicity potential of the substances was evaluated and compared with the toxicity calculated with the nominal concentrations. Significantly different results were obtained primarily for volatile or highly hydrophobic NSO-HET. The concentration of heterocyclic hydrocarbons can change significantly during the algae and Daphnia test. The EC50 values (effective concentration value: the concentration of a chemical that is required to produce a 50% effect) calculated with the nominal concentrations underestimate the toxicity by a factor of up to 50. Prioritizing the tested compounds according to toxicity, the mutagenic and toxic compounds quinoline, 6-methylquinoline, and xanthene have to be listed first. The greatest ecotoxic potential on algae and daphnids was determined for dibenzothiophene followed by acridine. In the Daphnia magna immobilization test, benzofuran, dibenzofuran, 2-methylbenzofuran, and 2,3-dimethylbenzofuran and also carbazole are ecotoxicologically relevant with EC50 values below 10 mg/L. These substances are followed by indole with a high ecotoxic effect to daphnids and less effect to algae. Only minor toxic effects were observed for 2-methylpyridine and 2,4,6-trimethylpyridine.

  17. Heterocyclic Aromatic Amines in Domestically Prepared Chicken and Fish from Singapore Chinese Households

    Energy Technology Data Exchange (ETDEWEB)

    Salmon, C P; Knize, M G; Felton, J S; Zhao, B; Seow, A


    Chicken and fish samples prepared by 42 Singapore Chinese in their homes were obtained. Researchers were present to collect data on raw meat weight, cooking time, maximum cooking surface temperature, and cooked meat weight. Each participant prepared one pan-fried fish sample and two pan-fried chicken samples, one marinated, one not marinated. The cooked samples were analyzed for five heterocyclic aromatic amine (HAA) mutagens, including MeIQx (2-amino 3,8-dimethylimidazo[4,5-f]quinoxaline); 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline); 7,8-DiMeIQx (2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline); PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), and IFP (2-amino-(1,6-dimethylfuro[3,2-e]imidazo [4,5-b])pyridine). A paired Student's t-test showed that marinated chicken had lower concentrations of PhIP (p<0.05), but higher concentrations of MeIQx (p<0.05) and 4,8-DiMeIQx (p<0.001) than non-marinated chicken, and also that weight loss due to cooking was less in marinated chicken than in non-marinated chicken (p<0.001). Interestingly, the maximum cooking surface temperature was higher for fish than for either marinated or non-marinated chicken (P<0.001), yet fish was lower in 4,8-DiMeIQx per gram than marinated or non-marinated chicken (p<0.001), lower in PhIP than non-marinated chicken (P<0.05), and lost less weight due to cooking than either marinated or non-marinated chicken (P<0.001). Fish was also lower in MeIQx and 7,8-DiMeIQx than marinated chicken (P<0.05). This study provides new information on HAA content in the Singapore Chinese diet.

  18. Separation of nitrogen heterocyclic compounds from model coal tar fraction by solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, S.J.; Chun, Y.J. [Chungwoon University, Chungnam (Republic of Korea). Dept. of Material Science & Applied Chemistry


    The separation of four kinds of nitrogen heterocyclic compounds (NHCs) from a model mixture comprising NHCs (indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)), three kinds of bicyclic aromatic compounds (BACs; 1-methyl-naphthalene (IMN), 2-methyl naphthalene (2MN), dimethylnaphthalene (DMN)), biphenyl (Bp) and phenyl ether (Pe) was examined by a solvent extraction. The model mixture used as a raw material of this work was prepared according to the components and compositions contained in coal tar fraction (the temperature ranges of fraction: 240-265{sup o}C). An aqueous solution of methanol, ethanol, iso-propyl alcohol, N,N-dimethyl acetamide, DMF, formamide, N-methylformamide/methanol, and formamide/methanol were used as solvents. An aqueous solution of formamide was found suitable for separating NHCs contained in coal tar fraction based on distribution coefficient and selectivity. The effect of operation factors on separating NHCs was investigated by the distribution equilibrium using an aqueous solution of formamide. Increasing the operation temperature and the volume ratio of solvent to feed at initial (S/F)(o) resulted in improving the distribution coefficients of each NHC, but increasing the volume fraction of water in the solvent at initial (y(w,O)) resulted in deteriorating the distribution coefficients of each NHC. With increasing y(w,O) and (S/F)(o), the selectivities of each NHC in reference to DMN increased. Increase in operation temperature resulted in decrease in selectivities of each NHC in reference to DMN. At an experimental condition fixed, the sequence of the distribution coefficient and selectivity in reference to DMN for each NHC was In {gt} iQ {gt} Q {gt} Qu, and also the sequence of the distribution coefficient for each BAC was IMN {gt} 2MN {gt} DMN. The sequence of the distribution coefficient for entire compounds analyzed by this work was In {gt} iQ {gt} Q {gt} Qu {gt} BP {gt} 1MN {gt} 2MN {gt} Pe {gt} DMN.

  19. Application of micro-solid-phase extraction for the on-site extraction of heterocyclic aromatic amines in seawater. (United States)

    Basheer, Chanbasha


    An efficient on-site extraction technique to determine carcinogenic heterocyclic aromatic amines in seawater has been reported. A micro-solid-phase extraction device placed inside a portable battery-operated pump was used for the on-site extraction of seawater samples. Before on-site applications, parameters that influence the extraction efficiency (extraction time, type of sorbent materials, suitable desorption solvent, desorption time, and sample volume) were investigated and optimized in the laboratory. The developed method was then used for the on-site sampling of heterocyclic aromatic amines determination in seawater samples close to distillation plant. Once the on-site extraction completed, the small extraction device with the analytes was brought back to the laboratory for analysis using high-performance liquid chromatography with fluorescence detection. Based on the optimized conditions, the calibration curves were linear over the concentration range of 0.05-20 μg/L with correlation coefficients up to 0.996. The limits of detection were 0.004-0.026 μg/L, and the reproducibility values were between 1.3 and 7.5%. To evaluate the extraction efficiency, a comparison was made with conventional solid-phase extraction and it was applied to various fortified real seawater samples. The average relative recoveries obtained from the spiked seawater samples varied in the range 79.9-95.2%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Jairton Dupont


    Full Text Available The liquid-liquid equilibrium for the ternary system formed by n-octane andaromatic (alkylbenzenes and heteroaromatic compounds (nitrogen and sulfur containingheterocyles and 1-alkyl-3-methylimidazolium ionic liquids (ILs associated with variousanions has been investigated. The selectivity on the extraction of a specific aromaticcompound is influenced by anion volume, hydrogen bond strength between the anion andthe 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 throughCH-π hydrogen bonds and the quantity of these aromatics in the IL phase decreases withthe increase of the steric hindrance imposed by the substituents on the aromatic nucleus. Inthe case of nitrogen heterocycles the interaction occurs preferentially throughN(heteroaromatic-H(imidazolium hydrogen bonds and the extraction process is largelycontrolled by the nitrogen heterocycle pKa. Competitive extraction experiments suggestthat benzene, pyridine and dibenzothiophene do not compete for the same hydrogen bondsites of the IL.

  1. Configurationally stable longitudinally twisted polycyclic aromatic compounds. (United States)

    Walters, Robert S; Kraml, Christina M; Byrne, Neal; Ho, Douglas M; Qin, Qian; Coughlin, Frederick J; Bernhard, Stefan; Pascal, Robert A


    Two strategies for the synthesis of configurationally stable twisted polycyclic aromatic compounds (PACs) were pursued. The first approach employed dissymmetrically positioned 1-naphthyl substituents to bias the direction of twist in highly substituted PACs. 2,3-Bis(1-naphthyl)-1,4-diphenyltriphenylene (7) was prepared, and its meso cis-dinaphthyl and enantiomeric trans-dinaphthyl isomers were resolved by preparative supercritical fluid chromatography (SFC) on chiral supports. Similarly, several naphthyl-substituted derivatives of the more highly twisted 9,10,11,12,13,14-hexaphenylbenzo[b]triphenylene (2) were prepared. Of these, 10-(1-naphthyl)-9,11,12,14-tetraphenylbenzo[b]triphenylene (13) was resolved by SFC on a chiral support. The pure enantiomers of trans-7 showed moderately large specific rotations ([alpha]D(25) = -330 and +320 degrees), but the specific rotations for the enantiomers of 13 were unexpectedly small ([alpha]D(25) = -23 and +23 degrees). Computational studies suggest that the latter result is due to presence of a minor conformation of 13 possessing a larger rotation of opposite sign than the major conformation. Both 7 and 13 showed strong circular dichroism and moderately strong circularly polarized luminescence. A byproduct of these syntheses was 9,10,19,21-tetraphenyldiphenanthro[9,10-b:9,10-h]carbazole (15), a very crowded carbazole that exhibits an 81 degree end-to-end twist but is not resolvable. In the second approach, the large, twisted, polycyclic aromatic ligand 9,10,11,12,13,14-hexaphenylbenzo[h]naphtho[2,3-f]quinoline (21, an aza-2) was used to prepare the chiral, cyclometallated iridium(III) complex 4. The ligand 21 was prepared via an unusually stable benzannulated norbornadienone, for which the free energy of activation for decarbonylation was a remarkable 33.5 kcal/mol. The iridium complex 4 proved to be configurationally stable and resolvable by analytical HPLC on chiral supports, but the low solubility of 4 prevented its

  2. Inhibitory effect of cellulose fibers on the formation of heterocyclic aromatic amines in grilled beef patties. (United States)

    Gibis, Monika; Weiss, Jochen


    Microcrystalline cellulose (MCC) or carboxymethyl cellulose (CMC) can be used as fat replacers; both are nondigestible fibers. As water-holding compounds, the impact of added CMC or MCC was studied concerning the formation of heterocyclic amines (HAAs). Low-fat patties with 0.5-3% MCC/CMC were prepared using 90% of beef and 10% of an aqueous fiber dispersion and were determined for HAA-levels after grilling. The HAAs in patties containing CMC(MCC) were found in the following concentrations; MeIQx (2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline) 0.6-2.7 (0.9-3.3)ng/g, 4,8-DiMeIQx (2-Amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) n.d.-1.5 (n.d.-2.2)ng/g and PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine) 0.03-0.3 (0.06-0.2)ng/g. The patties clearly contained lower HAA-levels with increasing addition of CMC or MCC. A continuous increase of the concentrations of comutagenic harman was observed (CMC: 1.2-13.2; MCC: 5.2-11.4ng/g) for increasing levels of fibers and a slight decrease of the content of norharman for MCC (0.5-1.6ng/g). No clear tendency was found for norharman using CMC (0.3-1.1ng/g). Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Abiotic synthesis of purines and other heterocyclic compounds by the action of electrical discharges (United States)

    Yuasa, S.; Flory, D.; Basile, B.; Oro, J.


    The synthesis of purines and pyrimidines using Oparin-Urey-type primitive earth atmospheres has been demonstrated by reacting methane, ethane, and ammonia in electrical discharges. Adenine, guaine, 4-aminoimidazole-5-carboxamide (AICA), and isocytosine have been identified by UV spectrometry and paper chromatography as the products of the reaction. The total yields of the identified heterocyclic compounds are 0.0023 percent. It is concluded that adenine synthesis occurs at a much lower concentration of hydrogen cyanide than has been shown by earlier studies. Pathways for the synthesis of purines from hydrogen cyanide are discussed, and a comparison of the heterocyclic compounds that have been identified in meteorites and in prebiotic reactions is presented.

  4. Mn(III-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Md. Aminul Haque


    Full Text Available The Mn(III-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

  5. Cytotoxicity and 2D-QSAR study of some heterocyclic compounds

    Directory of Open Access Journals (Sweden)

    M. Abul Kashem Liton


    Full Text Available Herein we have studied the cytotoxicity and quantitative structure–activity relationship (QSAR of heterocyclic compounds containing cyclic urea and thiourea nuclei. A set of 22 hydantoin and thiohydantoin related heterocyclic compounds were investigated with respect to their LC50 values (Log of LC50 against brine shrimp lethality bioassay in order to derive the 2D-QSAR models using MLR, PLS and ANN methods. The best predictive models by MLR, PLS and ANN methods gave highly significant square correlation coefficient (R2 values of 0.83, 0.81 and 0.91 respectively. The model also exhibited good predictive power confirmed by the high value of cross validated correlation coefficient Q2 (0.74.

  6. Synthesis and biological activity of some heterocyclic compounds ...

    Indian Academy of Sciences (India)

    A number of 1-substituted-2-methyl benzimidazole derivatives have been synthesized and tested for their antibacterial activities. The chemical structures of the newly synthesized compounds were verified on the basis of spectral and elemental methods of analyses. Investigation of antimicrobial activity of the compounds ...

  7. Chemotheraphy Efficiency of Phosphonium Heterocyclic Compounds with Pyrimidine Cycle in Models of Generalized Staph Infection

    Directory of Open Access Journals (Sweden)

    A.V. Humenna


    Full Text Available It was conducted the study of the effectiveness of chemotherapy with 2-phenyl-4-(1-pyrrolidinyl-6-izopropiltio-5-pyrimidyltriphenylphosphonium perchlorate, which refers to phosphonium heterocyclic compounds with pyrimidine cycle in the experiment on the model of generalized staph infection. The results were positive and they allow make a conclusion about the possibility of their use in clinical trials and develop promising antibacterial and antiseptic preparations on their basis.


    Directory of Open Access Journals (Sweden)



    Full Text Available It is well known that growth and morphogenesis of plant tissue cultures can be improved by small amounts of some organic compounds. Heterocyclic compounds such as chromanones and thiazoles derivatives, valuable because of their potential biological activities, have also been reported as pesticides, herbicides and plant-growth regulators. In the present study, different concentrations of chromanones and thiazoles derivatives were employed to evaluate their effects on plantlets growth of Ocimum basilicum L. and Echinacea purpurea L. The studied compounds were proved to be growth inhibitors at high concentrations. A growth stimulation effect was registered at low concentration.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Heterocyclic aromatic amine content in chicken burgers and chicken nuggets sold in fast food restaurants and effects of green tea extract and microwave thawing on their formation (United States)

    The aims of the current study were to investigate the presence of carcinogenic and mutagenic heterocyclic aromatic amines (HAAs) in chicken burgers (CBs) and chicken nuggets (CNs) purchased from fast food restaurants and the effects of green tea extract addition (GTE) to the covering material as wel...

  11. Some new azole type heterocyclic compounds as antifungal agents

    Directory of Open Access Journals (Sweden)

    Mohammad Russell


    Full Text Available Schiff’s base1-[(2,4-difluorophenyl-2-(1H-1,2,4-triazol-1-yl]ethanone thiosemicarbazone (compound 1A wasprepared by condensation of 1-(2,4-difluorophenyl-2- [1 (H-1,2,4-triazol-1-yl]ethanone (1with thiosemicarbazide. The compound 1A, on reaction with α-halogenoketones yielded 1-(2, 4-difluorophenyl-2-[(1H-1,2,4-triazol-1-yl] ethanone [2-[4-halogenophenyl] thiazolyl]hydrazone.Anti-fungal activity of all the compounds has been tested against four fungal organism: C. albicans , Colletotrichum spp., A. nigar and Fusarium spp. commonly responsible for fungal infections in Bangladesh.

  12. Meat intake and bladder cancer in a prospective study : a role for heterocyclic aromatic amines?

    NARCIS (Netherlands)

    Lumbreras, B.; Garte, S.; Overvad, K.; Tjonneland, A.; Clavel-Chapelon, F.; Linseisen, J. P.; Boeing, H.; Trichopoulou, A.; Palli, D.; Peluso, M.; Krogh, V.; Tumino, R.; Panico, S.; Bueno-De-Mesquita, H. B.; Peeters, P. H.; Lund, E.; Martinez, C.; Dorronsoro, M.; Barricarte, A.; Chirlaque, M. -D.; Quiros, J. R.; Berglund, G.; Hallmans, G.; Day, N. E.; Key, T. J.; Saracci, R.; Kaaks, R.; Malaveille, C.; Ferrari, P.; Boffetta, P.; Norat, T.; Riboli, E.; Gonzalez, C. A.; Vineis, P.

    Objective The suspect carcinogens, heterocyclic amines (HAAs), found in well-done meat require host-mediated metabolic activation before inducing DNA mutations. The role of SULT1A1 and of NAT2 on the activation of HAAs suggests that NAT2 rapid acetylator genotype and SULT1A1 allele variants can have

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

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


    The biological conversion of plant lignocellulose plays an essential role not only in carbon cycling in terrestrial ecosystems but also is an important part of the production of second generation biofuels and biochemicals. The presence of the recalcitrant aromatic polymer lignin is one of the major obstacles in the biofuel/biochemical production process and therefore microbial degradation of lignin is receiving a great deal of attention. Fungi are the main degraders of plant biomass, and in particular the basidiomycete white rot fungi are of major importance in converting plant aromatics due to their ability to degrade lignin. However, the aromatic monomers that are released from lignin and other aromatic compounds of plant biomass are toxic for most fungi already at low levels, and therefore conversion of these compounds to less toxic metabolites is essential for fungi. Although the release of aromatic compounds from plant biomass by fungi has been studied extensively, relatively little attention has been given to the metabolic pathways that convert the resulting aromatic monomers. In this review we provide an overview of the aromatic components of plant biomass, and their release and conversion by fungi. Finally, we will summarize the applications of fungal systems related to plant aromatics. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Sulfur-containing heterocyclic compounds with potential antidiabetic activity

    Directory of Open Access Journals (Sweden)

    E. A. Savateeva


    Full Text Available The essential link in the pathogenesis of diabetes mellitus and its complications is a non-enzymatic glycosylation of proteins. However, modern endocrinology lacks of clinically effective pharmaceuticals for its correction. The screening of 23 derivatives of 1,3,4-thiadiazine the ability to inhibit the reaction of non-enzymatic glycosylation of proteins in vitro was held, and 11 the most active compounds of them were selected, also the relationship «structure – activity» was investigated. An essential part of the pathogenesis of diabetes mellitus and its complications is non-enzymatic glycosylation of proteins. However, modern endocrinology lacks clinically effective medicines for its correction.

  15. Acetonitrile extraction coupled with UHPLC-MS/MS for the accurate quantification of 17 heterocyclic aromatic amines in meat products. (United States)

    Yan, Yan; Zhang, Shuang; Tao, Guan-Jun; You, Feng-Hui; Chen, Jie; Zeng, Mao-Mao


    This study proposed a simple and accurate acetonitrile extraction pretreatment method coupled with ultrahigh-performance liquid chromatography with tandem mass spectrometry for the simultaneous determination of 17 heterocyclic aromatic amines (HAAs) in meat products. With this new method, all 17 HAAs, including 11 polar and 6 nonpolarHAAs, were simultaneously extracted by acetonitrile and purified by one-step Oasis MCX cartridge purification. Compared with two different improved reference methods, the acetonitrile method could obtain higher recoveries (in the range of 42.5% to 99.0%) and better repeatability (lower than 12.2%). The limits of quantification were calculated between 0.028ngg(-1)and0.648ngg(-1) with high correlation coefficients (r>0.9976) in wide linear ranges. The proposed acetonitrile method was successfully applied to the analysis of the HAAs levels in 10 commercial meat products with satisfactory recoveries. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Heterocyclic Anticancer Compounds: Recent Advances and the Paradigm Shift towards the Use of Nanomedicine’s Tool Box

    Directory of Open Access Journals (Sweden)

    Pedro Martins


    Full Text Available The majority of heterocycle compounds and typically common heterocycle fragments present in most pharmaceuticals currently marketed, alongside with their intrinsic versatility and unique physicochemical properties, have poised them as true cornerstones of medicinal chemistry. Apart from the already marketed drugs, there are many other being investigated for their promising activity against several malignancies. In particular, anticancer research has been capitalizing on the intrinsic versatility and dynamic core scaffold of these compounds. Nevertheless, as for any other promising anticancer drugs, heterocyclic compounds do not come without shortcomings. In this review, we provide for a concise overview of heterocyclic active compounds and families and their main applications in medicine. We shall focus on those suitable for cancer therapy while simultaneously addressing main biochemical modes of action, biological targets, structure-activity relationships as well as intrinsic limitation issues in the use of these compounds. Finally, considering the advent of nanotechnology for effective selective targeting of drugs, we shall discuss fundamental aspects and considerations on nanovectorization of such compounds that may improve pharmacokinetic/pharmacodynamic properties of heterocycles.

  17. Inhibitory effect of synthetic aromatic heterocycle thiosemicarbazone derivatives on mushroom tyrosinase: Insights from fluorescence, (1)H NMR titration and molecular docking studies. (United States)

    Xie, Juan; Dong, Huanhuan; Yu, Yanying; Cao, Shuwen


    Three structurally similar aromatic heterocyclic compounds 2-thiophenecarboxaldehyde (a), 2-furaldehyde (b), 2-pyrrolecarboxaldehyde (c) were chosen and a series of their thiosemicarbazone derivatives(1a-3a, 1b-3b and 1c-3c) were synthesized to evaluate their biological activities as mushroom tyrosinase inhibitors. The inhibitory effects of these compounds on tyrosinase were investigated by using spectrofluorimetry, (1)H NMR titration and molecular docking techniques. From the results of fluorescence spectrum and (1)H NMR titration, it was found that forming complexes between the sulfur atom from thiourea and copper ion of enzyme center may play a key role for inhibition activity. Moreover, investigation of (1)H NMR spectra further revealed that formation of hydrogen bond between inhibitor and enzyme may be helpful to above complexes formation. The results were well coincident with the suggestion of molecular docking and obviously showed that 2-thiophone N(4)-thiosemicarbazone (1a), 2-furfuran N(4)-thiosemicarbazone (1b) and 2-pyrrole N(4)-thiosemicarbazone (1c) are potential inhibitors which deserves further investigation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. The AHA Moment: Assessment of the Redox Stability of Ionic Liquids Based on Aromatic Heterocyclic Anions (AHAs) for Nuclear Separations and Electric Energy Storage. (United States)

    Shkrob, Ilya A; Marin, Timothy W


    Because of their extended conjugated bond network, aromatic compounds generally have higher redox stability than less saturated compounds. We conjectured that ionic liquids (ILs) consisting of aromatic heterocyclic anions (AHAs) may exhibit improved radiation and electrochemical stability. Such properties are important in applications of these ILs as diluents in radionuclide separations and electrolytes in the electric energy storage devices. In this study, we systematically examine the redox chemistry of the AHAs. Three classes of these anions have been studied: (i) simple 5-atom ring AHAs, such as the pyrazolide and triazolides, (ii) AHAs containing an adjacent benzene ring, and (iii) AHAs containing electron-withdrawing groups that were introduced to reduce their basicity and interaction with metal ions. It is shown that fragmentation in the reduced and oxidized states of these AHAs does not generally occur, and the two main products, respectively, are the H atom adduct and the imidyl radical. The latter species occurs either as an N σ-radical or as an N π-radical, depending on the length of the N-N bond, and the state that is stabilized in the solid matrix is frequently different from that having the lowest energy in the gas phase. In some instances, the formation of the sandwich π-stack dimer radical anions has been observed. For trifluoromethylated anions, H adduct formation did not occur; instead, there was facile loss of fluoride from their fluorinated groups. The latter can be problematic in nuclear separations, but beneficial in batteries. Overall, our study suggests that AHA-based ILs are viable candidates for use as radiation-exposed diluents and electrolytes.

  19. Effect of charcoal types and grilling conditions on formation of heterocyclic aromatic amines (HAs) and polycyclic aromatic hydrocarbons (PAHs) in grilled muscle foods. (United States)

    Viegas, O; Novo, P; Pinto, E; Pinho, O; Ferreira, I M P L V O


    Grilling muscle foods involves high temperatures that lead to production of cooking toxicants, such as heterocyclic aromatic amines (HAs) and polycyclic aromatic hydrocarbons (PAHs). To obtain realistic exposure levels of these two groups of mutagens analyses of the same samples using similar separation/detection techniques were performed. HAs and PAHs were quantified in well-done meat and fish samples grilled with wood and coconut shell charcoal at 200°C. Quantitative HAs and PAHs profiles were different for beef and salmon using the same type of charcoal. Higher levels of HAs and PAHs were found in salmon samples. No significant differences were observed for HAs and PAHs in beef samples grilled with both charcoal types, whereas salmon grilled with coconut shell charcoal presented significantly lower amounts of HAs and PAHs than salmon grilled with usual wood charcoal. Continuous barbecuing with the same charcoal shown that combustion of fat that dropped along the grilling period contributed to higher formation of HAs and PAHs. Special attention must be given to the intake of barbecued foods since high amounts of HAs and PAHs can be taken in a single meal. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

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


    This study investigated the sorption to soil of water-soluble metabolites from polycyclic aromatic compounds (PACs). The soil fungus Cunninghamella elegans was used to produce PAC metabolites from two un-substituted PACs (phenanthrene, pyrene), three alkyl-substituted PACs (2-methylnaphthalene, 1-methylphenanthrene, 1-methylpyrene), and one sulfur-containing heterocyclic PAC (dibenzothiophene). Fifty-eight metabolites were tentatively identified; metabolites from the un-substituted PACs were hydroxylated and sulfate conjugated, whereas metabolites from alkyl-substituted PACs were sulfate conjugated and either hydroxylated or oxidized to carboxylic acids at the methyl group. The metabolism of the sulfur-containing heterocyclic PAC resulted in sulfate conjugates. The sorption of the PAC metabolites to three soils was determined using a batch equilibrium method, and partition coefficients (Kd's) were calculated for fourteen representative metabolites. Sulfate conjugated metabolites displayed Kd's below 70 whereas the metabolites with both a sulfate and a carboxylic acid group had Kd's below 2.8. The low Kd's of water-soluble PAC metabolites indicate high mobility in soil and a potential for leaching to surface- and groundwaters. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Aromatic nitrogen compounds in fossil fuels: a potential hazard

    Energy Technology Data Exchange (ETDEWEB)

    Ho, C H; Clark, B R; Guerin, M R; Ma, C Y; Rao, T K


    To achieve energy independence in the United States, converting coal to oil or extracting oil from shale will be required. Before commercial scale fossil fuel conversion facilities become a reality, chemical and biological studies of currently available synfuel samples derived from coal or shale are urgently needed in order to determine what the potential health problems, such as from occupational exposure, might be. Aromatic nitrogen compounds such as basic aza-arenes, neutral aza-arenes, and aromatic amines are considered environmentally important and several members of these classes of compounds possess biological activity. For example, dibenz(a,h)acridine, 7 H-dibenzo(c,g)carbazole, and 2-naphthylamine, are well known as carcinogens. The methods used to isolate the basic aromatic nitrogen compounds and neutral aza-arenes from one shale oil and one coal-derived oil are discussed. The mutagenic activities of these fractions, based on the Ames Salmonella typhimurium test, are compared.

  2. Global simulation of aromatic volatile organic compounds in the atmosphere (United States)

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


    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

  3. Aromatic Plants as a Source of Bioactive Compounds

    Directory of Open Access Journals (Sweden)

    Panagiota Florou-Paneri


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

  4. Composition of concentrates of heterocyclic petroleum compounds isolated by complexformation with titanium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Nesterenko, V.I.; Alekseyev, A.P.; Plyusnin, A.N.


    The group composition of nitrous bases and aromatic sulphur compounds isolated by complex-formation with titanium tetrachloride from Soviet and West Siberian (Fedorov) crude oils was studied. Homologous series of nitrous bases are characterized by practically identical compounds ranging from C /SUB n/ H /SUB 2n-5/ N to C /SUB n/ H /SUB 2n-21/ N. Pyridine and quinoline derivatives with alkyl substituents and naphthene rings predominate. Thiacycloparaffins with a number of naphthene rings in the molecule of 1 to 5 predominate among saturated sulphur compounds. Unsaturated sulphur compounds are represented mainly by homologues of thiophene, benzo- and dibenzothiophene.

  5. Halogenation of aromatic compounds: thermodynamic, mechanistic and ecological aspects

    NARCIS (Netherlands)

    Dolfing, J.


    Biological halogenation of aromatic compounds implies the generation of reducing equivalents in the form of e.g. NADH. Thermodynamic calculations show that coupling the halogenation step to a step in which the reducing equivalents are oxidized with a potent oxidant such as O2 or N2O makes the

  6. Degradation of aromatic compounds in plants grown under aseptic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Mithaishvili, T.; Ugrekhelidze, D.; Tsereteli, B.; Sadunishvili, T.; Kvesitadze, G. [Durmishidze Inst. of Biochemistry and Biotechnology, Academy of Sciences of Georgia, Tbilisi (Georgia); Scalla, R. [Lab. des Xenobiotiques, INRA, Toulouse (France)


    The aim of the work is to investigate the ability of higher plants to absorb and detoxify environmental pollutants - aromatic compounds via aromatic ring cleavage. Transformation of {sup 14}C specifically labelled benzene derivatives, [1-6-{sup 14}C]-nitrobenzene, [1-6-{sup 14}C]-aniline, [1-{sup 14}C]- and [7-{sup 14}C]-benzoic acid, in axenic seedlings of maize (Zea mays L.), kidney bean (Phaseolus vulgaris L.), pea (Pisum sativum L.) and pumpkin (Cucurbita pepo L.) were studied. After penetration in plants, the above xenobiotics are transformed by oxidative or reductive reactions, conjugation with cell endogenous compounds, and binding to biopolymers. The initial stage of oxidative degradation consists in hydroxylation reactions. The aromatic ring can then be cleaved and degraded into organic acids of the Krebs cycle. Ring cleavage is accompanied by {sup 14}CO{sub 2} evolution. Aromatic ring cleavage in plants has thus been demonstrated for different xenobiotics carrying different substitutions on their benzene ring. Conjugation with low molecular peptides is the main pathway of aromatic xenobiotics detoxification. Peptide conjugates are formed both by the initial xenobiotics (except nitrobenzene) and by intermediate transformation products. The chemical nature of the radioactive fragment and the amino acid composition of peptides participating in conjugation were identified. (orig.)

  7. Heterocyclic aromatic amines and their contribution to the bacterial mutagenicity of the particulate phase of cigarette smoke. (United States)

    Roemer, Ewald; Meisgen, Thomas; Diekmann, Joerg; Conroy, Lynda; Stabbert, Regina


    Heterocyclic aromatic amines (HAAs) rank among the strongest known mutagens. Approximately 30 HAAs have been found in cooked foods (broiled, fried, and grilled) and several HAAs have been characterized as animal carcinogens. Nine HAAs have also been reported to be constituents of cigarette smoke (CS) raising concerns that HAAs might contribute significantly to the known carcinogenicity of CS. As HAAs are found predominantly in the total particulate matter (TPM) of CS, an improved method for the quantification of HAAs in TPM is reported allowing detection and quantification of 8 HAAs in a single run. The mutagenic potency of these HAAs and that of TPM from the reference cigarette 2R4F was determined in the Salmonella Reverse Mutation Assay (Ames assay) with tester strain TA98 and a metabolic activation system. The 8 HAAs, when applied together in the Ames assay, showed a clear sub-additive response. Likewise, the combination of HAAs and TPM, if at all, gave rise to a slight sub-additive response. In both cases, however, the sub-additive response in the Ames assay was observed at HAA doses that are far above the amounts found in CS. The contribution of the individual HAAs to the total mutagenic activity of TPM was calculated and experimentally confirmed to be approximately 1% of the total mutagenic activity. Thus, HAAs do not contribute significantly to the bacterial in vitro mutagenicity of CS TPM. Copyright © 2015 Z. Published by Elsevier Ireland Ltd.. All rights reserved.

  8. Inhibitory effect of antioxidant-rich marinades on the formation of heterocyclic aromatic amines in pan-fried beef. (United States)

    Viegas, Olga; Amaro, L Filipe; Ferreira, Isabel M P L V O; Pinho, Olívia


    The inhibitory effect of antioxidant-rich marinades containing beer and white wine (with/without alcohol) alone or mixed with herbs commonly used as meat flavoring (garlic, ginger, thyme, rosemary, and red chili pepper) on the formation of heterocyclic aromatic amines (HAs) in pan-fried beef was studied. Radical-scavenging activity was evaluated by DPPH assay, before the addition of meat to the marinade (T0) and after 4 h of meat marinating (T4). At T0, wine with herbs possessed the highest scavenging activity (73.5%), followed by wine (72.5%), dealcoholized wine with herbs (53.4%), beer and herbs (41.7%), dealcoholized wine (39.6%), and beer (25.9%). At T4, a decrease in the radical-scavenging activity of all marinades was observed, although with a similar radical-scavenging profile. All of the six marinades under the study reduced the total amount of HAs, keeping meat with good overall sensory quality. Beer marinades were more efficient than white wine marinades, and the addition of herbs provided a superior inhibitory effect, reducing around 90% of HAs. No correlation was observed between radical-scavenging activity of marinades and total or individual HAs formation. Herbs explained around 30% of inhibition of PhIP formation, whereas alcohol increased PhIP formation.

  9. Influence of beer marinades on the reduction of carcinogenic heterocyclic aromatic amines in charcoal-grilled pork meat. (United States)

    Viegas, Olga; Moreira, Patrícia S; Ferreira, Isabel M P L V O


    The effect of beer marinades on the formation of heterocyclic aromatic amines (HAs) was examined in charcoal-grilled pork. Pilsner, non-alcoholic pilsner and black beers (coded respectively as PB, P0B and BB) were assayed and unmarinated samples cooked under similar conditions provided reference HAs levels. Two thermic (PhIP and 4,8-DiMeIQx) and three pyrolytic HAs (Trp-P-1, AαC, MeAαC) were quantified in unmarinated meat samples. Marinating meat in beer resulted in a significant decrease of PhIP, Trp-P-1 and AαC (p beers reduced total HA formation in charcoal-grilled pork, black beer being the most efficient with a level of 90% inhibition. A strong positive correlation was observed between the inhibitory effect of beer on total HA formation and their antioxidant activity. Beer marinades mitigate the impact of consumption of well-done grilled pork meat reducing the formation of cooking carcinogens.

  10. Cytotoxicity and aryl hydrocarbon receptor-mediated activity of n-heterocyclic polycyclic aromatic hydrocarbons: structure-activity relationships. (United States)

    Sovadinová, Iva; Bláha, Ludĕk; Janosek, Jaroslav; Hilscherová, Klára; Giesy, John P; Jones, Paul D; Holoubek, Ivan


    Toxic effects of many persistent organic pollutants (e.g., polychlorinated biphenyls or polychlorinated dibenzo-p-dioxins and furans) are mediated via the aryl hydrocarbon receptor (AhR). Although polycyclic aromatic hydrocarbons (PAHs) and their derivatives also activate AhR, their toxic effects remain to be fully elucidated. In the present study, we used the in vitro H4IIE-luc transactivation cell assay to investigate cytotoxicity and potencies to activate AhR by 29 individual PAHs and their N-heterocyclic derivatives (aza-PAHs). The aza-PAHs were found to be significantly more cytotoxic and more potent inducers of AhR than their unsubstituted analogues. Several aza-PAHs, such as dibenz[a,h]acridine or dibenz[a,i]acridine, activated AhR within picomolar concentrations, comparable to the effects of reference 2,3,7,8-tetrachlorodibenzo-p-dioxin. Ellipsoidal volume, molar refractivity, and molecular size were the most important descriptors derived from the modeling of quantitative structure-activity relationships for potencies to activate AhR. Comparable relative toxic potencies (induction equivalency factors) for individual aza-PAHs are derived, and their use for evaluation of complex contaminated samples is discussed.


    Directory of Open Access Journals (Sweden)



    Full Text Available Considering the well-known mechanism of adaptable resistance of microorganisms to chemical compounds through biofilms formation and the widespread use of N-heterocyclic quaternary ammonium salts (QAC as disinfectants, in this study we have evaluate the effect of 8 newly synthesized symmetrical and unsymmetrical diquaternary ammonium salts of 1,2-bis-(4-pyridil-ethane on bacterial biofilms produced by three different bacterial strains. The effect of the exposure to quaternary ammonium salts on biofilm communities was investigated within biofilms obtained in a conventional testing system, on stainless steel and glass surfaces. Differential plate counts were used to characterize the developed communities and the effects of QAC exposure and the results were correlated with epifluorescence microphotographs. The data obtained revealed a significant reduction of bacterial cells in the biofilms tested with 4-7 log CFU for all the QAC.

  12. Metagenomic screening for aromatic compound-responsive transcriptional regulators.

    Directory of Open Access Journals (Sweden)

    Taku Uchiyama

    Full Text Available We applied a metagenomics approach to screen for transcriptional regulators that sense aromatic compounds. The library was constructed by cloning environmental DNA fragments into a promoter-less vector containing green fluorescence protein. Fluorescence-based screening was then performed in the presence of various aromatic compounds. A total of 12 clones were isolated that fluoresced in response to salicylate, 3-methyl catechol, 4-chlorocatechol and chlorohydroquinone. Sequence analysis revealed at least 1 putative transcriptional regulator, excluding 1 clone (CHLO8F. Deletion analysis identified compound-specific transcriptional regulators; namely, 8 LysR-types, 2 two-component-types and 1 AraC-type. Of these, 9 representative clones were selected and their reaction specificities to 18 aromatic compounds were investigated. Overall, our transcriptional regulators were functionally diverse in terms of both specificity and induction rates. LysR- and AraC- type regulators had relatively narrow specificities with high induction rates (5-50 fold, whereas two-component-types had wide specificities with low induction rates (3 fold. Numerous transcriptional regulators have been deposited in sequence databases, but their functions remain largely unknown. Thus, our results add valuable information regarding the sequence-function relationship of transcriptional regulators.

  13. Dioxygen activation responsible for oxidation of aliphatic and aromatic hydrocarbon compounds: current state and variants. (United States)

    Morikawa, Masaaki


    The most significant aspect in microbial metabolisms, especially those of bacteria and archaea, is their marvelously wide acceptability of substrate electron donors and acceptors. This feature makes them to be attractive catalysts for environmental biotechnology in terms of degradation of harmful recalcitrant compounds, including hydrocarbons. Transformation of highly reduced and inert hydrocarbon compounds is with no doubt a challenging biochemical reaction for a single enzyme. However, several multi-component enzyme systems enable microorganisms to utilize hydrocarbons as carbon and energy (electron) sources. Initial biological attack to hydrocarbons is, in most cases, the hydroxylation that requires molecular dioxygen as a co-substrate. Dioxygen also contributes to the ring cleavage reaction of homo- and hetero-cyclic aromatic hydrocarbons. Although the molecular dioxygen is omnipresent and highly soluble in water, activation and splitting this triplet ground-state molecule to wed with difficult hydrocarbons need special devices. Non-heme iron, heme iron, or flavin nucleotide was designated as a major hidden dagger for this purpose.

  14. Combined genotoxic effects of a polycyclic aromatic hydrocarbon (B(aP and an heterocyclic amine (PhIP in relation to colorectal carcinogenesis.

    Directory of Open Access Journals (Sweden)

    Emilien L Jamin

    Full Text Available Colorectal neoplasia is the third most common cancer worldwide. Environmental factors such as diet are known to be involved in the etiology of this cancer. Several epidemiological studies have suggested that specific neo-formed mutagenic compounds related to meat consumption are an underlying factor involved in the association between diet and colorectal cancer. Heterocyclic amines (HCAs and polycyclic aromatic hydrocarbons (PAHs are known mutagens and possible human carcinogens formed at the same time in meat during cooking processes. We studied the genotoxicity of the model PAH benzo(apyrene (B(aP and HCA 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP, alone or in mixture, using the mouse intestinal cell line Apc(Min/+, mimicking the early step of colorectal carcinogenesis, and control Apc(+/+ cells. The genotoxicity of B(aP and PhIP was investigated using both cell lines, through the quantification of B(aP and PhIP derived DNA adducts, as well as the use of a genotoxic assay based on histone H2AX phosphorylation quantification. Our results demonstrate that heterozygous Apc mutated cells are more effective to metabolize B(aP. We also established in different experiments that PhIP and B(aP were more genotoxic on Apc (Min/+ cells compared to Apc (+/+ . Moreover when tested in mixture, we observed a combined genotoxicity of B(aP and PhIP on the two cell lines, with an increase of PhIP derived DNA adducts in the presence of B(aP. Because of their genotoxic effects observed on heterozygous Apc mutated cells and their possible combined genotoxic effects, both B(aP and PhIP, taken together, could be implicated in the observed association between meat consumption and colorectal cancer.

  15. Trace Analysis of Mutagenic Heterocyclic Aromatic Amines in Cigarette Smoke Condensate and its Base Fractions via Silylation-GC-MS

    Directory of Open Access Journals (Sweden)

    Liu S


    Full Text Available Among the more than 5000 chemicals reported in cigarette smoke condensate (CSC, heterocyclic aromatic amines (HAAs are considered to be a contributor to observed biological activity. HAAs are non-volatile and are reported at ppb levels in CSC. A new method for HAA analysis at the trace level is reported here. N, O-Bis(trimethylsilyl trifluoroacetamide (BSTFA containing 1% trimethylchlorosilane was employed to derivatize amino groups by heating the reagent containing a sample of CSC at 80 °C for 30 min followed by analysis employing gas chromatography-mass spectroscopy (GC-MS in the selected-ion-monitoring (SIM mode. This derivatization method afforded symmetrical peak shapes on a ZB-50 stationary phase and achieved instrumental limits of quantification (LOQ at 10:1 S/N from -1 ng/mL for AαC to120 ng/mL for Glu-P-1. The chemical identity of each derivative was confirmed by comparison of retention time and mass spectra of standards. The latter were characterized by the following ions: M·+ or [M-1]+, [M-15]+, and m/z 73 (i.e., trimethylsilyl. CSC and its base sub-fractions were studied using the GC-MS method. Ten HAAs were screened and five were quantified in cigarette smoke condensate, while 2-5 HAAs were quantified in each of three base sub-fractions. Values obtained with the new procedure agree well with values reported in the literature and with results obtained from a commercial laboratory via a different analytical method. The potential contribution of each HAA to the overall mutagenic activity observed for CSC and its base fractions is discussed. When considered together, HAAs account for only a small portion (-7.8% of the observed mutagenicity of the CSC.

  16. Ionic and Neutral Mechanisms for C-H Bond Silylation of Aromatic Heterocycles Catalyzed by Potassium tert-Butoxide. (United States)

    Banerjee, Shibdas; Yang, Yun-Fang; Jenkins, Ian D; Liang, Yong; Toutov, Anton A; Liu, Wen-Bo; Schuman, David P; Grubbs, Robert H; Stoltz, Brian M; Krenske, Elizabeth H; Houk, Kendall N; Zare, Richard N


    Exploiting C-H bond activation is difficult, although some success has been achieved using precious metal catalysts. Recently, it was reported that C-H bonds in aromatic heterocycles were converted to C-Si bonds by reaction with hydrosilanes under the catalytic action of potassium tert-butoxide alone. The use of Earth-abundant potassium cation as a catalyst for C-H bond functionalization seems to be without precedent, and no mechanism for the process was established. Using ambient ionization mass spectrometry, we are able to identify crucial ionic intermediates present during the C-H silylation reaction. We propose a plausible catalytic cycle, which involves a pentacoordinate silicon intermediate consisting of silane reagent, substrate, and the tert-butoxide catalyst. Heterolysis of the Si-H bond, deprotonation of the heteroarene, addition of the heteroarene carbanion to the silyl ether, and dissociation of tert-butoxide from silicon lead to the silylated heteroarene product. The steps of the silylation mechanism may follow either an ionic route involving K+ and tBuO- ions or a neutral heterolytic route involving the [KOtBu]4 tetramer. Both mechanisms are consistent with the ionic intermediates detected experimentally. We also present reasons why KOtBu is an active catalyst whereas sodium tert-butoxide and lithium tert-butoxide are not, and we explain the relative reactivities of different (hetero)arenes in the silylation reaction. The unique role of KOtBu is traced, in part, to the stabilization of crucial intermediates through cation-π interactions.

  17. Molecular docking and QSAR analyses of aromatic heterocycle thiosemicarbazone analogues for finding novel tyrosinase inhibitors. (United States)

    Dong, Huanhuan; Liu, Jing; Liu, Xiaoru; Yu, Yanying; Cao, Shuwen


    A collection of 36 thiosemicarbazone analogues possessed a broad span of tyrosinase inhibitory activities was designed and obtained. Robust and reliable CoMFA and CoMSIA models were gained to predict the structure-activity relationship and the new modifier direction. Inhibitory activities of the compounds were found to greatly depend upon molecular shape, size, and charge. The sterically bulky group at the C-4 position of the thiophene ring contributed a high capacity for biological activity. Some bulky substituents at the C1-position and C12-position, and electron-negative groups at the C3-position, helped to improve the activity of these analogues. The molecular docking results provided visual evidence for QSAR analysis and detailed information about binding mode, affinity, and the principal mechanism between the ligands and tyrosinase. Based on these, a prospective structure modification and optimization of the most potent compound, T32, was suggested for further research. Copyright © 2017. Published by Elsevier Inc.

  18. Formation of highly oxygenated organic molecules from aromatic compounds

    Directory of Open Access Journals (Sweden)

    U. Molteni


    Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

  19. Estimating the Physicochemical Properties of Polysubstituted Aromatic Compounds Using UPPER. (United States)

    Alantary, Doaa; Yalkowsky, Samuel H


    The UPPER model (Unified Physicochemical Property Estimation Relationships) has been used to predict 9 essential physicochemical properties of pure compounds. It was developed almost 25 years ago and has been validated by the Yalkowsky group for almost 2000 aliphatic, aromatic, and polyhalogenated hydrocarbons. UPPER is based on a group of additive and nonadditive descriptors along with a series of well-accepted thermodynamic relationships. In this model, the 2-dimensional chemical structure is the only input needed. This work extends the applicability of UPPER to hydrogen bonding and non-hydrogen bonding aromatic compounds with several functional groups such as alcohol, aldehyde, ketone, carboxylic acid, carbonate, carbamate, amine, amide, nitrile as well as aceto, and nitro compounds. The total data set includes almost 3000 compounds. Aside from the enthalpies and entropies of melting and boiling, no training set is used for the calculation of the properties. The results show that UPPER enables a reasonable estimation of all the considered properties. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  20. Microwave Field Effect on Polyphenolic Compounds from Aromatic Plants

    Directory of Open Access Journals (Sweden)

    Maria - Loredana Soran


    Full Text Available Nowadays, the use of mobile telephony and wire-less devices has become more demanding, generating electromagnetic radiations. Microwave radiation can affect the growth rate of plants. For this study, the aromatic plants i.e. parsley, celery, dill, basil, were chosen as irradiated plants. This study aims to investigate the effects of irradiation with microwave field on polyphenolic compounds from basil, celery and parsley.  The extracts were obtained by sonication. Quantitative analysis of polyphenolic compounds was performed by high performance liquid chromatography using an Altima C18 column. The elution was performed in gradient, with acetonitrile (eluent A and formic acid in water (1%, eluent B. It was observed that in the irradiated plants, the content of polyphenolic compounds was higher than in the controlled plant. This finding suggests that that plants were strongly influenced by stress due to electromagnetic fields.

  1. The relationship between mutagenicity and chemical composition of polycyclic aromatic compounds from coal pyrolysis. (United States)

    Wornat, M J; Braun, A G; Hawiger, A; Longwell, J P; Sarofim, A F


    The polycyclic aromatic compounds (PAC) produced from the pyrolysis of a bituminous coal at temperatures of 1125 to 1425 degrees K prove to be mutagenic to S. typhimurium, both in the presence and in the absence of postmitochondrial supernatant (PMS) prepared from Aroclor 1254-induced rat liver. Mutagenicity of the PAC samples measured in the absence of PMS exhibits little dependence on pyrolysis temperature; that measured in its presence is higher at the higher pyrolysis temperatures. However, because of the decrease in PAC yield as the temperature is raised, mutagenicity per mass of coal consumed falls with an increase in temperature if measured without PMS (-PMS) and peaks at an intermediate temperature of 1378 degrees K if measured with PMS (+PMS). Using a new chromatographic technique, we have split each coal-derived PAC sample into two fractions: LC1, containing PAC with alkyl and O-containing substitutions and LC2, consisting of unsubstituted PAC. Substituted (LC1) fractions show no significant +PMS mutagenicity, indicating that, as a whole, the alkylated PAC in our coal pyrolysis products are not mutagenic. Only at the higher temperatures do the substituted fractions exhibit significant -PMS mutagenicity, attributed to PAC with carbonyl or etheric functionalities. The extremely low yields of the substituted PAC under the conditions where they show some activity, however, ensure that they contribute little to overall mutagenicity. In contrast to the substituted fractions, the unsubstituted (LC2) fractions display significant mutagenicity under all conditions and appear to be responsible for virtually all of the mutagenicity in these coal-derived PAC samples. In this fraction, -PMS activity is attributed to nitrogen-containing heterocyclic aromatics. PMID:2190813

  2. Limited aromatic pathway genes diversity amongst aromatic compound degrading soil bacterial isolates

    Directory of Open Access Journals (Sweden)

    Minovska Gordana


    Full Text Available Identification and characterization of novel genes belonging to microbial aromatic biodegradation pathway is of great importance as they have been proven versatile biocatalysts. In this study, the selection of 19 environmental bacterial isolates capable to degrade a wide range of aromatic compounds has been screened for the presence of five genes from the lower and the upper aromatic biodegradation pathway using PCR methodology. In the case of 4-oxalocrotonate tautomerase and toluene dioxygenases, although present in the most of environmental isolates, very limited diversity of the genes has been encountered. Highly conserved sequences of these genes in environmental samples revealed high homology with gene sequences of the characterized corresponding genes from Pseudomonas putida species. The screen using degenerate primers based on known catechol-and naphthalene dioxygenases sequences resulted in a limited number of amplified fragments. Only two catechol 2,3-dioxygenase from two Bacillus isolates were amplified and showed no significant similarities with dioxygenases from characterized organisms, but 80-90% identities with partial catechol 2,3-dioxygenase sequences from uncultured organisms. Potentially three novel catechol 1,2-dioxygenases were identified from Bacillus sp. TN102, Gordonia sp. TN103 and Rhodococcus sp. TN112. Highly homologous tautomerase and toluene dioxygenases amongst environmental samples isolated from the contaminated environment suggested horizontal gene transfer while limited success in PCR detection of the other three genes indicates that these isolates may still be a source of novel genes. [Projekat Ministarstva nauke Republike Srbije, br. 173048

  3. Synthesis and evaluation of ?-hydroxy fatty acid-derived heterocyclic compounds with potential industrial interest

    Directory of Open Access Journals (Sweden)

    El-Sayed, R.


    Full Text Available T2-Hydroxyheptadecanoic acid chloride (2 reacted with anthranilic acid to produce 2-substituted-3,1-benzoxazin-4-one (3 which was used as starting material to synthesize some condensed and non-condensed heterocyclic compounds by reaction with nitrogen nucleophiles e.g., hydrazine hydrate, and formamide. The products were subjected to reaction with different moles of propylene oxide (n = 5, 10, 15 to produce a novel group of nonionic compounds having a double function as antibacterial and surface active agents which can be used in the manufacturing of drugs, cosmetics, pesticides or can be used as antibacterial and/or antifungal additives. The surface active properties as surface and interfacial tension, cloud point, foaming height, wetting time, and emulsification power were determined, the antimicrobial and biodegradability were also screened.El cloruro del ácido 2-hidroxiheptadecanoico (2 reaccionó con el ácido antranílico para producir 3,1-benzoxazin-4-onas 2-sustituidas que fueron usadas como material de partida en la síntesis de compuestos heterocíclicos condensados y no condensados por reacción con nucleófilos nitrogenados, como la hidracina o la formamida. Los productos fueron hechos reaccionar con diferentes moles de óxido de propileno (n = 5, 10, 15 para producir un grupo nuevo de compuestos no-iónicos teniendo una doble función como antibacterianos y tensoactivos que pueden ser usados en la manufactura de medicamentos, cosméticos, pesticidas, o pueden ser usados como aditivos antibacterianos y/o antifúngicos. Se determinaron diversas propiedades físicas de los compuestos preparados así como sus efectos antimicrobianos y sus biodegrabilidad.

  4. Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds. (United States)

    Fayet, Guillaume; Rotureau, Patricia; Minisini, Benoit


    The chemical mechanisms involved in the decomposition of trinitroethyl compounds were studied for both aliphatic and aromatic derivatives using density functional theory calculations. At first, in the case of 1,1,1-trinitrobutane, used as a reference molecule, two primary channels were highlighted among the five investigated ones: the breaking of the C-N bond and the HONO elimination. Then, the influence of various structural parameters was studied for these two reactions by changing the length of the carbon chain, adding substituents or double bonds along the carbon chain. If some slight changes in activation energies were observed for most of these features, no modification of the competition between the two investigated reactions was highlighted and the breaking of the C-N bond remained the favoured mechanism. At last, the reactions involving the trinitroalkyl fragments were highlighted to be more competitive than reactions involving nitro groups linked to aromatic cycles in two aromatic systems (4-(1,1,1-trinitrobutyl)-nitrobenzene and 2-(1,1,1-trinitrobutyl)-nitrobenzene). This showed that aromatic nitro compounds with trinitroalkyl derivatives decompose from their alkyl part and may be considered more likely as aliphatic than as aromatic regarding the initiation of their decomposition process.

  5. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora


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

  6. Mesoionic Compounds

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 11; Issue 10. Mesoionic Compounds - An Unconventional Class of Aromatic Heterocycles. Bharati V Badami. General Article Volume 11 Issue 10 October 2006 pp 40-48. Fulltext. Click here to view fulltext PDF. Permanent link:

  7. Effect of culture of accumulation white mold volatile aromatic compounds in cheese




    The influence of different cultures of white mold Penicillium caseicolum and Geotrichum candidum on the content of aromatic compounds in a soft cheese have been investigated, methodical approaches to the definition of aromatic compounds by capillary gas chromatography have been developed, a number of characteristic volatile compounds identified and defined that have a specific cheese flavor.

  8. Anaerobic Degradation of Aromatic Compounds by Magnetospirillum Strains: Isolation and Degradation Genes

    National Research Council Canada - National Science Library

    SHINODA, Yoshifumi; AKAGI, Junya; UCHIHASHI, Yasumitsu; HIRAISHI, Akira; YUKAWA, Hideaki; YURIMOTO, Hiroya; SAKAI, Yasuyoshi; KATO, Nobuo


    .... It was confirmed that the genus Magnetospirillum represents the third genus of denitrifying bacteria capable of degrading aromatic compounds under anaerobic conditions, besides the genera Thauera and Azoarcus.

  9. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Directory of Open Access Journals (Sweden)

    E.P. Martins


    Full Text Available Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.


    Directory of Open Access Journals (Sweden)

    M. Delnavaz ، B. Ayati ، H. Ganjidoust


    Full Text Available Three moving bed biofilm reactors were used to treat synthesized wastewater of aromatic amine compounds including aniline, para-diaminobenzene and para-aminophenol that are found in many industrial wastewaters. The reactors with cylindrical shape had an internal diameter and an effective depth of 10 and 60 cm, respectively. The reactors were filled with light expanded clay aggregate as carriers and operated in an aerobic batch and continuous conditions. Evaluation of the reactors' efficiency was done at different retention time of 8, 24, 48 and 72 h with an influent COD from 100 to 3500 mg/L (filling ratio of 50%. The maximum obtained removal efficiencies were 90% (influent COD=2000 mg/L, 87% (influent COD=1000 mg/L and 75% (influent COD=750 mg/L for aniline, para-diaminobenzene and para-aminophenol, respectively. In the study of decrease in filling ratio from 50 to 30 percent, 6% decrease for both para-diaminobenzene and para-aminophenol and 7% increase for aniline degradation were obtained. The removal efficiency was decreased to about 10% after 15 days of continuous loading for each of the above three substrates. In the shock loading test, initially the COD removal rate was decreased in all reactors, but after about 10 days, it has been approached to the previous values. Finally, biodegradability of aromatic amines has been proved by nuclear magnetic resonance system.

  11. Spatial distribution of heterocyclic organic matter compounds at macropore surfaces in Bt-horizons (United States)

    Leue, Martin; Eckhardt, Kai-Uwe; Gerke, Horst H.; Ellerbrock, Ruth H.; Leinweber, Peter


    The illuvial Bt-horizon of Luvisols is characterized by coatings of clay and organic matter (OM) at the surfaces of cracks, biopores and inter-aggregate spaces. The OM composition of the coatings that originate from preferential transport of suspended matter in macropores determines the physico-chemical properties of the macropore surfaces. The analysis of the spatial distribution of specific OM components such as heterocyclic N-compounds (NCOMP) and benzonitrile and naphthalene (BN+NA) could enlighten the effect of macropore coatings on the transport of colloids and reactive solutes during preferential flow and on OM turnover processes in subsoils. The objective was to characterize the mm-to-cm scale spatial distribution of NCOMP and BN+NA at intact macropore surfaces from the Bt-horizons of two Luvisols developed on loess and glacial till. In material manually separated from macropore surfaces the proportions of NCOMP and BN+NA were determined by pyrolysis-field ionization mass spectrometry (Py-FIMS). These OM compounds, likely originating from combustion residues, were found increased in crack coatings and pinhole fillings but decreased in biopore walls (worm burrows and root channels). The Py-FIMS data were correlated with signals from C=O and C=C groups and with signals from O-H groups of clay minerals as determined by Fourier transform infrared spectroscopy in diffuse reflectance mode (DRIFT). Intensive signals of C15 to C17 alkanes from long-chain alkenes as main components of diesel and diesel exhaust particulates substantiated the assumption that burning residues were prominent in the subsoil OM. The spatial distribution of NCOMP and BN+NA along the macropores was predicted by partial least squares regression (PLSR) using DRIFT mapping spectra from intact surfaces and was found closely related to the distribution of crack coatings and pinholes. The results emphasize the importance of clay coatings in the subsoil to OM sorption and stabilization

  12. Design and synthesis of a heterocyclic compound collection for probing the spatial charactistics of ATP binding sites

    CSIR Research Space (South Africa)

    Kenyon, CP


    Full Text Available stream_source_info parkinson_2006.pdf.txt stream_content_type text/plain stream_size 3323 Content-Encoding UTF-8 stream_name parkinson_2006.pdf.txt Content-Type text/plain; charset=UTF-8 Design and Synthesis of a... Heterocyclic Compound Collection for Probing the Spatial Charactistics of ATP Binding Sites Presented at the CSIR Conference Centre CSIR Biosciences C.P. Kenyon, P.M. Matlaba, C.J. Parkinson, A.L. Rousseau and C.W. van der Westhuyzen February 28, 2006...

  13. Biotechnological production of aromatic compounds of the extended shikimate pathway from renewable biomass. (United States)

    Lee, Jin-Ho; Wendisch, Volker F


    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Thrilling strain! Donor-acceptor-substituted cyclobutanes for the synthesis of (hetero)cyclic compounds. (United States)

    Reissig, Hans-Ulrich; Zimmer, Reinhold


    The analogy goes further: Following the often-studied donor-acceptor-substituted cyclopropanes, the corresponding cyclobutane derivatives were employed for the ring-strain-driven stereoselective syntheses of carbo- and heterocycles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Volatile Compounds in Dry Dog Foods and Their Influence on Sensory Aromatic Profile


    Koushik Adhikari; Kadri Koppel; Brizio Di Donfrancesco


    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 ...

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

    Directory of Open Access Journals (Sweden)

    A. Kornilova


    Full Text Available 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.

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

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


    Adsorption of 22 nonpolar and polar aromatic compounds on 10 carbon nanotubes (CNTs) with various diameters, lengths and surface oxygen-containing group contents was investigated to develop predictive correlations for adsorption, using the isotherm fitting of Polanyi theory-based Dubinin-Ashtakhov (DA) model. Adsorption capacity of aromatic compounds on CNTs is negatively correlated with melting points of aromatic compounds, and surface oxygen-containing group contents and surface area ratios of mesopores to total pores of CNTs, but positively correlated with total surface area of CNTs. Adsorption affinity is positively correlated with solvatochromic parameters of aromatic compounds, independent of tube lengths and surface oxygen-containing group contents of CNTs, but negatively correlated with surface area ratios of mesopores to total pores of CNTs. The correlations of adsorption capacity and adsorption affinity with properties of both aromatic compounds and CNTs clearly have physical significance, can be used successfully with DA model to predict adsorption of aromatic compounds on CNTs from the well-known physiochemical properties of aromatic compounds (i.e., solvatochromic parameters, melting points) and CNTs (i.e., surface area and total acidic group contents), and thus can facilitate the environmental application of CNTs as sorbents and environmental risk assessment of both aromatic contaminants and CNTs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Attachment chemistry of aromatic compounds on a Silicon(100) surface (United States)

    Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi


    A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

  19. Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review. (United States)

    Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao


    Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

  20. Process for removing halogenated aliphatic and aromatic compounds from petroleum products (United States)

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


    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.

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


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


    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 a...

  2. [Health effect of volatile aldehyde compounds in photocatalytic oxidation of aromatics compounds]. (United States)

    Zhao, Wei-rong; Liao, Qiu-wen; Yang, Ya-nan; Dai, Jiu-song


    Photocatalytic oxidation (PCO) of toluene and benzaldehyde in indoor air by N doped TiO2 (N-TiO2) was conducted under UV irradiation of 254 nm. The intermediates were identified and monitored on real-time by proton transfer reaction-mass spectrometry. The health risks of PCO of toluene and benzaldehyde were assessed based on health risk influence index (eta). Results indicated that both the conversion rate and mineralization rate of toluene and benzaldehyde were relatively high, however, the volatile aldehyde compounds (VAs), including acetaldehyde and formaldehyde generated from ring-opening, significantly influenced the health risks of PCO of toluene and benzaldehyde. Acetaldehyde played a crucial role on health risks, which was inclined to desorb from the surface of catalysts, accumulate in gas-phase, and increase the health risks of PCO of the aromatic compounds. The concentration of formaldehyde kept stable at a relatively low level, however its impact cannot be neglected. In the PCO process of toluene and benzaldehyde, eta reached the maximum values of 8 499.68 and 21.43, with the eta(VAs), contribution of VAs to the health risk influence index of outlet, reaching 99.3% and 98.3%, respectively. The average values of eta in the PCO process of 30 min were 932.86 and 8.52, and for which eta(VAs), reached 98.5% and 98.0%, respectively. When PCO of toluene and benzaldehyde reached steady state, eta were 236.09 and 2.30, and eta(VAs) reached 97.9% and 97.8%, respectively. Hence, eta(VAs), can be taken as a characteristic parameter in assessment of health risks of PCO of aromatic compounds.

  3. [The chemistry of pericyclic reactions and their application to syntheses of heterocyclic compounds]. (United States)

    Sakamoto, Masanori; Kawasaki, Tomomi; Ishii, Keitaro; Tamura, Osamu


    arising from the carbonyl ylides (Scheme 45). The photoinduced carbonyl ylides from the epoxy dinitriles 158 and 160-163 underwent 1,3-dipolar cycloaddition with enol ethers, leading to a tetrahydrofuran system (Schemes 49 and 50, Table 14). Electrocyclization of 3-butadienylindoles 184 to intermediary dihydrocarbazoles XXXII followed by elimination of MeOH gave 3-oxyganated carbazoles 185, which were transformed to carbazole alkaloids hyellazole 168, 4-demethoxycarbazomycin B 170 and carazostatin 171, respectively. Claisen rearrangement of 3-(1-amino-1-vinyloxy) indolines derived from 3-hydroxyindolines 192 and amide acetal 193 gave indol-4-ylacetamides 194, which was reduced to afford 4-(2-aminoethyl) indoles 198, which has a framework of biologically active 4-substituted indole compounds. Claisen rearrangement of 3-allyloxyindoles produced in situ by condensation of indolin-3-ones 202 with allyl alcohols 203 and 206-211 gave 2-allylindolin-3-ones 204, 205 and 212-220. The domino reactions, Horner-Wadsworth-Emmons olefination of 2-allyloxyindole 233, isomerization, and Claisen rearrangement produced 3-allylindolin-2-one 234, which was derivatized to 3a-allylpyrrolo [2,3-b] indole alkaloid, flustramine C 221. Reverse aromatic Cope rearrangement of 2-allyl-3-indolidene acetonitriles 241-243, formed by Horner-Wadsworth-Emmons reaction of 2-allylindolin-3-ones 238-240, afforded indoles 244-246.

  4. π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

    KAUST Repository

    Credendino, Raffaele


    In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

  5. Growth and coal-solubilizing activity of Penicillin simplicissimum on coal-related aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Achi, O.K. (Federal Polytechnic (Nigeria). Dept. of Science and Technology)


    Penicillium simplicissimum, a coal-degrading fungus, was shown to utilize aromatic coal-substructure compounds as the sole carbon source. Aromatic compounds were also mixed with soluble coal polymer and solubilization was studied over a 7-day period. The degradation of coal in supplemented samples measured as the amount of acid-precipitable coal polymer being formed was investigated. Although coal solubilization was produced with most of the aromatic compounds tested, wide differences in the extent of solubilization in the presence of each compound were recorded, depending on whether the intact organism or cell-free extract was used. The efficient conversion of the compounds by the fungus is related to the efficiency shown in the degradation of coal. The infrared spectra and elemental analysis of biodegraded coal and the undegraded parent material were used to draw conclusions concerning the cleavage of functional groups in the coal. Possible involvement of enzymes in the process is discussed.

  6. A Novel Spiro-Heterocyclic Compound Identified by the Silkworm Infection Model Inhibits Transcription in Staphylococcus aureus

    Directory of Open Access Journals (Sweden)

    Kazuhisa Sekimizu


    Full Text Available Synthetic compounds are a vital source of antimicrobial agents. To uncover therapeutically effective antimicrobial agents from a chemical library, we screened over 100,000 synthetic compounds for in vitro antimicrobial activity against methicillin-resistant Staphylococcus aureus and evaluated the in vivo therapeutic effectiveness of the hits in S. aureus-infected silkworms. Three antimicrobial agents exhibited therapeutic effects in the silkworm infection model. One of these, GPI0363, a novel spiro-heterocyclic compound, was bacteriostatic and inhibited RNA synthesis in S. aureus cells. GPI0363-resistant S. aureus strains harbored a point mutation in the gene encoding the primary sigma factor, SigA, of RNA polymerase, and this mutation was responsible for the resistance to GPI0363. We further revealed that GPI0363 could bind to SigA, inhibit promoter-specific transcription in vitro, and prolong the survival of mice infected with methicillin-resistant S. aureus. Thus, GPI0363 is an attractive candidate therapeutic agent against drug-resistant S. aureus infections.

  7. Volatile Compounds in Dry Dog Foods and Their Influence on Sensory Aromatic Profile

    Directory of Open Access Journals (Sweden)

    Koushik Adhikari


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

  8. Volatile compounds in dry dog foods and their influence on sensory aromatic profile. (United States)

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


    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.

  9. Comprehensive and Facile Synthesis of Some Functionalized Bis-Heterocyclic Compounds Containing a Thieno[2,3-b]thiophene Motif (United States)

    Mabkhot, Yahia N.; Barakat, Assem; Al-Majid, Abdullah M.; Alshahrani, Saeed A.


    A comprehensive and facile method for the synthesis of new functionalized bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif is described. The hitherto unknown bis-pyrazolothieno[2,3-b]thiophene derivatives 2a–c, bis-pyridazin othieno[2,3-b]thiophene derivatives 4, bis-pyridinothieno[2,3-b]thiophene derivatives 6a,b, and to an analogous bis-pyridinothieno[2,3-b]thiophene nitrile derivatives 7 are obtained. Additionally, the novel bis-pyradazinonothieno[2,3-b]thiophene derivatives 9, and nicotinic acid derivatives 10, 11 are obtained via bis-dienamide 8. The structures of all newly synthesized compounds have been elucidated by 1H, 13C NMR, GCMS, and IR spectrometry. These compounds represent a new class of sulfur and Nitrogen containing heterocycles that should also be of interest as new materials. PMID:22408452

  10. Water purification by reverse osmosis using heterocyclic polymer membranes (United States)

    Scott, H.


    Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.

  11. Oxidation of naphthenoaromatic and methyl-substituted aromatic compounds by naphthalene 1,2-dioxygenase

    Energy Technology Data Exchange (ETDEWEB)

    Selifonov, S.A. [Univ. of West Florida, Gulf Breeze, FL (United States)]|[Univ. of Minnesota, St. Paul, MN (United States); Eaton, R.W.; Chapman, P.J. [Environmental Protection Agency, Gulf Breeze, FL (United States)] [and others


    Naphthenoaromatic compounds constitute a group of aromatic chemicals with benzylic methylenic or methyne groups and are abundant constituents of polycyclic aromatic compound mixtures, one of the priority pollutants. Biodegradation of materials containing PACs may have value in the development of remedial technologies. Although broad substrate specificity is now a well recognized property of bacterial enzymes catalyzing early reactions of catabolic pathways for PACE, little is know of how bacterial arene dioxygenases act on naphthenaromatic compounds. This study focuses on nondioxygenase oxidative reactions catalyzed by napthalene dioxygenase encoded by the plasmid NAH7.

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

    NARCIS (Netherlands)

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


    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

  13. Microbial formation of hydroxylated aromatic compounds from 4-chloro- and 4-nitrobenzoate

    NARCIS (Netherlands)

    Groenewegen, P.


    In the introduction of this thesis several aspects of the production of hydroxylated aromatic compounds are described. These compounds are applied in the production of pharmaceuticals, polymers, flavors and dyes, but their chemical synthesis is rather difficult in preparative organic

  14. Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel, Dolores; De Canck, Els [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Jiménez-Sanchidrián, César [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Romero-Salguero, Francisco J., E-mail: [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Van Der Voort, Pascal, E-mail: [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)


    The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N{sub 2} adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, {sup 13}C and {sup 29}Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction.

  15. Synthesis of Heteroaromatic Compounds by Oxidative Aromatization Using an Activated Carbon/Molecular Oxygen System

    Directory of Open Access Journals (Sweden)

    Masahiko Hayashi


    Full Text Available A variety of heteroaromatic compounds, such as substituted pyridines, pyrazoles, indoles, 2-substituted imidazoles, 2-substituted imidazoles, 2-arylbenzazoles and pyrimidin-2(1H-ones are synthesized by oxidative aromatization using the activated carbon and molecular oxygen system. Mechanistic study focused on the role of activated carbon in the synthesis of 2-arylbenzazoles is also discussed. In the final section, we will disclose the efficient synthesis of substituted 9,10-anthracenes via oxidative aromatization.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wear, Jr., John Edmund [Wake Forest Univ., Winston-Salem, NC (United States)


    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.

  17. From organic pollutants to bioplastics: insights into the bioremediation of aromatic compounds by Cupriavidus necator. (United States)

    Berezina, Nathalie; Yada, Bopha; Lefebvre, Rodrigue


    Organic pollution by aromatic compounds is of increasing concern to our environment. Therefore, the transformation of aromatic pollutants into valuable aliphatic and biodegradable bioplastics was studied. Since benzoic acid was found to be the key compound for such bioremediation processes, its transformation, and metabolic pathways of digestion, by Cupriavidus necator were specifically analysed. It was found that the degradation of aromatic compounds follows the 2,3-dioxygenase pathway in this strain and that the batch transformations of benzoic acid with either fresh or adapted cells were limited to an initial concentration of 2.5 g/L of pollutant. The repeated fed-batch with partial withdrawal process, however, showed a 17.5-fold improvement, thus allowing the transformation of a total of 43.7 g/L in 12 weeks. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Process for reducing aromatic compounds in ethylenediamine with calcium (United States)

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


    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. Aromatic fluorine compounds. VIII. Plant growth regulators and intermediates (United States)

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


    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.

  20. Synthesis of new biologically active compounds containing linked thiazolyl-thiazolidinone heterocycles

    Directory of Open Access Journals (Sweden)

    Nagaraj Adki


    Full Text Available A new series of 1,3-benzothiazol-2-yl-1,3-thiazolan-4-one 5a-j has been synthesized by the reaction of 2-(4-methylphenyl-3-(5,5,7-trimethyl-4,5,6,7-tetrahydro-1,3-benzothiazol-2-yl-1,3-thiazolan-4-one 4 with aryl aldehydes. Chemical structures of all the new compounds were established by IR, 1H, 13C NMR, MS and elemental data. The compounds 5a-j were evaluated for their antibacterial activity against Gram-positive bacteria viz. Bacillus subtilis (MTCC 441, Bacillus sphaericus (MTCC 11, Staphylococcus aureus (MTCC 96 and Gram-negative bacteria viz. Pseudomonas aeruginosa (MTCC 741, Klebsiella aerogenes (MTCC 39, Chromobacterium violaceum (MTCC 2656. Amongst them, compounds containing [(4-chlorophenylmethyli- dene] moiety 5b, [(3-nitrophenylmethylidene] moiety 5d and [(2-thienylmethylidene] moiety 5j showed significant antibacterial activity, almost equal/more than the activity of the standard drug Streptomycin. Further, the compounds 5a-j were also screened for their antifungal activity against Candida albicans (ATCC 10231, Aspergillus fumigatus (HIC 6094, Trichophyton rubrum (IFO 9185, and Trichophyton mentagrophytes (IFO 40996. Most of these new compounds showed appreciable activity against test bacteria and fungi and emerged as potential molecules for further development.

  1. Azoarcus sp. CIB, an anaerobic biodegrader of aromatic compounds shows an endophytic lifestyle.

    Directory of Open Access Journals (Sweden)

    Helga Fernández

    Full Text Available 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.

  2. Divergent Synthesis of Novel Five-Membered Heterocyclic Compounds by Base-Mediated Rearrangement of Acrylamides Derived from a Novel Isocyanide-Based Multicomponent Reaction

    Directory of Open Access Journals (Sweden)

    Renata Riva


    Full Text Available We have recently reported a novel multicomponent reaction between arylacetic acids and isocyanides, affording α-acyloxyacrylamides through an unusual mechanism. The products of this novel multicomponent reaction can rearrange to five membered heterocyclic compounds when exposed to an alkaline environment. Depending on the reaction conditions and on the substitution pattern on the substrates, various pyrrolidine derivatives can be selectively obtained. We now wish to report that libraries endowed with skeletal diversity, thus responding to the requirements of Diversity Oriented Synthesis (DOS, can be efficiently prepared in this manner, and phenotypic biological assays have shown interesting properties of some representative compounds.

  3. A simple, convenient, and one pot synthetic route for the preparation of 1,3,5-thiadiazines-2-thione heterocyclic compounds and their antifungal activity

    Directory of Open Access Journals (Sweden)

    Sohail Saeed


    Full Text Available A series of new heterocyclic 1,3,5-thiadiazines-2-thione with aroyl/aryl substituents (3a-c were synthesized by reacting isothiocyanates with N- (propan-2-ylpropan-2- amine in the presence of tetrabutylammonium bromide as phase transfer catalyst. The structures of these novel compounds were characterized by IR, mass spectrometry, and elemental analysis. The crystal structures were determined from single-crystal X-ray diffraction data. The synthesized compounds were tested in vitro against Fusarium solani, A. fumigatus, and Aspergillus flavus using standard drugs.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. Formation of 2,6-dichloro-1,4-benzoquinone from aromatic compounds after chlorination. (United States)

    Kosaka, Koji; Nakai, Takahiko; Hishida, Yuta; Asami, Mari; Ohkubo, Keiko; Akiba, Michihiro


    Halobenzoquinones are a group of disinfection byproducts formed by chlorination of certain substances in water. However, to date, the identities of halobenzoquinone precursors remain unknown. In this study, the formation of 2,6-dichloro-1,4-benzoquinone (DCBQ), a typical halobenzoquinone, from 31 aromatic compounds was investigated after 60 min of chlorination. DCBQ was formed from 21 compounds at molar formation yields ranging from 0.0008% to 4.9%. Phenol and chlorinated phenols served as DCBQ precursors, as reported previously. Notably, DCBQ was also formed from para-substituted phenolic compounds. Compounds with alkyl and carboxyl groups as para-substituents led to relatively higher molar formation yields of DCBQ. Moreover, p-quinone-4-chloroimide, 2,6-dichloroquinone-4-chloroimide (2,6-DCQC), and para-substituted aromatic amines (e.g., aniline and N-methyl aniline) served as DCBQ precursors upon chlorination. It was deduced that DCBQ was formed from the para-substituted aromatic amines via 3,5-dichloroquinone-4-chloroimide, a structural isomer of 2,6-DCQC. These results suggested that DCBQ was formed by chlorination of natural organic matter containing para-substituted phenolic species and para-substituted aromatic amines, despite the absence of phenol in water. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Fruits and vegetables protect against the genotoxicity of heterocyclic aromatic amines activated by human xenobiotic-metabolizing enzymes expressed in immortal mammalian cells. (United States)

    Platt, K L; Edenharder, R; Aderhold, S; Muckel, E; Glatt, H


    Heterocyclic aromatic amines (HAAs) can be formed during the cooking of meat and fish at elevated temperatures and are associated with an increased risk for cancer. On the other hand, epidemiological findings suggest that foods rich in fruits and vegetables can protect against cancer. In the present study three teas, two wines, and the juices of 15 fruits and 11 vegetables were investigated for their protective effect against the genotoxic effects of 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). To closely mimic the enzymatic activation of these HAAs in humans, genetically engineered V79 Chinese hamster fibroblasts were employed that express human cytochrome P450-dependent monooxygenase (hCYP) 1A2 (responsible for the first step of enzymatic activation) and human N(O)-acetyltransferase (hNAT) 2*4 or human sulfotransferase (hSULT)1A1*1 (responsible for the second step of enzymatic activation): V79-hCYP1A2-hNAT2*4 for IQ activation and V79-hCYP1A2-hSULT1A1*1 for PhIP activation. HAA genotoxicity was determined by use of the comet assay. Black, green and rooibos tea moderately reduced the genotoxicity of IQ (IC(50)=0.8-0.9%), whereas red and white wine were less active. From the fruit juices, sweet cherry juice exhibited the highest inhibitory effect on IQ genotoxicity (IC(50)=0.17%), followed by juices from kiwi fruit, plum and blueberry (IC(50)=0.48-0.71%). The juices from watermelon, blackberry, strawberry, black currant, and Red delicious apple showed moderate suppression, whereas sour cherry, grapefruit, red currant, and pineapple juices were only weakly active. Granny Smith apple juice and orange juice proved inactive. Of the vegetable juices, strong inhibition of IQ genotoxicity was only seen with spinach and onion juices (IC(50)=0.42-0.54%). Broccoli, cauliflower, beetroot, sweet pepper, tomato, chard, and red-cabbage juices suppressed IQ genotoxicity only moderately, whereas cucumber juice was

  7. Preparation of arginine-modified reduced graphene oxide composite filled in an on-line solid-phase extraction disk and its application in the analysis of heterocyclic aromatic amines. (United States)

    Cai, Lemei; Xu, Na; Xia, Shujun; Wang, Yiru; Chen, Xi


    An arginine-modified reduced graphene oxide composite was prepared in an on-line solid-phase extraction disk and coupled to high-performance liquid chromatography for the re-enrichment of heterocyclic aromatic amines. The synthetic composite presented an excellent adsorption capability because of the ultrahigh active surface area of graphene and the abundant alkaline groups of arginine. The adsorption capacity of it was 52.7 mg 2-amino-3-methyl-imidazo[4,5-f]-quinoline per gram, nearly twice that of threonine-modified reduced graphene oxide composite, glutamic acid modified reduced graphene oxide composite, and reduced graphene oxide. This on-line method was successfully applied to the detection of a series of heterocyclic aromatic amines in beef jerky. After clean-up and re-enrichment of the on-line solid-phase extraction disk, the chromatographic background of the sample was low and the shape of chromatographic peaks was sharp. The method detection limit was in the range of 0.30-0.49 ng/g, and the recovery was in the range of 82.0-111.5%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Degradation of Chlorinated Aromatic Compounds in UASB Reactors

    DEFF Research Database (Denmark)

    Christiansen, Nina; Hendriksen, Hanne Vang; Järvinen, Kimmo T.


    Data on anaerobic degradation of chloroaromatic compounds in Upflow Anaerobic Sludge Blanket Reactors (UASB-reactor) are presented and compared. Special attention is given to the metabolic pathways for degradation of chlorinated phenols by granular sludge. Results indicate that PCP can be degraded...... in UASB-reactors via stepwise dechlorination to phenol. Phenol will subsequently be converted to benzoate before ring cleavage. Dechlorination proceeds via different pathways dependent upon the inocula used. Results are further presented on the design of special metabolic pathways in granules which do...

  9. Synthesis of high refractive spiro heterocyclic derivatives through thioacetalization of multi-carbonyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Jim Young; Maheswara, Muchchintala; Do, Jung Yun [Pusan National Univ., Busan (Korea, Republic of)


    Preparation of several new spirocyclic mercaptol derivatives is described. Thiol protection on multi-carbonyl compounds allows of high sulfur content necessary to induce high refractive index. Condensation of 1,3-dimercapto-2-propanol and cyclohexanone followed by successive oxidation and thioacetalization affords a dispiro cycle with four sulfurs. Selective S,S-protection of cyclohexane-1,4-dione is achieved with 1,3-dimercapto-2-propanol and 2,3-dimercapto-1-propanol to provide dispiro cycles with four sulfurs. Olefineoxidation of norbornene gives a useful dialdehyde intermediate which is transformed to 1,3-dithiolane for a linearly-bound-cyclic molecule. Refractive index of linearly-bound-cycles was below 1.60 and dispiro cycles exhibited high refractive index of 1.57-1.69.

  10. Inhibition of copper corrosion in aerated hydrochloric acid solution by heterocyclic compounds containing a mercapto group

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Daquan; Gao Lixin; Zhou Guoding


    Inhibition of copper corrosion by benzotriazole (BTA), 2-mercapto benzoxazole (MBO) and 2-mercapto benzimidazole (MBI) in 0.5 mol L{sup -1} HCl was investigated by weight-loss measurements, potentiodynamic polarization curves and electrochemical impedance spectroscopy. MBI was shown to be the most effective inhibitor among those tested. Potentiodynamic polarization results revealed that the three compounds acted as anodic inhibitors, particularly MBI strongly suppressed anodic current densities. Molecular structure parameters of BTA, MBO and MBI were obtained by using an MM2 forcefield program and PPP-SCF quantum chemical calculation. It was found that MBI has higher levels of HOMO and LUMO energy and the larger {pi}-electron density.

  11. Thermodynamic study on six tricyclic nitrogen heterocyclic compounds by thermal analysis and effusion techniques

    Energy Technology Data Exchange (ETDEWEB)

    Brunetti, Bruno [Istituto per lo Studio dei Materiali Nanostrutturati, Consiglio Nazionale delle Ricerche, Dipartimento di Chimica, Sapienza Università di Roma, P .le A. Moro 5, I-00185 Rome (Italy); Lapi, Andrea [Dipartimento di Chimica, Sapienza Università di Roma, and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, Dipartimento di Chimica, Sapienza Università di Roma, P. le A. Moro 5, I-00185 Rome (Italy); Vecchio Ciprioti, Stefano, E-mail: [Dipartimento S.B.A.I., Sapienza Università di Roma, Via del Castro Laurenziano 7, I-00161 Rome (Italy)


    Highlights: • Melting characteristics of tricyclic N-hetero tricyclic compounds were measured by DSC. • Vapor pressures of solid and liquid compounds were measured by effusion and iso-TG. • Thermochemical data from solid and liquid phases were compared with literature. • Good agreement between experimental and literature data with only few exceptions. - Abstract: The molar sublimation and vaporization enthalpies of acridine, phenanthridine, 1,7-phenanthroline, 1,10-phenanthroline, 4,7-phenanthroline and phenazine were determined at the averages of their respective experimental temperature ranges (Δ{sub cr}{sup g}H{sup 0}{sub m} () and Δ{sub l}{sup g}H{sup 0}{sub m} (), respectively) from the temperature dependencies of vapor pressure determined using Knudsen Effusion Mass Loss (KEML), Torsion Effusion (TE) and Isothermal Thermogravimetry (ITG) above their solid and liquid phases. The fusion characteristics (melting temperatures and the molar standard enthalpies of fusion at their melting temperatures) measured by Differential Scanning Calorimetry (DSC) were compared with the available literature values. Solid and liquid vapor pressure data determined by KEML, TE and ITG techniques as well as Δ{sub cr}{sup g}H{sup 0}{sub m} () and Δ{sub l}{sup g}H{sup 0}{sub m} () values, adjusted at 298.15 K by using the values of C{sub p}(cr) and C{sub p}(l) calculated by a well-known group additivity method, were found to be fairly correlated and are consistent with the available literature data. Final Δ{sub cr}{sup g}H{sup 0}{sub m}(298.15 K) values were also provided as weighted averages of all the available data.

  12. Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent. (United States)

    Hoffmann, Norbert


    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.

  13. Biosynthesis of polybrominated aromatic organic compounds by marine bacteria. (United States)

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


    Polybrominated diphenyl ethers (PBDEs) and polybrominated bipyrroles are natural products that bioaccumulate in the marine food chain. PBDEs have attracted widespread attention because of 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 brominases 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.

  14. Comprehensive database of Manufactured Gas Plant tars. Part B. Aliphatic and aromatic compounds. (United States)

    Gallacher, Christopher; Thomas, Russell; Lord, Richard; Kalin, Robert M; Taylor, Chris


    Coal tars are a mixture of organic and inorganic compounds that were produced as a by-product from the manufactured gas and coke making industries. The composition of the tar produced varies depending on many factors; these include the temperature of production and the type of retort used. As different production processes produce different tars, a comprehensive database of the compounds present within coal tars from different production processes is a valuable resource. Such a database would help to understand how their chemical properties differ and what hazards the compounds present within these tars might pose. This study focuses on the aliphatic and aromatic compounds present in a database of 16 different tars from five different production processes. Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatised post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatised samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). A total of 198 individual aliphatic and 951 individual aromatic compounds were detected within 16 tar samples produced by five different production processes. The polycyclic aromatic hydrocarbon (PAH) content of coal tars varies greatly depending on the production process used to obtain the tars and this is clearly demonstrated within the results. The aliphatic composition of the tars provided an important piece of analytical information that would have otherwise been missed with the detection of petrogenic compounds such as alkyl cyclohexanes. The aromatic compositions of the tar samples varied greatly between the different production processes investigated and useful analytical information was obtained about the individual production process groups. Alkyl cyclohexanes were detected in all samples from sites known to operate Carbureted Water Gas plants and not detected in

  15. The biological in vitro effect and selectivity of aromatic dicationic compounds on Trypanosoma cruzi

    Directory of Open Access Journals (Sweden)

    Cristiane França da Silva


    Full Text Available Trypanosoma cruzi is a parasite that causes Chagas disease, which affects millions of individuals in endemic areas of Latin America. One hundred years after the discovery of Chagas disease, it is still considered a neglected illness because the available drugs are unsatisfactory. Aromatic compounds represent an important class of DNA minor groove-binding ligands that exhibit potent antimicrobial activity. This study focused on the in vitro activity of 10 aromatic dicationic compounds against bloodstream trypomastigotes and intracellular forms of T. cruzi. Our data demonstrated that these compounds display trypanocidal effects against both forms of the parasite and that seven out of the 10 compounds presented higher anti-parasitic activity against intracellular parasites compared with the bloodstream forms. Additional assays to determine the potential toxicity to mammalian cells showed that the majority of the dicationic compounds did not considerably decrease cellular viability. Fluorescent microscopy analysis demonstrated that although all compounds were localised to a greater extent within the kinetoplast than the nucleus, no correlation could be found between compound activity and kDNA accumulation. The present results stimulate further investigations of this class of compounds for the rational design of new chemotherapeutic agents for Chagas disease.


    Directory of Open Access Journals (Sweden)

    B. Ayati, H. Ganjidoust, M. Mir Fattah


    Full Text Available For biological treatment of water, there are many different biofilm systems in use. Examples of them are trickling filters, rotating biological contactors, fixed media submerged biofilters, granular media biofilters and fluidized bed reactors. They all have their advantages and disadvantages. Hence, the Moving Bed Biofilm Reactor process was developed in Norway in the late 1980s and early 1990s to adopt the best features of the activated sludge process as well as those of the biofilter processes, without including the worst. Two cylindrical moving bed biofilm reactors were used in this study working in upflow stream conditions. Experiments have been done in aerobic batch flow regime. Laboratory experiments were conducted at room temperature (23–28C and synthetic wastewater comprising a composition of phenol and hydroquinone in each reactor as the main organic constituents, plus balanced nutrients and alkalinity were used to feed the reactor. The ratio of influent to effluent COD was determined at different retention times. The results indicated that the removal efficiency of each selected compound is affected by the detention time. At low phenol and hydroquinone concentration (from 700 to 1000 mg/L maximum removal efficiency (over 80 % was obtained. By further increasing in COD loading rate up to 3000 mg/L, a decrease in COD removal rate was occurred. In the reactor containing pyrogallol in COD of 1500 mg/L, the removal rate decreased to 10 percent because of its toxicity for microorganisms.

  17. Leaching of styrene and other aromatic compounds in drinking water from PS bottles. (United States)

    Ahmad, Maqbool; Bajahlan, Ahmad S


    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.

  18. The studies on the aromaticity of fullerenes and their holmium endohedral compounds. (United States)

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


    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.

  19. The key enzymes in the catabolism of aromatic compounds in Rhodococcus

    Energy Technology Data Exchange (ETDEWEB)

    Dugan, I.N.; Golovlev, E.L.


    The enzyme apparatus involved in the catabolism of aromatic compounds in rhodococci is characterized by the presence of pyrocatechase and protocatechoate-3,4-dioxygenase as principal enzymes cleaving the aromatic cycle. Metapyrocatechase was found in about 30% of the rhodococci. All the enzymes are inducible. The inductor of pyrocatechase seems to be cys-cys-muconate, and that of protocatechase appears to be 3-oxoadipate. The metapyrocatechase of rhodococci, in contrast to that of Pseudomonas, is not induced by benzoate, p-toluylate, p-xylene and phenol. The activity of metapyrocatechase rises 20-50 times comparing to the basal level only in the presence of p-cresol. The enzyme has a relatively low activity in rhodococci (50-200 nmole per 1 min per 1 mg of protein), though a very high affinity for methylcatechols. The activity of metapyrocatechase with methylcatechols is 2-5 times as high as that with catechol as a substrate, whereas the activity of pyrocatechase with methylcatechols is two times as low as that with catechol as a substrate. Such additional substrates as acetate, glycerol or fumarate have no effect on the qualitative composition of the key enzymes involved in the degradation of aromatic compounds in Rhodococcus corallinus 172. Glucose represses the synthesis of enzymes cleaving the aromatic ring by 100%. Fumarate taken in a 5-fold excess inhibits the activity of catechol oxygenases by 40%; if it is taken in a 1000-fold excess, it inhibits the enzyme activity by 100%.

  20. Volatile aromatic compounds in Mexico City atmosphere: levels and source apportionment

    Energy Technology Data Exchange (ETDEWEB)

    Mugica, V. [Universidad Autonoma Metropolitana - Unidad Azcapotzalco, Mexico, D.F. (Mexico); Ruiz, M.E. [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico); Watson, J.; Chow, J. [Desert Research Institute, Reno, Nevada (United States)


    Samples of ambient air were simultaneously collected at three different sites of Mexico City in March of 1997 in order to quantify the most abundant volatile aromatic compounds and estimate the source contributions by application of the chemical mass balance model (CMB). Volatile aromatic compounds were around 20% of the total of non-methane hydrocarbons present in morning air samples. The most abundant volatile aromatic species in urban air were toluene and xylenes followed by 1, 2, 4 trimethylbenzene, benzene, ethylbenzene, metaethyltoluene, 1, 3, 5 trimethylbenzene, styrene, n propylbenzene, and isopropylbenzene. Sampling campaigns were carried out at crossroads, a bus station, a parking place, and areas where solvents and petroleum distillates are used, with the objective of determining people's exposure to volatile aromatic compounds. The CMB was applied for estimating the contribution of different sources to the presence of each one of the most abundant aromatic compounds. Motor vehicle exhaust was the main source of all aromatic compounds, especially gasoline exhaust, although diesel exhausts and asphalt operations also accounted for toluene, xylenes, ethylbenzene, propylbenzenes, and styrene. Graphic arts and paint applications had an important impact on the presence of toluene. [Spanish] Se colectaron simultaneamente muestras de aire ambiente en tres sitios de la Ciudad de Mexico durante el mes de marzo de 1997 con el fin de conocer las concentraciones y el origen de compuestos aromaticos utilizando el modelo de balance de masa de especies quimicas (CMB). Los compuestos aromaticos volatiles representaron alrededor del 20% del total de hidrocarburos no metalicos presentes en las muestras matutinas colectadas. Las especies aromaticas volatiles mas abundantes en el ambiente fueron el tolueno y los xilenos, seguidos por 1, 2, 4 trimetilbenceno, benceno, etilbenceno, metaetiltolueno, nporpilbenceno, isopropilbenceno, 1, 3, 5 trimetilbenceno y estireno. Se

  1. Computational Methods to Predict the Regioselectivity of Electrophilic Aromatic Substitution Reactions of Heteroaromatic Systems

    DEFF Research Database (Denmark)

    Kruszyk, Monika; Jessing, Mikkel; Kristensen, Jesper L


    The validity of calculated NMR shifts to predict the outcome of electrophilic aromatic substitution reactions on different heterocyclic compounds has been examined. Based on an analysis of >130 literature examples it was found that the lowest calculated 13C and/or 1H chemical shift of a heterocycle...... correlates qualitatively with the regiochemical outcome of halogenation reactions in >80% of the investigated cases. In the remaining cases, the site of electrophilic aromatic substitution can be explained by the calculated HOMO orbitals obtained using density functional theory. Using a combination...

  2. Formation of N-Arylacylhydroxamic Acids from Nitroso Aromatic Compounds in Isolated Spinach Leaf Cells. (United States)

    Yoshioka; Uematsu


    The formation of N-arylacetohydroxamic acids from nitroso aromatic compounds in the presence of pyruvate was investigated using isolated spinach leaf cells. The activity was enhanced by the addition of TPP, MgSO(4), and pyruvate, requirements for pyruvate dehydrogenase complex (PDHC). Measurement of the kinetic parameters revealed that the K(m) values of nitroso aromatic compounds tested were identical and that electron-donating ring substituents decreased the catalytic efficiency. The activation energy of the formation of N-phenylacetohydroxamic acid was lower than that reported for porcine heart PDHC. With alpha-oxo acids tested, alpha-oxobutyrate served as a substrate to give the corresponding N-phenylpropionylhydroxamic acid. The activity of spinach leaf cells in N-phenylacetohydroxamic acid formation was found in both mitochondria and chloroplasts. The contribution of chloroplast PDHC to total activity in the formation of N-phenylacetohydroxamic acid was estimated to be 50% under the conditions used.

  3. Cholesteric Liquid Crystalline Copolymers for Gas Chromatographic Separation of Polycyclic Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Chih-Hung Lin


    Full Text Available A novel series of side-chain liquid crystalline copolysiloxanes containing [S]-1-(2-naphthyl ethyl 6-[4-(10-undecen-1-yloxy biphenyl--carbonyloxy]-2-naphthoate mesogenic and 4-biphenyl -allyloxybenzoate mesogenic side groups in the backbone and side chains liquid crystalline copolymers were prepared and evaluated as possible stationary phases for gas chromatography capillary columns. All copolymers display enantiotropic cholesteric phases. These mesomorphic polysiloxanes specimens with the widest temperature range were used as the stationary phase in a gas chromatography capillary column, and it showed good thermal and physical stability, excellent chemical inertness, and unique separation properties for polycyclic aromatic compounds. These cholesteric LC copolysiloxane stationary phases show much better separation effect for the polycyclic aromatic compound than those of the nematic and smectic LC copolysiloxanes.

  4. Studying the interaction between three synthesized heterocyclic sulfonamide compounds with hemoglobin by spectroscopy and molecular modeling techniques. (United States)

    Naeeminejad, Samane; Assaran Darban, Reza; Beigoli, Sima; Saberi, Mohammad Reza; Chamani, Jamshidkhan


    The interaction between synthesized heterocyclic benzene sulfonamide compounds, N-(7-benzyl-56-biphenyl-2m-tolyl-7H-pyrrolo[23-d]pyrimidine-4-yl)-benzene sulfonamide (HBS1), N-(7-benzyl-56-biphenyl-2-m-tolyl-7H-pyrrolo[23-d] pyrimidine-4-yl)-4-methyl- benzene sulfonamide (HBS2), and N-(7-benzyl-56-biphenyl-2-m-tolyl-7H-pyrrolo[23-d]pyrimidine-4-yl)-4-chloro-benzene sulfonamide (HBS3) with Hb was studied by fluorescence quenching, zeta potentional, circular dichroism, and molecular modeling techniques. The fluorescence spectroscopy experiments were performed in order to study the conformational changes, possibly due to a discrete reorganization of Trp residues during binding between HBS derivatives and Hb. The variation of the KSV value suggested that hydrophobic and electrostatic interactions were the predominant intermolecular forces stabilizing the complex. The KSV1 ans KSV2 values of HBS derivatives with Hb are .6 × 1013 and 3 × 1013 M-1 for Hb-HBS1, 1 × 1013 and 4 × 1013 M-1 for Hb-HBS2, .9 × 1013, and 6 × 1013 M-1 for Hb-HBS3, respectively. The molecular distances between Hb and HBS derivatives in binary and ternary systems were estimated according to Förster's theory of dipole-dipole non-radiation energy transfer. The quantitative analysis data of circular dichroism spectra demonstrated that the binding of the three HBS derivatives to Hb induced conformational changes in Hb. Changes in the zeta potential of the Hb-HBS derivatives complexes demonstrated a hydrophobic adsorption of the anionic ligand onto the surface of Hb as well as both electrostatic and hydrophobic adsorption in the case of the complex. The modeling data thus confirmed the experimental results. This study is expected to provide important insight into the interaction of Hb with three HBS derivatives to use in various toxicological and therapeutic processes.

  5. Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds (United States)

    Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang


    The novel class of luminescent Al3 +-based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2‧:6‧,2″-terpyridine]-4‧-ylbenzoic acid (Hcptpy) with Al3 + under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467 nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0 μM with a detection limit of 4.64 μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA.

  6. Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

    DEFF Research Database (Denmark)

    Nguyen, Ngoc-Lan Thi; Vo, Hong-Thom; Duus, Fritz


    The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylim...

  7. Investigation of aromatic compound degradation under atmospheric conditions in the outdoor simulation chamber SAPHIR (United States)

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


    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

  8. Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization. (United States)

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

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

  9. Uptake of aromatic compounds by DNA: Toward the environmental application of DNA for cleaning water. (United States)

    Fernández-Solis, Christian; Kuroda, Yasuhiro; Zinchenko, Anatoly; Murata, Shizuaki


    Although the interaction of DNA with various types of intercalating chemicals, such as planar polycyclic aromatic compounds, has been extensively investigated over the past several decades, little is known about the relationship between the structure of a DNA binder and its affinity for DNA. The use of DNA as an adsorbent for environmental cleaning purposes requires information on its affinity for organic chemicals with different structures. In the present study we investigated the binding of DNA to aromatic chemicals with various structures and charges by three methods: binding of organic chemicals to DNA followed by removal by precipitation with cationic nanoparticles (1) or a cationic surfactant (2), and absorption of organic chemicals by a DNA hydrogel (3). The results showed that, for most neutral organic chemicals, the hydrophobicity of the organic molecule is the main driving force for efficient binding to DNA. The double-helicity of DNA contributed to stronger binding to most of the compounds. The efficiency of the uptake of organic chemicals increased substantially when a hydrophobic cationic surfactant was used for DNA-complex condensation and removal. The potential environmental application of DNA as an adsorbent for the removal of aromatic organic pollutants from water is discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Reusable and Efficient Polystryrene-supported Acidic Ionic Liquid Catalyst for Mononitration of Aromatic Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Li, Li Xia; Ling, Qi Long; Liu, Zu Liang; Xing, Xiao Dong; Zhu, Xiao Qin; Meng, Xiao [Nanjing Univ. of Science and Technology, Nanjing (China)


    A series of polystyrene-supported 1-(propyl-3-sulfonate)-3-methyl-imidazolium hydrosulfate acidic ionic liquid (PS-[SO{sub 3}H-PMIM][HSO{sub 4}]) catalysts were prepared and tested for mononitration of simple aromatics compounds with nitric acid. It was found that the reactivity of the catalysts increased with increasing [SO{sub 3}HPMIM][HSO{sub 4}] content. The para-selectivity was not only related to the [SO{sub 3}H-PMIM][HSO{sub 4}] content but also the substituent groups in aromatics. A reaction mechanism of nitration over this new catalyst was proposed. The catalytic activity of this catalyst decreased slightly after fifth runs in the synthesis of nitrotoluene.

  11. Capacity of Aromatic Compound Degradation by Bacteria from Amazon Dark Earth

    Directory of Open Access Journals (Sweden)

    Fernanda Mancini Nakamura


    Full Text Available Amazon dark earth (ADE is known for its high organic matter content, biochar concentration and microbial diversity. The biochar amount suggests the existence of microorganisms capable of degrading aromatic hydrocarbons (AHs. In an effort to investigate the influence of bacteria on the resilience and fertility of these soils, we enriched five ADE soils with naphthalene and phenanthrene, and biodegradation assays with phenanthrene and diesel oil were carried out, as well. After DNA extraction, amplification and sequencing of the 16S rRNA bacterial gene, we identified 148 isolates as the Proteobacteria, Firmicutes and Actinobacteria phyla comprising genera closely related to AHs biodegradation. We obtained 128 isolates that degrade diesel oil and 115 isolates that degrade phenanthrene. Some isolates were successful in degrading both substrates within 2 h. In conclusion, the obtained isolates from ADE have degrading aromatic compound activity, and perhaps, the biochar content has a high influence on this.

  12. Antimutagenic effects and possible mechanisms of action of vitamins and related compounds against genotoxic heterocyclic amines from cooked food. (United States)

    Edenharder, R; Worf-Wandelburg, A; Decker, M; Platt, K L


    Possible antimutagenic activity of 26 vitamins and related compounds - ascorbic acid, beta-carotene, cyanocobalamin, folic acid, nicotinic acid, nicotinamide, pantothenic acid, pyridoxale, pyridoxamine, pyridoxine, retinal, retinol, retinoic acid, retinyl acetate, retinyl palmitate, riboflavin, riboflavin 5'-phosphate, flavin adenine dinucleotide (FAD), alpha-tocopherol, alpha-tocopherol acetate, vitamins K(1), K(3), K(4), 1, 4-naphthoquinone, and coenzyme Q(10) - was tested against six heterocyclic amine (HCA) mutagens, i.e., 2-amino-3-methyl-imidazo[4, 5-f]quinoline (IQ), 2-amino-3,4-dimethyl-imidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethyl-imidazo[4,5-f]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-6-methyl-dipyrido[1,2-a:3',2'-d]imidazole (Glu-P-1) and 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) in the Salmonella/reversion assay using tester strains Salmonella typhimurium TA 98 and TA 100. Retinol, retinal, riboflavin, riboflavin 5'-phosphate, FAD, vitamins K(1), K(3), K(4), 1, 4-naphthoquinone, and coenzyme Q(10) caused a concentration-dependent decrease in the mutagenicity of all six mutagens in both tester strains. Quantification of antimutagenic potencies by calculating ID(50)1000; vitamin K(1): 401-740; vitamin K(3) (menadione): 85-590; vitamin K(4): 45-313; 1,4-naphthoquinone: 170-290; coenzyme Q(10): 490-860. In general, there were no major differences between HCAs tested except in part with Trp-P-2 nor between the two tester strains. In enzyme kinetic experiments with Salmonella, retinol, vitamins K(3), and K(4) behaved as competitive inhibitors of IQ induced mutagenesis. However, at the highest concentration of menadione (200 nmol/plate) and of riboflavin 5'-phosphate (2000 nmol/plate), non-competitive inhibition was observed. At other concentrations of riboflavin 5'-phosphate and at all concentrations of FAD, meaningful interpretation of enzyme kinetics were not possible. Reduction of the activity of 7

  13. Bioactive compounds derived from the yeast metabolism of aromatic amino acids during alcoholic fermentation. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Albert Mas


    Full Text Available 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. Analysis and evaluation of compounds from Cichorium intybus aromatic water trade market samples

    Directory of Open Access Journals (Sweden)

    A. Hosseini*


    Full Text Available Background and objectives: Cichorium intybus products are one of the best sellers in market Because of their effect on treatment of infection, poisoning, diabetes and allergy. This is the first study about Cichorium intybus market samplephytochemical compounds and the aim of this study was to define a method to recognize the original products. Methods: The sample compounds were extracted by liquid-liquid method and evaluated by GC-MS and compared with the references like Adams 2007. The obtained phytochemical data were analyzed with SPSS and classified by dendrogram method and was compared with the data earned from the standard sample. Results: Forty one compounds were detected. Carvacrol was available in all samples from 1.14 to 39.34%. Also, thymol was present in most of samples from 1.24 to 69.32%. Moreover, we understood that some compounds like pulegone, carvone, carvacrol and piperitenone could be detected in all samples mostly with different percentages. Some linear hydrocarbon was detected in this method along with some other unexpected compounds like cinnamaldehyde. Conclusion: Existence of some impure compounds like: pulegone, carvone, piperitenone and cinnamaldehyde in trade samples showed cleaning of container might not have been proper. Carvacrol and thymol are common compounds to define acceptable standard for Cichorium intybus aromatic water.

  16. Pore size dynamics in interpenetrated metal organic frameworks for selective sensing of aromatic compounds. (United States)

    Myers, Matthew; Podolska, Anna; Heath, Charles; Baker, Murray V; Pejcic, Bobby


    The two-fold interpenetrated metal-organic framework, [Zn2(bdc)2(dpNDI)]n (bdc=1,4-benzenedicarboxylate, dpNDI=N'N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide) can undergo structural re-arrangement upon adsorption of chemical species changing its pore structure. For a competitive binding process with multiple analytes of different sizes and geometries, the interpenetrated framework will adopt a conformation to maximize the overall binding interactions. In this study, we show for binary mixtures that there is a high selectivity for the larger methylated aromatic compounds, toluene and p-xylene, over the small non-methylated benzene. The dpNDI moiety within [Zn2(bdc)2(dpNDI)]n forms an exciplex with these aromatic compounds. The emission wavelength is dependent on the strength of the host-guest CT interaction allowing these compounds to be distinguished. We show that the sorption selectivity characteristics can have a significant impact on the fluorescence sensor response of [Zn2(bdc)2(dpNDI)]n towards environmentally important hydrocarbons based contaminants (i.e., BTEX, PAH). Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

  17. Aromatic compounds in molecular phase of Baltic amber-synchronous luminescence analysis. (United States)

    Matuszewska, Aniela; Czaja, Maria


    Synchronous luminescence analysis was performed in order to identify aromatic compounds in solvent extracts of Baltic amber. The investigated extracts were obtained, for comparisons, as products of extraction by various techniques and solvents. Methylene chloride and ethanol were applied independently for extraction at the ambient temperature (conservative extraction), as well as at the temperature of solvent boiling (extraction in Soxhlet apparatus). Ethanol, as the solvent, was also used for extraction in an ultrasonic bath and for the decoction process. The extraction, by techniques mentioned, of the analysed amber has resulted in products generally containing the same groups of aromatics: mainly naphthalenes, phenanthrenes and anthracenes. Among phenanthrenes, in all samples the retene was also identified, being one of the characteristic links of the diagenetic chain of chemical transformations of vegetal precursors. The identification of a series of individual compounds made, using the synchronous luminescence technique, was verified by the record of conventional emission and excitation spectra. Presented identified compounds were also confirmed by the results of GC-MS analysis. The luminescence analysis was also performed comparatively for fossil resin from Galicia, Spain (Cretaceous) older than Baltic amber (Tertiary, Eocene). The obtained preliminary results of synchronous luminescence analysis suggest the possibility of diversification in this manner of fossil resins of various ages by characterisation of aromatisation degree and alkyl substitution of aromatic rings. It is since well known that aromatisation progress is an indicator of a natural process of maturation of fossil organic matter. However, a greater number of samples should be taken to further testify to the investigations.

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

    Directory of Open Access Journals (Sweden)

    Brzezinski Peter


    Full Text Available Abstract 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.

  19. National Status and Trends, Benthic Surveillance Project Fluorescent Aromatic Compounds (FAC) Data, 1984-1991, National Centers for Coastal Ocean Science (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The National Status and Trends (NSandT) Benthic Surveillance Fluorescent Aromatic Compounds (FAC) file reports the trace concentrations of Fluorescent Aromatic...

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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. Azomesogens with a heterocyclic moiety

    Indian Academy of Sciences (India)


    Abstract. Azobenzene derivatives were among the first ten liquid crystalline compounds. But there have been no detailed investigations on azomesogens consisting of a heterocyclic moiety. Twelve different azo compounds have been condensed with nicotinic acid to evaluate the effect of variation of terminal group on the ...

  2. Silaphenolates and Silaphenylthiolates: Two Unexplored Unsaturated Silicon Compound Classes Influenced by Aromaticity

    Directory of Open Access Journals (Sweden)

    Henrik Ottosson


    Full Text Available Monosilicon analogs of phenolates and phenylthiolates are studied by quantum chemical calculations. Three different silaphenolates and three different silaphenylthiolates are possible; the ortho-, meta-, and para-isomers. For the silaphenolates, the meta-isomer is the thermodynamically most stable, regardless if the substituent R at Si is H, t-Bu or SiMe3. However, with R = H and SiMe3 the energy differences between the three isomers are small, whereas with R = t-Bu the meta-isomer is ~5 kcal/mol more stable than the ortho-isomer. For the silaphenylthiolates the ortho-isomer is of lowest energy, although with R = H the ortho- and meta-isomers are isoenergetic. The calculated nucleus independent chemical shifts (NICS indicate that the silaphenolates and silaphenylthiolates are influenced by aromaticity, but they are less aromatic than the parent silabenzene. The geometries and charge distributions suggest that all silaphenolates and silaphenylthiolates to substantial degrees are described by resonance structures with an exocyclic C=O double bond and a silapentadienyl anionic segment. Indeed, they resemble the all-carbon phenolate and phenylthiolate. Silaphenylthiolates are less bond alternate and have slightly more negative NICS values than analogous silaphenolates, suggesting that this compound class is a bit more aromatic. Dimerization of the silaphenolates and silaphenylthiolates is hampered due to intramolecular Coulomb repulsion in the dimers, and silaphenolates with a moderately bulky SiMe3 group as substituent at Si should prefer the monomeric form.

  3. Antioxidant and Anti-Osteoporotic Activities of Aromatic Compounds and Sterols from Hericium erinaceum. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Wei Li


    Full Text Available 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, 13C, 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.

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


    monoadducts 1 and 3, respectively, by treatment of their sulfolane solutions with К2CO3 at 60 ºC for 3 h (Scheme 2). The extent of reaction was...DMF, sulfolane , etc.). Instead of diene, two allyl chlorides have been formed depending on reaction conditions. Heating at 55-60°C leads to...Proton transfer is a fast process for exothermic reactions between O-, N- and S-atoms but is relatively slow for CH-acids. It has been explained by

  6. Solvent effects on chemical processes. I: Solubility of aromatic and heterocyclic compounds in binary aqueous-organic solvents. (United States)

    Khossravi, D; Connors, K A


    The standard free energy change (delta G0) for equilibrium dissolution in binary solvent mixtures is written as a sum of effects arising from solvent-solvent interactions (the general medium effect), solvent-solute interactions (the solvation effect), and solute-solute interactions (the intersolute effect). The general medium effect is given by gA gamma, where g is a curvature correction factor to the surface tension (gamma) and A is the molecular cavity surface area. A new feature is the definition of gamma to be that value appropriate to the equilibrium mean solvation shell composition. The solvation effect is modeled by stoichiometric stepwise competitive equilibria between the two solvent components for the solute. The intersolute effect includes the crystal energy and solution phase interactions. In this work, water was solvent component 1, and various miscible organic cosolvents served as solvent component 2. Relating all data to the fully aqueous solution gives an explicit expression for delta M delta G0, the solvent effect on the free energy change, as a function of the mole fractions x1 and x2. This function is a binding isotherm. Nonlinear regression leads (for a two-step solvation scheme) to estimates of the solvation exchange constants K1 and K2 and the parameter gA. This relationship was applied to 44 systems comprising combinations of 31 solutes and eight organic cosolvents. Curve fits were good to excellent, and most of the parameter estimates had physically reasonable magnitudes.

  7. Porous Aromatic Frameworks for Size-Selective Halogenation of Aryl Compounds. (United States)

    Yang, Yajie; Zou, Xiaoqin; Cui, Peng; Zhou, Yingxi; Zhao, Shuai; Wang, Lili; Yuan, Ye; Zhu, Guangshan


    Organic halides are vitally important chemical precursors or intermediates in the fields of agrochemical synthesis, molecular recognition, and material science. However, it is difficult to selectively synthesize these compounds due to the multiple reactive sites in aryl fragments. In this work, we prepared the first fully fluorinated porous aromatic framework (PAF). Its -C-F bond and hierarchical porosity have great benefits for PAF functionalization. After being decorated with different cyclodextrins (CDs), CD-PAF materials can incorporate diverse aryl compounds to protect their ortho sites from being attacked to produce para-substituted molecules. This selectivity obviously increased with a decrease in the substrate size (from 0.97 to 0.41 nm). In addition, the CD-PAFs can undergo long-term use in both chlorination and bromination.

  8. Activity of Antifungal Organobismuth(III Compounds Derived from Alkyl Aryl Ketones against S. cerevisiae: Comparison with a Heterocyclic Bismuth Scaffold Consisting of a Diphenyl Sulfone

    Directory of Open Access Journals (Sweden)

    Toshihiro Murafuji


    Full Text Available A series of hypervalent organobismuth(III compounds derived from alkyl aryl ketones [XBi(5-R'C6H3-2-COR(Ar] was synthesized to investigate the effect of the compounds’ structural features on their antifungal activity against the yeast Saccharomyces cerevisiae. In contrast to bismuth heterocycles [XBi(5-RC6H3-2-SO2C6H4-1'-] derived from diphenyl sulfones, a systematic quantitative structure-activity relationship study was possible. The activity depended on the Ar group and increased for heavier X atoms, whereas lengthening the alkyl chain (R or introducing a substituent (R' reduced the activity. IBi(C6H4-2-COCH3(4-FC6H4 was the most active. Its activity was superior to that of the related acyclic analogues ClBi[C6H4-2-CH2N(CH32](Ar and ClBi(C6H4-2-SO2 tert-Bu(Ar and also comparable to that of heterocyclic ClBi(C6H4-2-SO2C6H4-1'-, which was the most active compound in our previous studies. Density function theory calculations suggested that hypervalent bismuthanes undergo nucleophilic addition with a biomolecule at the bismuth atom to give an intermediate ate complex. For higher antifungal activity, adjusting the lipophilicity-hydrophilicity balance, modeling the three-dimensional molecular structure around the bismuth atom, and stabilizing the ate complex appear to be more important than tuning the Lewis acidity at the bismuth atom.

  9. Sorption of polar and nonpolar aromatic compounds to four surface soils of eastern China

    Energy Technology Data Exchange (ETDEWEB)

    Liu Ping [State Key Laboratory of Pollution Control and Resource Reuse, and School of the Environment, Nanjing University, 22 Hankou Road, Jiangsu 210093 (China); Zhu Dongqiang [State Key Laboratory of Pollution Control and Resource Reuse, and School of the Environment, Nanjing University, 22 Hankou Road, Jiangsu 210093 (China)], E-mail:; Zhang Hua; Shi Xin; Sun Huiyu; Dang Fei [State Key Laboratory of Pollution Control and Resource Reuse, and School of the Environment, Nanjing University, 22 Hankou Road, Jiangsu 210093 (China)


    Improved predictions on the fate of organic pollutants in surface environments require a better understanding of the underlying sorption mechanisms that control their uptake by soils. In this study, we monitored sorption of nine aromatic compounds with varying physicochemical properties (hydrophobicity, electron-donor/acceptor ability and polarity), including two polycyclic aromatic hydrocarbons, two chlorobenzenes, two nitroaromatic compounds, dichlobenil, carbaryl and 2,4-dichlorophenol in aqueous suspension of four surface soils of eastern China. The tested soils were characterized with respect to organic carbon (OC) content, black carbon content, mineralogy, morphology and size fraction to assess the role of the diverse soil characteristics in sorption. The results of this study show that not only the solute hydrophobicity and the OC content of soil are important to the retention of organic pollutants, but also the solute molecular structure and the soil nature. - In addition to the hydrophobicity of solute and the organic carbon content of soil, the solute molecular structure and the soil nature also determine the retention of organic pollutants by soils.

  10. Suspended particulate matter collection methods influence the quantification of polycyclic aromatic compounds in the river system. (United States)

    Abuhelou, Fayez; Mansuy-Huault, Laurence; Lorgeoux, Catherine; Catteloin, Delphine; Collin, Valéry; Bauer, Allan; Kanbar, Hussein Jaafar; Gley, Renaud; Manceau, Luc; Thomas, Fabien; Montargès-Pelletier, Emmanuelle


    In this study, we compared the influence of two different collection methods, filtration (FT) and continuous flow field centrifugation (CFC), on the concentration and the distribution of polycyclic aromatic compounds (PACs) in suspended particulate matter (SPM) occurring in river waters. SPM samples were collected simultaneously with FT and CFC from a river during six sampling campaigns over 2 years, covering different hydrological contexts. SPM samples were analyzed to determine the concentration of PACs including 16 polycyclic aromatic hydrocarbons (PAHs), 11 oxygenated PACs (O-PACs), and 5 nitrogen PACs (N-PACs). Results showed significant differences between the two separation methods. In half of the sampling campaigns, PAC concentrations differed from a factor 2 to 30 comparing FT and CFC-collected SPMs. The PAC distributions were also affected by the separation method. FT-collected SPM were enriched in 2-3 ring PACs whereas CFC-collected SPM had PAC distributions dominated by medium to high molecular weight compounds typical of combustion processes. This could be explained by distinct cut-off threshold of the two separation methods and strongly suggested the retention of colloidal and/or fine matter on glass-fiber filters particularly enriched in low molecular PACs. These differences between FT and CFC were not systematic but rather enhanced by high water flow rates.

  11. Construction and Optimization of a Heterologous Pathway for Protocatechuate Catabolism in Escherichia coli Enables Bioconversion of Model Aromatic Compounds. (United States)

    Clarkson, Sonya M; Giannone, Richard J; Kridelbaugh, Donna M; Elkins, James G; Guss, Adam M; Michener, Joshua K


    The production of biofuels from lignocellulose yields a substantial lignin by-product stream that currently has few applications. Biological conversion of lignin-derived compounds into chemicals and fuels has the potential to improve the economics of lignocellulose-derived biofuels, but few microbes are able both to catabolize lignin-derived aromatic compounds and to generate valuable products. While Escherichia coli has been engineered to produce a variety of fuels and chemicals, it is incapable of catabolizing most aromatic compounds. Therefore, we engineered E. coli to catabolize protocatechuate, a common intermediate in lignin degradation, as the sole source of carbon and energy via heterologous expression of a nine-gene pathway from Pseudomonas putida KT2440. We next used experimental evolution to select for mutations that increased growth with protocatechuate more than 2-fold. Increasing the strength of a single ribosome binding site in the heterologous pathway was sufficient to recapitulate the increased growth. After optimization of the core pathway, we extended the pathway to enable catabolism of a second model compound, 4-hydroxybenzoate. These engineered strains will be useful platforms to discover, characterize, and optimize pathways for conversions of lignin-derived aromatics.IMPORTANCE Lignin is a challenging substrate for microbial catabolism due to its polymeric and heterogeneous chemical structure. Therefore, engineering microbes for improved catabolism of lignin-derived aromatic compounds will require the assembly of an entire network of catabolic reactions, including pathways from genetically intractable strains. Constructing defined pathways for aromatic compound degradation in a model host would allow rapid identification, characterization, and optimization of novel pathways. We constructed and optimized one such pathway in E. coli to enable catabolism of a model aromatic compound, protocatechuate, and then extended the pathway to a related

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

    Yao, Yung-Chen; Tsai, Jiun-Horng


    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. Oil distillation wastewaters from aromatic herbs as new natural source of antioxidant compounds. (United States)

    Celano, Rita; Piccinelli, Anna Lisa; Pagano, Imma; Roscigno, Graziana; Campone, Luca; De Falco, Enrica; Russo, Mariateresa; Rastrelli, Luca


    Distillation wastewaters (DWWs) are generated during the essential oil steam distillation from aromatic herbs. Despite of growing interest on novel source of natural antioxidant compounds as food additives, studies on DWWs are scarse. Herein, the potential of DWWs produced by the distillation of packaged fresh basil, rosemary and sage wastes was evaluated by chemical and antioxidant characterization. HPLC-DAD-HRMS profiling revealed that DWWs contain water-soluble phenolic compounds, mainly caffeic acid derivatives and flavonoid glycosides, with rosmarinic acid (RA) as predominant components (29-135mg/100mL). DWWs demonstrated high levels of total phenolic compounds (TPC, 152-443mg GAE/100mL) and strong antioxidant capacities, in ORAC, DPPH and ABTS assays (1101-4720, 635-4244 and 571-3145μmol TE/100mL, respectively). Highly significant correlations of TEAC values with TPC and RA contents revealed that phenolic compounds and high RA content were responsible of DWWs antioxidant properties.Thus, DWWs are proposed as a new promising source of natural food additives and/or functional ingredients for cosmetic, nutraceutical and food applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. MarR-Like Transcriptional Regulator Involved in Detoxification of Aromatic Compounds in Sulfolobus solfataricus▿ (United States)

    Fiorentino, Gabriella; Ronca, Raffaele; Cannio, Raffaele; Rossi, Mosè; Bartolucci, Simonetta


    A DNA binding protein, BldR, was identified in the crenarchaeon Sulfolobus solfataricus as a protein 5- to 10-fold more abundant in cells grown in the presence of toxic aldehydes; it binds to regulatory sequences located upstream of an alcohol dehydrogenase gene (Sso2536). BldR is homologous to bacterial representatives of the MarR (multiple antibiotic resistance) family of transcriptional regulators that mediate response to multiple environmental stresses. Transcriptional analysis revealed that the bldR gene was transcribed in a bicistronic unit composed of the genes encoding the transcriptional regulator (Sso1352) and a putative multidrug transporter (Sso1351) upstream. By homology to bacterial counterparts, the bicistron was named the mar-like operon. The level of mar-like operon expression was found to be increased at least 10-fold in response to chemical stress by aromatic aldehydes. Under the same growth conditions, similar enhanced in vivo levels of Sso2536 gene transcript were also measured. The gene encoding BldR was expressed in E. coli, and the recombinant protein was purified to homogeneity. DNA binding assays demonstrated that the protein is indeed a transcription factor able to recognize site specifically both the Sso2536 and mar-like promoters at sites containing palindromic consensus sequences. Benzaldehyde, the substrate of ADHSs, stimulates DNA binding of BldR at both promoters. The role of BldR in the auto-activation as well as in the regulation of the Sso2536 gene, together with results of increased operon and gene expression under conditions of exposure to aromatic aldehydes, indicates a novel coordinate regulatory mechanism in cell defense against stress by aromatic compounds. PMID:17675388

  15. Remediation of Groundwater Polluted by Aromatic Compounds by Means of Adsorption

    Directory of Open Access Journals (Sweden)

    Silvana Canzano


    Full Text Available In this work, an experimental and modeling analysis of the adsorption of four aromatic compounds (i.e., toluene, naphthalene, o-xylene and ethylbenzene onto a commercial activated carbon is carried out. The aim is to assess the suitability of the adsorption process for the treatment of polluted groundwater, also when a multiple contamination is detected. Batch adsorption tests from simulated polluted groundwater are performed in single-compound systems and in two binary systems (i.e., toluene + naphthalene and o-xylene + ethylbenzene, at constant temperature (20 °C and pH (7. Experimental results in single-compound systems reveal that all of the analytes are significantly adsorbed on the tested activated carbon. In particular, toluene and naphthalene adsorption capacities are the highest and of similar value, while for o-xylene and ethylbenzene, the performances are lower. The adsorption of these compounds seems to be influenced by a combined effect of several parameters, such as hydrophobicity, molecule size, structure of the molecule, etc. Experimental results in binary systems show a different behavior of the two systems, which confirms their complexity and explains the interest in these complex adsorption systems. In particular, toluene and naphthalene are mutually competitive, while in the case of o-xylene + ethylbenzene, only the former undergoes competitive effects. The analysis of the entire experimental data set is integrated with a dedicated modeling analysis using the extended Langmuir model. For both single-compound and binary systems, this model provides acceptable results, in particular for low equilibrium concentrations, like those more commonly found in groundwater, and for the compounds involved in adsorptive competitive effects.

  16. Hydrothermally generated aromatic compounds are consumed by bacteria colonizing in Atlantis II Deep of the Red Sea

    KAUST Repository

    Wang, Yong


    Hydrothermal ecosystems have a wide distribution on Earth and many can be found in the basin of the Red Sea. Production of aromatic compounds occurs in a temperature window of 60-150 °C by utilizing organic debris. In the past 50 years, the temperature of the Atlantis II Deep brine pool in the Red Sea has increased from 56 to 68 °C, whereas the temperature at the nearby Discovery Deep brine pool has remained relatively stable at about 44 °C. In this report, we confirmed the presence of aromatic compounds in the Atlantis II brine pool as expected. The presence of the aromatic compounds might have disturbed the microbes in the Atlantis II. To show shifted microbial communities and their metabolisms, we sequenced the metagenomes of the microbes from both brine pools. Classification based on metareads and the 16S rRNA gene sequences from clones showed a strong divergence of dominant bacterial species between the pools. Bacteria capable of aromatic degradation were present in the Atlantis II brine pool. A comparison of the metabolic pathways showed that several aromatic degradation pathways were significantly enriched in the Atlantis II brine pool, suggesting the presence of aromatic compounds. Pathways utilizing metabolites derived from aromatic degradation were also significantly affected. In the Discovery brine pool, the most abundant genes from the microbes were related to sugar metabolism pathways and DNA synthesis and repair, suggesting a different strategy for the utilization of carbon and energy sources between the Discovery brinse pool and the Atlantis II brine pool. © 2011 International Society for Microbial Ecology. All rights reserved.

  17. Polymer-assisted deposition of co-doped zinc oxide thin films for the detection of aromatic organic compounds. (United States)

    Li, Wei; Kim, Dojin


    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.

  18. Sorption of aromatic ionizable organic compounds to montmorillonites modified by hexadecyltrimethyl ammonium and polydiallyldimethyl ammonium. (United States)

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


    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. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  19. Enhanced Photoreduction of Nitro-aromatic Compounds by Hydrated Electrons Derived from Indole on Natural Montmorillonite. (United States)

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


    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.

  20. Effects and uptake of polycyclic aromatic compounds in snails (Helix aspersa). (United States)

    Sverdrup, Line Emilie; De Vaufleury, Annette; Hartnik, Thomas; Hagen, Snorre B; Loibner, Andreas Paul; Jensen, John


    The International Standardization Organization recently launched a soil toxicity test with snails (Helix aspersa). We assessed the sensitivity of this test for seven polycyclic aromatic compounds. Control animals had 100% survival and low variability for growth measurements. Maximum exposure concentrations of 2800 mg/kg (4000 mg/kg for acridine) had no effect on survival. Similarly, growth (biomass and shell size) was not affected by pyrene, fluoranthene, fluorene, carbazole, phenanthrene, or acridine, whereas dibenzothiophene gave a 10% effect concentration of 1600 mg/kg. Measured internal concentrations of carbazole, dibenzothiophene, and acridine increased with increasing soil concentrations, but biota-soil accumulation factors were low (0.002-0.1). Compared to previously tested organisms, with all being exposed in the same soil type and under similar test conditions, the H. aspersa test was relatively insensitive to all substances.

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

    Energy Technology Data Exchange (ETDEWEB)

    Öztekin, Aykut, E-mail: [Ataturk University, Science Faculty, Department of Chemistry, 25240-Erzurum (Turkey); Agri Ibrahim Cecen University Faculty of Arts and Sciences, Department of Chemistry, 04100-Agri (Turkey); Almaz, Züleyha, E-mail: [Ataturk University, Science Faculty, Department of Chemistry, 25240-Erzurum (Turkey); Mus Alparslan University Faculty of Sciences, Department of Moleculer Biology, 49250-Mus (Turkey); Özdemir, Hasan, E-mail: [Ataturk University, Science Faculty, Department of Chemistry, 25240-Erzurum (Turkey)


    Peroxidases (E.C. 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. IC{sub 50} 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).

  2. Laser induced rapid decontamination of aromatic compound from porous soil simulant (United States)

    Zheng, Wenjun; Hou, Sichao; Su, Ming


    Soil contamination with organic compounds can lead to the loss of farmable and habitable lands and cause long-term human and animal exposure to toxins. This paper reports a new laser based method for in situ soil decontamination at high efficiency, in which a focused excimer laser is used to remove organic contaminants from soil through burning by generating a local high temperature region. An aromatic compound, 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene, is used as an organic contaminant, and a porous silica plate is used as a soil simulant. A heat transfer model is created to simulate the interaction between the laser and the organic compound. The lithographic mode of operation allows the accurate quantitation of laser effects. The effects of power, speed, frequency, and energy consumption on the efficiency of decontamination have been examined with high accuracy. The decomposition area increases with the increase in the laser power and the decrease in the scan speed and frequency. Given the high energy conversion yield of the high power laser, this method would be promising for large scale in situ soil decontamination.

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

    Directory of Open Access Journals (Sweden)

    Ramar Perumal Samy


    Full Text Available 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.

  4. Investigation on Aromaticity Index and Double-Bond Equivalent of Aromatic Compounds and Ionic Liquids for Fuel Desulphurization

    Directory of Open Access Journals (Sweden)

    Syamsul B. Abdullah


    Full Text Available Aromaticity index (AI and double-bond equivalent (DBE were studied to seek a simpler approach in identifying suitable ionic liquids for the desulphurization process. Manifestation of interaction mechanism by COSMO-RS and Raman spectroscopy is discussed. The findings demonstrate that AI and DBE calculations can be used to analyze and arrogate potential combination of cation and anion for fuel desulphurization purposes.

  5. Heptaphyrins: Expanded porphyrins with seven heterocyclic rings

    Indian Academy of Sciences (India)

    The 30 heptaphyrins exhibit rich structural diversity where some of the heterocyclic rings in the macrocycle undergo a 180° ring flipping. An overview of the synthetic methods employed for the synthesis of heptaphyrins, their spectroscopic properties, structural behaviour and aromatic properties are highlighted in this paper ...

  6. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization : Identification of Renewable Aromatics and a Lignin-Derived Solvent

    NARCIS (Netherlands)

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin


    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges

  7. Toxicity of eight polycyclic aromatic compounds to the red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba)

    DEFF Research Database (Denmark)

    Sverdrup, L. E.; Krogh, P. H.; Nielsen, T.


    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...

  8. Toxicity of eight polycyclic aromatic compounds to red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba)

    DEFF Research Database (Denmark)

    Sverdrup, L.E.; Krogh, P.H.; Nielsen, T.


    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...

  9. Compounds having aromatic rings and side-chain amide-functionality and a method for transporting monovalent anions across biological membranes using the same (United States)

    Davis, Jeffery T [College Park, MD; Sidorov, Vladimir [Richmond, VA; Kotch, Frank W [New Phila., PA


    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.

  10. Determination of aromatic tracer compounds for environmental tobacco smoke aerosol by two step laser mass spectrometry (United States)

    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.

  11. Sources of SOA gaseous precursors in contrasted urban environments: a focus on mono-aromatic compounds and intermediate volatility compounds (United States)

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


    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

  12. Trophic transfer of naturally produced brominated aromatic compounds in a Baltic Sea food chain. (United States)

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


    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Dramatic Influence of Ionic Liquid and Ultrasound Irradiation on the Electrophilic Sulfinylation of Aromatic Compounds by Sulfinic Esters

    Directory of Open Access Journals (Sweden)

    Ngoc-Lan Thi Nguyen


    Full Text Available The sulfinylation reaction of aromatic and hetero-aromatic compounds with sulfinic esters as electrophiles has been investigated in different ionic liquids and by means of different Lewis acid salts in order to get moderate to good yields of asymmetrical sulfoxides. Mixtures of 1-butyl-3-methylimidazolium chloride and aluminum chloride were found to be the most efficient and recyclable reaction framework. Ultrasound sonication appeared to be the most useful and green activation method to afford the sulfoxides in yields better than or equivalent to those obtained under the longer-lasting conventional stirring conditions.

  14. A theoretical analysis of the extraction of heterocyclic organic compounds from an organic phase using chemically mediated electrochemically modulated complexation in ion exchange polymer beads

    Energy Technology Data Exchange (ETDEWEB)

    Ozekin, K.; Noble, R.D.; Koval, C.A.


    A cyclical electrochemical process for the removal of heterocyclic organic compounds (pollutants) from an organic solvent using an ion-exchange polymer is analyzed. In this analysis, there are three main steps: In the first step, the polymer beads containing the active form of the complexing agent are contacted with the contaminated (feed) hydrocarbon phase. The pollutant diffuses into the beads and binds with the complexing agent which is in the reduced state. It is a fast reversible reaction. For the second step, the beads which contain a pollutant are contacted with a waste (receiving) phase and a chemical mediator is then used to oxidize the complexing agent and to reduce its affinity towards the pollutant so that it can be released. The oxidation of the complexing agent is an irreversible reaction. This is a moving boundary problem with countercurrent diffusion. For each mole of mediator that goes into the bead, one mole of pollutant exits since each complexing agent binds one pollutant. In the third step, the waste hydrocarbon phase is removed and a second chemical mediator is then used to reduce the complexing agent. The reduction of the complexing agent is also an irreversible reaction. Partial differential equations are used to analyze this process. 26 refs., 9 figs.

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

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


    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

  16. Separation of heterocyclic compounds from hydropyrolysis oil and testing their activity as corrosion inhibitors in 1 M sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Studnicki, M. (Zaklad Karbochemii PAN, Gliwice (Poland))


    Investigates inhibiting properties of coal derived oil concentrates. Hard coal was subject to hydropyrolysis at 600 C and 4 MPa. Coal analysis was provided. Chromatography was employed to separate concentrates of N, O and S compounds from oil fractions. Columns were filled with Amberlite IRA-904 and Amberlyst 15 ion exchange resins as well as with Attapulgus clay. Ten fractions/concentrates were obtained. Their ability to protect StO steel against corrosion in 1 M solution of sulfuric acid was tested and compared to that of a standard compound (S-isothioureide-N-methine-m-phenylenediamine) and a petroleum-derived concentrate of strong bases. The results obtained are tabulated. Some concentrates were found to promote corrosion. It was possible in some cases to determine a threshold concentration of N, below which corrosion was promoted. High resolution mass spectrometry was applied to analyze eight concentrates. Molecular weights and molecular compositions for identified compounds are tabulated. 17 refs.

  17. Enhanced Accessibility of Polycyclic Aromatic Hydrocarbons (PAHs) and Heterocyclic PAHs in Industrially Contaminated Soil after Passive Dosing of a Competitive Sorbate

    DEFF Research Database (Denmark)

    Humel, Stefan; Nørgaard Schmidt, Stine; Sumetzberger-Hasinger, Marion


    To assess the exposure to polycyclic aromatic hydrocarbons (PAHs) it is important to understand the binding mechanisms between specific soil constituents and the organic pollutant. In this study, sorptive bioaccessibility extraction (SBE) was applied to quantify the accessible PAH fraction...... in industrially contaminated soil with and without passive dosing of a competitive sorbate. SBE experiments revealed an accessible PAH fraction of 41 ± 1% (∑16 US EPA PAHs + 5 further PAHs). The passive dosing of toluene below its saturation level revealed competitive binding and resulted in an average increase...... of the accessible fraction to 49 ± 2%, whereby primarily the accessibility of higher molecular weight PAHs (log Kow > 6) was affected. Competitive binding was verified using the same soil with only desorption-resistant PAHs present. In this experiment, passive dosing of toluene resulted in desorption of 13 ± 0...

  18. In Situ and Laboratory Studies on the Fate of Specific Organic Compounds in an Anerobic Landfill Leachate Plume, 2. Fate of Aromatic and Chlorinated Aliphatic Compounds

    DEFF Research Database (Denmark)

    Nielsen, Per Henning; Bjarnadóttir, Helga; Winter, Pia L.


    and laboratory batch microcosm experiments performed focusing on redox conditions, microbiology and the fate of 7 phenolic compounds. In this paper we present the results on the fate of 8 aromatic compounds and 4 chlorinated aliphatic compounds. Nitrobenzene was transformed at all distances from the landfill......The transformation of specific organic compounds was investigated by in situ and laboratory experiments in an anaerobic landfill leachate pollution plume at four different distances from the landfill. In a previous paper (Part 1, also published in this issue) we described the in situ microcosm...... the landfill. In general, good accordance with respect to compound transformation was observed between in situ and laboratory experiments, but in a few cases more compounds were transformed in in situ experiments than in the corresponding laboratory experiments....

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

    DEFF Research Database (Denmark)

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


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

  20. Bioaugmentation as a strategy for cleaning up of soils contaminated with aromatic compounds. (United States)

    Mrozik, Agnieszka; Piotrowska-Seget, Zofia


    The contamination of soil with aromatic compounds is of particular environmental concern as they exhibit carcinogenic and mutagenic properties. One of the methods of their removal from soil is bioaugmentation, defined as a technique for improvement of the degradative capacity of contaminated areas by introduction of specific competent strains or consortia of microorganisms. The efficiency of bioaugmentation is determined by many abiotic and biotic factors discussed in this paper. The first include chemical structure, concentration and availability of pollutants as well as physico-chemical properties of soil. In turn, among biotic factors the most important is the selection of proper microorganisms that can not only degrade contaminants but can also successfully compete with indigenous microflora. Several strategies are being developed to make augmentation a successful technology particularly in soils without degrading indigenous microorganisms. These approaches involve the use of genetically engineered microorganisms and gene bioaugmentation. The enhancement of bioaugmentation may be also achieved by delivering suitable microorganisms immobilized on various carriers or use of activated soil. Copyright 2009 Elsevier GmbH. All rights reserved.

  1. Aromatic compound emissions from municipal solid waste landfill: Emission factors and their impact on air pollution (United States)

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


    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.

  2. Adsorption and correlations of selected aromatic compounds on a KOH-activated carbon with large surface area. (United States)

    Yang, Kun; Zhu, Lianghong; Yang, Jingjing; Lin, Daohui


    Knowledge of adsorption mechanism and behavior of organic compounds by KOH-activated carbons (KOH-ACs) from wastewater is crucial to its environmental application in wastewater treatment as adsorbent. A superior adsorbent, KOH-activated carbon (KOH-AC), with large surface area (3143m2/g), total pore volume of 2.03cm3/g, relatively low micropore fraction of 53.2%, and having adsorption capacities of organic compounds up to >1000mg/g, was prepared. It is an adsorbent significantly different with common ACs because the molecular sieving effect, widely observed for common ACs, is insignificant for KOH-AC. This difference could be attributed to the lower micropore fraction of KOH-AC than common ACs. A negative relationship of adsorption capacity of 25 aromatic compounds (including phenols, anilines, nitrobenzenes and polycyclic aromatic hydrocarbons) with chemical melting point was observed, suggesting that adsorption is dependent on the packing efficiency and stacking density of molecules on KOH-AC. A linear solvation energy relationships of adsorption affinity of 25 aromatic compounds with solute solvatochromic parameters was also observed, that can be used to quantify the contributions of π-π interaction, hydrogen-bonding interaction and hydrophobic effect to adsorption on KOH-AC. Combined with the reported results of adsorption of organic compounds on carbon nanotubes and biochars, it was also observed that external surface area of adsorbents is controlling the packing efficiency and stacking density of molecules on adsorbents and thus affecting adsorption capacity of organic compounds. Moreover, micropore surface area and the fraction of micropores are the adsorbent properties mainly affecting adsorption affinity of organic compounds. The observations and the developed correlations in this study would be helpful in the application of KOH-AC as superior adsorbent by enhancing the understanding of adsorption mechanisms of organic compounds on KOH-AC and by giving a

  3. Self-Assembly and Drug Release Capacities of Organogels via Some Amide Compounds with Aromatic Substituent Headgroups

    Directory of Open Access Journals (Sweden)

    Lexin Zhang


    Full Text Available In this work, some amide compounds with different aromatic substituent headgroups were synthesized and their gelation self-assembly behaviors in 22 solvents were characterized as new gelators. The obtained results indicated that the size of aromatic substituent headgroups in molecular skeletons in gelators showed crucial effect in the gel formation and self-assembly behavior of all compounds in the solvents used. Larger aromatic headgroups in molecular structures in the synthesized gelator molecules are helpful to form various gel nanostructures. Morphological investigations showed that the gelator molecules can self-assembly and stack into various organized aggregates with solvent change, such as wrinkle, belt, rod, and lamella-like structures. Spectral characterizations suggested that there existed various weak interactions including π-π stacking, hydrogen bonding, and hydrophobic forces due to aromatic substituent headgroups and alkyl substituent chains in molecular structures. In addition, the drug release capacities experiments demonstrated that the drug release rate in present obtained gels can be tuned by adjusting the concentrations of dye. The present work would open up enormous insight to design and investigate new kind of soft materials with designed molecular structures and tunable drug release performance.

  4. Synthesis and study on biological activity of nitrogen-containing heterocyclic compounds – regulators of enzymes of nucleic acid biosynthesis

    Directory of Open Access Journals (Sweden)

    Alexeeva I. V.


    Full Text Available Results of investigations on the development of new regulators of functional activity of nucleic acid biosynthesis enzymes based on polycyclic nitrogen-containing heterosystems are summarized. Computer design and molecular docking in the catalytic site of target enzyme (T7pol allowed to perform the directed optimization of basic structures. Several series of compounds were obtained and efficient inhibitors of herpes family (simple herpes virus type 2, Epstein-Barr virus, influenza A and hepatitis C viruses were identified, as well as compounds with potent antitumor, antibacterial and antifungal activity. It was established that the use of model test systems based on enzymes participating in nucleic acids synthesis is a promising approach to the primary screening of potential inhibitors in vitro.

  5. Petroleum alteration by thermochemical sulfate reduction - A comprehensive molecular study of aromatic hydrocarbons and polar compounds (United States)

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


    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

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

    Misner, Bill D


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

    Directory of Open Access Journals (Sweden)

    Misner Bill D


    Full Text Available Abstract 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

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

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


    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

  9. Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

    Directory of Open Access Journals (Sweden)

    Ivana Biljan


    Full Text Available This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation or breaking of only one covalent bond between two nitrogen atoms. The crystalline molecular solids of nitroso dimers (azodioxides dissociate by photolysis under the cryogenic conditions, and re-dimerize by slow warming. The thermal re-dimerization reaction is examined under the different topotactic conditions in crystals: disordering, surface defects, and phase transformations. Depending on the conditions, and on the molecular structure, aromatic C-nitroso compounds can associate to form one-dimensional polymeric structures and are able to self-assemble on gold surfaces.

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


    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 c...


    The ability of several 4- and 5-ring polycyclic aromatic hydrocarbons (PAHs), heterocyclic PAHs, and their monohydroxy derivatives to interact with the estrogen receptor (ER) alpha and beta isoforms was examined. Only compounds possessing a hydroxyl group were able to compete wit...

  12. Extraction of aromatic compounds using ionic liquids and low transition temperature mixtures as separation agents


    Fernandez Requejo, Patricia


    The main objective of this thesis is the evaluation of the feasibility of two types of designer solvents, ionic liquids (ILs) and low transition temperature mixtures (LTTMs), as extraction agents to improve the efficiency and/or sustainability of the separation of aromatic hydrocarbons from their mixtures with aliphatic hydrocarbons. The research about the applicability of the ionic liquids as entrainers for the separation of aromatic/aliphatic mixtures was developed through the experimental ...

  13. New aspects of weak CH⋯π bonds: intermolecular interactions between alicyclic and aromatic rings in crystals of small compounds, peptides and proteins (United States)

    Ciunik, Z.; Berski, S.; Latajka, Z.; Leszczyński, J.


    The geometry of intermolecular contacts between alicyclic and aromatic rings in a number of crystal structures suggests an attractive interaction between the rings. An analysis of molecular packing of 444 different crystal structures collected in the Cambridge Structural Database shows that phenyl…cyclohexanonyl, cyclohexyl, and/or cyclopentyl ring interactions occur in 59-82% of studied crystals. Similar interactions are observed between aromatic rings and heterocyclic pyrrolidine rings of proline in peptides and proteins. An analysis of data collected in the Brookhaven Protein Data Bank reveals that interactions between proline CH groups and aromatic rings of phenylalanine, tyrosine, and tryptophan as acceptors are frequently observed in proteins. Based on these results, several geometric models of these interactions are proposed. Two of these models are fully optimized using quantum chemical calculations at the density functional theory level. Calculated energies suggest that the most important interaction between the cyclohexanone and benzene rings is described by the face-to-face model, in which three axial hydrogen atoms are directed toward the aromatic partner.

  14. Atmospheric chemistry of polycyclic aromatic compounds with special emphasis on nitro derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Feilberg, A.


    Field measurements of polycyclic aromatic compounds (PAC) have been carried out at a semi-rural site and at an urban site. Correlation analyses, PAC indicators, and PAC ratios have been used to evaluate the importance of various sources of nitro-PAHs. A major source of nitro-PAHs is atmospheric transformation of PAHs initiated by OH radicals. Especially during long-range transport (LRT) of air pollution from Central Europe, the nitro-PAH composition in Denmark is dominated by nitro-PAHs formed in the atmosphere. Locally emitted nitro-PAHs are primarily from diesel vehicles. Levels of unsubstituted PAHs can also be strongly elevated in connection with LRT episodes. The ratio of 2-nitrofluoranthene relative to 1-nitropyrene is proposed as a measure of the relative photochemical age of particulate matter. Using this ratio, the relative mutagenicity of particle extracts appears to increase with increasing photochemical age. In connection with the field measurements, a method for measuring nitro-PAHs in particle extracts based on MS-MS detection has been developed. The atmospheric chemistry of nitronaphthalenes has been investigated with a smog chamber system combined with simulation with photochemical kinetics software. A methodology to implement gas-particle partitioning in a model based on chemical kinetics is described. Equilibrium constants (KP) for gas-particle partitioning of 1- and 2-nitronaphthalene have been determined. Mass transfer between the two phases appears to occur on a very short timescale. The gas phase photolysis of the nitronaphthalenes depends upon the molecular conformation. Significantly faster photolysis of 1-nitronaphthalene than of 2-nitronaphthalene is observed. The photochemistry of nitro-PAHs, and to some extent other PAC, associated with organic aerosols, has been studied with model systems simulating organic aerosol material. A number of aerosol constituents, including substituted phenols, benzaldehydes, and oxy-PAHs, are demonstrated to

  15. Phenoxydifluoromethyl Substituted Nitrogen Heterocycles. Synthesis and Heterocyclization Reactions of Ethyl 4,4-Difluoro- 4-phenoxyacetoacetate

    Directory of Open Access Journals (Sweden)

    N. D. Chkanikov


    Full Text Available Ethyl 4,4-difluoro-4-phenoxyacetoacetate was obtained and studied as a precursor to new heterocyclic compounds. 6-Hydroxypyrimidine, 1,3-dihydro-1,5- benzodiazepin-2-one, quinolin-2-one and 6-hydroxypyrazolo[3,4-b]pyridine derivatives containing phenoxydifluoromethyl groups were synthesized. These results make it possible to introduce aryloxydifluoromethyl substituents for the design of biologically active heterocycles.

  16. Polycyclic Aromatic Compounds as Anticancer Agents: Synthesis and Biological Evaluation of Methoxy Dibenzofluorene Derivatives

    Directory of Open Access Journals (Sweden)

    Bimal Krishna Banik


    Full Text Available 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.

  17. Enzymatic transformation of nitro-aromatic compounds by a flavin-free NADH azoreductase from Lysinibacillus sphaericus. (United States)

    Misal, Santosh A; Lingojwar, Devendra P; Lokhande, Mahendra N; Lokhande, Pradeep D; Gawai, Kachru R


    Azo dyes and nitro-aromatic compounds are the largest group of pollutants released in the environment as industrial wastes. They create serious health and environmental problems. Azoreductases catalyze the reduction of azo dyes and nitro compounds to their respective amines. AN azoreductase was purified up to 12-fold from Lysinibacillus sphaericus using ion-exchange and size exclusion chromatography. It was optimally active at pH 7.4 and 75 °C. It was stable at 70 °C for 30 min. The purified enzyme utilized NADH rather than NADPH as an electron donor to reduce substrates. The molecular weight of the purified enzyme was ~29 kDa. The enzyme also acted as nitroreductase and could selectively reduce the nitro group of 2-nitrophenol, 4-nitrobenzoic acid, 2-nitro-benzaldehyde and 3-nitrophenol. Reduction products of these compounds were identified by IR and NMR.

  18. Biochemical interpretation of quantitative structure-activity relationships (QSAR) for biodegradation of N-heterocycles: a complementary approach to predict biodegradability. (United States)

    Philipp, Bodo; Hoff, Malte; Germa, Florence; Schink, Bernhard; Beimborn, Dieter; Mersch-Sundermann, Volker


    Prediction of the biodegradability of organic compounds is an ecologically desirable and economically feasible tool for estimating the environmental fate of chemicals. We combined quantitative structure-activity relationships (QSAR) with the systematic collection of biochemical knowledge to establish rules for the prediction of aerobic biodegradation of N-heterocycles. Validated biodegradation data of 194 N-heterocyclic compounds were analyzed using the MULTICASE-method which delivered two QSAR models based on 17 activating (OSAR 1) and on 16 inactivating molecular fragments (GSAR 2), which were statistically significantly linked to efficient or poor biodegradability, respectively. The percentages of correct classifications were over 99% for both models, and cross-validation resulted in 67.9% (GSAR 1) and 70.4% (OSAR 2) correct predictions. Biochemical interpretation of the activating and inactivating characteristics of the molecular fragments delivered plausible mechanistic interpretations and enabled us to establish the following biodegradation rules: (1) Target sites for amidohydrolases and for cytochrome P450 monooxygenases enhance biodegradation of nonaromatic N-heterocycles. (2) Target sites for molybdenum hydroxylases enhance biodegradation of aromatic N-heterocycles. (3) Target sites for hydratation by an urocanase-like mechanism enhance biodegradation of imidazoles. Our complementary approach represents a feasible strategy for generating concrete rules for the prediction of biodegradability of organic compounds.

  19. Chemoselective Reductive Amination of Carbonyl Compounds for the Synthesis of Tertiary Amines Using SnCl2·2H2O/PMHS/MeOH. (United States)

    Nayal, Onkar S; Bhatt, Vinod; Sharma, Sushila; Kumar, Neeraj


    Stannous chloride catalyzed chemoselective reductive amination of a variety of carbonyl compounds with aromatic amines has been developed for the synthesis of a diverse range of tertiary amines using inexpensive polymethylhydrosiloxane as reducing agent in methanol. The present method is also applicable for the synthesis of secondary amines including heterocyclic ones.

  20. Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation. (United States)

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


    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

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

    Directory of Open Access Journals (Sweden)

    Yiming Feng


    Full Text Available 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, Takanori, E-mail: [Faculty of Pharmacy, Yasuda Women' s University, 6-13-1 Yasuhigashi, Asaminami-ku, Hiroshima 731-0153 (Japan); Yanagihara, Kazuyoshi [Faculty of Pharmacy, Yasuda Women' s University, 6-13-1 Yasuhigashi, Asaminami-ku, Hiroshima 731-0153 (Japan); Division of Genetics, National Cancer Center Research Institute, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Takei, Yoshifumi [Department of Biochemistry, Nagoya University Graduate School of Medicine, 65 Tsurumi-cho, Showa-ku, Nagoya 466-8550 (Japan); Mihara, Keichiro [Department of Hematology and Oncology, Research Institute for Radiation Biology and Medicine, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553 (Japan); Sato, Yuichiro; Seyama, Toshio [Faculty of Pharmacy, Yasuda Women' s University, 6-13-1 Yasuhigashi, Asaminami-ku, Hiroshima 731-0153 (Japan)


    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.

  3. Microwave-Accelerated Iodination of Some Aromatic Amines, Using Urea-Hydrogen Peroxide Addition Compound (UHP as the Oxidant

    Directory of Open Access Journals (Sweden)

    Lech Skulski


    Full Text Available A fast and simple method for the oxidative iodination of some aromatic amines, under microwave irradiation, is reported, using diiodine and the the strongly Hbonded urea-hydrogen peroxide addition compound (H2NCONH2···H2O2, UHP as the oxidant. The reactions were carried out in boiling CHCl3 under a reflux condenser to afford, within 10 minutes, the purified monoiodinated products in 40-80% yields.

  4. Laccase production and differential transcription of laccase genes in Cerrena sp. in response to metal ions, aromatic compounds and nutrients


    Jie eYang; Guozeng eWang; Tzi Bun eNg; Juan eLin; Xiuyun eYe


    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 d. Laccase production and laccase gene transcriptio...

  5. Cyclopropyl Group: An Excited-State Aromaticity Indicator? (United States)

    Ayub, Rabia; Papadakis, Raffaello; Jorner, Kjell; Zietz, Burkhard; Ottosson, Henrik


    The cyclopropyl (cPr) group, which is a well-known probe for detecting radical character at atoms to which it is connected, is tested as an indicator for aromaticity in the first ππ* triplet and singlet excited states (T 1 and S 1 ). Baird's rule says that the π-electron counts for aromaticity and antiaromaticity in the T 1 and S 1 states are opposite to Hückel's rule in the ground state (S 0 ). Our hypothesis is that the cPr group, as a result of Baird's rule, will remain closed when attached to an excited-state aromatic ring, enabling it to be used as an indicator to distinguish excited-state aromatic rings from excited-state antiaromatic and nonaromatic rings. Quantum chemical calculations and photoreactivity experiments support our hypothesis; calculated aromaticity indices reveal that openings of cPr substituents on [4n]annulenes ruin the excited-state aromaticity in energetically unfavorable processes. Yet, polycyclic compounds influenced by excited-state aromaticity (e.g., biphenylene), as well as 4nπ-electron heterocycles with two or more heteroatoms represent limitations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A Novel and Chemoselective Process of N-Alkylation of Aromatic Nitrogen Compounds Using Quaternary Ammonium Salts as Starting Material

    Directory of Open Access Journals (Sweden)

    Carlos A. González-González


    Full Text Available The process of N-alkylation of several pyrroles, indoles, and derivative heterocycles is herein described, using quaternary ammonium salts as the source of an alkylating agent. These reactions were carried out on several heterocyclic rings with triethylbenzylammonium chloride or tetradecyltrimethylammonium bromide and an NaOH solution at 50%, leading to a chemoselective N-alkylated product and an average yield of 73%. This is an alternative process to the traditional benzylation and methylation of N-heterocycles with direct handling of alkyl halides.

  7. A knowledge-based expert rule system for predicting mutagenicity (Ames test) of aromatic amines and azo compounds. (United States)

    Gadaleta, Domenico; Manganelli, Serena; Manganaro, Alberto; Porta, Nicola; Benfenati, Emilio


    Cancer is one of the main causes of death in Western countries, and a major issue for human health. Prolonged exposure to a number of chemicals was observed to be one of the primary causes of cancer in occupationally exposed persons. Thus, the development of tools for identifying hazardous chemicals and the increase of mechanistic understanding of their toxicity is a major goal for scientific research. We constructed a new knowledge-based expert system accounting the effect of different substituents for the prediction of mutagenicity (Ames test) of aromatic amines, a class of compounds of major concern because of their widespread application in industry. The herein presented model implements a series of user-defined structural rules extracted from a database of 616 primary aromatic amines, with their Ames test outcomes, aimed at identifying mutagenic and non-mutagenic chemicals. The chemical rationale behind such rules is discussed. Besides assessing the model's ability to correctly classify aromatic amines, its predictivity was further evaluated on a second database of 354 azo dyes, another class of chemicals of major concern, whose toxicity has been predicted on the basis of the toxicity of aromatic amines potentially generated from the metabolic reduction of the azo bond. Good performance in classification on both the amine (MCC, Matthews Correlation Coefficient=0.743) and the azo dye (MCC=0.584) datasets confirmed the predictive power of the model, and its suitability for use on a wide range of chemicals. Finally, the model was compared with a series of well-known mutagenicity predicting software. The good performance of our model compared with other mutagenicity models, especially in predicting azo dyes, confirmed the usefulness of this expert system as a reliable support to in vitro mutagenicity assays for screening and prioritization purposes. The model has been fully implemented as a KNIME workflow and is freely available for downstream users. Copyright

  8. ortho-Quinone methides as key intermediates in cascade heterocyclizations (United States)

    Osipov, D. V.; Osyanin, V. A.; Klimochkin, Yu N.


    Development of new methods of heterocyclic synthesis is still a topical issue. In this connection, the trend related to the use of highly reactive o-quinone methides for the synthesis and functionalization of heterocycles appears rather promising. Since most of o-quinone methides are unstable, the choice of precursors and generation conditions is highly important for subsequent transformations involving them. Various methods of generation of o-quinone methides and cascade heterocyclizations in which the formation of these compounds is a key step are surveyed in the review. The trends of using o-quinone methides in the synthesis of various heterocycles are analyzed and the heterocyclization reactions involving these compounds are classified. The bibliography includes 395 references.

  9. Synthesis and phtoluminescence study of Microporous Metal Organic Frameworks (MMOFs) for sensing and detection of nitroexplosives and aromatic compounds (United States)

    Pramanik, Sanhita

    Due to the increased terrorist activity worldwide and the use of modern bombs in those attacks, the development of a new method capable of rapidly and cost-efficiently detecting trace vapor of explosives is highly desirable. Chemical explosives composed of a diverse group of compounds, including nitroaromatics, nitramines, nitrate esters as well as some inorganic/organic nitrates and peroxides. Current methodologies include use of well trained dogs and sophisticated instrumentation such as gas chromatography coupled with a mass spectrometer, nuclear quadruple resonance, ionization mass spectrometry (IMS). These methods are highly sensitive and selective, but often expensive, not always easily accessible, and require intense training for operation. As a complementary method, chemical sensors can provide new ways to the rapid detection of ultra trace explosives, and can be easily incorporated into inexpensive and portable microelectronic devices. Fluorescence based sensors utilizing conjugated polymers have attracted enormous attention in the recent years for their excellent performance. In this thesis, a systematic study was performed in a series of luminescent MMOFs and their behavior upon exposure to the vapor of different analytes. For example, [Zn2(oba)2(bpy)]·DMA, one of the MMOFs made of paddle-wheel SBU, selectively responds to nitroaromatics (with electron-withdrawing groups) and other aromatic compounds, like benzene, toluene (with electron-donating groups) via fluorescent quenching and enhancement respectively. The study also shows that nitro-containing non-aromatic analytes (nitroaliphatics) make negligible effect on the fluorescence of [Zn2(oba)2(bpy)]·DMA . The results demonstrate the exceptional ability of this particular MMOF to selectively detect explosives of different types (e.g. aromatic DNT vs. non-aromatic or aliphatic DMNB). Another series of highly luminescent MMOFs made of the same metal center (Zn) and similar ligands (bpdc, bpy, 2,2'dmbpy

  10. Synthesis and in vitro biological evaluation of new pyrazole chalcones and heterocyclic diamides as potential anticancer agents

    Directory of Open Access Journals (Sweden)

    Sankappa Rai U.


    Full Text Available Synthesis and characterization of new heterocyclic pyrazole chalcones (4a–e and diamide (6a–e derivatives are described. Pyrazole chalcones were synthesized by the reaction of pyrazole aldehydes and suitable aromatic ketones. Diamides were synthesized by the reaction of phthalic acid and amines. Newly synthesized compounds were characterized by spectral studies and their biological activity was assessed in vitro using MCF-7 (human breast adenocarcinoma and HeLa (human cervical tumor cells cell lines. Few of the synthesized molecules inhibited the growth of the human breast cancer cell lines and human cervical tumor cell lines at low micromolar to nanomolar concentrations.

  11. Synthesis and Antimicrobial Activity of New Schiff Base Compounds Containing 2-Hydroxy-4-pentadecylbenzaldehyde Moiety

    Directory of Open Access Journals (Sweden)

    Gadada Naganagowda


    Full Text Available Various novel Schiff base compounds have been synthesized by reaction of 2-hydroxy-4-pentadecylbenzaldehyde with substituted benzothiophene-2-carboxylic acid hydrazide and different substituted aromatic or heterocyclic amines in the presence of acetic acid in ethanol. The structures of all these compounds were confirmed by elemental analysis, IR, 1H-NMR, 13C-NMR, and mass spectral data and have been screened for antibacterial and antifungal activity.

  12. Phenotype fingerprinting suggests the involvement of single-genotype consortia in degradation of aromatic compounds by Rhodopseudomonas palustris.

    Directory of Open Access Journals (Sweden)

    Tatiana V Karpinets

    Full Text Available Anaerobic degradation of complex organic compounds by microorganisms is crucial for development of innovative biotechnologies for bioethanol production and for efficient degradation of environmental pollutants. In natural environments, the degradation is usually accomplished by syntrophic consortia comprised of different bacterial species. This strategy allows consortium organisms to reduce efforts required for maintenance of the redox homeostasis at each syntrophic level. Cellular mechanisms that maintain the redox homeostasis during the degradation of aromatic compounds by one organism are not fully understood. Here we present a hypothesis that the metabolically versatile phototrophic bacterium Rhodopseudomonas palustris forms its own syntrophic consortia, when it grows anaerobically on p-coumarate or benzoate as a sole carbon source. We have revealed the consortia from large-scale measurements of mRNA and protein expressions under p-coumarate, benzoate and succinate degrading conditions using a novel computational approach referred as phenotype fingerprinting. In this approach, marker genes for known R. palustris phenotypes are employed to determine the relative expression levels of genes and proteins in aromatics versus non-aromatics degrading condition. Subpopulations of the consortia are inferred from the expression of phenotypes and known metabolic modes of the R. palustris growth. We find that p-coumarate degrading conditions may lead to at least three R. palustris subpopulations utilizing p-coumarate, benzoate, and CO2 and H2. Benzoate degrading conditions may also produce at least three subpopulations utilizing benzoate, CO2 and H2, and N2 and formate. Communication among syntrophs and inter-syntrophic dynamics in each consortium are indicated by up-regulation of transporters and genes involved in the curli formation and chemotaxis. The N2-fixing subpopulation in the benzoate degrading consortium has preferential activation of the

  13. Formation of chemical compounds from irradiated mixtures of aromatic hydrocarbons and nitrogen oxides

    NARCIS (Netherlands)

    Besemer, A.C.


    The paper describes the analysis of products of the photochemical degradation of toluene and toluene-14C in smog chamber experiments. Compounds identified included methylglyoxal, possibly the recently postulated butenedial and other carbonyl compounds. The main product of photochemical degradation


    Directory of Open Access Journals (Sweden)

    Ticuţa Negreanu-Pîrjol


    Full Text Available In this paper we report the synthesis, physical-chemical characterization and antimicrobial activity of some new complex compounds of hetero-aromatic biguanides ligands, chlorhexidine base (CHX and chlorhexidine diacetate (CHXac2 with metallic ions Cu(II and Zn(II, in different molar ratio. The synthesized complexes were characterized by elemental chemical analysis and differential thermal analysis. The stereochemistry of the metallic ions was determined by infrared spectra, UV-Vis, EPR spectroscopy and magnetic susceptibility in the aim to establish the complexes structures. The biological activity of the new complex compounds was identified in solid technique by measuring minimum inhibition diameter of bacterial and fungal culture, against three standard pathogen strains, Escherichia coli ATCC 25922, Staphilococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results show an increased specific antimicrobial activity for the complexes chlorhexidine:Cu(II 1:1 and 1:2 compared with the one of the Zn(II complexes.

  15. Aromatic compounds in crude oils and source rocks and their application to oil-source rock correlations in the Tarim basin, NW China (United States)

    Jinggui, Li; Philp, Paul; Zifang, Meng; Wenhui, Liu; Jianjing, Zheng; Guojun, Chen; Mei, Li; Zhaoyun, Wang


    Ten series of aromatic hydrocarbons (biphenyls; naphthalenes; phenanthrenes; anthracenes; retenes; chrysenes; benzoanthracenes; dibenzofurans; fluorenes; and dibenzothiophenes) isolated from Cambrian and Ordovician marine carbonate source rocks in Tabei and Tazhong areas of the Tarim Basin, and Triassic and Jurassic lacustrine mudstones and swamp coals in the Kuche depression have been characterized by GC-MS. The same series of aromatic compounds have been isolated and characterized from crude oils of the Tabei and Tazhong uplift. Results presented in this paper describe the distribution of these aromatic compounds in crude oils and source rocks from the three different kinds of sedimentary environments. Similarities in distributions of the fluorenes and the dibenzothiophenes in the aromatic fractions suggest the Tabei uplift oils are derived predominantly from the Lower Ordovician marine source rocks of Tabei Lunnan area (on the south of Luntai) and the oils from Tazhong uplift are mainly derived from Upper Cambrian, Lower Ordovician, and Middle-Upper Ordovician marine source rocks of Tazhong area.

  16. Laccase production and differential transcription of laccase genes in Cerrena sp. in response to metal ions, aromatic compounds and nutrients

    Directory of Open Access Journals (Sweden)

    Jie eYang


    Full Text Available 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 d. 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 indispensible 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gritti, Fabrice [University of Tennessee, Knoxville (UTK); Guiochon, Georges A [ORNL; Mayfield, Kirsty [University of Western Sydney, Australia; Dennis, Gary [University of Western Sydney, Australia; Shalliker, R. Andrew [University of Western Sydney, Australia


    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.

  18. SiRNAs conjugated with aromatic compounds induce RISC-mediated antisense strand selection and strong gene-silencing activity. (United States)

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


    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. Copyright © 2012 Elsevier Inc. All rights reserved.

  19. Production of Monomeric Aromatic Compounds from Oil Palm Empty Fruit Bunch Fiber Lignin by Chemical and Enzymatic Methods (United States)

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


    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

  20. The dependence of the fluorescence properties, laser properties and photochemical stability of aromatic compounds on the molecular symmetry (United States)

    Nijegorodov, N.; Mabbs, R.


    It is known that the spectral properties of organic compounds are, to a large extent, determined by the molecular symmetry. Numerous articles and monographs have been devoted to this problem. However, the influence of the molecular symmetry on fluorescence and, hence, laser parameters has not been fully investigated. In this paper, the fluorescence and laser properties of 20 aromatic compounds are experimentally studied at room temperature. The compounds studied are arranged in family-related π-structure pairs. In each pair, even-numbered compounds belong to a higher symmetry group than odd-numbered compounds due to symmetrical substitution. All main fluorescence parameters such as quantum yield, γ, decay time, τf, fluorescence rate constant, kf (Einstein coefficient, A), and intersystem crossing rate constant, kST, are measured or calculated. It has been found that for most of the symmetrically substituted molecules, the value of kST decreases, sometimes very significantly. For example, the transition from 9-phenylanthracene ( C2 symmetry) to 9,10-diphenylanthracene ( D2 symmetry) is accompanied by an 18-fold decrease in the value of kST. This phenomenon is explained by the fact that, in a molecule of higher symmetry, not all triplet states mix with the fluorescing S 1 state. It is also found that the symmetry of a molecule greatly affects laser parameters such as the threshold of laser action and the photochemical stability of a laser solution. It is observed that the threshold for even-numbered compounds is much lower and the photochemical stability, in most cases, is much higher than for odd-numbered compounds. These phenomena are discussed and explained.

  1. Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates. (United States)

    Haji, Mohammad


    Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given.

  2. Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism. (United States)

    Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming


    In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)desulfurization is attributed to the charge transfer effect. During extractive desulfurization, electrons on aromatic sulfur compounds transfer into the Lewis part of ionic liquid, namely, [FeCl4](-). Furthermore, it is better to consider the Lewis acidity of Fe-containing ionic liquid by the whole unit (such as [FeCl4](-) and aromatic sulfur compounds (X)) rather than only Fe or S atom. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Enzymic oxidation of. cap alpha. ,. beta. -unsaturated alcohols in the side chains of lignin-related aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Iwahara, S. (Kagawa Univ., Kagawa-ken, Japan); Nishihira, T.; Jomori, T.; Kuwahara, M.; Higuchi, T.


    An enzyme which catalyzed oxidation of the ..cap alpha..,..beta..-unsaturated primary alcohol group in the side chain of dehydrodiconiferyl alcohol to the corresponding aldehyde was excreted into the culture media by several molds that degraded synthetic lignin-a dehydrogenation polymer of coniferyl alcohol and lignosulfonate. The enzyme produced by Fusarium solani M-13-1, partially purified by gel filtration, specifically oxidized ..cap alpha..,..beta..-unsaturated alcohols in the side chains of lignin-related aromatic compounds such as coniferyl alcohol, cinnamyl alcohol, dehydrodiconiferyl alcohol and guaiacylglycerol-..beta..-coniferyl ether, but did not oxidize aromatic alcohols such as benzyl o-, m- and p-methoxybenzyl, and vanillyl alcohols or aliphatic alcohols such as methanol, ethanol, butanol. The reaction required one mole of oxygen to oxidize one mole of substrate and produced one mole of hydrogen peroxide. It is suggested that this enzyme also oxidizes ..cap alpha..,..beta..-unsaturated alcohol groups in the side chains of high molecular weight lignins.

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

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


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

  5. Chitosan-based film supported copper nanoparticles: A potential and reusable catalyst for the reduction of aromatic nitro compounds. (United States)

    de Souza, Jaqueline F; da Silva, Gabriela T; Fajardo, André R


    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. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Degradation of specific aromatic compounds migrating from PEX pipes into drinking water. (United States)

    Ryssel, Sune Thyge; Arvin, Erik; Lützhøft, Hans-Christian Holten; Olsson, Mikael Emil; Procházková, Zuzana; Albrechtsen, Hans-Jørgen


    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

    Directory of Open Access Journals (Sweden)

    Hai Ming Wang


    Full Text Available 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.

  8. Biologically important compounds in synfuels processes

    Energy Technology Data Exchange (ETDEWEB)

    Clark, B R; Ho, C; Griest, W H; Guerin, M R


    Crude products, by-products and wastes from synfuel processes contain a broad spectrum of chemical compounds - many of which are active in biological systems. Discerning which compound classes are most important is necessary in order to establish effective control over release or exposure. Polycyclic aromatic hydrocarbons (PAH), multialkylated PAH, primary aromatic amines and N-heterocyclic PAH are significant contributors to the overall mutagenic activities of a large number of materials examined. Ames test data show that the basic, primary aromatic amine fraction is the most active. PAHs, multialkylated PAHs and N-heterocyclic PAHs are all components of the neutral fraction. In nearly all cases, the neutral fractions contribute the largest portion of the mutagenic activity, while the basic primary aromatic amine fractions have the highest specific activity. Neutral fractions are usually the largest (wt %) whereas the total basic fractions are small by comparison; thus, the overall greater contribution of the neutral fraction to the mutagenic activity of most samples. Biologically active constituents are isolated in preparative scale amounts from complex mixtures utilizing combinations of liquid-liquid extraction and various liquid chromatographic column-eluant combinations. Fractions are characterized using a combination of spectroscopic techniques and gas chromatography/mass spectrometry.

  9. N-Heterocycle-Forming Amino/Carboperfluoroalkylations of Aminoalkenes by Using Perfluoro Acid Anhydrides: Mechanistic Studies and Applications Directed Toward Perfluoroalkylated Compound Libraries. (United States)

    Kawamura, Shintaro; Dosei, Kento; Valverde, Elena; Ushida, Kiminori; Sodeoka, Mikiko


    This work describes a practical and efficient method for synthesizing a diverse array of perfluoroalkylated amines, including N-heterocycles, to afford perfluoroalkylated chemical libraries as potential sources of drug candidates, agrochemicals, and probe molecules for chemical-biology research. Perfluoro acid anhydrides, which are commonly used in organic synthesis, were employed as a perfluoroalkyl source for intramolecular amino- and carbo-perfluoroalkylations of aminoalkenes, affording perfluoroalkylated N-heterocycles, including: aziridines, pyrrolidines, benzothiazinane dioxides, indolines, and hydroisoquinolinones. Diacyl peroxides were generated in situ from the perfluoro acid anhydrides with urea·H 2 O 2 , and allowed to react with aminoalkenes in the presence of copper catalyst to control the product selectivity between amino- and carbo-perfluoroalkylations. To illustrate the synthetic utility of bench-stable trifluoromethylated aziridine, which was prepared on a gram scale, we used it to synthesize a wide variety of trifluoromethylated amines including complex molecules, such as trifluoromethylated tetrahydroharmine and spiroindolone. A mechanistic study of the role of the copper catalyst in the aminotrifluoromethylation of allylamine suggested that Cu(I) accelerates CF 3 radical formation via decomposition of diacyl peroxide, which appears to be the turnover-limiting step, while Cu(II) controls the product selectivity.

  10. Treatment of sludge containing nitro-aromatic compounds in reed-bed mesocosms - Water, BOD, carbon and nutrient removal. (United States)

    Gustavsson, L; Engwall, M


    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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Adsorption kinetics of aromatic compounds on carbon nanotubes and activated carbons. (United States)

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


    Adsorption kinetics of two organic compounds on four types of carbonaceous adsorbents (a granular activated carbon [HD4000], an activated carbon fiber [ACF10], a single-walled carbon nanotube [SWNT], and a multiwalled carbon nanotube [MWNT]) was examined in aqueous solutions. The times needed for the adsorption to reach apparent equilibrium on the four carbons followed the order of ACF10 > HD4000 > SWNT > MWNT. Ultrasonication of the carbon nanotubes (CNTs) accelerated their adsorption kinetics but had no effect on their equilibrium adsorption capacities. The pseudo-second order model (PSOM) provided good fitting for the kinetic data. The fitting of kinetic data with the intraparticle diffusion model indicated that external mass transfer controls the sorption process in the organic compound-CNT systems, whereas intraparticle diffusion dominates in the sorption of organic compounds onto activated carbons. Copyright © 2011 SETAC.

  12. (Liquid + liquid) equilibrium for ternary mixtures of {l_brace}heptane + aromatic compounds + [EMpy][ESO{sub 4}]{r_brace} at T = 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Mirkhani, S.A. [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Vossoughi, M., E-mail: [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Pazuki, G.R. [Department of Chemical Engineering, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Safekordi, A.A. [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of); Heydari, A.; Akbari, J. [Department of Chemistry, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Yavari, M. [Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran (Iran, Islamic Republic of)


    Highlights: > This paper reports the LLE data of ternary systems {l_brace}heptane (1) + aromatic compounds (2) + [EMpy][ESO{sub 4}] (3){r_brace}. > The distribution coefficient and the selectivity were obtained from the experimental data. > The consistency of LLE data was successfully correlated with Othmer-Tobias and Hand equation. - Abstract: (Liquid + liquid) equilibrium (LLE) data for the ternary systems (heptane + toluene + 1-ethyl-3-methylpyridinium ethylsulfate) and (heptane + benzene + 1-ethyl-3-methylpyridinium ethylsulfate) were measured at T = 298.15 K and atmospheric pressure. The selectivity and aromatic distribution coefficients, calculated from the equilibrium data, were used to determine if this ionic liquid can be used as a potential extracting solvent for the separation of aromatic compounds from heptane. The consistency of tie-line data was ascertained by applying the Othmer-Tobias and Hand equations.

  13. Economical post-CCSD(T) computational thermochemistry protocol and applications to some aromatic compounds. (United States)

    Karton, Amir; Kaminker, Ilya; Martin, Jan M L


    To achieve a kilojoules-per-mole level of accuracy consistently in computational thermochemistry, the inclusion of post-CCSD(T) correlation effects cannot be avoided. Such effects are included in the W4 and HEAT computational thermochemistry protocols. The principal bottleneck in carrying out such calculations for larger systems is the evaluation of the T(3)-(T) term. We propose a cost-effective empirical approximation for this term that does not entail any reliance on experimental data. For first-row molecules, our W3.2lite protocol yields atomization energies with a 95% confidence interval of approximately 0.4 kcal/mol at the expense of introducing two such parameters. W3.2lite has been successfully applied to aromatic and aliphatic hydrocarbons such as benzene, fulvene, phenyl radical, pyridine, furan, benzyne isomers, trans-butadiene, cyclobutene, [1.1.1]propellane, and bicyclo[1.1.1]pentane. The W3.2lite predictions for fulvene, phenyl radical, cyclobutene, and [1.1.1]propellane are impossible to reconcile with experiment and suggest that remeasurement may be in order.

  14. Pyrolysis Products as Soil Fertilizers: Screening of Potentially Hazardous Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Frišták Vladimír


    Full Text Available This study investigated the concentrations of polycyclic aromatic hydrocarbons (PAHs in pyrogenic carbonaceous materials (PCM produced from three waste materials during slow pyrolysis at 400 and 500°C. As feedstocks bone meal (BM, biogas slurry (BC and chicken manure (CM were used. As potentially problematic substances 1- and 2- methylnaphthalene were analysed as indicators for methylated hydrocarbons in pyrolysis products. The phytotoxic effect of soil amendments was evaluated by a standard cress germination test with Lepidium sativum L. The analysis showed higher concentrations of the sum of 16 US-EPA PAHs in samples produced at lower temperature and in samples produced from biogas slurry. Concentrations of 1- and 2-methylnaphthalene showed similar trends with concentrations in a range of 35-205% of the sum of 16 PAHs. Germination tests showed inhibition effects of products from biogas slurry when applied in concentrations of ≥ 10 % to standard substrate. Apparently pyrolysis of biogas slurry requires special attention to avoid accumulation of PAHs and methylated naphthalenes.

  15. Degradation of specific aromatic compounds migrating from PEXpipes into drinking water

    DEFF Research Database (Denmark)

    Ryssel, Sune Thyge; Arvin, Erik; Lützhøft, Hans-Christian Holten


    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 (2e4 weeks). Neither inhibition nor co-metabolism was observed in the presence of acetate or PEX pipe...

  16. Novel loop-like aromatic compounds: a further step on the road to nanobelts and nanotubes

    Directory of Open Access Journals (Sweden)

    Venkataramana Rajuri


    Full Text Available The synthesis and crystal structural characterization of new compounds 2–6 were accomplished. As a common synthetic methodology, the Diels–Alder reaction was applied to 9,9′,10,10′-tetradehydrodianthracene (TDDA (7 to furnish the [12]annulenes 2 and 3 [16]annulene 6 and adduct 5.

  17. The pollution characteristics of odor, volatile organochlorinated compounds and polycyclic aromatic hydrocarbons emitted from plastic waste recycling plants. (United States)

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


    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.

  18. Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water (United States)


    Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r2 ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs 95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE. PMID:28791049

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

    NARCIS (Netherlands)

    Favre-Bulle, Olivier


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

  20. Greener Friedel-Crafts Acylation using Microwave-enhanced reactivity of Bismuth Triflate in the Friedel-Crafts Benzoylation of Aromatic Compounds with Benzoic Anhydride

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Nguyen, Hai Truong; Hansen, Poul Erik


    An efficient and facile bismuth trifluoromethanesulfonate-catalyzed benzoylation of aromatic compounds using benzoic anhydride under solvent-free microwave irradiation has been developed. The microwave-assisted Friedel-Crafts benzoylation results in good yields within short reaction times. Bismuth...

  1. 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 (United States)

    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...

  2. Biological responses to dioxin-like compounds and polycyclic aromatic hydrocarbons in eelpout Zoarces viviparus. Contributions to an integrated environmental assessment approach

    DEFF Research Database (Denmark)

    Tairova, Zhanna

    This PhD project attempts to link exposure to environmentally persistent organic pollutants (POPs) such as dioxin-like compounds (DLCs) and polycyclic aromatic hydrocarbons (PAHs) to effects in the marine fish eelpout Zoarces viviparus by combining different in vivo and in vitro biomarkers in both...

  3. Effect of biofilm formation by Oenococcus oeni on malolactic fermentation and the release of aromatic compounds in wine

    Directory of Open Access Journals (Sweden)

    Alexandre eBastard


    Full Text Available The winemaking process involves the alcoholic fermentation of must, often followed by malolactic fermentation. 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 malolactic fermentation and aging by decreasing furfural, gaiacol and eugenol in

  4. Bioremediation of polynitrated aromatic compounds: plants and microbes put up a fight. (United States)

    Ramos, Juan L; González-Pérez, M Mar; Caballero, Antonio; van Dillewijn, Pieter


    Industrialization and the quest for a more comfortable lifestyle have led to increasing amounts of pollution in the environment. To address this problem, several biotechnological applications aimed at removing this pollution have been investigated. Among these pollutants are xenobiotic compounds such as polynitroaromatic compounds--recalcitrant chemicals that are degraded slowly. Whereas 2,4,6-trinitrophenol (TNP) can be mineralized and converted into carbon dioxide, nitrite and water, 2,4,6-trinitrotoluene (TNT) is more recalcitrant--although several microbes can use it as a nitrogen source. The most effective in situ biotreatments for TNT are the use of bioslurry (which can be preceded by an abiotic step) and phytoremediation. Phytoremediation can be enhanced by using transgenic plants alone or together with microbes.

  5. Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry (United States)

    Zaugg, Steven D.; Burkhardt, Mark R.; Burbank, Teresa L.; Olson, Mary C.; Iverson, Jana L.; Schroeder, Michael P.


    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

  6. Application of a dynamic in vitro gastrointestinal tract model to study the availability of food mutagens, using heterocyclic aromatic amines as model compounds

    NARCIS (Netherlands)

    Krul, C.A.M.; Luiten-Schuite, A.; Baan, R.; Verhagen, H.; Mohn, G.; Feron, V.; Havenaar, R.


    The TNO gastro-Intestinal tract Model (TIM) is a dynamic computer-controlled in vitro system that mimics the human physiological conditions in the stomach and small intestine. In the current TIM physiological parameters such as pH, temperature, peristaltic movements, secretion of digestion enzymes,

  7. Role of aromatic substituents on the antiproliferative effects of diphenyl ferrocenyl butene compounds. (United States)

    Zekri, Ouardia; Hillard, Elizabeth A; Top, Siden; Vessières, Anne; Pigeon, Pascal; Plamont, Marie-Aude; Huché, Michel; Boutamine, Sultana; McGlinchey, Michael J; Müller-Bunz, Helge; Jaouen, Gérard


    We have been exploring the cytotoxic effects of conjugated phenylferrocene systems on breast cancer cells. Complexes with p-OH, p-NH(2), and p-NHC(O)CH(3) substitution show particularly high activity, with IC(50) values in the low or sub micromolar range for both the hormone-dependent MCF-7 and hormone-independent MDA-MB-231 breast cancer cell lines. We now present the synthesis, X-ray crystal structures and biochemical studies of analogous halogen or pseudo-halogen para-substituted compounds with R = Cl, (Z)-7a; Br, (Z)-7b; CF(3), (E)-7c; and CN, (E)-7d and (Z)-7d. Lacking hydrogen bonding groups, the compounds have low, but non-zero, relative binding affinity values for the oestrogen receptor alpha (RBA compounds show estrogenic (proliferative) activity on the MCF-7 cell line. On MDA-MB-231 cells, the cyano complex (Z)-7d shows a reasonable cytotoxic effect (IC(50) = 11 microM), its isomer (E)-7d is only slightly cytotoxic (IC(50) = 60 microM), while the Cl, Br, and CF(3) derivatives have no effect. Cytotoxic properties, while they correlate somewhat with the resonance donating abilities of the substituent, are more strongly dependent on the presence of a proton in the functional group, supporting our prior proposition that electrophilic quinoid forms of the compounds could be active species in the cell. A correlation of the redox potential of the ferrocenyl moiety with the Hammett-Taft constants of the substituents was observed.

  8. Evolution of aromatic compounds during the second fermentation and aging of Brazilian sparkling wine

    Directory of Open Access Journals (Sweden)

    Verzeletti Andrelise


    Full Text Available In this work, we evaluate the physic-chemical characteristics and volatile compounds during the second fermentation and aging of typical Brazilian sparkling wines. For this purpose, second fermentations were conducted by the traditional method using a base wine elaborated with Pinot Noir, Chardonnay and Riesling Italic, and fermented with S. cerevisiae vr. bayanus EC1118 strain. Samples were collected from 0 to 360 days, and evaluated with respect to the basic physic-chemical characteristics, yeast population, and the concentration of volatile compounds. The results showed that the second fermentation, other than an increment in the alcohol concentration leads to a small increase in volatile acidity, where total acidity decreased during fermentation, and increase again during aging. Yeast population declined rapidly after fermentation, but autolysis initiated just after 9 month of aging. Based on the concentration of volatile compounds, three profiles could be defined: (1 a fermentation profile defined by higher concentrations of acetates and lower concentrations of ethylates and fatty acids; (2 a post-fermentation profile with intermediary concentrations of acetates, and increased concentrations of fatty acids, and their ethyl esters; and (3 a mature profile with higher concentrations of diethyl succinate, fusel alcohols, volatile fatty acids, and their ethyl esters, and lower concentrations of acetates.

  9. Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids (United States)

    Dutka, V. S.; Matsyuk, N. V.; Dutka, Yu. V.


    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.

  10. Oxidation of heteroleptic diarylpalladium compounds with tert-butyl hydroperoxide. Substituent effects in aromatic oxidation reactions

    NARCIS (Netherlands)

    Koten, G. van; Valk, J.-M.; Boersma, J.


    A series of heteroleptic diarylpalladium compounds, containing both a naphthyl (1-C10H6CH2NMe2-2 or 1-C10H5CH2NMe2-2-Me-3) and a phenyl (1-C6H4CH2NMe2-2 or 1-C6H3CH2NMe2-2-Me-x, x = 3, 5, 6) monoanionic C,N-bidentate ligand, was reacted with tert-butyl hydroperoxide (TBHP) to give selective oxygen

  11. Analysis of the interaction of polycyclic aromatic compounds in a model organism: integration of genotoxic and histopathological effects

    Directory of Open Access Journals (Sweden)

    Sofia Pereira


    Full Text Available Due to their toxicity, especially their carcinogenic potential, polycyclic aromatic hydrocarbons (PAHs are considered priority in biomonitoring programmes. Many of these compounds are listed through the European Water Framework Directive as priority pollutants. Benzo(bfluoranthene (B[b]F, considered potentially carcinogenic, and phenanthrene (Phe, non-carcinogenic, are two common PAHs in coastal waters and own distinct proprieties that are reflected in their mechanisms of toxicity. Still, their interaction effects onto the aquatic biota remain largely unknown. This work aimed to analyze the genotoxic effects caused by the interaction of B[b]F and Phe and their relation to histopathological alterations in the liver. The model organism was the seabass Dicentrarchus labrax, an important coastal species for fisheries and aquaculture. For the purpose, fish were injected with the two compounds (5 µg/g fish ww, isolated or in mixture, and incubated for 24h. The results only revealed minor clastogenic and aneugenic alterations, determined through erythrocytic nuclear abnormalities. On the other hand, the Comet assay showed significant DNA strand breakage in the individuals injected with B[b]F and the combination of the two compounds. On the contrary, Phe failed to cause significant genotoxic effects. Significant hepatic histopathological alterations were also found in animals injected with B[b]F, relating especially to inflammation-related responses. Overall, the results indicate no significant additive effect between B[b]F and Phe, under the current experimental conditions. Nonetheless, the seabass revealed to be sensitive to exposure to B[b]F (a higher molecular weight PAH, likely due to more efficient bioactivation of the pollutant (yielded genotoxic metabolites and reactive oxygen species, when compared to Phe. It is of paramount importance to understand the long-term interaction effects between PAHs under ecologically-relevant scenarios, since

  12. Dibasic Ammonium Phosphate Application Enhances Aromatic Compound Concentration in Bog Bilberry Syrup Wine. (United States)

    Wang, Shao-Yang; Li, Yi-Qing; Li, Teng; Yang, Hang-Yu; Ren, Jie; Zhang, Bo-Lin; Zhu, Bao-Qing


    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.

  13. Study of major aromatic compounds in port wines from carotenoid degradation. (United States)

    Silva Ferreira, António César; Monteiro, Judith; Oliveira, Carla; Guedes de Pinho, Paula


    The carotenoids degradation and the formation of volatiles were examined by simulating Port wine aging. A two year old red Port wine was saturated with oxygen, supplemented with lutein and β-carotene and kept at 60°C during 87h. A similar study was performed in a model wine solution. Results showed that the percentage decrease in lutein levels was, respectively, 79% and 95%, in the wine model solution and in the Port wine, and 55% and 10% for β-carotene, indicating that lutein was more sensitive to degradation than β-carotene. Two other unknown degradation carotenoid compounds were identified by HPLC/DAD (reverse phase λmax: 422; 445; 475 and 422; 445; 472) in the lutein supplemented wine. Levels of β-ionone and β-cyclocitral increased (2.5 times) in both, wine and wine model solution, supplemented with β-carotene. Along with these compounds, the same behaviour was observed in β-damascenone in the supplemented lutein wine and wine model solution. New insights were provided into the understanding of aroma modifications occurring during Port wine aging. The relationship between carotenoid molecules (β-carotene and lutein) and some volatiles has also been provided. Copyright © 2008 Elsevier Ltd. All rights reserved.

  14. Aromatic fluorine compounds. X. The 2,3- and 2,6-difluoropyridines (United States)

    Finger, G.C.; Starr, L.D.; Roe, A.; Link, W.J.


    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).

  15. Limiting activity coefficients of some aromatic and aliphatic nitro compounds in water

    Energy Technology Data Exchange (ETDEWEB)

    Benes, M.; Dohnal, V. [Inst. of Chemical Technology, Prague (Czech Republic). Dept. of Physical Chemistry


    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.

  16. Self-Assembly and Nanostructures in Organogels Based on a Bolaform Cholesteryl Imide Compound with Conjugated Aromatic Spacer

    Directory of Open Access Journals (Sweden)

    Ti-Feng Jiao


    Full Text Available The self-assembly of small functional molecules into supramolecular structures is a powerful approach toward the development of new nanoscale materials and devices. As a class of self-assembled materials, low weight molecular organic gelators, organized in special nanoarchitectures through specific non-covalent interactions, has become one of the hot topics in soft matter research due to their scientific values and many potential applications. Here, a bolaform cholesteryl imide compound with conjugated aromatic spacer was designed and synthesized. The gelation behaviors in 23 solvents were investigated as efficient low-molecular-mass organic gelator. The experimental results indicated that the morphologies and assembly modes of as-formed organogels can be regulated by changing the kinds of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecule self-assemble into different aggregates, from wrinkle and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes. Finally, some rational assembly modes in organogels were proposed and discussed. The present work may give some insight to the design and character of new organogelators and soft materials with special structures.

  17. Self-Assembly and Nanostructures in Organogels Based on a Bolaform Cholesteryl Imide Compound with Conjugated Aromatic Spacer (United States)

    Jiao, Ti-Feng; Gao, Feng-Qing; Shen, Xi-Hai; Zhang, Qing-Rui; Zhang, Xian-Fu; Zhou, Jing-Xin; Gao, Fa-Ming


    The self-assembly of small functional molecules into supramolecular structures is a powerful approach toward the development of new nanoscale materials and devices. As a class of self-assembled materials, low weight molecular organic gelators, organized in special nanoarchitectures through specific non-covalent interactions, has become one of the hot topics in soft matter research due to their scientific values and many potential applications. Here, a bolaform cholesteryl imide compound with conjugated aromatic spacer was designed and synthesized. The gelation behaviors in 23 solvents were investigated as efficient low-molecular-mass organic gelator. The experimental results indicated that the morphologies and assembly modes of as-formed organogels can be regulated by changing the kinds of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecule self-assemble into different aggregates, from wrinkle and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes. Finally, some rational assembly modes in organogels were proposed and discussed. The present work may give some insight to the design and character of new organogelators and soft materials with special structures. PMID:28788428

  18. Polycyclic aromatic compounds via radical cyclizations of benzannulated enyne-allenes derived from Ireland-Claisen rearrangement. (United States)

    Yang, Yonghong; Petersen, Jeffrey L; Wang, Kung K


    A new synthetic sequence involving the use of Ireland-Claisen rearrangement of propargylic acetates to form the corresponding benzannulated enyne-allenes followed by Schmittel cyclization to generate benzofulvene biradicals for radical cyclizations leading to polycyclic aromatic compounds was established. Treatment of 9-fluorenone (8) with the lithium acetylide 9 followed by acetic anhydride produced the propargylic acetate 10. A sequence of reactions occurred after 10 was converted to the corresponding silyl ketene acetal 11. An initial Ireland-Claisen rearrangement produced the benzannulated enyne-allene 12, which then underwent a Schmittel cyclization reaction to generate the benzofulvene biradical 13. A subsequent intramolecular radical-radical coupling then produced the formal Diels-Alder adduct 14, which in turn underwent a prototropic rearrangement to give the silyl ester 15 and, after hydrolysis, the carboxylic acid 16 in 57% overall yield from 10 in a single operation. An intramolecular acylation reaction of 16 produced the ketone 17. The carboxylic acids 24-26 were likewise prepared from the diaryl ketones 18-20, respectively. However, the intramolecular [2 + 2] cycloaddition reaction of the benzannulated enyne-allene 33 having a tert-butyl group at the allenic terminus occurred preferentially, producing the 1H-cyclobut[a]indenyl acetic acid 35 as the predominant product.

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

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


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

  20. One-step, green synthesis of a supramolecular organogelator based on mellitic triimide for the recognition of aromatic compounds. (United States)

    Mamada, Masashi; Minami, Tsuyoshi; Katagiri, Hiroshi; Omiya, Takafumi; Tokito, Shizuo


    Mellitic triimide derivatives with N-benzyl groups form conformations with concave cavities, that are capable of including aromatic molecules such as benzene, nitrobenzene, etc. In addition, they act as supramolecular gelators, which enable the detection of aromatic molecules as a gel-sol phase transition.

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

    NARCIS (Netherlands)

    Rathi, Akansha; Hernández, M.; Dierkes, Wilma K.; Bergmann, C.; Noordermeer, Jacobus W.M.; Trimbach, J.; Blume, Anke


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

  2. Comparison of different exhaustive and biomimetic extraction techniques for chemical and biological analysis of polycyclic aromatic compounds in river sediments

    Energy Technology Data Exchange (ETDEWEB)

    Schulze, Tobias [Free Univ. Berlin (Germany). Dept. of Earth Sciences, Hydrogeology; Seiler, Thomas B.; Hollert, Henner [RWTH Aachen Univ. (Germany). Dept. of Ecosystem Analysis; Streck, Georg [UFZ Helmholtz-Centre for Environmental Research, Leipzig (Germany). Dept. of Effect-Directed Analysis; Braunbeck, Thomas


    The importance of the bioaccessible fractions of particle-bound contaminants is a key feature for the assessment of their likely risks to the aquatic environment. The present study investigated the extractability and potential toxicity of polycyclic aromatic hydrocarbons (PAHs) in river sediments. This study combined chemical with bioanalytical tools to establish a more in-depth insight into the relationship between the extractability of sediment contaminants, the chemodynamic properties of each extraction approach, and resulting toxicity. Sediment samples were treated with different extraction methods, namely Soxhlet extraction with acetone (SOX), membrane dialysis extraction (MDE) with n-hexane, ultrasonic extraction with acetone (USE), and extraction with (2-hydroxpropyl)-{beta}-cyclodextrin (HBCD). The extracts were analyzed for PAHs using gas chromatography/mass spectrometry and tested using the neutral red retention assay and the ethoxyresorufin-O-deethylase (EROD) induction assay with the permanent fish cell line RTL-W1. The SOX and MDE approaches were comparable in their extraction power regarding PAHs and their cytotoxicity. However, the EROD activity differed between SOX and MDE, possibly due to retardation effects of the polyethylene membrane used in MDE. Thus, macromolecular components of the sediment were not extracted and therefore did not contribute to toxicity. HBCD extraction provided 3.4 % of the total PAH content in the sediments and might be an appropriate approach to predict the bioaccessible fraction. USE showed an extraction power between the HBCD approach and the MDE as well as SOX and MDE method. Hence, USE is neither appropriate for exhaustive extraction nor for biomimetic extraction. MDE and SOX have been approved for the exhaustive extraction of PAHs from sediments for a worst case assessment of effect potentials. The influence of the low-density polyethylene membrane and the experimental conditions on the diffusion of compounds with

  3. Innovative method of direct determination of the content of paraffins, naphthenes, aromatics and sulfur compounds by capillary high-resolution gas chromatography

    Directory of Open Access Journals (Sweden)

    R. Baizhumanova


    Full Text Available Based on determination of individual Hydrocarbon (paraffins, naphthenes, aromatics and Sulphur components of fuels and their mixture on the thin bonded of absorber (the stationary phase is a 100-metre silica capillary column, containing 0.5μm film thickness of bonded dimethylpolysiloxane phase by means of the selective solvents (mobile phase combined with technique of ionization of separated compounds by Flame Ionization Detector (FID and Sulphur Chemiluminescence Detector (SCD.

  4. Electron spin relaxation of a boron-containing heterocyclic radical (United States)

    Eaton, Sandra S.; Huber, Kirby; Elajaili, Hanan; McPeak, Joseph; Eaton, Gareth R.; Longobardi, Lauren E.; Stephan, Douglas W.


    Preparation of the stable boron-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), by frustrated Lewis pair chemistry has been reported recently. Electron paramagnetic resonance measurements of this radical were made at X-band in toluene:dichloromethane (9:1) from 10 to 293 K, in toluene from 180 to 293 K and at Q-band at 80 K. In well-deoxygenated 0.1 mM toluene solution at room temperature hyperfine splittings from 11B, four pairs of 1H, and 5 pairs of 19F contribute to an EPR spectrum with many resolved lines. Observed hyperfine couplings were assigned based on DFT calculations and account for all of the fluorines and protons in the molecule. Rigid lattice g values are gx = 2.0053, gy = 2.0044, and gz = 2.0028. Near the melting point of the solvent 1/Tm is enhanced due to motional averaging of g and A anisotropy. Increasing motion above the melting point enhances 1/T1 due to contributions from tumbling-dependent processes. The overall temperature dependence of 1/T1 from 10 to 293 K was modeled with the sum of contributions of a process that is linear in T, a Raman process, spin rotation, and modulation of g anisotropy by molecular tumbling. The EPR measurements are consistent with the description of this compound as a substituted aromatic radical, with relatively small spin density on the boron.

  5. A simple, comprehensive, and miniaturized solvent extraction method for determination of particulate-phase polycyclic aromatic compounds in air. (United States)

    Santos, Aldenor G; Regis, Ana Carla D; da Rocha, Gisele O; Bezerra, Marcos de A; de Jesus, Robson M; de Andrade, Jailson B


    The method allowed simultaneous characterization of PAHs, nitro-PAHs and quinones in atmospheric particulate matter. This method employs a miniaturized micro-extraction step that uses 500 μL of an acetonitrile-dichloromethane mix and instrumental analysis by means of a high-resolution GC-MS. The method was validated using the SRM1649b NIST standard reference material as well as deuterated internal standards. The results are in good agreement with the certified values and show recoveries between 75% and 145%. Limit of detection (LOD) values for PAHs were found to be between 0.5 pg (benzo[a]pyrene) to 2.1 pg (dibenzo[a,h]anthracene), for nitro-PAHs ranged between 3.2 pg (1-nitrobenzo[e]pyrene) and 22.2 pg (3-nitrophenanthrene), and for quinones ranged between 11.5 pg (1,4-naphthoquinone) and 458 pg (9,10-phenanthraquinone). The validated method was applied to real PM10 samples collected on quartz fiber filters. Concentrations in the PM10 samples ranged from 0.06 to 15 ng m(-3) for PAHs, fromaromatic compounds in airborne particles from both polluted and non-polluted atmospheres. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. A Naphtho-p-quinodimethane Exhibiting Baird's (Anti)Aromaticity, Broken Symmetry, and Attractive Photoluminescence. (United States)

    Shokri, Siamak; Li, Jingbai; Manna, Manoj K; Wiederrecht, Gary P; Gosztola, David J; Ugrinov, Angel; Jockusch, Steffen; Rogachev, Andrey Yu; Ayitou, A Jean-Luc


    We report a novel reductive desulfurization reaction involving π-acidic naphthalene diimides (NDI) 1 using thionating agents such as Lawesson's reagent. Along with the expected thionated NDI derivatives 2-6, new heterocyclic naphtho-p-quinodimethane compounds 7 depicting broken/reduced symmetry were successfully isolated and fully characterized. Empirical studies and theoretical modeling suggest that 7 was formed via a six-membered ring oxathiaphosphenine intermediate rather than the usual four-membered ring oxathiaphosphetane of 2-6. Aside from the reduced symmetry in 7 as confirmed by single-crystal XRD analysis, we established that the ground state UV-vis absorption of 7 is red-shifted in comparison to the parent NDI 1. This result was expected in the case of thionated polycyclic diimides. However, unusual low energy transitions originate from Baird 4nπ aromaticity of compounds 7 in lieu of the intrinsic Hückel (4n + 2)π aromaticity as encountered in NDI 1. Moreover, complementary theoretical modeling results also corroborate this change in aromaticity of 7. Consequently, photophysical investigations show that, compared to parent NDI 1, 7 can easily access and emit from its T 1 state with a phosphorescence 3 (7a)* lifetime of τ P = 395 μs at 77 K indicative of the formation of the corresponding "aromatic triplet" species according to the Baird's rule of aromaticity.

  7. Effect of phenolic compounds from spices consumed in China on heterocyclic amine profiles in roast beef patties by UPLC-MS/MS and multivariate analysis. (United States)

    Zeng, Maomao; Li, Yang; He, Zhiyong; Qin, Fang; Chen, Jie


    Ultra performance liquid chromatography-tandem mass spectrometry and multivariate analysis were used to exploit the effect and further synergistic or antagonistic interactions of main phenolic compounds with the same ratios as in spices consumed in China, on the profiles of HAs in roast beef patties. Quantitative levels of harman (1-methyl-9H-pyrido[3,4-b]indole), norharman (9H-pyrido[3,4-b]indole), PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), DMIP (2-amino-1,6-dimethylimidazo[4,5-b]pyridine), 1,5,6-TMIP (2-amino-1,5,6-trimethylimidazo[4,5-b]pyridine), MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline) and 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) were detected in all of the beef patties. The formation of most of these seven HAs was significantly (Pphenolic compounds. Mixed and corresponding single phenolic compounds had different effects on HA profiles. DMIP, 1,5,6-TMIP and 4,8-DiMeIQx were investigated as differentiating factors for single compounds, while harman and MeIQx for mixed ones. Moreover, certain combination of phenolic compounds have synergistic on harman, norharman and MeIQx, but antagonistic effects on the formation of DMIP and 4,8-DiMeIQx. The results may shed light on the mechanism for the effects of spices on the formation of HAs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Comparison of aryl hydrocarbon hydroxylase and acetanilide 4-hydroxylase induction by polycyclic aromatic compounds in human and mouse cell lines. (United States)

    Jaiswal, A K; Nebert, D W; Eisen, H W


    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.

  9. Acute toxicity and synergistic and antagonistic effects of the aromatic compounds of some essential oils against Culex quinquefasciatus Say larvae. (United States)

    Pavela, Roman


    The efficacy of 30 aromatic compounds and their mutual binary combinations was assessed for acute toxicity against the larvae Culex quinquefasciatus. Based on comparison of the lethal doses, thymol and p-cymene were selected as the most effective (LD50 = 18 and 21 mg L(-1), respectively, and LD90 = 25 and 30 mg L(-1), respectively). Although the LD50 for terpinolene and trans-anethole was also estimated at 21 mg L(-1), their LD90 was significantly higher compared to the substances above (245 and 34 mg L(-1), respectively). In total, 435 binary combinations were tested, of which 249 combinations showed a significant synergistic effect, while 74 combinations showed a significant antagonistic effect on mortality. Only nine substances were identified as being able to create a synergistic effect with more than 20 substances: limonene, trans-anethole, 4-allylanisole, carvacrol, isoeugenol, menthone, carvone, borneol, and camphor. The highest synergistic effect on larval mortality was achieved for the combinations: eugenol and isoeugenol, carvone and carvacrol, carvone and 4-allylanisole, carvone and α-terpineol, carvone and menthone, limonene and trans-anethole, limonene and menthone, α-pinene and menthone, β-citronellol and menthone, carvacrol and 4-allylanisole, carvacrol and terpineol, α-terpinene and trans-anethole, camphor and menthone, camphene and menthone, and 4-allylanisole and menthone. Significant differences between achieved mortality and the mutual mixing ratio were found for the five selected binary mixtures that had shown the most significant synergistic effect in the previous tests. The mixture of limonene and trans-anethole showed the highest mortality, with the mixing ratio 1:1; the mixture of eugenol and isoeugenol caused 90.2% mortality, with the mixing ratio 1:3. One hundred percent mortality was achieved if carvacrol was contained in a mixture with carvone in a ratio >2. After a comparison of all our results, based on our experiments, we

  10. Heterocyclic N-Oxides - An Emerging Class of Therapeutic Agents. (United States)

    Mfuh, A M; Larionov, O V


    Heterocyclic N-oxides have emerged as potent compounds with anticancer, antibacterial, antihypertensive, antiparasitic, anti-HIV, anti-inflammatory, herbicidal, neuroprotective, and procognitive activities. The N-oxide motif has been successfully employed in a number of recent drug development projects. This review surveys the emergence of this scaffold in the mainstream medicinal chemistry with a focus on the discovery of the heterocyclic N-oxide drugs, N-oxide-specific mechanisms of action, drug-receptor interactions and synthetic avenues to these compounds. As the first review on this subject that covers the developments since 1950s to date, it is expected that it will inspire wider implementation of the heterocyclic N-oxide motif in the rational design of new medicinal agents.

  11. Description of aromaticity in porphyrinoids. (United States)

    Wu, Judy I; Fernández, Israel; Schleyer, Paul v R


    Like the larger nonplanar Möbius rings, porphyrinoid aromaticity is not due primarily to the macrocyclic π conjugation of the corresponding annulene perimeters. The block-localized wave function (BLW)-derived aromatic stabilization energies (ASE) of several porphyrinoids reveal that, on a per atom basis, the appended 6π electron heterocycles of porphyrinoids confer aromaticity much more effectively than the macrocyclic 4n+2 π electron conjugations. There is no direct relationship between thermochemical stability of porphyrinoids and their macrocyclic 4n or 4n+2 π electron counts. Porphyrinoids having an "antiaromatic" macrocyclic 4n+2 π electron conjugation pathway (e.g., 4) as well as those having no macrocyclic conjugation (e.g., 9) can be stabilized by aromaticity. Computed nucleus independent chemical shifts (NICS) and the anisotropy of the induced current density (ACID) disclose the intricate local versus macrocyclic circulation interplay for several porphyrinoids.

  12. Monoamine oxidase inhibitory activities of heterocyclic chalcones. (United States)

    Minders, Corné; Petzer, Jacobus P; Petzer, Anél; Lourens, Anna C U


    Studies have shown that natural and synthetic chalcones (1,3-diphenyl-2-propen-1-ones) possess monoamine oxidase (MAO) inhibition activities. Of particular importance to the present study is a report that a series of furanochalcones acts as MAO-B selective inhibitors. Since the effect of heterocyclic substitution, other than furan (and more recently thiophene, piperidine and quinoline) on the MAO inhibitory properties of the chalcone scaffold remains unexplored, the aim of this study was to synthesise and evaluate further heterocyclic chalcone analogues as inhibitors of the human MAOs. For this purpose, heterocyclic chalcone analogues that incorporate pyrrole, 5-methylthiophene, 5-chlorothiophene and 6-methoxypyridine substitution were examined. Seven of the nine synthesised compounds exhibited IC50 values chalcones are reversible and competitive MAO inhibitors. 4h, however, may exhibit tight-binding to MAO-B, a property linked to its thiophene moiety. We conclude that high potency chalcones such as 4h represent suitable leads for the development of MAO-B inhibitors for the treatment of Parkinson's disease and possibly other neurodegenerative disorders. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Recent advances in the electrochemical construction of heterocycles

    Directory of Open Access Journals (Sweden)

    Robert Francke


    Full Text Available Due to the fact that the major portion of pharmaceuticals and agrochemicals contains heterocyclic units and since the overall number of commercially used heterocyclic compounds is steadily growing, heterocyclic chemistry remains in the focus of the synthetic community. Enormous efforts have been made in the last decades in order to render the production of such compounds more selective and efficient. However, most of the conventional methods for the construction of heterocyclic cores still involve the use of strong acids or bases, the operation at elevated temperatures and/or the use of expensive catalysts and reagents. In this regard, electrosynthesis can provide a milder and more environmentally benign alternative. In fact, numerous examples for the electrochemical construction of heterocycles have been reported in recent years. These cases demonstrate that ring formation can be achieved efficiently under ambient conditions without the use of additional reagents. In order to account for the recent developments in this field, a selection of representative reactions is presented and discussed in this review.

  14. Uma metodologia simples e eficiente para a cloração de compostos aromáticos ativados utilizando o ácido tricloro-isocianúrico A simple and efficient methodology for chlorination of activated aromatic compounds using trichloroisocyanuric acid

    Directory of Open Access Journals (Sweden)

    Gabriela F. Mendonça


    Full Text Available The chlorination of activated aromatic rings is efficiently achieved under mild conditions by reaction of aromatic compounds with trichloroisocyanuric acid in acetonitrile, at room temperature, leading to products in 60-95% isolated yields and good regioselectivity.

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

    NARCIS (Netherlands)

    Rathi, Akansha; Hernández, M.; Dierkes, Wilma K.; Bergmann, C.; Trimbach, J.; Blume, Anke


    In this study, the effect of TDAE-oil was investigated in functionalized, medium styrene/high vinyl solution styrene butadiene rubber (FsS-SBR) and high cispolybutadiene rubber (BR). Three properties were evaluated: (i) molecular structure (polarity/aromaticity), (ii) molecular weight and (iii)

  16. Thermally stable and chemically resistant polymer membranes : aromatic polyoxadiazoles and polytriazoles

    NARCIS (Netherlands)

    Gebben, Bert


    This thesis concerns the preparation of membranes from thermally stable and chemically resistant polymers. Two polymer families from the category of heterocyclic and aromatic polymers have been selected for investigation, the polyoxadiazoles and the polytriazoles, respectively. A major problem

  17. Solid-phase synthesis of complex and pharmacologically interesting heterocycles

    DEFF Research Database (Denmark)

    Nielsen, Thomas Eiland


    Efficient routes for the creation of heterocycles continue to be one of the primary goals for solid-phase synthesis. Recent advances in this field rely most notably on transition-metal-catalysis and N-acyliminium chemistry to mediate a range of cyclization processes for the generation of compound...

  18. Stereochemical trends of metal derivatives of some heterocyclic-2 ...

    Indian Academy of Sciences (India)


    and mercury(II) is briefly described. As regards thiosemicarbazones, focus is only on two compounds, namely organomercury(II) and organothallium(III). A variety of new molecules, well characterised by NMR and X-ray crystallography, is introduced. Keywords. Heterocyclic thiones; thiosemicarbazones; tertiary phosphines;.

  19. Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

    KAUST Repository

    Gómez-Herrera, Alberto


    The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

  20. Heterolytic Activation of Hydrogen Promoted by Ruthenium Nanoparticles immobilized on Basic Supports and Hydrogenation of Aromatic Compounds (United States)

    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

  1. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando


    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  2. A novel heterocyclic compound CE-104 enhances spatial working memory in the radial arm maze in rats and modulates the dopaminergic system

    Directory of Open Access Journals (Sweden)

    Yogesh D Aher


    Full Text Available Various psychostimulants targeting monoamine neurotransmitter transporters (MAT have been shown to rescue cognition in patients with neurological disorders and improve cognitive abilities in healthy subjects at low doses. Here, we examined the effects upon cognition of a chemically synthetized novel MAT inhibiting compound 2-(benzhydrylsulfinylmethyl-4-methylthiazole (named as CE-104. The efficacy of CE-104 in blocking MAT (DAT – dopamine transporter, SERT – serotonin transporter and NET – norepinephrine transporter was determined using in vitro neurotransmitter uptake assay. The effect of the drug at low doses (1 and 10mg/kg on spatial memory was studied in male rats in the radial arm maze (RAM. Furthermore, the dopamine receptor and transporter complex levels of frontal cortex (FC tissue of trained and untrained animals treated either with the drug or vehicle were quantified on blue native PAGE (BN-PAGE. The drug inhibited dopamine (IC50: 27.88µM and norepinephrine uptake (IC50: 160.40µM, but had a negligible effect on SERT. In the RAM, both drug-dose groups improved spatial working memory during the performance phase of RAM as compared to vehicle. BN-PAGE western blot quantification of dopamine receptor and transporter complexes revealed that D1, D2, D3 and DAT complexes were modulated due to training and by drug effects. The drug’s ability to block DAT and its influence on dopamine transporter and receptor complex levels in the FC is proposed as a possible mechanism for the observed learning and memory enhancement in the RAM.

  3. Optimization of H3O+/O2+ Dual-mode Ionization in PTR-MS for Simultaneous Detection of Alkanes, Olefins and Aromatic Compounds (United States)

    Amador-Muñoz, O.; Misztal, P. K.; Weber, R.; Drozd, G.; Worton, D. R.; Goldstein, A. H.


    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

  4. Aromatic compound in different peach cultivars and effect of preservatives on the final aroma of cooked fruits

    Directory of Open Access Journals (Sweden)

    Bavcon-Kralj Mojca


    Full Text Available In our study, we were used four yellow-fleshed peach cultivars ‟Royal Glory‟, „Redhaven", 'Maria Marta' and 'Norman', during two-year period. The characterization of aromatic constituents of investigated cultivars was done using headspace solid phase micro-extraction (HS-SPME. The intention was to make implicit discrimination between cultivars by analysis of components present in all cultivars during two-year period. Also, the impact of added preservatives (Na-benzoate and citric acid on the final aroma of cooked peaches was studied. The cultivars' differences and the impact of preservatives (Na-benzoate and citric acid were statistically evaluated. Multiple discriminant analysis of peaches‟ aromatic profile was used to segregate investigated peach cultivars. Although they were very similar, the cultivars were segregated by two discriminant function, function 1 (which accounted for 56.9% of this peach model and function 2 (31.7%. The use of preservatives had also an important impact on the aromatic profile of cooked peaches. The statistical analysis indicated that from 57 identified volatiles, 40 volatiles showed statistically significant difference regarding the way of preservation. The main negative impact had Na-benzoate compared to control or samples preserved with citric acid.

  5. Graphene stabilized ultra-small CuNi nanocomposite with high activity and recyclability toward catalysing the reduction of aromatic nitro-compounds. (United States)

    Fang, Hao; Wen, Ming; Chen, Hanxing; Wu, Qingsheng; Li, Weiying


    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.

  6. Dancing with Energetic Nitrogen Atoms: Versatile N-Functionalization Strategies for N-Heterocyclic Frameworks in High Energy Density Materials. (United States)

    Yin, Ping; Zhang, Qinghua; Shreeve, Jean'ne M


    Nitrogen-rich heterocycles represent a unique class of energetic frameworks featuring high heats of formation and high nitrogen content, which have generated considerable research interest in the field of high energy density materials (HEDMs). Although traditional C-functionalization methodology of aromatic hydrocarbons has been fully established, studies on N-functionalization strategies of nitrogen-containing heterocycles still have great potential to be exploited by virtue of forming diverse N-X bonds (X = C, N, O, B, halogen, etc.), which are capable of regulating energy performance and the stability of the resulting energetic compounds. In this sense, versatile N-functionalization of N-heterocyclic frameworks offers a flexible strategy to meet the requirements of developing new-generation HEDMs. In this Account, the role of strategic N-functionalization in designing new energetic frameworks, including the formation of N-C, N-N, N-O, N-B and N-halogen bonds, is emphasized. In the family of N-functionalized HEDMs, energetic derivatives, by virtue of forming N-C bonds, are the most widely used type due to the good nucleophilic capacity of most heterocyclic backbones. Although introduction of carbon tends to decrease energetic performance, significant improvement in material sensitivity makes this strategy attractive for safety concerns. More importantly, most "explosophores" can be readily introduced into the N-C linkage, thus providing a promising route to various HEDMs. Formation of additional N-N bonds typically gives rise to higher heats of formation, implying the potential enhancement in detonation performance. In many cases, the increased hydrogen bonding interactions within N-N functionalized heterocycles also improve thermal stability accordingly. Introduction of a single N,N'-azo bridge into several azole moieties leads to an extended nitrogen chain, demonstrating a new strategy for designing high-nitrogen compounds. The strategy of N-O functionalization

  7. The solid-state synthesis of tritium labelled heterocyclic bases

    Energy Technology Data Exchange (ETDEWEB)

    Sidorov, G.V.; Myasoedov, N.F. (AN SSSR, Moscow (Russian Federation). Inst. Molekulyarnoj Genetiki)


    The results of a study of the solid-state catalytic hydrogenation and the synthesis of tritium labelled native heterocyclic bases are presented. The effect of different palladium catalysts and reaction conditions on yield and molar radioactivity of final compounds was investigated. For some compounds, data on the intramolecular distribution of tritium were obtained by using the isotope exchange reaction and tritium NMR. Tritium labelled purine and pyrimidine bases (25-180 Ci/mmol.) were synthesized. (Author).

  8. Study of gas-phase reactions of NO2+ with aromatic compounds using proton transfer reaction time-of-flight mass spectrometry. (United States)

    Li, Jianquan; Du, Xubing; Guo, Teng; Peng, Zhen; Xu, Li; Dong, Junguo; Cheng, Ping; Zhou, Zhen


    The study of ion chemistry involving the NO2+ is currently the focus of considerable fundamental interest and is relevant in diverse fields ranging from mechanistic organic chemistry to atmospheric chemistry. A very intense source of NO2+ was generated by injecting the products from the dielectric barrier discharge of a nitrogen and oxygen mixture upstream into the drift tube of a proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) apparatus with H3 O+ as the reagent ion. The NO2+ intensity is controllable and related to the dielectric barrier discharge operation conditions and ratio of oxygen to nitrogen. The purity of NO2+ can reach more than 99% after optimization. Using NO2+ as the chemical reagent ion, the gas-phase reactions of NO2+ with 11 aromatic compounds were studied by PTR-TOF-MS. The reaction rate coefficients for these reactions were measured, and the product ions and their formation mechanisms were analyzed. All the samples reacted with NO2+ rapidly with reaction rate coefficients being close to the corresponding capture ones. In addition to electron transfer producing [M]+ , oxygen ion transfer forming [MO]+ , and 3-body association forming [M·NO2 ]+ , a new product ion [M-C]+ was also formed owing to the loss of C═O from [MO]+ .This work not only developed a new chemical reagent ion NO2+ based on PTR-MS but also provided significant interesting fundamental data on reactions involving aromatic compounds, which will probably broaden the applications of PTR-MS to measure these compounds in the atmosphere in real time. Copyright © 2017 John Wiley & Sons, Ltd.

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

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


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

  10. Photointeraction between substituted benzoquinones and heterocyclic compounds (United States)

    Porkhun, V. I.; Aristova, Yu. V.; Sharkevich, I. V.


    It is shown that mechanisms of photoreactions, investigated using the effects of chemically-induced dynamic nuclear polarization (CIDNP), can serve as models of primary electron transfer during photosynthesis from sensitizers (chlorophyll or porphyrin) to acceptors (membrane-associated quinone in media with different polarities).

  11. Modern advances in heterocyclic chemistry in drug discovery. (United States)

    Taylor, Alexandria P; Robinson, Ralph P; Fobian, Yvette M; Blakemore, David C; Jones, Lyn H; Fadeyi, Olugbeminiyi


    New advances in synthetic methodologies that allow rapid access to a wide variety of functionalized heterocyclic compounds are of critical importance to the medicinal chemist as it provides the ability to expand the available drug-like chemical space and drive more efficient delivery of drug discovery programs. Furthermore, the development of robust synthetic routes that can readily generate bulk quantities of a desired compound help to accelerate the drug development process. While established synthetic methodologies are commonly utilized during the course of a drug discovery program, the development of innovative heterocyclic syntheses that allow for different bond forming strategies are having a significant impact in the pharmaceutical industry. This review will focus on recent applications of new methodologies in C-H activation, photoredox chemistry, borrowing hydrogen catalysis, multicomponent reactions, regio- and stereoselective syntheses, as well as other new, innovative general syntheses for the formation and functionalization of heterocycles that have helped drive project delivery. Additionally, the importance and value of collaborations between industry and academia in shaping the development of innovative synthetic approaches to functionalized heterocycles that are of greatest interest to the pharmaceutical industry will be highlighted.

  12. Mesoionic Compounds

    Indian Academy of Sciences (India)

    Sydnone, the representative mesoionic compound has been extensively studied because of its unusual structure, chemi- cal properties and synthetic utility. Sydnone is used as a versatile synthon in heterocyclic synthesis. This article gives a brief account of the comparative studies of the structural features of mesoionic ...

  13. Strong room-temperature chemiresistive effect of TiO2 nanowires to nitro-aromatic compounds (United States)

    Wang, Danling; Chen, Antao; Zhang, Qifeng; Cao, Guozhong


    Nanostructured TiO2 thin films are found to be highly responsive to trace vapors of common nitro-explosives at room temperature. Thin films of TiO2 nanowires, made with high yield hydrothermal synthesis, present very reliable sensing characteristics to nitro-aromatic molecules with high sensitivity and fast response at ambient condition. The detection limit of 2, 4-dinitrotoluene (DNT) vapor at room temperature could reach up to 3ppb. The experimental results indicate titania nanowires as a novel chemical sensor to explosive gas have a great commercial potential due to its unique advantages: high sensitivity, rapid response and recovery, small size suitable for intergration with microelectronics and low fabrication cost. Experimental results and a theoretical model are presented.

  14. Polybenzoxazole via aromatic nucleophilic displacement (United States)

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


    Polybenzoxazoles (PBO) are heterocyclic macromolecules which were first synthesized in a two-step process by the initial formation of aromatic diacid chlorides with bis(o-aminophenol)s through solution condensation of aromatic diacid chlorides with bis(o-aminophenol)s followed by thermal cyclodehydration. Since then several methods were utilized in their synthesis. The most common synthetic method for PBO involves a polycondensation of bis(o-aminophenol)s with aromatic diacid diphenyl esters. Another preparative route involves the solution polycondensation of the hydrochloride salts of bis(o-amino phenol)s with aromatic diacids in polyphosphoric acid. Another synthetic method involves the initial formation of poly(o-hydroxy amide)s from silylated bis(o-aminophenol)s with aromatic diacid chlorides followed by thermal cyclodehydration to PBO. A recent preparative route involves the reaction of aromatic bisphenols with bis(fluorophenyl) benzoxazoles by the displacement reaction to form PBO. The novelty of the present invention is that high molecular weight PBO of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

  15. Soil microbial toxicity of eight polycyclic aromatic compounds: effects on nitrification, the genetic diversity of bacteria, and the total number of protozoans

    DEFF Research Database (Denmark)

    Sverdrup, Line Emilie; Ekelund, Flemming; Krogh, Paul Henning


    Eight polycyclic aromatic compounds (PACs) were tested for their toxic effect on the soil nitrification process, bacterial genetic diversity, and the total number of protozoans (naked amoebae and heterotrophic flagellates). After four weeks of exposure in a well-characterized agricultural soil......, toxic effects were evaluated by comparison to uncontaminated control soils. All PACs affected the nitrification process, and the calculated no-observed-effect concentrations (NOECs) for nitrification were 79 mg/kg for pyrene, 24 mg/kg for fluoranthene, 26 mg/kg for phenanthrene, 72 mg/kg for fluorene......, 23 mg/kg for carbazole, 22 mg/kg for dibenzothiophene, 75 mg/kg for dibenzofuran, and 1,100 mg/kg for acridine. For all substances but acridine, nitrification was the most sensitive of the three toxicity indicators evaluated. No effect of the tested substances on bacterial diversity was found...

  16. Analysis of Naturally Occurring Phenolic Compounds in Aromatic Plants by RP-HPLC Coupled to Diode Array Detector (DAD and GC-MS after Silylation

    Directory of Open Access Journals (Sweden)

    Charalampos Proestos


    Full Text Available The following aromatic plants of Greek origin, Origanum dictamnus (dictamus, Eucalyptus globulus (eucalyptus, Origanum vulgare L. (oregano, Mellisa officinalis L. (balm mint and Sideritis cretica (mountain tea, were examined for the content of phenolic substances. Reversed phase HPLC coupled to diode array detector (DAD was used for the analysis of the plant extracts. The gas chromatography-mass spectrometry method (GC-MS was also used for identification of phenolic compounds after silylation. The most abundant phenolic acids were: gallic acid (1.5–2.6 mg/100 g dry sample, ferulic acid (0.34–6.9 mg/100 g dry sample and caffeic acid (1.0–13.8 mg/100 g dry sample. (+-Catechin and (−-epicatechin were the main flavonoids identified in oregano and mountain tea. Quercetin was detected only in eucalyptus and mountain tea.

  17. Degradation of aromatic compounds through the β-ketoadipate pathway is required for pathogenicity of the tomato wilt pathogen Fusarium oxysporum f. sp. lycopersici. (United States)

    Michielse, Caroline B; Reijnen, Linda; Olivain, Chantal; Alabouvette, Claude; Rep, Martijn


    Plant roots react to pathogen attack by the activation of general and systemic resistance, including the lignification of cell walls and increased release of phenolic compounds in root exudate. Some fungi have the capacity to degrade lignin using ligninolytic extracellular peroxidases and laccases. Aromatic lignin breakdown products are further catabolized via the β-ketoadipate pathway. In this study, we investigated the role of 3-carboxy-cis,cis-muconate lactonizing enzyme (CMLE), an enzyme of the β-ketoadipate pathway, in the pathogenicity of Fusarium oxysporum f. sp. lycopersici towards its host, tomato. As expected, the cmle deletion mutant cannot catabolize phenolic compounds known to be degraded via the β-ketoadipate pathway. In addition, the mutant is impaired in root invasion and is nonpathogenic, even though it shows normal superficial root colonization. We hypothesize that the β-ketoadipate pathway in plant-pathogenic, soil-borne fungi is necessary to degrade phenolic compounds in root exudate and/or inside roots in order to establish disease. © 2012 THE AUTHORS. MOLECULAR PLANT PATHOLOGY © 2012 BSPP AND BLACKWELL PUBLISHING LTD.

  18. Cycloaddition of 1,3-Butadiynes: Efficient Synthesis of Carbo- and Heterocycles

    Directory of Open Access Journals (Sweden)

    Tauqir A. Nizami


    Full Text Available Cycloaddition reactions of alkynes are elegant, atom-efficient transformations for the synthesis of carbo- and heterocycles, mostly aromatic, involving the construction of challenging skeletons of complex molecules. Therefore significant efforts have recently been devoted to the development of novel methodologies, efficient strategies and different catalytic systems to broaden the scope of these reactions. We summarize in this review the recent advances in the cycloaddition reactions of 1,3-butadiynes to provide facile and reliable approaches to various functionalized carbo- and heterocycles.

  19. Synthesis of benzo-fused heterocycles by intramolecular α-arylation of ketone enolate anions. (United States)

    Guastavino, Javier F; Rossi, Roberto A


    A two-step synthesis of six-, seven-, eight-, and nine-member benzo-fused heterocycles in good to excellent yields is reported. The synthetic strategy involves the generation of a new intramolecular α-aryl ketone bond by the photostimulated S(RN)1 reaction of ketone enolate anions linked to a pendant haloarene as the key step. On the other hand, an intramolecular C(Ar)-C(Ar) coupling led to the formation of five- and six-member benzo-fused heterocycles (9H-carbazole and phenanthridine) when an aromatic amide anion is competitively formed.

  20. Luminescent properties and structure of new CAPh-based lanthanide complexes [LnL3Q], containing additional bis-heterocyclic aromatic ligand-antenna 2-(1,3,4-oxadiazole-2-yl) pyridine (United States)

    Yakovlev, Oleksii O.; Kariaka, Nataliia S.; Trush, Victor A.; Smola, Sergii S.; Siczek, Milosz; Amirkhanov, Vladimir M.


    The new lanthanide coordination compounds of general formula [LnL3Q], where Ln = Eu, Gd, Tb; L = dimethyl-N-trichloroacetylamidophosphate and Q = 2-(1,3,4-oxadiazole-2-yl)pyridine, have been synthesized and isolated in crystalline state with the purpose of finding new interesting optical materials. X-ray data reveal that complexes have molecular structure with numerous Van-der-Vaals contacts between molecules. All the ligands are coordinated in bidentate chelate manner, coordination polyhedron was interpreted as distored square antiprism (CN 8). The obtained complexes were investigated by means of IR, absorption and luminescence spectroscopy as well and thermal gravimetric analysis. It was found that complex [TbL3Q] is resistant to temperature of 200 °C. The Eu3+ and Tb3+ complexes exhibit bright metal-centered emission with decay time 1.65 and 1.74 ms respectively. Intrinsic quantum yield for [EuL3Q] equals 85% that is one of the highest values, known to date for CAPh based europium complexes.

  1. An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

    Directory of Open Access Journals (Sweden)

    Nikzad Nikbin


    Full Text Available This review presents a comprehensive overview on selected synthetic routes towards commercial drug compounds as published in both journal and patent literature. Owing to the vast number of potential structures, we have concentrated only on those drugs containing five-membered heterocycles and focused principally on the assembly of the heterocyclic core. In order to target the most representative chemical entities the examples discussed have been selected from the top 200 best selling drugs of recent years.

  2. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Scorzo, Cecilia M.; Fascio, Mirta L.; D' Accorso, Norma B. [Universidad de Buenos Aires, Buenos Aires (Argentina). Facultad de Ciencias Exactas y Naturales. Dept. de Quimica Organica; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo [Universidad de Talca (Chile). Inst. de Quimica de Productos Naturales. Lab. de Sintesis Organica


    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by {sup 1}H and {sup 13}C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  3. Effects of flue gas composition on the catalytic destruction of chlorinated aromatic compounds with a V-oxide catalyst. (United States)

    Stoll, M; Furrer, J; Seifert, H; Schaub, G; Unruh, D


    When using catalytic flue gas cleaning, several flue gas compounds may influence oxidation reactions of hazardous volatile organic compounds, possibly leading to lower reaction rates and, thus, to an incomplete destruction. Experimental investigations were performed with regard to the influence of selected flue gas compounds, like hydrogen chloride, sulfur dioxide, oxygen, and water vapour, on the catalytic destruction behavior of chlorobenzenes under flue gas cleaning conditions of an incineration plant. For this purpose, a metal oxide catalyst was operated at different temperatures at a space velocity of 3600 h-1 in a laboratory-scale fixed bed reactor with model flue gases, and with real flue gases generated from the TAMARA waste incineration plant. The results obtained from the studies with model flue gas were analyzed with respect to reaction kinetics. These kinetics were applied for comparison with the experimental data gained in the real flue gas.

  4. Syntheses, characterizations and photoluminescent properties of two novel coordination polymers constructed by poly-carboxylate and N-heterocyclic ligands (United States)

    Yan, Li; Li, Chuanbi; Wang, Yifei


    Two novel coordination compounds constructed from aromatic acid and N-heterocyclic ligands, namely, [Mn(dipt)2(n-BDC)]n (1) [dipt = 2-(2,4-dichlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, n-BDC = 5-nitrobenzene-1,3-dioic acid] and [Cu2(bip)2(m-BDC)2(H2O)3]ṡ2H2O (2) [bip = 2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC = isophthalic acid] have been synthesized by hydrothermal reaction: compounds 1 and 2 were characterized by elemental analysis, infrared spectrum (IR), single crystal X-ray diffraction and thermogravimetric analysis (TGA). In 1, n-BDC anions link the adjacent Mn(II) centers to generate a one-dimensional (1D) zigzag chain. Furthermore, unprecedented intersections of C-H⋯O bonds lead 1D chain into 2D sheet supra-molecular architecture. Differed from 1, 2 exhibits 0D structure, and displays a 2D topology via strong H-bond and π-π stacking interactions. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The structure-related solid-state fluorescence spectra of compounds 1 and 2 have been determined, and the result displays that compounds 1 and 2 are potential luminescent material.

  5. Characterization of aromatic organosulfur model compounds relevant to fossil fuels by using atmospheric pressure chemical ionization with CS2 and high-resolution tandem mass spectrometry. (United States)

    Tang, Weijuan; Sheng, Huaming; Jin, Chunfen; Riedeman, James S; Kenttämaa, Hilkka I


    The chemistry of desulfurization involved in processing crude oil is greatly dependent on the forms of sulfur in the oil. Sulfur exists in different chemical bonding environments in fossil fuels, including those in thiophenes and benzothiophenes, thiols, sulfides, and disulfides. In this study, the fragmentation behavior of the molecular ions of 17 aromatic organosulfur compounds with various functionalities was systematically investigated by using high-resolution tandem mass spectrometry. Multiple-stage tandem mass spectrometric experiments were carried out using a linear quadrupole ion trap (LQIT) equipped with an atmospheric pressure chemical ionization (APCI) source. (+)APCI/CS2 was used to generate stable dominant molecular ions for all the compounds studied except for three sulfides that also showed abundant fragment ions. The LQIT coupled with an orbitrap mass spectrometer was used for elemental composition analysis, which facilitated the identification of the neutral molecules lost during fragmentation. The characteristic fragment ions generated in MS(2) and MS(3) experiments provide clues for the chemical bonding environment of sulfur atoms in the examined compounds. Upon collision-induced dissociation (CID), the molecular ions can lose the sulfur atom in a variety of ways, including as S (32 Da), HS(•) (33 Da), H2 S (34 Da), CS (44 Da), (•) CHS (45 Da) and CH2 S (46 Da). These neutral fragments are not only indicative of the presence of sulfur, but also of the type of sulfur present in the compound. Generally, losses of HS(•) and H2 S were found to be associated with compounds containing saturated sulfur functionalities, while losses of S, CS and (•) CHS were more common for heteroaromatic sulfur compounds. High-resolution tandem mass spectrometry with APCI/CS2 ionization is a viable approach to determining the types of organosulfur compounds. It can potentially be applied to analysis of complex mixtures, which is beneficial to improving the

  6. Additive effects of CuSO4 and aromatic compounds on laccase production by Pleurotus sajor-caju PS-2001 using sucrose as a carbon source

    Directory of Open Access Journals (Sweden)

    F. Bettin


    Full Text Available Laccase enzymes are now commercially available, and a laccase/mediator combination is currently marketed for indigo dye bleaching in textile manufacturing; replacing traditional chemical-based processes with enzymatic technology reduces the need for effluent treatment. However, an inexpensive source of these enzymes will be needed to enable wider application of this technology. In the present work, the main objective was to increase laccase production by the mushroom Pleurotus sajor-caju strain PS-2001 grown on sucrose derived from sugar cane, one of most economical carbon sources known, by the addition of compounds that are known to affect laccase production. High laccase activities (45-62 U mL-1 were obtained with additions of syringaldazine, benzoic acid, gallic acid, and vanillin. When CuSO4 was used in conjunction with these aromatic compounds, the levels of laccase activity were further improved, reaching 58-80 U mL-1. These laccase activities indicate the potential of this strain as an enzyme producer, which has also been detected in media containing glucose, but with activity lower than that observed with sucrose.

  7. 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). (United States)

    Kannan, Kurunthachalam; Moon, Hyo-Bang; Yun, Se Hun; Agusa, Tetsuro; Thomas, Nancy J; Tanabe, Shinsuke


    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.

  8. Characterization of Rhizobium naphthalenivorans sp. nov. with special emphasis on aromatic compound degradation and multilocus sequence analysis of housekeeping genes. (United States)

    Kaiya, Shinichi; Rubaba, Owen; Yoshida, Naoko; Yamada, Takeshi; Hiraishi, Akira


    Three strains of aerobic chemoorganotrophic naphthalene-degrading bacteria (designated TSY03b(T), TSY04, and TSW01) isolated from sediment of a polychlorinated-dioxin-transforming microcosm were characterized. These strains had Gram-negative-stained, rod-shaped cells measuring 0.6‒0.9 μm in width and 1.2‒3.0 μm in length and were motile by means of peritrichous flagella. Naphthalene was utilized as the sole carbon and energy source, and the transcription of a putative aromatic-ring hydroxylating gene was inducible by naphthalene. The major component of cellular fatty acids was summed feature 8 (C18:1ω7c and/or C18:1ω6c), and significant proportions of C18:0 and C19:0 cyclo ω8cis were also found. The major respiratory quinone was ubiquinone-10. The G+C content of the DNA was 60.3‒60.9 mol%. Phylogenetic analyses by studying sequence information on the housekeeping atpD, dnaK, glnII, gyrB, and recA genes as well as on 16S rRNA genes and the 16S-23S rDNA internal transcribed spacer region revealed that the strains grouped with members of the genus Rhizobium, with Rhizobium selenitireducens as their closest relative but formed a distinct lineage at the species level. This was confirmed by genomic DNA-DNA hybridization studies. These phenotypic, genotypic, and phylogenetic data strongly suggest that our isolates should be classified under a novel species of the genus Rhizobium. Thus, we propose the name Rhizobium naphthalenivorans sp. nov. to accommodate the novel isolates. The type strain is TSY03b(T) (= NBRC 107585T = KCTC 23252T).

  9. Extraterrestrial Organic Compounds in Meteorites (United States)

    Botta, Oliver; Bada, Jeffrey L.; Meyer, Michael (Technical Monitor)


    Many organic compounds or their precursors found in meteorites originated in the interstellar or circumstellar medium and were later incorporated into planetesimals during the formation of the solar system. There they either survived intact or underwent further processing to synthesize secondary products on the meteorite parent body. The most distinct feature of CI and CM carbonaceous chondrites, two types of stony meteorites, is their high carbon content (up to 3% of weight), either in the form of carbonates or of organic compounds. The bulk of the organic carbon consists of an insoluble macromolecular material with a complex structure. Also present is a soluble organic fraction, which has been analyzed by several separation and analytical procedures. Low detection limits can be achieved by derivatization of the organic molecules with reagents that allow for analysis by gas chromatography/mass spectroscopy and high performance liquid chromatography. The CM meteorite Murchison has been found to contain more than 70 extraterrestrial amino acids and several other classes of compounds including carboxylic acids, hydroxy carboxylic acids, sulphonic and phosphonic acids, aliphatic, aromatic and polar hydrocarbons, fullerenes, heterocycles as well as carbonyl compounds, alcohols, amines and amides. The organic matter was found to be enriched in deuterium, and distinct organic compounds show isotopic enrichments of carbon and nitrogen relative to terrestrial matter.

  10. Elemental carbon and polycyclic aromatic compounds in a 150-year sediment core from Lake Qinghai, Tibetan Plateau, China: influence of regional and local sources and transport pathways. (United States)

    Han, Y M; Wei, C; Bandowe, B A M; Wilcke, W; Cao, J J; Xu, B Q; Gao, S P; Tie, X X; Li, G H; Jin, Z D; An, Z S


    Elemental carbon (EC) and polycyclic aromatic compounds (PACs) are potential proxies for the reconstruction of change in human activities and the origin of air masses in historic times. In this study, the historic deposition of char and soot (the two subtypes of EC) and PACs in a 150-year sediment core from different topographic subbasins of Lake Qinghai on the Qinghai Tibetan Plateau (QTP) were reconstructed. The objective was to explore how the variations in the concentrations of EC and PACs, in the ratios of char to soot and of oxygenated polycyclic aromatic hydrocarbons (OPAHs) to parent PAHs, and in the composition of the PAC mixtures reflect historical changes in climate and human activity and the origin of air masses arriving at the QTP. The deposition fluxes of soot in the different subbasins were similar, averaging 0.18 (range of 0.15-0.25) and 0.16 (0.13-0.23) g m(-2) year(-1), respectively, but they varied for char (averaging 0.11 and 0.22 g m(-2) year(-1), respectively), suggesting ubiquitous atmospheric deposition of soot and local river inputs of char. The different vertical distributions of the char/soot ratios in the different subbasins can be interpreted in terms of the different transport mechanisms of char and soot. An abrupt increase in soot concentrations since 1980 coincides with results from the QTP ice cores that were interpreted to be indicative of soot transport from South Asia. Similar concentration patterns of PAHs with soot and 9,10-anthraquinone/anthracene (9,10-AQ/ANT) ratios all >2.0 suggest regional PAC sources. Increasing PAH/soot ratios and decreasing 9,10-AQ/ANT ratios since the beginning of the 1970s indicate increasing local emissions. The historical trends of these diagnostic ratios indicate an increase in the fossil-fuel contribution since the beginning of the 1970s. The increase of perylene concentrations with increasing core depth and the ratio of perylene to its penta-aromatic isomers indicate that perylene originates

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

    DEFF Research Database (Denmark)

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


    Prediction of 1-octanol water partition coefficients for a range of polar N-PAC from HPLC capacity coefficients has been investigated. Two commercially available columns, an ODS column and a Diol column were tested with water-methanol eluents. The best prediction of log K-ow for N-PAC was achieved...... using a Diol column with an eluent of 35 % MeOH and 65 % water. The results indicate that the Diol column, in reversed phase mode, is able to form hydrogen bonds with a solute. Different LFERs between retention and log K-ow was found for polar and nonpolar compounds. In general log K-ow increased...

  12. Design, synthesis and cytotoxic activity of certain novel chalcone analogous compounds. (United States)

    El-Meligie, S; Taher, Azza T; Kamal, Aliaa M; Youssef, A


    A series of chalcone analogous compounds were designed and synthesized. Replacing/substituting the enone or ethylenic bridge of the parent chalcone with rigid heterocyclic moieties or substituted aromatic amines gave nineteen target compounds. Their cytotoxic activities were screened against both breast and liver cancer cells as well as breast and liver normal cells. Target compounds were also evaluated for their inhibition activity of tubulin beta polymerization. Target compound 2e, 3a, 3b, 3c, 4a-4d, 5a, 5b and 6 showed broad spectrum excellent anticancer activity against both MCF-7 and HepG2. Compound 4a showed the most TUBb inhibition activity. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  13. Changes in the Aromatic Profile, Sugars, and Bioactive Compounds When Purple Garlic Is Transformed into Black Garlic. (United States)

    Martínez-Casas, Lucía; Lage-Yusty, María; López-Hernández, Julia


    Black garlic is an elaborated product obtained from fresh garlic (Allium sativum L.) at a controlled high humidity and temperature, which leads to modifications in color, taste, and texture. To clarify the physicochemical changes that occur during the thermal process, this work aimed to evaluate and contrast the antioxidant capacity and that of other compounds between purple garlic ecotype "Purple from Las Pedroñeras" and its black garlic derivative. Our results showed numerous differences between both, because black garlic presented a significant divergence in its volatile profile, a decreased amount of ascorbic acid, an increment in sugar and polyphenol contents, a greater antioxidant capacity, and a different composition of phenolic acids and flavonoids.

  14. Synthesis and antimycobacterial activity of novel heterocycles

    Directory of Open Access Journals (Sweden)



    Full Text Available In the present investigation 4-hydroxy-3-methylacetophenone on condensation with various aromatic aldehydes in methanolic KOH solution yielded the corresponding chalcones (CI–CXI. These chalcones were further reacted with hydrazine hydrate in ethanol which led to the formation of pyrazoline derivatives (HI–HXI. The newly synthesized heterocyles were characterized on the basis of their chemical properties and spectroscopic data. All newly synthesized compounds were evaluated for their antimycobacterial activities against Mycobacterium tuberculosis H37Rv.

  15. Contributions of nitrated aromatic compounds to the light absorption of water-soluble and particulate brown carbon in different atmospheric environments (United States)

    Teich, Monique; van Pinxteren, Dominik; Wang, Michael; Kecorius, Simonas; Wang, Zhibin; Müller, Thomas; Močnik, Griša; Herrmann, Hartmut


    Recently the importance of light absorbing carbon, so-called brown carbon (BrC), on aerosol light absorption properties became more and more evident. The presence of BrC can enhance the light absorption of aerosols and therefore have an impact on the earth climate system. Despite the numerous studies published in the past few years little is known about the molecular composition and sources of BrC or the impact of single organic molecules on the BrC light absorption. The present study aims to deepen the understanding of atmospheric particulate and water soluble BrC by determining the ambient concentrations of eight individual nitrated aromatic compounds (nitrophenols and nitrated salicylic acids), and connecting the obtained chemical information with the light absorption properties of aqueous particle extracts (indicating water soluble BrC) and the overall particulate BrC light absorption. High-volume filter samples were collected during six campaigns, performed at five locations in two seasons: (I) two campaigns with strong influence of biomass burning (BB) aerosol - at the TROPOS institute (winter, 2014, urban background, Leipzig, Germany) and the Melpitz research site (winter, 2014, rural background); (II) two campaigns with strong influence from biogenic emissions - at Melpitz (summer, 2014) and the forest site Waldstein (summer, 2014, Fichtelgebirge, Germany), and (III) two CAREBeijing-NCP campaigns - at Xianghe (summer, 2013, anthropogenic polluted background) and Wangdu (summer, 2014, anthropogenic polluted background with a distinct BB-episode), both in the North China Plain. The light absorption properties of the aqueous particle extracts were determined by UV/Vis spectrometry for the same set of filter samples. Particulate BrC light absorption properties were derived from a seven-wavelength Aethalometer for a subset of these samples. A clear seasonality was observed in the data from the German sites where higher concentrations as well as higher light

  16. Seasonal variations and sources of atmospheric polycyclic aromatic hydrocarbons and organochlorine compounds in a high-altitude city: Evidence from four-year observations

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Ping; Wang, Xiaoping; Sheng, Jiujiang; Wang, Hailong; Yuan, Xiaohua; He, Yuanqing; Qian, Yun; Yao, Tandong


    Lijiang is a high-altitude city located on the eastern fringe of the Tibetan Plateau, with complex seasonal atmospheric circulations (i.e. westerly wind, Indian Monsoon, and East Asia Monsoon). Very few previous studies have focused on seasonal variations and sources of organic pollutants in Lijiang. In this study, a four-year air campaign from June 2009 to July 2013 was conducted to investigate the temporal trends and the sources of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds [including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs)]. The atmospheric PAH concentrations in winter are 2-3 times of those in summer, probably because of the combined result of enhanced local emission and long-range atmospheric transport (LRAT) during winter. Traffic pollution was the primary local source of PAHs, while biomass burning is the dominant LRAT source. Different from PAHs, OCPs and PCBs mainly underwent LRAT to reach Lijiang. The peak concentrations of most of OCPs occurred in pre-monsoon season and winter, which are carried by air masses from Myanmar and India through westerly winds. As compared with other sites of the Tibetan Plateau, without the direct barrier of the Himalaya, Lijiang is easily contaminated by the incursion of polluted air masses.

  17. Biomimetic synthesis of silver nanoparticles using the fish scales of Labeo rohita and their application as catalysts for the reduction of aromatic nitro compounds (United States)

    Sinha, Tanur; Ahmaruzzaman, M.; Sil, A. K.; Bhattacharjee, Archita


    In this article, a cleaner, greener, cheaper and environment friendly method for the generation of self assembled silver nanoparticles (Ag NPs) applying a simple irradiation technique using the aqueous extract of the fish scales (which is considered as a waste material) of Labeo rohita is described. Gelatin is considered as the major ingredient responsible for the reduction as well as stabilisation of the self assembled Ag NPs. The size and morphology of the individual Ag NPs can be tuned by controlling the various reaction parameters, such as temperature, concentration, and pH. Studies showed that on increasing concentration and pH Ag NPs size decreases, while on increasing temperature, Ag NPs size increases. The present process does not need any external reducing agent, like sodium borohydride or hydrazine or others and gelatin itself can play a dual role: a ‘reducing agent' and ‘stabilisation agent' for the formation of gelatin-Ag NPs colloidal dispersion. The synthesized Ag NPs were characterised by Ultraviolet-Visible spectroscopy (UV-Vis), Transmission electron microscopy (TEM) and Selected area electron diffraction (SAED) analyses. The synthesized Ag NPs was used to study the catalytic reduction of various aromatic nitro compounds in aqueous and three different micellar media. The hydrophobic and electrostatic interaction between the micelle and the substrate is responsible for the catalytic activity of the nanoparticles in micelle.

  18. Development of urine standard reference materials for metabolites of organic chemicals including polycyclic aromatic hydrocarbons, phthalates, phenols, parabens, and volatile organic compounds. (United States)

    Schantz, Michele M; Benner, Bruce A; Heckert, N Alan; Sander, Lane C; Sharpless, Katherine E; Vander Pol, Stacy S; Vasquez, Y; Villegas, M; Wise, Stephen A; Alwis, K Udeni; Blount, Benjamin C; Calafat, Antonia M; Li, Zheng; Silva, Manori J; Ye, Xiaoyun; Gaudreau, Éric; Patterson, Donald G; Sjödin, Andreas


    Two new Standard Reference Materials (SRMs), SRM 3672 Organic Contaminants in Smokers' Urine (Frozen) and SRM 3673 Organic Contaminants in Non-Smokers' Urine (Frozen), have been developed in support of studies for assessment of human exposure to select organic environmental contaminants. Collaborations among three organizations resulted in certified values for 11 hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and reference values for 11 phthalate metabolites, 8 environmental phenols and parabens, and 24 volatile organic compound (VOC) metabolites. Reference values are also available for creatinine and the free forms of caffeine, theobromine, ibuprofen, nicotine, cotinine, and 3-hydroxycotinine. These are the first urine Certified Reference Materials characterized for metabolites of organic environmental contaminants. Noteworthy, the mass fractions of the environmental organic contaminants in the two SRMs are within the ranges reported in population survey studies such as the National Health and Nutrition Examination Survey (NHANES) and the Canadian Health Measures Survey (CHMS). These SRMs will be useful as quality control samples for ensuring compatibility of results among population survey studies and will fill a void to assess the accuracy of analytical methods used in studies monitoring human exposure to these organic environmental contaminants.

  19. Organochlorine compounds (polychlorinated biphenyls and pesticides) and polycyclic aromatic hydrocarbons in populations of Hexaplex trunculus affected by imposex in the lagoon of Venice, Italy. (United States)

    Maran, Chiara; Centanni, Elena; Pellizzato, Francesca; Pavoni, Bruno


    Concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides, and polycyclic aromatic hydrocarbons (PAHs) were measured in gastropods from the Lagoon of Venice, Italy. The visceral coil and the rest of the soft body of organisms (Hexaplex trunculus) sampled at two stations inside the lagoon and three stations on the seaward side were analyzed to evaluate their contamination levels. Preferential accumulation of PCBs and pesticides in the visceral coil (>80%) compared with the rest of the soft body was observed, whereas on average, PAHs showed no preferential partitioning. Differences between levels of organochlorine contaminants in the gastropods highlighted a gradient of pollution from the stations inside the lagoon (PCBs, 45-363 ng/g; pesticides, 4-51 ng/g) to the sea (PCBs, 13-131 ng/g; pesticides, 2-29 ng/g). The possible role of the three classes of contaminants, in addition to that of organotin compounds (OTCs), previously analyzed in the same samples, in causing one of the anatomic modifications because of imposex in this gastropod also was studied. A modeling approach by partial least squares (PLS) in latent variables was applied to explain the penis length of imposex-affected females with concentrations of organic pollutants. The synergistic role of PCBs, pesticides, and OTCs was evidenced, whereas the contribution of PAHs appeared to be very low.

  20. Development of urine standard reference materials for metabolites of organic chemicals including polycyclic aromatic hydrocarbons, phthalates, phenols, parabens, and volatile organic compounds (United States)

    Schantz, Michele M.; Benner, Bruce A.; Heckert, N. Alan; Sander, Lane C.; Sharpless, Katherine E.; Vander Pol, Stacy S.; Vasquez, Y.; Villegas, M.; Wise, Stephen A.; Alwis, K. Udeni; Blount, Benjamin C.; Calafat, Antonia M.; Li, Zheng; Silva, Manori J.; Ye, Xiaoyun; Gaudreau, Éric; Patterson, Donald G.; Sjödin, Andreas


    Two new Standard Reference Materials (SRMs), SRM 3672 Organic Contaminants in Smokers’ Urine (Frozen) and SRM 3673 Organic Contaminants in Non-Smokers’ Urine (Frozen), have been developed in support of studies for assessment of human exposure to select organic environmental contaminants. Collaborations among three organizations resulted in certified values for 11 hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and reference values for 11 phthalate metabolites, 8 environmental phenols and parabens, and 24 volatile organic compound (VOC) metabolites. Reference values are also available for creatinine and the free forms of caffeine, theobromine, ibuprofen, nicotine, cotinine, and 3-hydroxycotinine. These are the first urine Certified Reference Materials characterized for metabolites of organic environmental contaminants. Noteworthy, the mass fractions of the environmental organic contaminants in the two SRMs are within the ranges reported in population survey studies such as the National Health and Nutrition Examination Survey (NHANES) and the Canadian Health Measures Survey (CHMS). These SRMs will be useful as quality control samples for ensuring compatibility of results among population survey studies and will fill a void to assess the accuracy of analytical methods used in studies monitoring human exposure to these organic environmental contaminants. PMID:25651899

  1. Highly Active and Specific Tyrosine Ammonia-Lyases from Diverse Origins Enable Enhanced Production of Aromatic Compounds in Bacteria and Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Jendresen, Christian Bille; Stahlhut, Steen Gustav; Li, Mingji


    Phenylalanine and tyrosine ammonia-lyases form cinnamic acid and p-coumaric acid, which are precursors of a wide range of aromatic compounds of biotechnological interest. Lack of highly active and specific tyrosine ammonia-lyases has previously been a limitation in metabolic engineering approache...... were also efficient in Saccharomyces cerevisiae, where p-coumaric acid accumulation was improved 5-fold over that in strains expressing previously characterized tyrosine ammonia-lyases....... Dictyostelium discoideum, and a phenylalanine ammonia-lyase from the moss Physcomitrella patens (producing 230 μM cinnamic acid per unit of optical density at 600 nm [OD600]) in the medium using Escherichia coli as the heterologous host). Novel tyrosine ammonia-lyases having higher reported substrate...... specificity than previously characterized enzymes were also identified. Enzymes from Herpetosiphon aurantiacus and Flavobacterium johnsoniae resulted in high production of p-coumaric acid in Escherichia coli (producing 440 μM p-coumaric acid OD600 unit−1 in the medium) and in Lactococcus lactis. The enzymes...

  2. Kinetics and thermodynamics of adsorption of ionizable aromatic compounds from aqueous solutions by as-prepared and oxidized multiwalled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Sheng, G.D.; Shao, D.D.; Ren, X.M. [Key Laboratory of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, 230031 Hefei (China); Wang, X.Q. [Key Laboratory of Ion Beam Bioengineering, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, 230031 Hefei (China); Li, J.X. [Key Laboratory of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, 230031 Hefei (China); School of Nuclear Science and Engineering, North China Electric Power University, Beijing 102206 (China); Chen, Y.X. [School of Nuclear Science and Engineering, North China Electric Power University, Beijing 102206 (China); Wang, X.K., E-mail: [Key Laboratory of Novel Thin Film Solar Cells, Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, 230031 Hefei (China)


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

  3. Remarkable effect of halogenation of aromatic compounds on efficiency of nanowire formation through polymerization/crosslinking by high-energy single particle irradiation (United States)

    Horio, Akifumi; Sakurai, Tsuneaki; Kayama, Kazuto; Lakshmi, G. B. V. S.; Kumar Avasthi, Devesh; Sugimoto, Masaki; Yamaki, Tetsuya; Chiba, Atsuya; Saito, Yuichi; Seki, Shu


    Irradiation of high-energy ion particles on organic films induced solid-state polymerization and crosslinking reactions of the materials along the ion trajectories, resulting in the formation of insoluble uniform nanowires with a precise diameter. The nanowires were isolated by the development process i.e. the irradiated film was immersed in organic solvents, and their morphology was visualized by atomic force microscopy. The target organic materials are 4-vinyltriphenylamine, poly(4-vinyltriphenylamine), and polystyrene derivatives with/without the partial substitutions by halogen atoms. It was found that 4-vinyltriphenylamines, in spite of their small molecular sizes, afforded nanowires more clearly than poly(4-vinyltriphenylamine)s. Moreover, the efficiency of demonstrated polymerization/crosslinking reactions obviously depends on the substituted halogen atom species. The averaged diameters of nanowires from bromo- or iodo- substituted 4-vinyltriphenylamine (9.3 and 9.4 nm, respectively) were larger than that obtained from simple 4-vinyltriphenylamine (6.8 nm). The remarkable effect of halogenation of aromatic compounds on the efficiency of the radiation-induced reactions was also observed for polystyrene derivatives. This contrast was considered to originate from the sum of the efficiency of elementary reactions including dissociative electron attachment.

  4. On Benzene and Aromaticity

    Indian Academy of Sciences (India)

    a flavour of all of these in the classroom and not just presented with dry facts. The development of the field over the last two centuries should be placed often in a ... The creativity of scientists has an appeal that transcends the subject. Chemistry of aromatic compounds provides ample opportunities for the teacher to cover ...

  5. Graphenes – Aromatic Giants

    Indian Academy of Sciences (India)

    Graphenes – Aromatic Giants. (benzene) rings. Until recently it was believed [5] that their chemical investigations are limited to compounds with not more than 15 rings. The reason for this is based on the fact that large. PAHs are practically insoluble in water or organic solvents, which makes their purification and chemical ...

  6. Graphenes – Aromatic Giants

    Indian Academy of Sciences (India)


    Polycyclic aromatic hydrocarbons (often abbreviated as PAH) are an important class of organic compounds. Students learn about them in any course on organic chemistry. The best known representatives are benzene (which, in fact, is cyclic, not polycy- clic), naphthalene, anthracene, phenanthrene and pyrene. Today.

  7. Cytotoxicity study of dimethylisatin and its heterocyclic derivatives

    Directory of Open Access Journals (Sweden)

    Mohammad Mamun Hossain


    Full Text Available Isatin derivatives are bioactive molecules. To study the cytotoxicity and eventually the anticancer activities against cancer cell lines, a series of dimethyl-substitituted isatin derivatives (4-8 starting from isatin thiosemicarbazones (3 had been synthesized in high yields. Investigation of the cytotoxicity of these compounds was carried out against brine shrimp by lethality bioassay. The present study shows that compounds 4, 5, 6 and 8/ with heterocyclic moiety had pronounced cytotoxicity whereas 7, 7/ and 8 were moderately active. It is remarkable that the substituent, X = -OCH3 has greater activity than the bromine atom in this series.

  8. Compound

    Indian Academy of Sciences (India)

    UV-vis spectra showing solvent effects on compounds (6). Figure S4. UV-vis spectra showing solvent effects on compounds (9). Figure S5. UV-vis spectra showing solvent ___, acidic--- and basic -□- effects on compound (8) in CH2Cl2 solution. Table S1. 1H and 13C NMR spectral data of salicylaldimine Schiff bases (5-8).

  9. Prediction of sorption of aromatic and aliphatic organic compounds by carbon nanotubes using poly-parameter linear free-energy relationships. (United States)

    Hüffer, Thorsten; Endo, Satoshi; Metzelder, Florian; Schroth, Sarah; Schmidt, Torsten C


    The accurate prediction of distribution coefficients of organic compounds from water to carbon-based nanomaterials (CNM) is of major importance for the understanding of environmental processes and a risk assessment of released CNM. Poly-parameter linear free-energy relationships (ppLFER) have previously been shown to offer such an accurate prediction of sorption processes. The aim of this study was to identify and quantify the contribution of individual molecular interactions to overall sorption by multi-walled carbon nanotubes (MWCNTs). To this end, a large data set of experimental sorption isotherms by MWCNTs of 20 aliphatic and 14 aromatic compounds covering various relevant molecular interactions was produced. A thermodynamic cycle was used to obtain MWCNT-air distribution coefficients (KMWCNT/a) for the interpretation of direct sorbate-MWCNTs interactions. The thereby derived ppLFER log KMWCNT/a = (0.59 ± 0.59)E + (2.23 ± 0.59)S + (3.90 ± 0.67)A + (3.23 ± 0.71)B + (0.98 ± 0.17)L - (0.05 ± 0.50) shows the contribution of non-specific interactions, represented by the hexadecane-air partitioning constant (L), and specific interactions related to the solute polarity (S) as well as the H-bond interactions (A, B). Measured MWCNT-water distribution coefficients were clearly more accurately calculated by the ppLFER equations (R(2) 0.85-0.86) compared to the classical prediction by single parameter model based on the octanol-water partitioning constant (R(2) 0.64-0.78). In addition, the ppLFER presented here allow a more accurately prediction of sorption by MWCNTs compared to literature ppLFER, especially for aliphatic compounds and at environmentally relevant concentrations. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Synthesis and optimization of N-heterocyclic pyridinones as catechol-O-methyltransferase (COMT) inhibitors. (United States)

    Zhao, Zhijian; Harrison, Scott T; Schubert, Jeffrey W; Sanders, John M; Polsky-Fisher, Stacey; Zhang, Nanyan Rena; McLoughlin, Debra; Gibson, Christopher R; Robinson, Ronald G; Sachs, Nancy A; Kandebo, Monika; Yao, Lihang; Smith, Sean M; Hutson, Pete H; Wolkenberg, Scott E; Barrow, James C


    A series of N-heterocyclic pyridinone catechol-O-methyltransferase (COMT) inhibitors were synthesized. Physicochemical properties, including ligand lipophilic efficiency (LLE) and clogP, were used to guide compound design and attempt to improve inhibitor pharmacokinetics. Incorporation of heterocyclic central rings provided improvements in physicochemical parameters but did not significantly reduce in vitro or in vivo clearance. Nevertheless, compound 11 was identified as a potent inhibitor with sufficient in vivo exposure to significantly affect the dopamine metabolites homovanillic acid (HVA) and dihydroxyphenylacetic acid (DOPAC), and indicate central COMT inhibition. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Synthesis and antimicrobial activity of some novel fused heterocyclic 1,2,4-triazolo [3,4-b][1,3,4] thiadiazine derivatives

    Directory of Open Access Journals (Sweden)

    Jagdish K. Sahu


    Full Text Available In the present investigation, the synthesis and antimicrobial evaluation of 1,2,4-triazolo [3,4-b][1,3,4] thiadiazine including different pharmacophores are aimed at. In this study, a series of 6-aryl-3- (3,4 -dialkoxyphenyl-7H -[1,2,4]triazolo [3,4-b][1,3,4] thiadiazine (7a-7k was synthesized by condensing 4-amino-5-(3,4-dialkoxyphenyl-4H-[1,2,4]- triazole-3-thiol (6 with various aromatic carboxylic acids in the presence of phenacyl bromides through one-pot reaction. Eleven fused heterocyclic derivatives were successfully synthesized. The structures of these newly synthesized compounds were characterized by IR, 1 H NMR and mass spectroscopic studies. All the synthesized compounds were screened for their antimicrobial evaluation. Some of the compounds exhibited promising antimicrobial activity. From the present study it may be concluded that synthesized compounds are fruitful in terms of their structural novelty and marked biological activities. These compounds could be further modified to develop potential and safer antifungal agents.

  12. Role of human sulfotransferase 1A1 and N-acetyltransferase 2 in the metabolic activation of 16 heterocyclic amines and related heterocyclics to genotoxicants in recombinant V79 cells. (United States)

    Chevereau, Matthieu; Glatt, Hansruedi; Zalko, Daniel; Cravedi, Jean-Pierre; Audebert, Marc


    Heterocyclic aromatic amines (HAAs) are primarily produced during the heating of meat or fish. HAAs are mutagenic and carcinogenic, and their toxicity in model systems depend on metabolic activation. This activation is mediated by cytochrome P450 (CYP) enzymes, in particular CYP1A2. Some studies have indicated a role of human sulfotransferase (SULT) 1A1 and N-acetyltransferase (NAT) 2 in the terminal activation of HAAs. In this study, we conducted a metabolism/genotoxicity relationship analysis for 16 HAAs and related heterocyclics. We used the γH2AX genotoxicity assay in V79 cells (deficient in CYP, SULT and NAT) and V79-derived cell lines genetically engineered to express human CYP1A2 alone or in combination with human SULT1A1 or NAT2. Our data demonstrated genotoxic properties for 13 out of the 16 compounds tested. A clear relationship between metabolic bioactivation and genotoxicity allowed to distinguish four groups: (1) Trp-P-1 genotoxicity was linked to CYP1A2 bioactivation only-with negligible effects of phase II enzymes; (2) Glu-P-2, Glu-P-1, Trp-P-2, APNH, MeAαC and AαC were bioactivated by CYP1A2 in combination with either phase II enzyme tested (NAT2 or SULT1A1); (3) IQ, 4-MeIQ, IQx, 8-MeIQx, and 4,8-DiMeIQx required CYP1A2 in combination with NAT2 to be genotoxic, whereas SULT1A1 did not enhance their genotoxicity; (4) PhIP became genotoxic after CYP1A2 and SULT1A1 bioactivation-NAT2 had not effect. Our results corroborate some previous data regarding the genotoxic potency of seven HAAs and established the genotoxicity mechanism for five others HAAs. This study also permits to compare efficiently the genotoxic potential of these 13 HAAs.

  13. The doping effect of fluorinated aromatic solvents on the rate of ruthenium-catalysed olefin metathesis. (United States)

    Samojłowicz, Cezary; Bieniek, Michał; Pazio, Aleksandra; Makal, Anna; Woźniak, Krzysztof; Poater, Albert; Cavallo, Luigi; Wójcik, Jacek; Zdanowski, Konrad; Grela, Karol


    A study concerning the effect of using a fluorinated aromatic solvent as the medium for olefin metathesis reactions catalysed by ruthenium complexes bearing N-heterocyclic carbene ligands is presented. The use of fluorinated aromatic hydrocarbons (FAH) as solvents for olefin metathesis reactions catalysed by standard commercially available ruthenium pre-catalysts allows substantially higher yields of the desired products to be obtained, especially in the case of demanding polyfunctional molecules, including natural and biologically active compounds. Interactions between the FAH and the second-generation ruthenium catalysts, which apparently improve the efficiency of the olefin metathesis transformation, have been studied by X-ray structure analysis and computations, as well as by carrying out a number of metathesis experiments. The optimisation of reaction conditions by using an FAH can be regarded as a complementary approach for the design of new improved ruthenium catalysts. Fluorinated aromatic solvents are an attractive alternative medium for promoting challenging olefin metathesis reactions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Genotoxicity of heterocyclic PAHs in the micronucleus assay with the fish liver cell line RTL-W1.

    Directory of Open Access Journals (Sweden)

    Markus Brinkmann

    Full Text Available Heterocyclic aromatic hydrocarbons are, together with their un-substituted analogues, widely distributed throughout all environmental compartments. While fate and effects of homocyclic PAHs are well-understood, there are still data gaps concerning the ecotoxicology of heterocyclic PAHs: Only few publications are available investigating these substances using in vitro bioassays. Here, we present a study focusing on the identification and quantification of clastogenic and aneugenic effects in the micronucleus assay with the fish liver cell line RTL-W1 that was originally derived from rainbow trout (Oncorhynchus mykiss. Real concentrations of the test items after incubation without cells were determined to assess chemical losses due to, e.g., sorption or volatilization, by means of gas chromatography-mass spectrometry. We were able to show genotoxic effects for six compounds that have not been reported in vertebrate systems before. Out of the tested substances, 2,3-dimethylbenzofuran, benzothiophene, quinoline and 6-methylquinoline did not cause substantial induction of micronuclei in the cell line. Acridine caused the highest absolute induction. Carbazole, acridine and dibenzothiophene were the most potent substances compared with 4-nitroquinoline oxide, a well characterized genotoxicant with high potency used as standard. Dibenzofuran was positive in our investigation and tested negative before in a mammalian system. Chemical losses during incubation ranged from 29.3% (acridine to 91.7% (benzofuran and may be a confounding factor in studies without chemical analyses, leading to an underestimation of the real potency. The relative potency of the investigated substances was high compared with their un-substituted PAH analogues, only the latter being typically monitored as priority or indicator pollutants. Hetero-PAHs are widely distributed in the environment and even more mobile, e.g. in ground water, than homocyclic PAHs due to the higher water

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

    Indian Academy of Sciences (India)


    Keywords. Bronze; inhibitors; quinoxalin compounds; chloride solution; electrochemical studies. 1. Introduction. Heterocyclic organic compounds containing nitrogen, sulphur or oxygen atoms are often used to protect copper and copper alloy metals from corrosion. Among them, azoles compounds like triazoles, imidazoles ...

  16. In-situ bitumen extraction associated with increased petrogenic polycyclic aromatic compounds in lake sediments from the Cold Lake heavy oil fields (Alberta, Canada). (United States)

    Korosi, Jennifer B; Cooke, Colin A; Eickmeyer, David C; Kimpe, Linda E; Blais, Jules M


    Most future growth in the Alberta bituminous sands will be based on thermal in-situ recovery technologies. To date, however, most attention on the environmental effects of bitumen recovery has focused on surface mining in the Athabasca region. Recent uncontrolled bitumen flow-to-surface incidents (FTS; appearance at the surface of bitumen emulsions from deep subsurface recovery zones) reported at the Cold Lake heavy oil fields highlight the need to better understand the potential role of in-situ extraction as a source of contaminants to landscapes and surface waters. We analyzed sediment cores from a lake located ∼2 km away from a recent bitumen FTS incident to provide a long-term perspective on the delivery of metals, polycyclic aromatic compounds (PACs), and polychlorinated biphenyls (PCBs) to surface freshwaters, and to assess whether the onset of local in-situ bitumen extraction can be linked to contaminant increases in nearby lakes. An increase in alkyl PACs coincided with the onset and expansion of commercial in-situ bitumen extraction, and multiple lines of evidence indicate a petrogenic source for recent alkyl PAC enrichment. However, no coincident increase in vanadium (enriched in bitumen) occurred that would suggest the source of petrogenic PAC enrichment is direct input of bituminous particles. Our results show that, similar to surface mining in the Athabasca region, activities associated with in-situ extraction can increase the burden of petrogenic PACs in nearby lakes, but many questions still remain regarding the exact sources and pathways of PACs into the environment. Given that more than 80% of Alberta's bitumen reserves can only be accessed using in-situ technologies, we recommend that this be made a research priority. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Computational study of the effect of dispersion interactions on the thermochemistry of aggregation of fused polycyclic aromatic hydrocarbons as model asphaltene compounds in solution. (United States)

    Moreira da Costa, Leonardo; Stoyanov, Stanislav R; Gusarov, Sergey; Seidl, Peter R; Walkimar de M Carneiro, José; Kovalenko, Andriy


    Density functional theory (DFT), Møller-Plesset second-order perturbation theory (MP2), and semiempirical methods are employed for the geometry optimization and thermochemistry analysis of π-π stacked di-, tri-, tetra-, and pentamer aggregates of the fused polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, phenanthrene, tetracene, pyrene, and coronene as well as benzene. These aggregates (stabilized by dispersion interactions) are highly relevant to the intermolecular aggregation of asphaltenes, major components of heavy petroleum. The strength of π-π stacking interaction is evaluated with respect to the π-stacking distance and thermochemistry results, such as aggregation enthalpies, entropies, and Gibbs free energies (ΔG(298)). For both π-stacking interplanar distances and thermochemistry, the ωB97X-D functional with an augmented damped R(-6) dispersion correction term and MP2 are in the closest agreement with the highly accurate spin-component scaled MP2 (SCS-MP2) method that we selected as a reference. The ΔG(298) values indicate that the aggregation of coronene is spontaneous at 298 K and the formation of pyrene dimers occurs spontaneously at temperature lower than 250 K. Aggregates of smaller PAHs would be stable at even lower temperature. These findings are supported by X-ray crystallographic determination results showing that among the PAHs studied only coronene forms continuous stacked aggregates in single crystals, pyrene forms dimers, and smaller PAHs do not form π-π stacked aggregates. Thermochemistry analysis results show that PAHs containing more than four fused benzene rings would spontaneously form aggregates at 298 K. Also, round-shaped PAHs, such as phenanthrene and pyrene, form more stable aggregates than linear PAHs, such as anthracene and tetracene, due to decreased entropic penalty. These results are intended to help guide the synthesis of model asphaltene compounds for spectroscopic studies so as to help understand

  18. Synthesis and Antimicrobial Studies of New Series of Pyrazoline Bearing Bis-Heterocycles via 1,3-Dipolar Cycloaddition Reactions

    Directory of Open Access Journals (Sweden)

    B. Jayashankara


    Full Text Available Biologically interesting bis-heterocycles bearing pyrazoline and imidazole moieties have been synthesized. 1H NMR, 13C NMR, IR and elemental analyses characterized the newly synthesized compounds. All the synthesized compounds were evaluated for their antimicrobial activity and were compared with the standard drugs. All the compounds demonstrated potent to weak antimicrobial activity.

  19. Heterocyclic N-Oxides – An Emerging Class of Therapeutic Agents (United States)

    Mfuh, Adelphe M.; Larionov, Oleg V.


    Heterocyclic N-oxides have emerged as potent compounds with anticancer, antibacterial, antihypertensive, antiparasitic, anti-HIV, anti-inflammatory, herbicidal, neuroprotective, and procognitive activities. The N-oxide motif has been successfully employed in a number of recent drug development projects. This review surveys the emergence of this scaffold in the mainstream medicinal chemistry with a focus on the discovery of the heterocyclic N-oxide drugs, N-oxide-specific mechanisms of action, drug-receptor interactions and synthetic avenues to these compounds. As the first review on this subject that covers the developments since 1950s to date, it is expected that it will inspire wider implementation of the heterocyclic N-oxide motif in the rational design of new medicinal agents. PMID:26087764

  20. Synthesis and Selective Cytotoxic Activities on Rhabdomyosarcoma and Noncancerous Cells of Some Heterocyclic Chalcones

    Directory of Open Access Journals (Sweden)

    Tuong-Ha Do


    Full Text Available Chemically diverse heterocyclic chalcones were prepared and evaluated for cytotoxicity, aiming to push forward potency and selectivity. They were tested against rhabdomyosarcoma (RMS and noncancerous cell line (LLC-PK1. The influence of heteroaryl patterns on rings A and B was studied. Heterocycle functionalities on both rings, such as phenothiazine, thiophene, furan and pyridine were evaluated. Notably, the introduction of three methoxy groups at positions 3, 4, 5 on ring B appears to be critical for cytotoxicity. The best compound, with potent and selective cytotoxicity (IC50 = 12.51 μM in comparison with the value 10.84 μM of paclitaxel, contains a phenothiazine moiety on ring A and a thiophene heterocycle on ring B. Most of the potential compounds only show weak cytoxicity on the noncancerous cell line LLC-PK1.

  1. One-year study of polycyclic aromatic compounds at an urban site in Grenoble (France): Seasonal variations, gas/particle partitioning and cancer risk estimation

    Energy Technology Data Exchange (ETDEWEB)

    Tomaz, Sophie [Institut National de l' Environnement industriel et des RISques (INERIS), Parc Technologique Alata BP2, 60550 Verneuil en Halatte (France); CNRS, EPOC, UMR 5805, F-33405 Talence Cedex (France); Université de Bordeaux, EPOC, UMR 5805, F-33405, Talence Cedex (France); Shahpoury, Pourya [Max Planck Institute for Chemistry, Multiphase Chemistry Department, Mainz (Germany); Jaffrezo, Jean-Luc [Laboratoire de Glaciologie et Géophysiques de l' Environnement (LGGE), Université de Grenoble-Alpes/CNRS, Grenoble (France); Lammel, Gerhard [Max Planck Institute for Chemistry, Multiphase Chemistry Department, Mainz (Germany); Masaryk University, Research Centre for Toxic Compounds in the Environment, Brno (Czech Republic); Perraudin, Emilie; Villenave, Eric [CNRS, EPOC, UMR 5805, F-33405 Talence Cedex (France); Université de Bordeaux, EPOC, UMR 5805, F-33405, Talence Cedex (France); Albinet, Alexandre, E-mail: [Institut National de l' Environnement industriel et des RISques (INERIS), Parc Technologique Alata BP2, 60550 Verneuil en Halatte (France)


    21 PAHs, 27 oxy-PAHs and 32 nitro-PAHs were measured every third day over a year in both gaseous (G) and particulate PM{sub 10} (P) phases in ambient air of Grenoble (France). Mean total concentrations (G + P) of PAHs and oxy-PAHs were in the same range and about 10 ng m{sup −3}. Nitro-PAHs were 50 to 100 times less concentrated averaging 100 pg m{sup −3}. Polycyclic aromatic compound (PAC) concentrations were 5 to 7 times higher in “cold” period (October to March) than in “warm” period (April to September). Seasonal variations may be explained by higher primary emissions from residential heating, especially biomass burning in “cold” season. Meteorological conditions and influence of the geomorphology around Grenoble, with the formation of thermal inversion layers leading to the stagnation of pollutants, were additional key parameters. Maximum individual PAC concentrations were observed during two PM{sub 10} pollution events in December and February–March. Chemical processes and secondary formation of oxy- and nitro-PAH were probably enhanced by the accumulation of the pollutants during these events. PAC gas/particle partitioning depended on compound molecular weight and vapour pressure. Gas/particle partitioning of oxy- and nitro-PAHs were evaluated using a multi-phase poly-parameter linear free energy relationship model. The PAC cancer risk was assessed using toxic equivalency factors available in the literature (19 PAHs, 10 nitro-PAHs and 1 oxy-PAH). Overall, particle-bound PACs contributed about 76% of the cancer risk. While PAHs accounted for most of the total PAC cancer risk, oxy- and nitro-PAHs could account for up to 24%. The risk quantification across substance classes is limited by toxicological data availability. - Highlights: • The most comprehensive study about PAH, nitro- and oxy-PAH in ambient air. • 80 species studied in gaseous and particle phases over a year at French urban site. • Concentration seasonality governed by

  2. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura


    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  3. An Evaluation of Uncertainty Associated to Analytical Measurements of Selected Polycyclic Aromatic Compounds in Ambient Air; Estudio sobre las Incertidumbres Asociadas al Metodo de Determinacion de PAC's Seleccionados en Muestras de Aire Ambiente

    Energy Technology Data Exchange (ETDEWEB)

    Barrado, A. I.; Garcia, S.; Perez, R. M.


    This paper presents an evaluation of uncertainty associated to analytical measurement of eighteen polycyclic aromatic compounds (PACs) in ambient air by liquid chromatography with fluorescence detection (HPLC/FD). The study was focused on analyses of PM{sub 1}0, PM{sub 2}.5 and gas phase fractions. Main analytical uncertainty was estimated for eleven polycyclic aromatic hydrocarbons (PAHs), four nitro polycyclic aromatic hydrocarbons (nitro-PAHs) and two hydroxy polycyclic aromatic hydrocarbons (OH-PAHs) based on the analytical determination, reference material analysis and extraction step. Main contributions reached 15-30% and came from extraction process of real ambient samples, being those for nitro- PAHs the highest (20-30%). Range and mean concentration of PAC mass concentrations measured in gas phase and PM{sub 1}0/PM{sub 2}.5 particle fractions during a full year are also presented. Concentrations of OH-PAHs were about 2-4 orders of magnitude lower than their parent PAHs and comparable to those sparsely reported in literature. (Author) 7 refs.

  4. Synthesis, characterization and dyeing behavior of heterocyclic acid dyes and mordent acid dyes on wool and silk fabrics

    Directory of Open Access Journals (Sweden)

    Patel Hitendra M.


    Full Text Available Novel heterocyclic acid and mordent acid dyes were synthesized by the coupling of diazonium salt solution of different aromatic amines with 2- butyl-3-(4-hydroxybenzoylbenzofuran. The resulting heterocyclic acid dyes were characterized by spectral techniques, i.e., elemental analysis, IR, 1HNMR, 13C-NMR spectral studies and UV- visible spectroscopy. The dyeing performance of all the heterocyclic acid dyes was evaluated on wool and silk fabrics. The dyeing of chrome pre treated wool and silk fabrics showed better hues on mordented fabrics. Dyeing of wool and silk fabrics resulted in pinkish blue to red shades with very good depth and levelness. The dyed fabrics showed excellent to very good light, washing, perspiration, sublimation and rubbing fastness.

  5. Anticancer Gold N-Heterocyclic Carbene Complexes : A Comparative in vitro and ex vivo Study

    NARCIS (Netherlands)

    Estrada-Ortiz, Natalia; Guarra, Federica; de Graaf, Inge A. M.; Marchetti, Lorella; de Jager, Marina H.; Groothuis, Geny M. M.; Gabbiani, Chiara; Casini, Angela


    A series of organometallic AuI N-heterocyclic carbene (NHC) complexes was synthesized and characterized for anticancer activity in four human cancer cell lines. The compounds' toxicity in healthy tissue was determined using precision-cut kidney slices (PCKS) as a tool to determine the potential

  6. Molecular diversity through novel organosulfur synthons: versatile templates for heterocycle synthesis. (United States)

    Ila, Hiriyakkanavar; Junjappa, Hiriyakkanavar


    This review highlights some of our recent work on design and development of new synthetic methods for diverse classes of heterocycles employing novel organosulfur synthons i.e. polarized ketene dithioacetals, N, S-acetals, β-oxodithioesters and 2,3-(hetero)aryl-3-(methylthio)acrylonitriles, easily accessible from a wide range of active methylene compounds.

  7. Synthesis, characterization and biological evaluation of some novel nitrogen and sulphur containing organometallic heterocycles


    Parveen, Humaira; Alatawi, Raedah Aiyed Suliman; El Sayed, Nadia Hussein; Hasan, Sadaf; Mukhtar, Sayeed; Khan, Asad U.


    A series of some novel sulphur and nitrogen containing ferrocenyl linked heterocyclic compounds were synthesized by multistep reactions and evaluated for in vitro antimicrobial activity against 15 ATCC strains out of which 8 were bacterial (Pseudomonas aeruginosa, Streptococcus bovis, Enterococcus faecalis, Klebsiella pneumoniae, Escherichia coli, Enterobacter cloacae, Methicillin-resistant Staphylococcus aureus and Streptococcus mutans) and 7 were fungal (Candida albicans, Candida dubliniens...

  8. Exposure to polycyclic aromatic hydrocarbons and volatile organic compounds among recently pregnant rural Guatemalan women cooking and heating with solid fuels. (United States)

    Weinstein, John R; Asteria-Peñaloza, Renée; Diaz-Artiga, Anaité; Davila, Gilberto; Hammond, S Katharine; Ryde, Ian T; Meyer, Joel N; Benowitz, Neal; Thompson, Lisa M


    Household air pollution is a major contributor to death and disability worldwide. Over 95% of rural Guatemalan households use woodstoves for cooking or heating. Woodsmoke contains carcinogenic or fetotoxic polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Increased PAHs and VOCs have been shown to increase levels of oxidative stress. We examined PAH and VOC exposures among recently pregnant rural Guatemalan women exposed to woodsmoke and compared exposures to levels seen occupationally or among smokers. Urine was collected from 23 women who were 3 months post-partum three times over 72h: morning (fasting), after lunch, and following dinner or use of wood-fired traditional sauna baths (samples=68). Creatinine-adjusted urinary concentrations of metabolites of four PAHs and eight VOCs were analyzed by liquid chromatography-mass spectrometry. Creatinine-adjusted urinary biomarkers of oxidative stress, 8-isoprostane and 8-OHdG, were analyzed using enzyme-linked immunosorbent assays (ELISA). Long-term (pregnancy through 3 months prenatal) exposure to particulate matter and airborne PAHs were measured. Women using wood-fueled chimney stoves are exposed to high levels of particulate matter (median 48h PM2.5 105.7μg/m3; inter-quartile range (IQR): 77.6-130.4). Urinary PAH and VOC metabolites were significantly associated with woodsmoke exposures: 2-naphthol (median (IQR) in ng/mg creatinine: 295.9 (74.4-430.9) after sauna versus 23.9 (17.1-49.5) fasting; and acrolein: 571.7 (429.3-1040.7) after sauna versus 268.0 (178.3-398.6) fasting. Urinary PAH (total PAH: ρ=0.89, p0.85) or PAH and VOC biomarkers (ρ=-0.20 to 0.38, p>0.07). Urinary metabolite concentrations were significantly greater than those of heavy smokers (mean cigarettes/day=18) across all PAHs. In 15 (65%) women, maximum 1-hydroxypyrene concentrations exceeded the occupational exposure limit of coke-oven workers. The high concentrations of urinary PAH and VOC metabolites among

  9. Facile synthesis, characterization and antimicrobial activities of diphenylphosphoryl derivatives of substituted aryl and nitrogen heterocycles

    Directory of Open Access Journals (Sweden)

    G. Subba Reddy


    Full Text Available Diphenylphosphoryl derivatives of substituted aryl and nitrogen heterocycles were prepared by a one-pot process involving sequential reaction of diphenylphosphine chloride with dry methyl alcohol/ethyl alcohol and then with different halides of substituted nitrogen heterocycles/aryl halides. The title compounds (5a-j structures were established by analytical, IR, NMR ( 1H, 13C and 31P and mass spectra, and they have been screened for their antimicrobial activity. They exhibited significant antibacterial and antifungal activity.

  10. Formation and Human Risk of Carcinogenic Heterocyclic Amines Formed from Natural Precursors in Meat

    Energy Technology Data Exchange (ETDEWEB)

    Knize, M G; Felton, J S


    A group of heterocyclic amines that are mutagens and rodent carcinogens form when meat is cooked to medium and well-done states. The precursors of these compounds are natural meat components: creatinine, amino acids and sugars. Defined model systems of dry-heated precursors mimic the amounts and proportions of heterocyclic amines found in meat. Results from model systems and cooking experiments suggest ways to reduce their formation and, thus, to reduce human intake. Human cancer epidemiology studies related to consumption of well-done meat products are listed and compared.

  11. Heterocyclic amines: human carcinogens in cooked food? (United States)

    Pfau, W; Knasmueller, S; Glatt, H R; Frandsen, H; Alexander, J; Murkovic, M; Sontag, G; Galceran, T; Edenharder, R; Skog, K


    During the frying of meat and fish, genotoxic heterocyclic amines (HCAs) are formed. The dietary exposure to HCAs may be implicated in the aetiology of human cancer, but there may be other factors in our diet that prevent the genotoxic effects of these compounds. Within the project described here, we plan to identify regional and individual cooking habits that affect HCA-levels in our food. These are determined with a validated analytical method and the exposure to HCAs is estimated by dietary assessment. Biomarker analysis will be employed to estimate recent or long-term exposure to HCAs. In order to identify genetically determined risk factors in humans, cell lines are genetically engineered expressing allelic variants of acetyl- and sulfotransferases implicated in HCA metabolism. Species differences of metabolism and toxicity of HCAs are assessed and the influence of the intestinal microflora on HCA-induced toxicity is evaluated. Dietary constituents that may reduce the genotoxicity of HCAs are screened for potential protective effects in in vitro and in vivo model systems. Finally, we will aim at human intervention studies to investigate if these protective factors are relevant for man. The objectives of this project are to estimate and possibly reduce the exposure levels to HCAs in Europe, to identify populations highly susceptible to HCA toxicity, and to reduce the toxic effects of HCAs by protective factors.

  12. Heterocyclic amines in meat and meat products

    Directory of Open Access Journals (Sweden)

    Aliye BULGAN


    Full Text Available Heterocyclic amines (HA are the mutagenic/carcinogenic compounds which generate as a result of cooking of red meat, poultry meat and fish fillets at high temperatures. Up to 20 different HAs were detected and classified in the researches that conducted on these types of meats cooked at high temperatures. HAs are the products of Maillard reactions and the Strecker degredation of main precursors such as creatine/creatinine, aminoacid and the polysaccharides. Many physical and chemical factors effect the formation of HAs. Thus, it was reported by many researchers that utilizing coating and marination processes in addition to using natural and synthetic antioxidants and seasonings-plant extracts were effective on inhibiting/decreasing the formation of HAs. Additionally, boiling/steaming and microwave cooking methodologies were recommended instead of barbecuing, grilling or frying to inhibit/decrease the formation of HAs. The HAs formed in meat and meat products and the factors which have effects on the formation of HAs are presented in this review.

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

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz


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

  14. The Domino Way to Heterocycles (United States)

    Padwa, Albert; Bur, Scott K.


    Sequential transformations enable the facile synthesis of complex target molecules from simple building blocks in a single preparative step. Their value is amplified if they also create multiple stereogenic centers. In the ongoing search for new domino processes, emphasis is usually placed on sequential reactions which occur cleanly and without forming by-products. As a prerequisite for an ideally proceeding one-pot sequential transformation, the reactivity pattern of all participating components has to be such that each building block gets involved in a reaction only when it is supposed to do so. The development of sequences that combine transformations of fundamentally different mechanisms broadens the scope of such procedures in synthetic chemistry. This mini review contains a representative sampling from the last 15 years on the kinds of reactions that have been sequenced into cascades to produce heterocyclic molecules. PMID:17940591

  15. A universal isocyanide for diverse heterocycle syntheses

    NARCIS (Netherlands)

    Patil, Pravin; Dömling, Alexander; Khoury, Kareem; Herdtweck, Eberhardt


    Novel scaffolds are of uttermost importance for the discovery of functional material. Three different heterocyclic scaffolds easily accessible from isocyanoacetaldehyde dimethylacetal 1 by multicomponent reaction (MCR) are described. They can be efficiently synthesized by a Ugi tetrazole

  16. Extension of the analytical window for characterizing aromatic compounds in oils using a comprehensive suite of high-resolution mass spectrometry techniques and double bond equivalence versus carbon number plot (United States)

    Cho, Yunju; Birdwell, Justin E.; Hur, Manhoi; Lee, Joonhee; Kim, Byungjoo; Kim, Sunghwan


    In this study, comprehensive two-dimensional (2D) gas chromatography–mass spectrometry (GC–MS), atmospheric pressure photoionization (APPI) quadrupole-Orbitrap mass spectrometry (MS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were used to study the aromatic fractions of crude oil and oil shale pyrolysates (shale oils). The collected data were compared and combined in the double bond equivalence (DBE) versus carbon number plot to obtain a more complete understanding of the composition of the oil fractions. The numbers of peaks observed by each technique followed the order 2D GC–MS carbon number distributions of the 2D GC–MS and Orbitrap MS data were similar for crude oil aromatics. The FT-ICR MS plots of DBE and carbon number showed an extended range of higher values relative to the other methods. For the aromatic fraction of an oil shale pyrolysate generated by the Fischer assay, only a few nitrogen-containing compounds were observed by 2D GC–MS but a large number of these compounds were detected by Orbitrap MS and FT-ICR MS. This comparison clearly shows that the data obtained from these three techniques can be combined to more completely characterize oil composition. The data obtained by Orbitrap MS and FT-ICR MS agreed well with one another, and the combined DBE versus carbon number plot provided more complete coverage of compounds present in the fractions. In addition, the chemical structure information provided by 2D GC–MS could be matched with the chemical formulas in the DBE versus carbon number plots, providing information not available in ultrahigh-resolution MS results. It was therefore concluded that the combination of 2D GC–MS, Orbitrap MS, and FT-ICR MS in the DBE versus carbon number space facilitates structural assignment of heavy oil components.

  17. Quantitative Analysis of Bioactive Compounds from Aromatic Plants by Means of Dynamic Headspace Extraction and Multiple Headspace Extraction-Gas Chromatography-Mass Spectrometry

    NARCIS (Netherlands)

    Omar, Jone; Olivares, Maitane; Alonso, Ibone; Vallejo, Asier; Aizpurua-Olaizola, Oier; Etxebarria, Nestor


    Seven monoterpenes in 4 aromatic plants (sage, cardamom, lavender, and rosemary) were quantified in liquid extracts and directly in solid samples by means of dynamic headspace-gas chromatography-mass spectrometry (DHS-GC-MS) and multiple headspace extraction-gas chromatography-mass spectrometry

  18. Sulfonium salts as leaving groups for aromatic labelling of drug-like small molecules with fluorine-18. (United States)

    Sander, Kerstin; Gendron, Thibault; Yiannaki, Elena; Cybulska, Klaudia; Kalber, Tammy L; Lythgoe, Mark F; Årstad, Erik


    Positron emission tomography (PET) is unique in that it allows quantification of biochemical processes in vivo, but difficulties with preparing suitably labelled radiotracers limit its scientific and diagnostic applications. Aromatic [(18)F]fluorination of drug-like small molecules is particularly challenging as their functional group compositions often impair the labelling efficiency. Herein, we report a new strategy for incorporation of (18)F into highly functionalized aromatic compounds using sulfonium salts as leaving groups. The method is compatible with pharmacologically relevant functional groups, including aliphatic amines and basic heterocycles. Activated substrates react with [(18)F]fluoride at room temperature, and with heating the reaction proceeds in the presence of hydrogen bond donors. Furthermore, the use of electron rich spectator ligands allows efficient and regioselective [(18)F]fluorination of non-activated aromatic moieties. The method provides a broadly applicable route for (18)F labelling of biologically active small molecules, and offers immediate practical benefits for drug discovery and imaging with PET.

  19. Assessing the hydroxyl radical and volatilization roles in aquatic fate estimations of sulfur heterocycles: Dibenzothiophene derivatives. (United States)

    Saranjampour, Parichehr; Armbrust, Kevin L; Marx, Brian D


    Polycyclic aromatic sulfur heterocycles (PASHs) and their alkyl derivatives can be released into aquatic systems via crude oil spills or runoff from petroleum-treated areas, such as asphalt. Dibenzothiophene (DBT) and its derivatives (C1-DBT, C2-DBT, and C4-DBT) were chosen as model compounds to investigate the relative impact of volatilization and hydroxyl radical degradation on estimates of their overall dissipation after entry into aquatic ecosystems as a function of depth using the exposure analysis modeling system (EXAMS). The hydroxyl radical rate constant (K · OH ) and Henry's law constant of PASHs were determined in distilled water. The analogue C1-DBT reacted fastest with · OH relative to other PASHs. The C2-DBT and C4-DBT analogues had higher Henry's law constants compared with other derivatives. Steric hindrance by alkyl substituents on the sulfur moiety most strongly impacted measured rate and Henry's law constants between DBT and individual alkyl derivatives. These steric effects do not appear to be considered in the physical property estimation software EPI Suite. Simulated dissipation of PASHs using EXAMS suggests that volatilization is a dominant fate pathway for the higher molecular weight and less polar C2-DBT and C4-DBT at all depths and DBT and C1-DBT at 0.1-m. However, model scenarios suggest that hydroxyl radical degradation may significantly contribute to the degradation of more polar DBT and C1-DBT at 1-m and 2-m depths. Environ Toxicol Chem 2017;36:1998-2004. © 2017 SETAC. © 2017 SETAC.

  20. The design and synthesis of novel spirocyclic heterocyclic sulfone ROMK inhibitors as diuretics. (United States)

    Chobanian, Harry R; Guo, Yan; Pio, Barbara; Tang, Haifeng; Teumelsan, Nardos; Clements, Matthew; Frie, Jessica; Ferguson, Ronald; Guo, Zach; Thomas-Fowlkes, Brande S; Felix, John P; Liu, Jessica; Kohler, Martin; Priest, Birgit; Hampton, Caryn; Pai, Lee-Yuh; Corona, Aaron; Metzger, Joseph; Tong, Vincent; Joshi, Elizabeth M; Xu, Ling; Owens, Karen; Maloney, Kevin; Sullivan, Kathleen; Pasternak, Alexander


    A spirocyclic class of ROMK inhibitors was developed containing a structurally diverse heterocyclic sulfone moiety and spirocyclic core starting from lead 1. These compounds not only displayed exquisite ROMK potency but significantly improved selectivity over hERG. The lead compounds were found to have favorable pharmacokinetic properties and displayed robust diuretic, natriuretic and blood pressure lowering effects in spontaneously hypertensive rats. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Inhibition of T24 and RT4 Human Bladder Cancer Cell Lines by Heterocyclic Molecules


    Zhi-feng ZHAO; Wang, Kai; Guo, Feng-Fu; Lu, Hua


    Background Bladder cancer is a major widespread tumor of the genitourinary tract. Around 30% of patients with superficial cancers develop invasive and metastatic pathology. Material/Methods Some new heterocyclic 4-methyl coumarin derivatives were designed using molecular modeling studies to evaluate their potential against bladder cancer lines T24 and RT-4. The designed compounds that showed good binding affinity to T24 and RT4 were synthesized, with excellent yield. The synthesized compounds...

  2. Metabolic Effects of Dietary Proteins, Amino Acids and The Other Amine Consisting Compounds on Cardiovascular System.

    Directory of Open Access Journals (Sweden)

    Elif Uğur


    Full Text Available During the prevention and treatment of cardiovascular diseases, first cause of deaths in the world, diet has a vital role. While nutrition programs for the cardiovascular health generally focus on lipids and carbohydrates, effects of proteins are not well concerned. Thus this review is written in order to examine effect of proteins, amino acids, and the other amine consisting compounds on cardiovascular system. Because of that animal or plant derived proteins have different protein composition in different foods such as dairy products, egg, meat, chicken, fish, pulse and grains, their effects on blood pressure and regulation of lipid profile are unlike. In parallel amino acids made up proteins have different effect on cardiovascular system. From this point, sulfur containing amino acids, branched chain amino acids, aromatic amino acids, arginine, ornithine, citrulline, glycine, and glutamine may affect cardiovascular system in different metabolic pathways. In this context, one carbon metabolism, synthesis of hormone, stimulation of signaling pathways and effects of intermediate and final products that formed as a result of amino acids metabolism is determined. Despite the protein and amino acids, some other amine consisting compounds in diet include trimethylamine N-oxide, heterocyclic aromatic amines, polycyclic aromatic hydrocarbons and products of Maillard reaction. These amine consisting compounds generally increase the risk for cardiovascular diseases by stimulating oxidative stress, inflammation, and formation of atherosclerotic plaque.

  3. Separation of alkanes and aromatic compounds by packed column gas chromatography using functionalized multi-walled carbon nanotubes as stationary phases. (United States)

    Speltini, Andrea; Merli, Daniele; Quartarone, Eliana; Profumo, Antonella


    In the present work, we show a novel application of pristine and functionalized Multi-Walled Carbon Nanotubes (MWCNTs) as stationary phase in low-cost packed columns for the gas chromatographic separation of alkanes and aromatic hydrocarbons. The MWCNTs were deeply investigated by means of physical and chemical methods, like thermal analysis, IR and atomic force microscopy, and Inverse Gas Chromatography (IGC) in order to correlate the adsorption process and surface properties with the material purity level and functionalization degree. The derivatization process of the pristine nanotubes was a key factor to achieve a successful separation of both the light n-alkanes (C3-C5) and the related isomers (C4-C5 branched alkanes). Satisfactory results were similarly obtained in the case of separation of aromatic hydrocarbons (BTX). Copyright 2010 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. Use of 13C nuclear magnetic resonance to assess fossil fuel biodegradation: fate of [1-13C]acenaphthene in creosote polycyclic aromatic compound mixtures degraded by bacteria. (United States)

    Selifonov, S A; Chapman, P J; Akkerman, S B; Gurst, J E; Bortiatynski, J M; Nanny, M A; Hatcher, P G


    [1-13C]acenaphthene, a tracer compound with a nuclear magnetic resonance (NMR)-active nucleus at the C-1 position, has been employed in conjunction with a standard broad-band-decoupled 13C-NMR spectroscopy technique to study the biodegradation of acenaphthene by various bacterial cultures degrading aromatic hydrocarbons of creosote. Site-specific labeling at the benzylic position of acenaphthene allows 13C-NMR detection of chemical changes due to initial oxidations catalyzed by bacterial enzymes of aromatic hydrocarbon catabolism. Biodegradation of [1-13C]acenaphthene in the presence of naphthalene or creosote polycyclic aromatic compounds (PACs) was examined with an undefined mixed bacterial culture (established by enrichment on creosote PACs) and with isolates of individual naphthalene- and phenanthrene-degrading strains from this culture. From 13C-NMR spectra of extractable materials obtained in time course biodegradation experiments under optimized conditions, a number of signals were assigned to accumulated products such as 1-acenaphthenol, 1-acenaphthenone, acenaphthene-1,2-diol and naphthalene 1,8-dicarboxylic acid, formed by benzylic oxidation of acenaphthene and subsequent reactions. Limited degradation of acenaphthene could be attributed to its oxidation by naphthalene 1,2-dioxygenase or related dioxygenases, indicative of certain limitations of the undefined mixed culture with respect to acenaphthene catabolism. Coinoculation of the mixed culture with cells of acenaphthene-grown strain Pseudomonas sp. strain A2279 mitigated the accumulation of partial transformation products and resulted in more complete degradation of acenaphthene. This study demonstrates the value of the stable isotope labeling approach and its ability to reveal incomplete mineralization even when as little as 2 to 3% of the substrate is incompletely oxidized, yielding products of partial transformation. The approach outlined may prove useful in assessing bioremediation performance.

  6. The preparation of a new type of ferrocene-based compounds with large conjugated system containing symmetrical aromatic vinyl with Schiff base moieties and the study of their third-order nonlinear optical properties (United States)

    Yu, Weiguo; Jia, Jianhong; Gao, Jianrong; Han, Liang; Li, Yujin


    Herein we reported the preparation of a new type of ferrocene-based compounds with large conjugated system containing symmetrical aromatic vinyl and Schiff base moieties and the study of their third-order nonlinear optical (NLO) properties. Their third-order NLO properties were measured using femtosecond laser and degenerate four-wave mixing (DFWM) technique. The obtained χ(3), n2 and γ values of these molecules were found in the range of 0.998-1.429 × 10-12 esu,1.847-2.646 × 10-11 esu and 1.026-1.449 × 10-30 esu, respectively. The response time ranged from 43.65 fs to 61.71 fs. The results indicate that these compounds have potential nonlinear optical applications.

  7. Enhancing the laccase production and laccase gene expression in the white-rot fungus Trametes velutina 5930 with great potential for biotechnological applications by different metal ions and aromatic compounds.

    Directory of Open Access Journals (Sweden)

    Yang Yang

    Full Text Available Laccase is useful for various biotechnological and industrial applications. The white-rot fungus Trametes velutina 5930 and its laccase, isolated from the Shennongjia Nature Reserve in China by our laboratory, has great potential for practical application in environmental biotechnology. However, the original level of laccase produced by Trametes velutina 5930 was relatively low in the absence of any inducer. Therefore, in order to enhance the laccase production by Trametes velutina 5930 and make better use of this fungus in the field of environmental biotechnology, the regulation of laccase production and laccase gene expression in Trametes velutina 5930 were investigated in this study. Different metal ions such as Cu(2+ and Fe(2+ could stimulate the laccase synthesis and laccase gene transcription in Trametes velutina 5930. Some aromatic compounds structurally related to lignin, such as tannic acid, syringic acid, cinnamic acid, gallic acid and guaiacol, could also enhance the level of laccase activity and laccase gene transcription. We also found that there existed a positive synergistic effect of aromatic compound and metal ion on the laccase production and laccase gene transcription in Trametes velutina 5930. Taken together, our study may contribute to the improvement of laccase productivity by Trametes velutina 5930.

  8. Aromatic graphene

    Energy Technology Data Exchange (ETDEWEB)

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


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

  9. Synthesis of heterocycles: Indolo (2,1-a) isoquinolines, renewables, and aptamer ligands for cellular imaging

    Energy Technology Data Exchange (ETDEWEB)

    Beasley, Jonathan [Ames Laboratory (AMES), Ames, IA (United States)


    In this thesis, we explore both total syntheses and methodologies of several aromatic heterocyclic molecules. Extensions of the Kraus indole synthesis toward 2-substituted and 2,3-disubstituted indoles, as well as biologically attractive indolo[2,1-a]isoquinolines are described. Recent renewable efforts directed to commodity maleic acid and the first reported furan-based ionic liquids are described. Our total synthesis of mRNA aptamer ligand PDC-Gly, and its dye coupled forms, plus aminoglycoside dye coupled ligands used in molecular imaging, are described.

  10. 40 CFR 721.10003 - Manganese heterocyclic tetraamine complex (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese heterocyclic tetraamine... Specific Chemical Substances § 721.10003 Manganese heterocyclic tetraamine complex (generic). (a) Chemical... as manganese heterocyclic tetraamine complex (PMNs P-98-625/626/627/628/629 and P-00-614/617) are...

  11. 40 CFR 721.5925 - Bis heterocyclic phenylene derivative (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Bis heterocyclic phenylene derivative... Specific Chemical Substances § 721.5925 Bis heterocyclic phenylene derivative (generic). (a) Chemical... as bis heterocyclic phenylene derivative (PMN P-01-0432) is subject to reporting under this section...

  12. Quantitative Analysis of Bioactive Compounds from Aromatic Plants by Means of Dynamic Headspace Extraction and Multiple Headspace Extraction-Gas Chromatography-Mass Spectrometry. (United States)

    Omar, Jone; Olivares, Maitane; Alonso, Ibone; Vallejo, Asier; Aizpurua-Olaizola, Oier; Etxebarria, Nestor


    Seven monoterpenes in 4 aromatic plants (sage, cardamom, lavender, and rosemary) were quantified in liquid extracts and directly in solid samples by means of dynamic headspace-gas chromatography-mass spectrometry (DHS-GC-MS) and multiple headspace extraction-gas chromatography-mass spectrometry (MHSE), respectively. The monoterpenes were 1st extracted by means of supercritical fluid extraction (SFE) and analyzed by an optimized DHS-GC-MS. The optimization of the dynamic extraction step and the desorption/cryo-focusing step were tackled independently by experimental design assays. The best working conditions were set at 30 °C for the incubation temperature, 5 min of incubation time, and 40 mL of purge volume for the dynamic extraction step of these bioactive molecules. The conditions of the desorption/cryo-trapping step from the Tenax TA trap were set at follows: the temperature was increased from 30 to 300 °C at 150 °C/min, although the cryo-trapping was maintained at -70 °C. In order to estimate the efficiency of the SFE process, the analysis of monoterpenes in the 4 aromatic plants was directly carried out by means of MHSE because it did not require any sample preparation. Good linearity (r2) > 0.99) and reproducibility (relative standard deviation % plants obtaining concentrations in the range of 2 to 6000 ng/g and 0.25 to 110 μg/mg, respectively. © 2016 Institute of Food Technologists®

  13. Sodium Perborate Oxidation of an Aromatic Amine (United States)

    Juestis, Laurence


    Describes an experiment involving the oxidation of aromatic primary amines to the corresponding azo compound; suggests procedures for studying factors that influence the yield of such a reaction, including the choice of solvent and the oxidant-amine ratio. (MLH)

  14. Influence of the aromatic substitutes in the thermal and kinetic behavior of mesoionic compounds of the 1,3-thiazole-5-tiolate system

    Energy Technology Data Exchange (ETDEWEB)

    Alves de Morais, Soraya, E-mail: [Universidade Estadual da Paraiba, Departamento de Quimica, Av. Baraunas, s/n, Campina Grande, PB (Brazil); Rogrigues da Silva Morais, Crislene, E-mail: crislene@pq.cnpq.b [Universidade Federal de Campina Grande, Unidade Academica de Engenharia de Materiais, Av. Aprigio Veloso, 882, Campina Grande, PB (Brazil); Filgueiras de Athayde Filho, Petronio, E-mail: athayde-filho@pq.cnpq.b [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil); Freitas Lira, Bruno, E-mail: [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil); Feitosa de Souza, Marcos Antonio, E-mail: [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil)


    In this work, three mesoionic compounds of the 1,3-thiazole-5-tiolat system were studied, derived from amino acids of the glycerin through 1,3-dipolar cyclo-addition/reversion reaction. The mesoionic compounds were characterized as: MI-1 (mesoionic 2-(4-chlorophenyl)-3-methyl-4-phenyl-1,3-thiazole-5-tiolat); MI-2 (mesoionic 2-(4-chlorophenyl)-3-methyl-4-(4-isopropylphenyl)-1,3-thiazole-5-tiolat) and MI-3 (Mesoionic 2-(4-clorophenyl)-3-methyl-4-(methoxyphenyl)-1,3-thiazole-5-tiolate). These compounds were characterized by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), thermogravimetry (TG) and differential scanning calorimeter (DSC). Also, the kinetic study of the thermal decomposition by non-isothermal thermogravimetry has been realized, presenting, the kinetic and thermal behavior of these compounds. The results of the spectroscopic analysis confirmed the structure of the synthesized mesoionic compounds. The DSC curves of the mesoionic compounds MI-1, MI-2, and MI-3 indicated the fusion of two of them followed by a subsequent decomposition. The TG/DTG curves showed that the decomposition of the mesoionic compounds MI-1, MI-2 and MI-3 occurred in several steps.

  15. Rapid trifluoromethylation and perfluoroalkylation of five-membered heterocycles by photoredox catalysis in continuous flow. (United States)

    Straathof, Natan J W; Gemoets, Hannes P L; Wang, Xiao; Schouten, Jaap C; Hessel, Volker; Noël, Timothy


    Trifluoromethylated and perfluoroalkylated heterocycles are important building blocks for the synthesis of numerous pharmaceutical products, agrochemicals and are widely applied in material sciences. To date, trifluoromethylated and perfluoroalkylated hetero-aromatic systems can be prepared utilizing visible light photoredox catalysis methodologies in batch. While several limitations are associated with these batch protocols, the application of microflow technology could greatly enhance and intensify these reactions. A simple and straightforward photocatalytic trifluoromethylation and perfluoroalkylation method has been developed in continuous microflow, using commercially available photocatalysts and microflow components. A selection of five-membered hetero-aromatics were successfully trifluoromethylated (12 examples) and perfluoroalkylated (5 examples) within several minutes (8-20 min). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Discovery and evaluation of potent P1 aryl heterocycle-based thrombin inhibitors. (United States)

    Young, Mary Beth; Barrow, James C; Glass, Kristen L; Lundell, George F; Newton, Christina L; Pellicore, Janetta M; Rittle, Kenneth E; Selnick, Harold G; Stauffer, Kenneth J; Vacca, Joseph P; Williams, Peter D; Bohn, Dennis; Clayton, Franklin C; Cook, Jacquelynn J; Krueger, Julie A; Kuo, Lawrence C; Lewis, S Dale; Lucas, Bobby J; McMasters, Daniel R; Miller-Stein, Cynthia; Pietrak, Beth L; Wallace, Audrey A; White, Rebecca B; Wong, Bradley; Yan, Youwei; Nantermet, Philippe G


    In an effort to discover potent, clinically useful thrombin inhibitors, a rapid analogue synthetic approach was used to explore the P(1) region. Various benzylamines were coupled to a pyridine/pyrazinone P(2)-P(3) template. One compound with an o-thiadiazole benzylic substitution was found to have a thrombin K(i) of 0.84 nM. A study of ortho-substituted five-membered-ring heterocycles was undertaken and subsequently demonstrated that the o-triazole and tetrazole rings were optimal. Combination of these potent P(1) aryl heterocycles with a variety of P(2)-P(3) groups produced a compound with an extraordinary thrombin inhibitory activity of 1.4 pM. It is hoped that this potency enhancement in P(1) will allow for more diversification in the P(2)-P(3) region to ultimately address additional pharmacological concerns.

  17. Phenolic compounds and aroma‐impact odorants in herb liqueurs elaborated by maceration of aromatic and medicinal plants in grape marc distillates

    National Research Council Canada - National Science Library

    Rodríguez‐Solana, Raquel; Salgado, José Manuel; Domínguez, José Manuel; Cortés‐Diéguez, Sandra


    ...‐performance liquid chromatography with UV detection. All compounds showed significant differences among the samples analysed as consequence of the initial composition of the distillate and the plants and spices used in the liqueur elaboration...

  18. Is Gamma Radiation Suitable to Preserve Phenolic Compounds and to Decontaminate Mycotoxins in Aromatic Plants? A Case-Study with Aloysia citrodora Paláu

    Directory of Open Access Journals (Sweden)

    Eliana Pereira


    Full Text Available 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.

  19. Is Gamma Radiation Suitable to Preserve Phenolic Compounds and to Decontaminate Mycotoxins in Aromatic Plants? A Case-Study with Aloysia citrodora Paláu. (United States)

    Pereira, Eliana; Barros, Lillian; Antonio, Amilcar L; Cabo Verde, Sandra; Santos-Buelga, Celestino; Ferreira, Isabel C F R; Rodrigues, Paula


    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.

  20. -Heterocyclic Carbene Complexes of Mineral Acids

    KAUST Repository

    Brill, Marcel


    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  1. Reduction of (Formazanate)boron Difluoride Provides Evidence for an N-Heterocyclic B(I) Carbenoid Intermediate

    NARCIS (Netherlands)

    Chang, Mu-Chieh; Otten, Edwin


    Despite the current interest in structure and reactivity of sub-valent main group compounds, neutral boron analogues of N-heterocyclic carbenes have been elusive due to their high reactivity. Here we provide evidence that 2-electron reduction of a (formazanate)BF2 precursor leads to NaF elimination

  2. The Chemistry of Formazan Dyes: Synthesis and Characterization of a Stable Verdazyl Radical and a Related Boron-Containing Heterocycle (United States)

    Berry, David E.; Hicks, Robin G.; Gilroy, Joe B.


    This experiment describes the synthesis and characterization of a formazan dye, and its subsequent conversion to a stable verdazyl radical and a boron-nitrogen heterocycle (boratatetrazine). Each of these compounds is intensely colored and is prepared and handled under aerobic conditions, which often surprises students as free radicals are…

  3. Caffeine-Based Gold(I) N-Heterocyclic Carbenes as Possible Anticancer Agents : Synthesis and Biological Properties

    NARCIS (Netherlands)

    Bertrand, Benoit; Stefan, Loic; Pirrotta, Marc; Monchaud, David; Bodio, Ewen; Richard, Philippe; Le Gendre, Pierre; Warmerdam, Elena; de Jager, Marina H.; Groothuis, Geny M. M.; Picquet, Michel; Casini, Angela


    A new series of gold(I) N-heterocyclic carbene (NHC) complexes based on xanthine ligands have been synthesized and characterized by mass spectrometry, NMR, and X-ray diffraction. The compounds have been tested for their antiproliferative properties in human cancer cells and nontumorigenic cells in

  4. Insights into the structural patterns of the antileishmanial activity of bi- and tricyclic N-heterocycles. (United States)

    Herrera, Lizzi; Stephens, David E; D'Avila, Abigail; George, Kathryn G; Arman, Hadi; Zhang, Yu; Perry, George; Lleonart, Ricardo; Larionov, Oleg V; Fernández, Patricia L


    The influence of various structural patterns in a series of novel bi- and tricyclic N-heterocycles on the activity against Leishmania major and Leishmania panamensis has been studied and compounds that are active in the low micromolar region have been identified. Both quinolines and tetrahydrooxazinoindoles (TOI) proved to have significant antileishmanial activities, while substituted indoles were inactive. We have also showed that a chloroquine analogue induces Leishmania killing by modulating macrophage activation.

  5. The flow synthesis of heterocycles for natural product and medicinal chemistry applications. (United States)

    Baumann, Marcus; Baxendale, Ian R; Ley, Steven V


    This article represents an overview of recent research from the Innovative Technology Centre in the field of flow chemistry which was presented at the FROST2 meeting in Budapest in October 2009. After a short introduction of this rapidly expanding field, we discuss some of our results with a main focus on the synthesis of heterocyclic compounds which we use in various natural product and medicinal chemistry programmes.

  6. Diversity Oriented Syntheses of Conventional Heterocycles by Smart Multi Component Reactions (MCRs of the Last Decade

    Directory of Open Access Journals (Sweden)

    Heiner Eckert


    Full Text Available A collection of smart multicomponent reactions (MCRs with continuative post condensation cyclizations (PCCs is presented to construct conventional three- to seven-membered heterocyclic compounds in diversity oriented syntheses (DOS. These will provide a high degree of applying economical and ecological advantages as well as of practicability. Water, ionic liquids, and solvent-less syntheses as well as use of various forms of energy as microwave and ultrasonic irradiation are examined and discussed.

  7. Regiospecificity in the heterocyclization of b-oxonitriles to 5-substituted 4-oxothiazolidine derivatives

    Directory of Open Access Journals (Sweden)



    Full Text Available A study on the regiospecificity of the base-catalyzed reaction of activated b-oxonitriles 1 with diethyl mercaptosuccinate affording the title compounds 3 is reported. Other competitive heterocyclic products, that is 4-oxo-1,3-thiazinanes 4, derivatives of tetrahydrothiophene 5 and/or thiacyclohexane 6 which on the grounds of mechanistic considerations could be formed, were not observed. Spectroscopic and experimental evidence, together with theoretical considerations, provides a reasonable explanation for the observed regiospecificity.

  8. Optical characterization of heterocyclic azo dyes containing polymers thin films (United States)

    Derkowska-Zielinska, B.; Skowronski, L.; Biitseva, A.; Grabowski, A.; Naparty, M. K.; Smokal, V.; Kysil, A.; Krupka, O.


    In this paper we present the optical properties of heterocyclic azo dyes containing polymers thin films. From spectroscopic ellipsometry combined with transmittance measurements we estimated the absorption coefficients, refractive indices and optical energy band gaps of studied compounds. One can notice that the optical properties of azo dyes polymers strongly depend on the type of substitution in the azobenzene moiety. The different substitution pattern in azobenzene moiety leads to a change in the value of refractive index and red shifts in the absorption spectrum. We also found that different polymer systems (such as guest-host system or side-chain) result in changes of the optical properties (such as the values of refractive index, optical energy band gap) of azo dyes.

  9. Recent advances in novel heterocyclic scaffolds for the treatment of drug-resistant malaria. (United States)

    Kumar, Sahil; Singh, Rajesh K; Patial, Babita; Goyal, Sachin; Bhardwaj, T R


    Malaria is a major public health problem all over the world, particularly in tropical and subtropical countries due to the development of resistance and most deadly infection is caused by Plasmodium falciparum. There is a direct need for the discovery of new drugs with unique structures and mechanism of action to treat sensitive and drug-resistant strains of various plasmodia for radical cure of this disease. Traditional compounds such as quinine and related derivatives represent a major source for the development of new drugs. This review presents recent modifications of 4-aminoquinoline and 8-aminoquinolone rings as leads to novel active molecules which are under clinical trials. The review also encompasses the other heterocyclic compounds emerged as potential antimalarial agents with promising results such as acridinediones and acridinone analogues, pyridines and quinolones as antimalarials. Miscellaneous heterocyclics such as tetroxane derivatives, indole derivatives, imidazolopiperazine derivatives, biscationic choline-based compounds and polymer-linked combined antimalarial drugs are also discussed. At last brief introduction to heterocyclics in natural products is also reviewed. Most of them have been under clinical trials and found to be promising in the treatment of drug-resistant strains of Plasmodium and others can be explored for the same purpose.

  10. Is gamma radiation suitable to preserve phenolic compounds and to decontaminate mycotoxins in aromatic plants? A case-study with aloysia citrodora paláu


    Pereira E.; Pereira, Eliana; Barros, Lillian; Antonio, Amilcar L.; Verde, Sandra Cabo; Santos-Buelga, Celestino; Ferreira, Isabel C.F.R.; Rodrigues, Paula


    © 2017 by the authors. 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 ...

  11. Is Gamma Radiation Suitable to Preserve Phenolic Compounds and to Decontaminate Mycotoxins in Aromatic Plants? A Case-Study with Aloysia citrodora Paláu


    Eliana Pereira; Lillian Barros; Amilcar L. Antonio; Sandra Cabo Verde; Celestino Santos-Buelga; Isabel C. F. R. Ferreira; Paula Rodrigues


    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-fluo...

  12. Hydrotreatment of Irati shale oil; Behavior of the aromatic fraction

    Energy Technology Data Exchange (ETDEWEB)

    Afonso, J.C.; Schmal, M. (Federal Univ. of Rio de Janeiro, COPPE/EQ/UFRJ, C.P. 68502, 21945 Rio de Janeiro (BR)); Cardoso, J.N. (Inst. of Chemistry/UFRJ, Centro de Tecnologia, bloco A, Sala A-603, 21910 Rio de Janeiro (BR)); Frety, R. (Inst. de Recherches sur la Catalyse, CNRS, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (FR))


    This paper presents the chemical transformations that occur in the aromatic fraction of Irati shale oil under rather drastic hydrotreating conditions, at 400{degrees} C and 125 atm, using a commercial Ni-Mo/Al{sub 2}O{sub 3} catalyst in sulfided form. The aromatic fraction was analyzed before and after reaction by gas chromatography/ mass spectrometry. Several compounds were identified by using this method. The main reactions are the partial hydrogenation of the aromatic rings forming hydroaromatic compounds and the cracking of the lateral alkyl chains. Hydrotreatment leads to a more complex aromatic fraction due to the formation of new compounds.

  13. Polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) mitigation in the pyrolysis process of waste tires using CO₂ as a reaction medium. (United States)

    Kwon, Eilhann E; Oh, Jeong-Ik; Kim, Ki-Hyun


    Our work reported the CO2-assisted mitigation of PAHs and VOCs in the thermo-chemical process (i.e., pyrolysis). To investigate the pyrolysis of used tires to recover energy and chemical products, the experiments were conducted using a laboratory-scale batch-type reactor. In particular, to examine the influence of the CO2 in pyrolysis of a tire, the pyrolytic products including C1-5-hydrocarbons (HCs), volatile organic carbons (VOCs), and polycyclic aromatic hydrocarbons (PAHs) were evaluated qualitatively by gas chromatography (GC) with mass spectroscopy (MS) as well as with a thermal conductivity detector (TCD). The mass balance of the pyrolytic products under various pyrolytic conditions was established on the basis of their weight fractions of the pyrolytic products. Our experimental work experimentally validated that the amount of gaseous pyrolytic products increased when using CO2 as a pyrolysis medium, while substantially altering the production of pyrolytic oil in absolute content (7.3-17.2%) and in relative composition (including PAHs and VOCs). Thus, the co-feeding of CO2 in the pyrolysis process can be considered an environmentally benign and energy efficient process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Synthesis of New Fluorine Substituted Heterocyclic Nitrogen Systems Derived from p-Aminosalicylic Acid as Antimycobacterial Agents

    Directory of Open Access Journals (Sweden)

    Mohammed Saleh I. T. Makki


    Full Text Available Some new fluorine substituted heterocyclic nitrogen systems 2–17 have been synthesized from ring closure reactions of substituted p-amino salicylic acids (PAS. The Schiffs base of PAS was cyclized with chloroacetyl chloride and mercaptoacetic acid to give azetidinone 2, thiazolidinone 3, and spiro-fluoroindolothiazoline-dione 10. However, PAS when reacted directly with 4-fluorobenzoyl chloride and 5-oxazolinone yielded derivatives 4, 5, and 7. Aminomethylation of PAS using formaldehyde and piperidine or piperazine formed N-alkyl and N,N′-dialkyl derivatives (11 and 12 respectively upon fluorinated benzoylation gave compounds 13 and 14. Similarly, treatment of PAS with thiosemicarbazide 15 and subsequent cyclization with diethyl oxalate yielded the fluorinated heterocycle 17. The structures of the fluorinated heterocyclic systems have been established on the basis of elemental analysis, 1H NMR, 13C NMR, and MS spectral data. Some of the targets exhibited a high inhibition towards Mycobacterium strain with favorable log P values.

  15. Degradation of aromatic compounds through the beta-ketoadipate pathway is required for pathogenicity of the tomato wilt pathogen Fusarium oxysporum f. sp. lycopersici.

    NARCIS (Netherlands)

    Michielse, C.B.; Reijnen, L.; Olivain, C.; Alabouvette, C.; Rep, M.


    Plant roots react to pathogen attack by the activation of general and systemic resistance, including the lignification of cell walls and increased release of phenolic compounds in root exudate. Some fungi have the capacity to degrade lignin using ligninolytic extracellular peroxidases and laccases.

  16. Comparison of different extraction methods for the determination of essential oils and related compounds from aromatic plants and optimization of solid-phase microextraction/gas chromatography. (United States)

    Richter, Jana; Schellenberg, Ingo


    Different extraction methods for the subsequent gas chromatographic determination of the composition of essential oils and related compounds from marjoram (Origanum majorana L.), caraway (Carum carvi L.), sage (Salvia officinalis L.), and thyme (Thymus vulgaris L.) have been compared. The comparison was also discussed with regard to transformation processes of genuine compounds, particularly in terms of expenditure of time. Hydrodistillation is the method of choice for the determination of the essential oil content of plants. For investigating the composition of genuine essential oils and related, aroma-active compounds, hydrodistillation is not very useful, because of discrimination and transformation processes due to high temperatures and acidic conditions. With cold solvent extraction, accelerated solvent extraction, and supercritical fluid extraction, discrimination of high and non-volatile aroma-active components as well as transformation processes can be diminished, but non-aroma-active fats, waxes, or pigments are often extracted, too. As solid-phase microextraction is a solvent-free fully automizable sample preparation technique, this was the most sparing to sensitive components and the most time-saving method for the rapid determination of the aroma compounds composition in marjoram, caraway, sage, and thyme. Finally, solid-phase microextraction could be successfully optimized for the extraction of the aroma components from the plants for their subsequent gas chromatographic determination.

  17. Pushing Chemical Boundaries with N-Heterocyclic Olefins (NHOs): From Catalysis to Main Group Element Chemistry. (United States)

    Roy, Matthew M D; Rivard, Eric


    N-Heterocyclic olefins (NHOs) have gone from the topic of a few scattered (but important) reports in the early 1990s to very recently being a ligand/reagent of choice in the far-reaching research fields of organocatalysis, olefin and heterocycle polymerization, and low oxidation state main group element chemistry. NHOs are formally derived by appending an alkylidene (CR2) unit onto an N-heterocyclic carbene (NHC), and their pronounced ylidic character leads to high nucleophilicity and soft Lewis basic character at the ligating carbon atom. These olefinic donors can also be structurally derived from imidazole, triazole, and thiazole-based heterocyclic carbenes and, as a result, have highly tunable electronic and steric properties. In this Account, we will focus on various synthetic routes to imidazole-2-ylidene derived NHOs (sometimes referred to as deoxy-Breslow intermediates) followed by a discussion of the electron-donor ability of this structurally tunable ligand group. It should be mentioned that NHOs have a close structural analogy with Breslow-type intermediates, N-heterocyclic ketene aminals, and β-azolium ylides; while these latter species play important roles in advancing synthetic organic chemistry, discussion in this Account will be confined mostly to imidazole-2-ylidene derived NHOs. In addition, we will cover selected examples from the literature where NHOs and their anionic counterparts, N-heterocyclic vinylenes, are used to access reactive main group species not attainable using traditional ligands. Added motivation for these studies comes from the emerging number of low coordinate main group element based compounds that display reactivity once reserved for precious metal complexes (such as H-H and C-H bond activation). Moreover, NHOs are versatile precursors to new mixed element (P/C and N/C), and potentially bidentate, ligand constructs of great potential in catalysis, where various metal oxidation states and coordination environments need to be

  18. Extraction of aromatics from naphtha with ionic liquids


    Meindersma, G.W.


    The objective of this study was the development of a separation technology for the selective recovery and purification of aromatic compounds benzene, toluene, ethylbenzene and xylenes (BTEX) from liquid ethylene cracker feeds. Most ethylene cracker feeds contain 10 ¿ 25% of aromatic components, depending on the source of the feed (naphtha or gas condensate). The aromatic compounds are not converted to olefins and even small amounts are formed during the cracking process in the cracker furnace...

  19. A review on antioxidant potential of bioactive heterocycle benzofuran: Natural and synthetic derivatives. (United States)

    Chand, Karam; Rajeshwari; Hiremathad, Asha; Singh, Mahak; Santos, M Amelia; Keri, Rangappa S


    The majority of heterocycle compounds and typically common heterocycle fragments present in most pharmaceuticals currently marketed, alongside with their intrinsic versatility and unique physicochemical properties, have poised them as true cornerstones of medicinal chemistry. In this context, oxygen heterocycles exhibit diverse biological and pharmacological activities due in part to the similarities with many natural and synthetic molecules with known biological activity. Among oxygen containing heterocycles, benzofuran (synthetic and natural isolated) and its derivatives have attracted medicinal chemists and pharmacologists due to their pronounced biological activities and their potential applications as pharmacological agents such as antioxidant, antitumor, antiplatelet, antimalarial, antiinflammatory, antidepressant and anticonvulsant properties. There are also an amazing number of approved benzofuran-containing drugs in the market as well as compounds currently going through different clinical phases or registration statuses. Due to the wide range of biological activities of benzofurans, their structure activity relationships have generated interest among medicinal chemists, and this has culminated in the discovery of several lead molecules in numerous disease conditions. Recently, this scaffold has emerged as a pharmacophore of choice for designing antioxidant drug development as their derivatives have shown excellent results through different mechanism of action. This review focused on the recent development of benzofuran derivatives as antioxidant agents (including natural products) and their antioxidant activities; summarize the structure property, hoping to inspire new and even more creative approaches. Also, this study systematically provides a comprehensive report on current developments in benzofuran-based compounds as antioxidant agents and is also helpful for the researchers working on a substitution pattern around the nucleus, with an aim to help

  20. Mn²⁺-deficiency reveals a key role for the Pleurotus ostreatus versatile peroxidase (VP4) in oxidation of aromatic compounds. (United States)

    Knop, Doriv; Ben-Ari, Julius; Salame, Tomer M; Levinson, Dana; Yarden, Oded; Hadar, Yitzhak


    The manganese peroxidase gene family (mnps) is a part of the ligninolytic system of Pleurotus ostreatus. This gene family is comprised of nine members, mnp1-9, encoding short manganese peroxidases (short-MnPs) or versatile peroxidases (VPs). We show that unlike in Mn(2+)-amended glucose-peptone (GP) medium, where redundancy among mnps was reported, in Mn(2+)-deficient GP medium mnp4 [encoding versatile peroxidase isoenzyme 4 (VP4)] has a key and nonredundant function. The abundance of mnps transcripts at time points corresponding to the tropophase (active growth), early idiophase, and idiophase indicates that mnp4 is the predominantly expressed mnp gene and that its relative predominance is dependent on the age of the culture. In this medium, azo dye, Orange II (OII) decolorization occurs only during the idiophase and a Δmnp4 strain showed a drastic reduction in this decolorization. Three degradation metabolites were identified by liquid chromatography-mass spectroscopy (LC-MS), indicating both asymmetric and symmetric enzymatic cleavage of the azo-bond. In addition, the culture filtrate of Δmnp4 showed negligible values of oxidation capability of four typical VP substrates: Mn(2+), 2,6-dimethoxyphenol, phenol red, and Reactive Black 5 (RB5), compared to the wild-type strain PC9. We concluded that under Mn(2+)-deficient GP culture, VP4 (encoded by mnp4) is the main active ligninolytic enzyme able to oxidize Mn(2+) as well as high and low redox potential aromatic substrate, including dyes. Furthermore, other VPs/MnPs do not compensate for the lack of VP4 activity.

  1. Synthetic studies on heterocyclic natural products. (United States)

    Ciufolini, Marco A


    This article reviews past and ongoing research in the author's laboratory directed toward the synthesis of natural products displaying an azaspirocyclic framework, or incorporating a medium-ring nitrogen heterocycle. New synthetic technologies were devised in order to address the synthetic problems posed by the target molecules. Thus, efforts in the area of azaspirocyclic substances have relied on an oxidative amidation of phenols promoted by iodobenzene diacetate, whereas access to medium-ring nitrogen heterocycles has been secured by means of a ring expansion sequence that relies on the fragmentation of an aziridine triggered by a homo-Brook transposition. Details of the development of these technologies are presented, together with applications to the total synthesis of FR-901483, TAN-1251C, cylindricines, and mitomycinoids.

  2. Biodegradation Rates of Aromatic Contaminants in Biofilm Reactors

    DEFF Research Database (Denmark)

    Arcangeli, Jean-Pierre; Arvin, Erik


    This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols, chlorophe......This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols...... compounds was typically controlled by first order kinetics. The first-order surface removal rate constants were surprisingly similar, ranging from 2 to 4 m/d. It appears that NSO-compounds inhibit the degradation of aromatic hydrocarbons, even at very low concentrations of NSO-compounds. Under nitrate...

  3. Synthesis and properties of heterocyclic acene diimides. (United States)

    Li, Cheng; Xiao, Chengyi; Li, Yan; Wang, Zhaohui


    A series of heterocyclic acene diimides were synthesized effectively based on the condensation of o-phenylenediamine, 1,2-benzenedithiol, and 2-aminothiophenol with 2,3,6,7-tetrabromo-1,4,5,8-naphthalene tetracarboxylic diimide. The diimides exhibit interesting optical and electrical properties with one of them showing a hole mobility up to 0.02 cm(2) V(-1) s(-1).

  4. Synthesis of Pharmacological Heterocyclic Derivatives Based Surfactants. (United States)

    El-Sayed, Refat; Fadda, Ahmed A


    Synthesis of chromenopyrimidine derivatives and the related fused system carried out by the reaction of chromene derivative 1 with various reagents under suitable reaction conditions. Condensation of stearoyl chloride with these heterocycles, then, propoxylated the products using propylene oxide to produce surface active agents having a twofold capacity as surface and antimicrobial dynamic specialists which may be served in the production of medications, pesticides, beautifying agents or may be utilized as an antimicrobial. Some of the surface properties and antimicrobial activity were resolved.

  5. Deletion of the 2-acyl-glycerophosphoethanolamine cycle improve glucose metabolism in Escherichia coli strains employed for overproduction of aromatic compounds. (United States)

    Aguilar, César; Flores, Noemí; Riveros-McKay, Fernando; Sahonero-Canavesi, Diana; Carmona, Susy Beatriz; Geiger, Otto; Escalante, Adelfo; Bolívar, Francisco


    As a metabolic engineering tool, an adaptive laboratory evolution (ALE) experiment was performed to increase the specific growth rate (µ) in an Escherichia coli strain lacking PTS, originally engineered to increase the availability of intracellular phosphoenolpyruvate and redirect to the aromatic biosynthesis pathway. As result, several evolved strains increased their growth fitness on glucose as the only carbon source. Two of these clones isolated at 120 and 200 h during the experiment, increased their μ by 338 and 373 %, respectively, compared to the predecessor PB11 strain. The genome sequence and analysis of the genetic changes of these two strains (PB12 and PB13) allowed for the identification of a novel strategy to enhance carbon utilization to overcome the absence of the major glucose transport system. Genome sequencing data of evolved strains revealed the deletion of chromosomal region of 10,328 pb and two punctual non-synonymous mutations in the dhaM and glpT genes, which occurred prior to their divergence during the early stages of the evolutionary process. Deleted genes related to increased fitness in the evolved strains are rppH, aas, lplT and galR. Furthermore, the loss of mutH, which was also lost during the deletion event, caused a 200-fold increase in the mutation rate. During the ALE experiment, both PB12 and PB13 strains lost the galR and rppH genes, allowing the utilization of an alternative glucose transport system and allowed enhanced mRNA half-life of many genes involved in the glycolytic pathway resulting in an increment in the μ of these derivatives. Finally, we demonstrated the deletion of the aas-lplT operon, which codes for the main components of the phosphatidylethanolamine turnover metabolism increased the further fitness and glucose uptake in these evolved strains by stimulating the phospholipid degradation pathway. This is an alternative mechanism to its regeneration from 2-acyl-glycerophosphoethanolamine, whose utilization

  6. Bioremediation of polycyclic aromatic hydrocarbon (PAH compounds: (acenaphthene and fluorene in water using indigenous bacterial species isolated from the Diep and Plankenburg rivers, Western Cape, South Africa

    Directory of Open Access Journals (Sweden)

    Oluwadara Oluwaseun Alegbeleye

    Full Text Available Abstract This study was conducted to investigate the occurrence of PAH degrading microorganisms in two river systems in the Western Cape, South Africa and their ability to degrade two PAH compounds: acenaphthene and fluorene. A total of 19 bacterial isolates were obtained from the Diep and Plankenburg rivers among which four were identified as acenaphthene and fluorene degrading isolates. In simulated batch scale experiments, the optimum temperature for efficient degradation of both compounds was determined in a shaking incubator after 14 days, testing at 25 °C, 30 °C, 35 °C, 37 °C, 38 °C, 40 °C and 45 °C followed by experiments in a Stirred Tank Bioreactor using optimum temperature profiles from the batch experiment results. All experiments were run without the addition of supplements, bulking agents, biosurfactants or any other form of biostimulants. Results showed that Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila efficiently degraded both compounds at 37 °C, 37 °C, 30 °C and 35 °C respectively. The degradation of fluorene was more efficient and rapid compared to that of acenaphthene and degradation at Stirred Tank Bioreactor scale was more efficient for all treatments. Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila degraded a mean total of 98.60%, 95.70%, 90.20% and 99.90% acenaphthene, respectively and 99.90%, 97.90%, 98.40% and 99.50% fluorene, respectively. The PAH degrading microorganisms isolated during this study significantly reduced the concentrations of acenaphthene and fluorene and may be used on a larger, commercial scale to bioremediate PAH contaminated river systems.

  7. Muscarinic receptor subtype selectivity of novel heterocyclic QNB analogues

    Energy Technology Data Exchange (ETDEWEB)

    Baumgold, J.; Cohen, V.I.; Paek, R.; Reba, R.C. (George Washington Univ. Medical Center, Washington, DC (USA))


    In an effort at synthesizing centrally-active subtype-selective antimuscarinic agents, the authors derivatized QNB (quinuclidinyl benzilate), a potent muscarinic antagonist, by replacing one of the phenyl groups with less lipophilic heterocyclic moieties. The displacement of ({sup 3}H)-N-methyl scopolamine binding by these novel compounds to membranes from cells expressing ml - m4 receptor subtypes was determined. Most of the novel 4-bromo-QNB analogues were potent and slightly selective for ml receptors. The 2-thienyl derivative was the most potent, exhibiting a 2-fold greater potency than BrQNB at ml receptors, and a 4-fold greater potency than BrQNB at ml receptors, and a 4-fold greater potency at m2 receptors. This compound was also considerably less lipophilic than BrQNB as determined from its retention time on C18 reverse phase HPLC. This compound may therefore be useful both for pharmacological studies and as a candidate for a radioiodinated SPECT imaging agent for ml muscarinic receptors in human brain.

  8. Dialkylamino and nitrogen heterocyclic analogues of hexadecylphosphocholine and cetyltrimetylammonium bromide: effect of phosphate group and environment of the ammonium cation on their biological activity. (United States)

    Lukác, Milos; Mojzis, Ján; Mojzisová, Gabriela; Mrva, Martin; Ondriska, Frantisek; Valentová, Jindra; Lacko, Ivan; Bukovský, Marián; Devínsky, Ferdinand; Karlovská, Janka


    A series of dialkylamino and nitrogen heterocyclic analogues of hexadecylphosphocholine and cetyltrimethylammonium bromide have been synthesized. The prepared compounds exhibit significant cytotoxic, antifungal and antiprotozoal activities. Alkylphosphocholines possess higher antifungal activity against Candida albicans in comparison with quaternary ammonium compounds. However, quaternary ammonium compounds exhibit significant higher activity against human tumor cells and Acanthamoeba lugdunensis compared to alkylphosphocholines. In addition, their haemolytic toxicity has been investigated. The relationship between structure and biological activity of the tested compounds is discussed.

  9. Page 1 HETEROCYCLIC COMPOUNDS Part I. Experiments in ...

    Indian Academy of Sciences (India)

    With acetone, acetophenone, cyclohexanone and a-tetralone all gave diguino- line carboxylic acids according to the following general reaction. COOH. /TN_/TN - = HN jº —NH 2–N. * Nº - --> -->. CO . N-. COOH alternative, purification after esterification Was tried. The Bis cinchoninic acid) and the bis-(2-phenyl cinchoninic ...

  10. Small Molecule Activation for the Formation of Heterocyclic Compounds


    Laserna Ayora, Victor


    La tesis se centra en la actividad de los aminotrifenolatos de aluminio en la activación de epoxidos y su posterior acoplamiento a otras moleculas en la formación de distintos heterociclos. El catalizador es un acido de Lewis que al interaccionar con el epóxido aumenta la electrofilia de este, favoreciendo procesos de apertura de ciclo y acoplamiento a heterocumulenos como el CO2 o el SO2. Hemos conseguido describir metodologías para la sintesis de oxazolidinonas, carbamatos, sulfitos cíclico...

  11. Synthesis and biological activity of some heterocyclic compounds ...

    Indian Academy of Sciences (India)


    antiprotozoal. 20,21 and anti-hepatitis B virus activity. 22. In addition, a large number of antibiotics contain the 2-azetidinone. (commonly known as β-lactam) moiety. 23 such as penicillin, cephalosporin and carbapenem (figure 2). It is also associated with a variety of therapeutic activities. 24–28. In continuation of our work to.

  12. Ring-opening/ring-closing protocols from nitrothiophenes: six-membered versus unusual eight-membered sulfur heterocycles through Michael-type addition on nitrobutadienes. (United States)

    Bianchi, Lara; Giorgi, Gianluca; Maccagno, Massimo; Petrillo, Giovanni; Sancassan, Fernando; Severi, Elda; Spinelli, Domenico; Stenta, Marco; Tavani, Cinzia


    When Ar is a low-aromaticity homo- or heterosystem, the sulfonyl-stabilized anion of nitrobutadienes 4 (which derive from the initial ring opening of 3-nitrothiophene) undergoes a rather surprising addition onto the aromatic ring itself, thereby leading to the construction of an unusual eight-membered sulfur heterocycle condensed with the original Ar ring. The competitiveness of such a pathway with respect to the formation of the thiopyran ring (i.e., addition onto the nitrovinyl moiety) is favored at low temperatures, thus revealing its nature as a kinetically controlled process.


    Directory of Open Access Journals (Sweden)



    Full Text Available Botanical insecticides have long been touted as attractive alternatives to synthetic chemical insecticides for pest management because botanicals reputedly pose little threat to the environment or to human health. The body of scientific literature documenting bioactivity of plant derivatives to arthropods pests continues to expand i.e. repellents based on essential oils extracted from Chenopodium ambrosioides, Eucalyptus saligna, Rosmarinus officinalis to mosquitoes, or cinnamon oil, sandalwood oil and turmeric oil are previously reported as insect repellents evaluatede in the laboratory conditions. With the constantly increasing problems of insecticide resistance and increasing public concerns regarding pesticide safety, new, safer active ingredients are becoming necessary to replace existing compounds on the market. The present study carried out in the period 2010-2012 comprises a review of two insect repellents, followed by some new research conducted in our laboratory on plant-derived insect repellents. The two alkaloids tested against the Colorado potato beetle, Leptinotarsa decemlineata Say in laboratory conditions was obtained by water and alchohol extraction from two vegetal species, Cichorium intybus L. (Asterales:Asteraceae and Delphinium consolida L. (Ranales:Ranunculaceae. The tests carried out in laboratory and field experimentally plots under cages permit to evaluate several other compounds for repellent activity of lacctucin alkaloids.

  14. Electrochemical C-H amination: synthesis of aromatic primary amines via N-arylpyridinium ions. (United States)

    Morofuji, Tatsuya; Shimizu, Akihiro; Yoshida, Jun-ichi


    We have developed a new method for C-H amination of aromatic compounds based on electrochemical oxidation of aromatic compounds in the presence of pyridine followed by the reaction of the resulting N-arylpyridinium ions with an alkylamine. This new transformation serves as a powerful method for synthesizing aromatic primary amines from aromatic compounds without using metal catalysts and harsh chemical reagents. High chemoselectivity of the present method is demonstrated by C-H amination of aromatic compounds bearing a nitro group to give a key intermediate for the synthesis of VLA-4 antagonist.

  15. Synthesis and Biological Evaluation of Novel Benzimidazole Derivatives Bearing a Heterocyclic Ring at 4/5 Position

    Energy Technology Data Exchange (ETDEWEB)

    Wubulikasimu, Reyila; Yang, Yanbing; Xue, Fei; Luo, Xianjin; Shao, Dongping [Shanghai Jiaotong Univ., Shanghai (China); Li, Yuhuan; Gao, Rongmei [Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing (China); Ye, Weidong [Zhejiang Medicine Co. Ltd., Zhejiang (China)


    A series of novel benzimidazole derivatives bearing a heterocyclic ring as oxadiazole (21-32), thiadiazole (33-34), triazole (35-36) were synthesized and evaluated for their activities against Coxsackie virus B3 and B6 in Vero cells. Compounds 21-26, 31-36 with moieties of 2'-pyridyl, 3'-pyridyl and 4'-pyridyl at the 2-position and oxadiazoles, thiadiazole, or triazole substituent at the 4- or 5-position generally displayed activities against CVB3 and CVB6. Especially compound 24 (IC{sub 50} = 1.08 μg/mL, SI = 61.7 against CVB3) was the promising candidate as lead compound for anti-enteroviral drug. It was observed in the incorporation of heterocyclic rings in benzimidazole at the 5-position could enhance their biological activities.

  16. Synthesis, photophysical properties and structures of organotin-Schiff bases utilizing aromatic amino acid from the chiral pool and evaluation of the biological perspective of a triphenyltin compound. (United States)

    Basu Baul, Tushar S; Kehie, Pelesakuo; Duthie, Andrew; Guchhait, Nikhil; Raviprakash, Nune; Mokhamatam, Raveendra B; Manna, Sunil K; Armata, Nerina; Scopelliti, Michelangelo; Wang, Ruimin; Englert, Ulli


    Five new organotin(IV) complexes of compositions [Me2SnL1] (1), [Me2SnL2]n (2), [Me2SnL3] (3), [Ph3SnL1H]n (4) and [Ph3SnL3H] (5) (where L1=(2S)-2-((E)-((Z)-4-hydroxypent-3-en-2-ylidene)amino)-3-(1H-indol-3-yl)propanoate, L2=(2S)-(E)-2-((2-hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoate and L3=(2S)-(E)-2-((1-(2-hydroxyphenyl)ethylidene)amino)-3-(1H-indol-3-yl)propanoate were synthesized and spectroscopically characterized. The crystal structures of 1-4 were determined. For the dimethyltin derivative 2, a polymeric chain structure was observed as a result of a long Sn∙∙∙O contact involving the exocyclic carbonyl oxygen-atom from the tridentate ligand of a neighboring Sn-complex unit. The tin atom in this complex has a distorted octahedral coordination geometry, in which the long Sn-O bond is almost trans to the tridentate ligand nitrogen-atom. In contrast, the dimethyltin(IV) complexes 1 and 3 displayed discrete monomeric structures where the tin atom has distorted trigonal-bipyramidal geometry with the two coordinating L oxygen atoms defining the axial positions. On the other hand, 4 is a chain polymer in the solid state. The ligand-bridged Sn atoms adopt a trans-Ph3SnO2 trigonal-bipyramidal configuration with equatorial phenyl groups. A carboxylato oxygen atom from one and the hydroxyl oxygen of the successive ligand in the chain occupy the axial positions. The solution structures were predicted by the use of 119Sn NMR chemical shifts. The photophysical properties of the complexes were investigated in the solid and in solution. The triphenyltin(IV) compound 4 was tested in detail ex vivo against A375 (human melanoma) cell line, exhibiting an IC50 value of 261nM to induce cell death as assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay without significant alteration of cytolysis as determined by lactate dehydrogenase (LDH) assay. Compound 4-mediated potent cell death was also determined by Live and Dead assay and

  17. Anaerobic Degradation of Phenolic Compounds


    Schink, Bernhard; Philipp, Bodo; Jochen A Müller


    Mononuclear aromatic compounds are degraded anaerobically through three main pathways, the benzoyl-CoA pathway, the resorcinol pathway, and the phloroglucinol pathway. Various modification reactions channel a broad variety of mononuclear aromatics including aromatic hydrocarbons into either one of these three pathways. Recently, a further pathway was discovered with hydroxyhydroquinone as central intermediate through which especially nitrate-reducing bacteria degrade phenolic compounds and so...

  18. An Unconventional Redox Cross Claisen Condensation-Aromatization of 4-Hydroxyprolines with Ketones. (United States)

    Tang, Mi; Sun, Rengwei; Li, Hao; Yu, Xinhong; Wang, Wei


    Reaction of α-amino acids, particularly prolines and their derivatives with carbonyl compounds via decarboxylative redox process, is a viable strategy for synthesis of structurally diverse nitrogen centered heterocyclics. In these processes, the decarboxylation is the essential driving force for the processes. The realization of the redox process without decarboxylation may offer an opportunity to explore new reactions. Herein, we report the discovery of an unprecedented redox Claisen-type condensation aromatization cascade reaction of 4-substituted 4-hydroxyproline and its esters with unreactive ketones. We found that the use of propionic acid as a catalyst and a co-solvent can change the reaction course. The commonly observed redox decarboxylation and aldol condensation reactions are significantly minimized. Moreover, unreactive ketones can effectively participate in the Claisen condensation reaction. The new reactivity enables a redox cyclization via an unconventional Claisen-type condensation reaction of in situ formed enamine intermediates from ketone precursors with 4-substituted 4-hydroxyproline and its esters as electrophilic acylation partners. Under the reaction conditions, the cascade process proceeds highly regio- and stereoselectively to afford highly synthetically and biologically valued cis-2,3-dihydro-1H-pyrrolizin-1-ones with a broad substrate scope in efficient 'one-pot' operation, whereas such structures generally require multiple steps.

  19. Platinum-Based Organometallic Folders for the Recognition of Electron-Deficient Aromatic Substrates. (United States)

    Nuevo, Daniel; Gonell, Sergio; Poyatos, Macarena; Peris, Eduardo


    A series of platinum complexes with cis-oriented polyaromatic N-heterocyclic carbene ligands were prepared and characterized. The relative disposition of the polyaromatic ligands about the metal cause these compounds to behave as metallofolders, featuring a cavity defined by the void space between the polyaromatic functionalities. The complexes were used as receptors of organic molecules, whereby selective affinity was displayed for electron-deficient aromatic substrates, such as 1,2,4,5-tetracyanobenzene (TCNB), 2,4,7-trinitro-9-fluorenone (TNFLU), and 1,4,5,8-naphtalenetetracarboxylic dianhydride (NTCDA). The binding affinities of two of the metallofolders with these substrates were determined by means of 1 H NMR titrations. Electrospray mass spectrometry (ESI-MS) was also used to assess the affinities. The molecular structure of one of the platinum folders was determined in the presence of TCNB, showing the clear interaction between this guest molecule and the folder formed by the two mutually cis-oriented polyaromatic ligands. This work demonstrates how the presence of the mutually cis-oriented polyaromatic ligands may be a very useful tool for the preparation of metal-based receptors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Experimental study and kinetic modeling of the thermal degradation of aromatic volatile organic compounds (benzene, toluene and xylene-para) in methane flames; Etude experimentale et modelisation cinetique de la degradation thermique des composes organiques volatils aromatiques benzenes, toluene et para-xylene dans des flammes de methane

    Energy Technology Data Exchange (ETDEWEB)

    Dupont, L.


    This study treats of the thermal degradation of a family of aromatic volatile organic compounds (VOCs) in laminar premixed methane flames at low pressure. The experimental influence of benzene, toluene and xylene-para on the structure of a reference methane flame has been studied. The molar fraction profiles of the stable and reactive, aliphatic, aromatic and cyclic species have been established by the coupling of the molecular beam sampling/mass spectroscopy technique with the gas chromatography/mass spectroscopy technique. Temperature profiles have been measured using a covered thermocouple. A detailed kinetic mechanism of oxidation of these compounds in flame conditions has been developed. Different available sub-mechanisms have been used as references: the GDF-Kin 1.0 model for the oxidation of methane and the models of Tan and Franck (1996) and of Lindstedt and Maurice (1996) in the case of benzene and toluene. In the case of para-xylene, a model has been developed because no mechanisms was available in the literature. These different mechanisms have been refined, completed or adjusted by comparing the experimental results with those obtained by kinetic modeling. The complete kinetic mechanism, comprising 156 chemical species involved in 1072 reactions allows to reproduce all the experimental observations in a satisfactory manner. The kinetic analysis of reactions velocity has permitted to determine oxidation kinetic schemes for benzene, toluene, xylene-para and for the cyclopentadienyl radical, main species at the origin of the rupture of the aromatic cycle. Reactions of recombination with the methyl radicals formed during methane oxidation, of the different aromatic or aliphatic radicals created during the oxidation of aromatics, play an important role and lead to the formation of several aromatic pollutants (ethyl-benzene for instance) or aliphatic pollutants (butadiene or penta-diene for instance) in flames. (J.S.)

  1. Structural Correlation of Some Heterocyclic Chalcone Analogues and Evaluation of Their Antioxidant Potential

    Directory of Open Access Journals (Sweden)

    Hoong-Kun Fun


    Full Text Available A series of six novel heterocyclic chalcone analogues 4(a–f has been synthesized by condensing 2-acetyl-5-chlorothiophene with benzaldehyde derivatives in methanol at room temperature using a catalytic amount of sodium hydroxide. The newly synthesized compounds are characterized by IR, mass spectra, elemental analysis and melting point. Subsequently; the structures of these compounds were determined using single crystal X-ray diffraction. All the synthesized compounds were screened for their antioxidant potential by employing various in vitro models such as DPPH free radical scavenging assay, ABTS radical scavenging assay, ferric reducing antioxidant power and cupric ion reducing antioxidant capacity. Results reflect the structural impact on the antioxidant ability of the compounds. The IC50 values illustrate the mild to good antioxidant activities of the reported compounds. Among them, 4f with a p-methoxy substituent was found to be more potent as antioxidant agent.

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

    NARCIS (Netherlands)

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


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

  3. Hidden Components in Aqueous "Gold-144" Fractionated by PAGE: High-Resolution Orbitrap ESI-MS Identifies the Gold-102 and Higher All-Aromatic Au-pMBA Cluster Compounds. (United States)

    Alvarez, Marcos M; Chen, Jenny; Plascencia-Villa, Germán; Black, David M; Griffith, Wendell P; Garzón, Ignacio L; José-Yacamán, Miguel; Demeler, Borries; Whetten, Robert L


    Experimental and theoretical evidence reveals the resilience and stability of the larger aqueous gold clusters protected with p-mercaptobenzoic acid ligands (pMBA) of composition Aun(pMBA)p or (n, p). The Au144(pMBA)60, (144, 60), or gold-144 aqueous gold cluster is considered special because of its high symmetry, abundance, and icosahedral structure as well as its many potential uses in material and biological sciences. Yet, to this date, direct confirmation of its precise composition and total structure remains elusive. Results presented here from characterization via high-resolution electrospray ionization mass spectrometry on an Orbitrap instrument confirm Au102(pMBA)44 at isotopic resolution. Further, what usually appears as a single band for (144, 60) in electrophoresis (PAGE) is shown to also contain the (130, 50), recently determined to have a truncated-decahedral structure, and a (137, 56) component in addition to the dominant (144, 60) compound of chiral-icosahedral structure. This finding is significant in that it reveals the existence of structures never before observed in all-aromatic water-soluble species while pointing out the path toward elucidation of the thermodynamic control of protected gold nanocrystal formation.

  4. Exploration of Visible-Light Photocatalysis in Heterocycle Synthesis and Functionalization: Reaction Design and Beyond. (United States)

    Chen, Jia-Rong; Hu, Xiao-Qiang; Lu, Liang-Qiu; Xiao, Wen-Jing


    pyridazine derivatives in good yields and selectivity. Moreover, we have demonstrated that this photocatalysis can serve as a mild and highly selective tool for direct functionalization of heterocycles because of its powerful capability to controllably generate diverse reactive intermediates under mild reaction conditions. Guided by the fundamental principles of photocatalysis and the redox properties of the photocatalysts, we successfully developed an array of dual-catalyst systems by combining the photocatalysts with palladium, nickel, or amine, enabling efficient and selective coupling reactions. An intriguing phototandem catalytic system using a single photocatalyst was also identified for the development of cascade reactions. Notably, some of the newly developed methodologies have also been successfully utilized for late-stage modification of biologically active natural compounds and complex molecules and as key steps for formal synthesis of natural products. This Account presents a panoramic view and the logic of our recent contributions to the design, development, and application of photocatalytic systems and reactions that provide not only methods for the efficient synthesis of heterocycles but also useful insights into the exploration of new photochemical reactions.

  5. Nickel N-heterocyclic carbene complexes in homogeneous catalysis

    NARCIS (Netherlands)

    Berding, Joris


    Described in this thesis are the investigations into the chemistry of N-heterocyclic carbene (NHC) ligands and transition-metal complexes thereof. Specifically, a variety of N-heterocyclic carbene complexes of nickel were prepared, characterized and used as catalysts in three types of homogeneous

  6. Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis (United States)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

  7. Thermally stable and chemically resistant polymer membranes : aromatic polyoxadiazoles and polytriazoles


    Gebben, Bert


    This thesis concerns the preparation of membranes from thermally stable and chemically resistant polymers. Two polymer families from the category of heterocyclic and aromatic polymers have been selected for investigation, the polyoxadiazoles and the polytriazoles, respectively. A major problem concerning these types of polymers is their bad processability due to their insolubility and infusibility. For the polyoxadiazoles this problem is circumvented by using a two-step preparation process th...

  8. Experimental and Computational Studies of the Reactions of N and O Atoms with Small Heterocyclic Anions. (United States)

    Wang, Zhe-Chen; Bierbaum, Veronica M


    The existence of heterocyclic aromatic anions in extraterrestrial environments, such as the upper atmosphere of Titan, has been recently confirmed by data from the Cassini spacecraft. Nitrogen and oxygen atoms are also common species in the ionospheres of planets and moons and in the interstellar medium. In the current work, we extend previous studies to explore the reactivity of five-membered ring aromatic anions that contain nitrogen, oxygen, or sulfur (deprotonated pyrrole, furan, and thiophene) with N and O atoms both experimentally and computationally. Furanide and thiophenide anions react with the N atom by associative electron detachment (AED). All three anions react with the O atom both by AED and by processes that form ionic products. The reaction of pyrrolide anion with the O atom generates only one ionic product C4H3NO(-), corresponding to an O addition and H loss process. The corresponding process is observed as the major channel for the reaction of furanide anion with the O atom while other ionic products HCOO(-) and C2H(-) are also formed. The reaction of thiophenide with the O atom is more complex, and four ionic products are generated, of which three are sulfur-containing ions. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions, which are relevant to ionospheric and interstellar chemistry.

  9. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)


    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  10. Heterocyclic replacements for benzene: Maximising ADME benefits by considering individual ring isomers. (United States)

    Ritchie, Timothy J; Macdonald, Simon J F


    The impact of replacing a mono-substituted benzene (phenyl) ring with thirty three aromatic and nine aliphatic heterocycles on nine ADME-related screens (solubility, lipophilicity, permeability, protein binding CYP450 inhibition and metabolic clearance) was assessed using matched molecular pair analysis. The results indicate that the influence on the ADME profile can differ significantly depending on the ring identity and importantly on the individual regioisomers that are possible for some rings. This information enables the medicinal chemist to make an informed choice about which rings and regioisomers to employ as mono-substituted benzene replacements, based upon the knowledge of how such replacements are likely to influence ADME-related parameters, for example to target higher solubility whilst avoiding CYP450 liabilities. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  11. Inhibition of T24 and RT4 Human Bladder Cancer Cell Lines by Heterocyclic Molecules. (United States)

    Zhao, Zhi-Feng; Wang, Kai; Guo, Feng-Fu; Lu, Hua


    BACKGROUND Bladder cancer is a major widespread tumor of the genitourinary tract. Around 30% of patients with superficial cancers develop invasive and metastatic pathology. MATERIAL AND METHODS Some new heterocyclic 4-methyl coumarin derivatives were designed using molecular modeling studies to evaluate their potential against bladder cancer lines T24 and RT-4. The designed compounds that showed good binding affinity to T24 and RT4 were synthesized, with excellent yield. The synthesized compounds after structural evaluation were further evaluated for their antiproliferative activity by cell viability assay, cell cycle analysis, and apoptosis assay. RESULTS The compound BC-14 exhibited the best cytotoxicity against T24 cells, but were not highly active against RT4 cells. CONCLUSIONS The results of the present study may suggest the selectivity pattern of the synthesized compounds. These results should be explored further with chemical modification for other cancer types.

  12. Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-Catalyzed Enyne Cycloisomerization, and Automated Amide Synthesis (United States)

    Cui, Jiayue; Chai, David I.; Miller, Christopher; Hao, Jason; Thomas, Christopher; Wang, JingQi; Scheidt, Karl A.; Kozmin, Sergey A.


    We describe a unified synthetic strategy for efficient assembly of four new heterocyclic libraries. The synthesis began by creating a range of structurally diverse pyrrolidinones or piperidinones. Such compounds were obtained in a simple one-flask operation starting with readily available amines, ketoesters, and unsaturated anhydrides. The use of tetrahydropyran-containing ketoesters, which were rapidly assembled by our Prins cyclization protocol, enabled efficient fusion of pyran and piperidinone cores. A newly developed Au(I)-catalyzed cycloisomerization of alkyne-containing enamides further expanded heterocyclic diversity by providing rapid entry into a wide range of bicyclic and tricyclic dienamides. The final stage of the process entailed diversification of each of the initially produced carboxylic acids using a fully automated platform for amide synthesis, which delivered 1872 compounds in high diastereomeric and chemical purity. PMID:22860634

  13. Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia. (United States)

    Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett


    Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

  14. Formation of a new copper(II) dimer through heterocyclic ligand ring opening reaction: Supramolecular features and magnetic properties (United States)

    Gonçalves, Bruna Lisboa; Gervini, Vanessa Carratu; Flores, Alex Fabiani Claro; Junior, Jorge Luiz Pimentel; Bortoluzzi, Adailton João; Burrow, Robert Alan; Duarte, Rafael; da Silva, Robson Ricardo; Vicenti, Juliano Rosa de Menezes


    Two new compounds were synthesized and characterized in this work: the heterocycle (Z)-1-(4-(hydroxyimino)-3,5-dimethyl-1-(methylcarbamothioyl)-4,5-dihydro-1H-pyrazol-5-yl)-4-methylthiosemicarbazide and a copper(II) thiosemicarbazonato dimeric complex. Green prismatic single crystals of the dimer were obtained by the reaction of the heterocycle with copper(II) chloride dihydrate. Both compounds were essentially characterized by spectroscopic methods and X-ray diffraction crystallography. The crystal structures revealed molecules connected through supramolecular hydrogen bond interactions and copper(II) centers in a slightly distorted square-pyramidal environment. SQUID magnetometry performed for the dimer revealed both ferromagnetic and antiferromagnetic interactions in the studied complex, presenting a critical temperature of 19 K.

  15. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation (United States)

    Lewis, Jared C.; Bergman, Robert G.; Ellman, Jonathan A.


    Conspectus Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct functionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes our work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. We initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. We then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, we discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. We then synthesized analogous Rh–NHC complexes directly by treating precursors to the intermediate [RhCl(PCy3)2] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazoline, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy3)2 fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, we developed conditions that efficiently and intermolecularly alkylate a variety of heterocycles, including

  16. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan


    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  17. A review on bis-hydrazonoyl halides: Recent advances in their synthesis and their diverse synthetic applications leading to bis-heterocycles of biological interest

    Directory of Open Access Journals (Sweden)

    Ahmad Sami Shawali


    Full Text Available This review covers a summary of the literature data published on the chemistry of bis-hydrazonoyl halides over the last four decades. The biological activities of some of the bis-heterocyclic compounds obtained from these bis-hydrazonoyl halides are also reviewed and discussed.

  18. Synthesis of palladium(0) and -(II) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation


    Sluijter, S.N.; Warsink, S.; Lutz, M.; Elsevier, C.J.


    A transmetallation route, using silver(I) precursors, to several zero-and di-valent palladium complexes with chelating bis(N-heterocyclic carbene) ligands bearing various N-substituents has been established. The resulting complexes have been characterized by NMR and mass spectroscopy. In addition, the structure of a representative compound, [Pd-0(bis-(Mes)NHC)(eta(2)-ma)] (3a), was confirmed by X-ray crystal structure determination. In contrast to the transfer semihydrogenation, in which only...

  19. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex (United States)

    Ortega-Arizmendi, Aldo I.; Aldeco-Pérez, Eugenia; Cuevas-Yañez, Erick


    A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields. PMID:24307866

  20. Extraction of aromatics from naphtha with ionic liquids

    NARCIS (Netherlands)

    Meindersma, G.W.


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

  1. Synthesis, antimicrobial activity and molecular docking of novel tetracyclic scaffolds incorporating a flavonoid framework with medium sized oxygen heterocycles. (United States)

    Dongamanti, Ashok; Aamate, Vikas Kumar; Devulapally, Mohan Gandhi; Gundu, Srinivas; Kotni, Meena Kumari; Manga, Vijjulatha; Balasubramanian, Sridhar; Ernala, Prasad


    A convenient approach for the synthesis of novel tetracyclic scaffolds incorporating a flavonoid framework with medium sized heterocyclic rings (eight-, nine-, ten- and eleven-membered rings) containing two oxygen atoms from flavonols through alkylation using different dibromoalkanes was described. The synthesized compounds were established based on the spectral data and X-ray crystal structure for 6c. The synthesized compounds were evaluated for their in vitro antimicrobial activity. Docking studies were carried out for most active two compounds 6f and 6i. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

    Energy Technology Data Exchange (ETDEWEB)

    Turov, A.V.; Khilya, V.P. [Taras Shevchenko Kiev Univ. (Russian Federation)


    The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

  3. New metathesis catalyst bearing chromanyl moieties at the N-heterocyclic carbene ligand

    Directory of Open Access Journals (Sweden)

    Agnieszka Hryniewicka


    Full Text Available The synthesis of a new type of Hoveyda–Grubbs 2nd generation catalyst bearing a modified N-heterocyclic carbene ligands is reported. The new catalyst contains an NHC ligand symmetrically substituted with chromanyl moieties. The complex was tested in model CM and RCM reactions. It showed very high activity in CM reactions with electron-deficient α,β-unsaturated compounds even at 0 °C. It was also examined in more demanding systems such as conjugated dienes and polyenes. The catalyst is stable, storable and easy to purify.

  4. Practical and Efficient Synthesis of α-Aminophosphonic Acids Containing 1,2,3,4-Tetrahydroquinoline or 1,2,3,4-Tetrahydroisoquinoline Heterocycles

    Directory of Open Access Journals (Sweden)

    Mario Ordóñez


    Full Text Available We report here a practical and efficient synthesis of α-aminophosphonic acid incorporated into 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroisoquinoline heterocycles, which could be considered to be conformationally constrained analogues of pipecolic acid. The principal contribution of this synthesis is the introduction of the phosphonate group in the N-acyliminium ion intermediates, obtained from activation of the quinoline and isoquinoline heterocycles or from the appropriate δ-lactam with benzyl chloroformate. Finally, the hydrolysis of phosphonate moiety with simultaneous cleavage of the carbamate afforded the target compounds.

  5. Mutagenic Potency of Food-Derived Heterocyclic Amines

    Energy Technology Data Exchange (ETDEWEB)

    Felton, J S; Knize, M G; Wu, R W; Colvin, M E; Hatch, F T; Malfatti, M A


    The understanding of mutagenic potency has been primarily approached using ''quantitative structure activity relationships'' (QSAR). Often this method allows the prediction of mutagenic potency of the compound based on its structure. But it does not give the underlying reason why the mutagenic activities differ. We have taken a set of heterocyclic amine structures and used molecular dynamic calculations to dock these molecules into the active site of a computational model of the cytochrome P-450 1A1 enzyme. The calculated binding strength using Boltzman distribution constants was then compared to the QSAR value (HF/6-31G* optimized structures) and the Ames/Salmonella mutagenic potency. Further understanding will only come from knowing the complete set of mutagenic determinants. These include the nitrenium ion half-life, DNA adduct half-life, efficiency of repair of the adduct, and ultimately fixation of the mutation through cellular processes. For two isomers, PhIP and 3-Me-PhIP, we showed that for the 100-fold difference in the mutagenic potency a 5-fold difference can be accounted for by differences in the P450 oxidation. The other factor of 20 is not clearly understood but is downstream from the oxidation step. The application of QSAR (chemical characteristics) to biological principles related to mutagenesis is explored in this report.

  6. CEC separation of heterocyclic amines using methacrylate monolithic columns. (United States)

    Barceló-Barrachina, Elena; Moyano, Encarnación; Puignou, Lluís; Galceran, Maria Teresa


    Two methacrylate-based monolithic columns, one with a negatively charged group (sulfonic group) and another with a new monomer N,N-dimethylamino ethyl acrylate (DMAEA), were prepared and tested for the separation of basic compounds by CEC. This new monolithic stationary phase was prepared by the in situ polymerization of DMAEA with butyl methacrylate and ethylene dimethacrylate, using a ternary porogenic solvent consisting of water, 1-propanol and 1,4-butanediol. The performance of this column was evaluated by means of the analysis of a family of heterocyclic amines. Separation conditions such as pH, amount of organic modifier, ionic strength and elution mode (normal or counterdirectional flow) were studied. At the optimal running electrolyte composition, and using the counterdirectional mode, symmetrical electrochromatographic peaks were obtained, with the number of theoretical plates up to 30,000 and a good resolution between closely related peaks. The 2-acrylamido-2-methyl-1-propane-sulfonic acid column was used for CEC-MS, taking advantage of the compatibility of its elution mode (normal flow) with the MS coupling.

  7. Dissolution and transport of coal tar compounds in fractured clay-rich residuum. (United States)

    Vulava, Vijay M; McKay, Larry D; Broholm, Mette M; McCarthy, John F; Driese, Steven G; Sayler, Gary S


    We investigated the dissolution and transport of organic contaminants from a crude coal tar mixture in a monolith of fractured clay-rich residuum. An electrolyte solution was eluted through the residuum monolith containing a small emplaced source of coal tar under biologically inhibited and mildly acidic conditions. Concentrations of 10 coal tar compounds, representing mono-, poly-, and heterocyclic aromatic hydrocarbons that constitute crude coal tar were monitored in the effluent over a period of 377 days. Most compounds appeared in the effluent within the first 0.1 pore volume eluted indicating the importance of rapid dissolution and transport through the fracture networks. The concentrations continued to rise but did not reach the corresponding effective solubility limit in most cases. Compounds that were less soluble and those that were more susceptible to sorption or matrix diffusion eluted at a much slower rate. Analysis of contaminant concentrations in microcore residuum samples indicated that all 10 compounds had spread throughout the entire monolith and had diffused into the fine-grained matrix between fractures. These data suggest that the predominantly fine pore structure did not appear to inhibit coal tar dissolution and subsequent transport, even though only a small portion of tar was in direct contact with fractures and macropores that control most flow. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Cytotoxic Effect of a Novel Synthesized Carbazole Compound on A549 Lung Cancer Cell Line.

    Directory of Open Access Journals (Sweden)

    Refilwe P Molatlhegi

    Full Text Available Increased death rates due to lung cancer have necessitated the search for potential novel anticancer compounds such as carbazole derivatives. Carbazoles are aromatic heterocyclic compounds with anticancer, antibacterial and anti-inflammatory activity. The study investigated the ability of the novel carbazole compound (Z-4-[9-ethyl-9aH-carbazol-3-yl amino] pent-3-en-2-one (ECAP to induce cytotoxicity of lung cancer cells and its mechanism of action. ECAP was synthesized as a yellow powder with melting point of 240-247 °C. The 3-(4,5-dimethythiazol-2-yl-2,5-diphenyl tetrazolium bromide (MTT, lipid peroxidation and comet assays were used to assess the cytotoxic effect of the compound on A549 lung cancer cells. Protein expression was determined using western blots, apoptosis was measured by luminometry (caspase-3/7, -8 and -9 assay and flow cytometry was used to measure phosphatidylserine (PS externalisation. ECAP induced a p53 mediated apoptosis of lung cancer cells due to a significant reduction in the expression of antioxidant defence proteins (Nrf2 and SOD, Hsp70 (p < 0.02 and Bcl-2 (p < 0.0006, thereby up-regulating reactive oxygen species (ROS production. This resulted in DNA damage (p < 0.0001, up-regulation of Bax expression and caspase activity and induction of apoptosis in lung cancer cells. The results show the anticancer potential of ECAP on lung cancer.

  9. Separation of aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Grishchenko, N.F.; Yablochkina, M.N.; Shapiro, L.P.; Rogozkin, V.A.


    An optimal system of extraction has been developed making it possible to produce benzene, toluene and xylenes economically and with high efficiency.The raw material used for catalytic reforming consists of narrow-boiling-range gasoline fractiions at 62 to 85, 62 to 105 and 105 to 140/sup 0/C. Processing of the first fraction makes it possible to produce benzene; the second, benzene and toluene; and the third, toluene and xylenes. The addition of reforming extraction units has made it possible to produce aromatic hydrocarbons suitable for any specialized application. At the current time the output of benzene with extraction plants is about 60 percent of the total output, of toluene more than 80 percent and of xylene more than 50 percent. The key technological indicators are given for the processes of extraction with hydrous polyglycols. For new higher-capacity plants, in addition to extraction with tetraethylene glycol, the 'Ekstars' process has been developed for extraction with a hybrid solvent based on propylene carbonate. For eliminating the presence of unsaturated compounds, a process has been developed for the selective hydrogenation of reforming catalysis products. The process is carried out in an additional reactor included in the catalytic reforming system, at 160 to 250/sup 0/C with an aluminoplatinic catalyst in a combined steam and gas mixture flow at a pressure of 1.5 to 3.5 MPa. (JMT)

  10. Volatilisation of aromatic hydrocarbons from soil

    DEFF Research Database (Denmark)

    Lindhardt, B.; Christensen, T.H.


    The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic...

  11. Structure-activity relationships of estrogen derivatives as aromatase inhibitors. Effects of heterocyclic substituents. (United States)

    Numazawa, Mitsuteru; Komatsu, Sachiko; Tominaga, Takako; Yamashita, Kouwa


    Aromatase, which is responsible for the conversion of androgens to estrogens, is a potential therapeutic target for the selective lowering estrogen level in patients with estrogen-dependent breast cancer. We prepared and tested series of the pyridine- and other heterocyclic ring-containing derivatives of 2- and 4-aminoestrones, estrone, and estradiol, compounds 5, 10, 12 and 15. The isonicotinyl derivatives of 2- and 4-aminoestrone, compounds 5c and 10c, were fairly potent competitive inhibitors of aromatase (K(i), 2.1+/-0.14 and 1.53+/-0.08 microM for 5c and 10c, respectively) and other compounds did not show, to a significant extent, the aromatase inhibitory activity. This result suggests that the isonicotinyl-substituted derivatives 5c and 10c would be accessible to the active site of aromatase.

  12. Synthesis and characterization of various ruthenium small molecules and metallopolymers for potential use in photovoltaic devices and luminescence properties of N-heterocyclic carbenes and trifluoro methylated tris(pyrazolyl)borate silver (I) acid-base adducts (United States)

    Chitikuri, Shylaja

    This thesis with its 66 pages, 1 table, 29 figures and 47 references, deals with two major topics involving structure and properties of selected metal complexes and their use in electronic devices. The first chapter discusses the development of ruthenium-based metallopolymer and small molecular complexes toward possible utilization as active materials for solar cells. Such complexes have been found to be good "black absorbers" with solid-state absorption that spans the entire visible region into the near-infrared, representing an impressive overlap with the solar radiation that is more favorable than common molecular solar cell active materials. The second chapter includes photophysical studies of different metallo N-heterocyclic carbenes and acid-base adducts comprising fluorinated tris(pyrazolyl)borate silver(I) complexes coordinated to different solvent and aromatic molecules. These species have been investigated and found to exhibit unusual photophysical properties, including metal-free phosphorescence at room temperature with high quantum yield, multi-color emission from a single compound, and selective sensing of temperature and hazardous vapors.

  13. Pharmacokinetic Studies of Oxathio-Heterocycle Fused Chalcones. (United States)

    Okoniewska, Krystyna; Konieczny, Marek T; Lemke, Krzysztof; Grabowski, Tomasz


    Chalcone constitutes one of the most used molecular frameworks in medicinal chemistry and its derivatives exhibit a broad spectrum of biological activities. Low absolute bioavailability, poor distribution, intensive metabolism and elimination of chalcones are the main problems in designing new drugs based on their structure. One of the fundamental steps in evaluation of drug candidates is a comparative analysis of pharmacokinetic parameters. The aim of the studies was the pharmacokinetic characterization of the selected oxathio-heterocycle fused chalcones. The pharmacokinetic parameters of 19 compounds were reported. The analyzed chalcones were examined after a single intravenous administration to forty 7-week-old mature male rats of Wistar stock. Pharmacokinetic analysis was performed independently using SHAM (slopes, highest, amounts, and moments) and the two-compartment model. Basic physiochemical parameters were calculated. The bioanalytical methods were validated in terms of repeatability, linearity, accuracy, precision, and selectivity. The pharmacokinetics of the examined group of chalcones are compatible with the two-compartment model. The physicochemical characteristics of this group are quite homogeneous. The kinetics of the examined chalcones are indicative of a distribution to the tissue compartment with the predominance of a rate constant from central to peripheral compartments (k12) over the rate constant from peripheral to central compartments (k21). The elimination from the central compartment (k10) is higher than the transfer from the central compartment to the tissues (k10 > k12) in almost all examined cases. The presented group of compounds may form a starting point for studies into drugs treating autoimmune diseases of the gastro-intestinal tract.

  14. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul


    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  15. Azaborines: Unique Isosteres of Aromatic and Heteroaromatic Systems (United States)

    Davies, Geraint H. M.

    The azaborine motif provides a unique opportunity to develop core isosteres by inserting B-N units in place of C=C bonds within aromatic scaffolds. These boron/nitrogen-containing heteroaromatic systems provide molecular frameworks that have similar, but not identical, geometrical shapes and electronic distributions to the analogous all carbon systems. Synthetic routes to the 1,3,2-benzodiazaborole core have been developed utilizing entirely bench-stable starting materials, including organotrifluoroborates, enabling a wider array of substrate analogues under facile reaction conditions. The physical, structural, and electronic properties of these compounds were explored computationally to understand the influence of the B-N replacement on structure, aromaticity, and the isosteric viability of these analogues. The class of azaborininones could similarly be accessed from both organotrifluoroborates and boronic acids. An inexpensive, common reagent, SiO2, was found to serve as both a fluorophile and desiccant to facilitate the annulation process across three different azaborininone platforms. Computationally-derived pK a values, NICS aromaticity calculations, and electrostatic potential surfaces revealed a unique isoelectronic/isostructural relationship between these azaborines and their carbon isosteres that changed based on boron connectivity. The 2,1-borazaronaphthalene motif can be accessed through robust methods of synthesis and subsequent functionalization strategies, affording an ideal platform to use for a variety of applications. However, the initial scope of substructures for this archetype has been limited by the lack of nitrogen-containing heteroaryls that can be incorporated within them. Modified reaction conditions enabled greater tolerance to provide access to a wider range of substructures. Additionally, computational and experimental studies of solvent decomposition demonstrate that substitution off boron is important to stability. Post

  16. Graphenes–Aromatic Giants

    Indian Academy of Sciences (India)

    Graphenes - Aromatic Giants. Ivan Gutman Boris Furtula. Volume 16 Issue 12 December 2011 pp 1238-1245. Fulltext. Click here to view fulltext PDF. Permanent link: Keywords. Graphenes; polycyclic aromatic hydrocarbons; polyphenyls; condensed benzenes.

  17. Boron-Heteroatom Addition Reactions via Borylative Heterocyclization: Oxyboration, Aminoboration, and Thioboration. (United States)

    Issaian, Adena; Tu, Kim N; Blum, Suzanne A


    Organoboron compounds and heterocycles are powerful building blocks and precursors for organic synthesis, including for drug discovery and agrochemical and material synthesis. The common strategy for the synthesis of borylated heterocycles involves two separate synthetic steps: first, synthesis of the heterocyclic core, and second, borylation of the core through established methods such as transition-metal-catalyzed C-H or C-X activation/borylation or lithiation/borylation. In this Account, we describe our laboratory's development of borylative heterocyclization reactions that access the heterocyclic core and install boron in one synthetic step. These methods provide complementary bond disconnections, regiochemistry, and functional-group compatibility to current methods. We describe our methods with two categories: a direct borylation method that refers to addition reactions starting from a preformed B-element σ bond, which is essential in the mechanistic route to product formation, and a formal borylation method that refers to addition reactions that do not require formation of a B-element bond but instead proceed through carbon-carbon π-bond activation by an electrophilic boron source followed by dealkylation or deacylation. Through electrophilic activation of the alkyne rather than activation of the B-element bond, formal borylation provides a complementary strategy toward neutral organoboron reagents. We first studied direct oxyboration toward the formation of borylated benzofurans, where a preformed boron-oxygen σ bond is added across an alkyne activated by a carbophilic gold catalyst. We describe detailed mechanistic and kinetic studies of this class of reactions. Application of the knowledge gained from these studies aided in the future development of additional direct borylation reactions involving boron-nitrogen and boron-oxygen σ bonds to form borylared indoles and isoxazoles, respectively. Formal addition of boron/oxygen equivalents to effect

  18. Ruthenium Catalysts Supported by Amino-Substituted N-Heterocyclic Carbene Ligands for Olefin Metathesis of Challenging Substrates. (United States)

    César, Vincent; Zhang, Yin; Kośnik, Wioletta; Zieliński, Adam; Rajkiewicz, Adam A; Ruamps, Mirko; Bastin, Stéphanie; Lugan, Noël; Lavigne, Guy; Grela, Karol


    N-Heterocyclic carbene (NHC) ligands IMesNMe2 and IMes(NMe2)2 derived from the well-known IMes ligand by substituting the carbenic heterocycle with one and two dimethylamino groups, respectively, were employed for the synthesis of second-generation Grubbs- and Grubbs-Hoveyda-type ruthenium metathesis precatalysts. Whereas the stability of the complexes was found to depend on the degree of dimethylamino-substitution and on the type of complex, the backbone-substitution was shown to have a positive impact on their catalytic activity in ring-closing metathesis, with a more pronounced effect in the second-generation Grubbs-type series. The new complexes were successfully implemented in a number of challenging olefin metathesis reactions leading to the formation of tetra-substituted C=C double bonds and/or functionalized compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Comet-assay parameters as rapid biomarkers of exposure to dietary/environmental compounds -- an in vitro feasibility study on spermatozoa and lymphocytes. (United States)

    Baumgartner, A; Kurzawa-Zegota, M; Laubenthal, J; Cemeli, E; Anderson, D


    Twelve chemical compounds have been selected for the European NewGeneris study on the basis of their potential to damage DNA, in order to establish adequate and reliable biomarkers of exposure. These genotoxic chemicals include heterocyclic amines, organochlorines, polycyclic aromatic hydrocarbons, mycotoxins, lipid peroxidation products and alcohol. Damage in somatic cells such as lymphocytes could give rise to cancer, while damage in germ cells could not only give rise to cancer but also to heritable defects. The alkaline Comet assay, with and without metabolic activation, as well as the neutral Comet assay were used to assess DNA integrity in spermatozoa and lymphocytes after in vitro treatment with low, middle and high doses of each chemical. DNA-reactive aldehydes generated by lipid peroxidation, food mutagens such as heterocyclic amines, nitrosamine and benzo[a]pyrene produced the highest amounts of DNA damage, even without metabolic activation. Damage seen with the neutral Comet assay - detecting primarily double-strand breaks - was lower than with the alkaline assay. In general, there was increased damage in the spermatozoa by comparison with the lymphocytes, with altered slopes in the dose-response curves. The Comet assay with sperm was generally very sensitive in assessing genotoxic damage, with the Comet parameters being good biomarkers of induced DNA damage. Establishing reliable biomarkers of exposure for the evaluation of dietary/environmental carcinogens is of utmost importance to protect our health and the health of our offspring. © 2012 Elsevier B.V. All rights reserved.

  20. Analytical Procedure Development to Determine Polycyclic Aromatic Compounds in the PM{sub 2}.5-PM{sub 1}0 Fraction of Atmospheric Aerosols; Desarrollo de una Metodologia Analitica para la Determinacion de Compuestos Aromaticos Policiclicos en las Fracciones PM{sub 2}.5-PM{sub 1}0 del Aerosol Atmosferico

    Energy Technology Data Exchange (ETDEWEB)

    Barrado, A. I.; Garcia, S.; Perez, R. M.


    This paper presents an optimized and validated analytical methodology for the determination of various polycyclic aromatic compounds in ambient air using liquid chromatography with fluorescence detection. This analysis method was applied to samples obtained during more than one year in an area of Madrid. Selected compounds have included thirteen polycyclic hydrocarbons considered priorities by the EPA, and hydroxylated derivatives, which have been less investigated in air samples by liquid chromatography with fluorescence detection. We have characterized and compared the concentration ranges of compounds identified and studied seasonal and monthly variations. In addition, the techniques have been applied to study multivariate correlations, factor analysis and cluster analysis to extract as much information as possible for interpretation and more complete and accurate characterization of the results and their relationship with meteorological parameters and physicochemical. (Author) 50 refs.