Sample records for heterocyclic azo compounds

  1. 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.


    African Journals Online (AJOL)

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    KEY WORDS: Azo dyes, 5-Bromo-2,4-dichloro-6-alkyllpyrimidines, Dithizone, Cyclocondensation,. Pyrimido[4,5- e][1,3,4]thiadiazine. INTRODUCTION. A variety of biological activities of pyrimido[4,5-e][1,3,4]thiadiazines is a strong motive to search for more efficient synthetic methods for this class of heterocyclic compounds.

  3. Enzymatic reduction of azo and indigoid compounds. (United States)

    Pricelius, S; Held, C; Murkovic, M; Bozic, M; Kokol, V; Cavaco-Paulo, A; Guebitz, G M


    A customer- and environment-friendly method for the decolorization azo dyes was developed. Azoreductases could be used both to bleach hair dyed with azo dyes and to reduce dyes in vat dyeing of textiles. A new reduced nicotinamide adenine dinucleotide-dependent azoreductase of Bacillus cereus, which showed high potential for reduction of these dyes, was purified using a combination of ammonium sulfate precipitation and chromatography and had a molecular mass of 21.5 kDa. The optimum pH of the azoreductase depended on the substrate and was within the range of pH 6 to 7, while the maximum temperature was reached at 40 degrees C. Oxygen was shown to be an alternative electron acceptor to azo compounds and must therefore be excluded during enzymatic dye reduction. Biotransformation of the azo dyes Flame Orange and Ruby Red was studied in more detail using UV-visible spectroscopy, high-performance liquid chromatography, and mass spectrometry (MS). Reduction of the azo bonds leads to cleavage of the dyes resulting in the cleavage product 2-amino-1,3 dimethylimidazolium and N approximately 1 approximately ,N approximately 1 approximately -dimethyl-1,4-benzenediamine for Ruby Red, while only the first was detected for Flame Orange because of MS instability of the expected 1,4-benzenediamine. The azoreductase was also found to reduce vat dyes like Indigo Carmine (C.I. Acid Blue 74). Hydrogen peroxide (H(2)O(2)) as an oxidizing agent was used to reoxidize the dye into the initial form. The reduction and oxidation mechanism of Indigo Carmine was studied using UV-visible spectroscopy.

  4. Novel push-pull heterocyclic azo disperse dyes containing piperazine moiety: Synthesis, spectral properties, antioxidant activity and dyeing performance on polyester fibers. (United States)

    Mohammadi, Asadollah; Khalili, Behzad; Tahavor, Marzieh


    Six novel push-pull azo disperse dyes were synthesized via classical azo coupling reaction using 2-amino-thiazolyl derivatives as the diazo components and 1-(4-bromobenzyl)-4-phenylpiperazine as a key coupling intermediate. The structures of the dyes and synthesized intermediate were confirmed by FT-IR, (1)H NMR, (13)C NMR and UV-vis analyses. The solvatochromic behavior of the dyes was studied in a set of 10 solvents of different polarity and considerable results were obtained. The prepared heterocyclic azo dyes were applied for dyeing polyester fibers and their dyeing properties were studied. The fastness properties of the dyed fabrics such as wash, light and rubbing fastness degrees were measured by standard methods. Investigation of antioxidant activity of compounds was carried out by ferric reducing antioxidant power (FRAP) method. The synthesized dyes exhibited significant antioxidant activities. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. 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.

  6. 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 ...

  7. Azo compound degradation kinetics and halonitromethane formation kinetics during chlorination. (United States)

    Fu, Jing; Wang, Xiaomao; Bai, Weiliang; Yang, Hongwei; Xie, Yuefeng F


    The chlorination of azo compounds can produce halonitromethanes (HNMs), which have attracted increasing concern due to their high genotoxicity. By impacting the speciation of chlorine and azo compounds, pH impacts apparent second-order rate constants of Methyl Orange (MO, 27.5-1.4 × 10(3) M(-1) s(-1)), Acid Orange II (AO, 16.7-99.3 M(-1) s(-1)), and Acid Red 1 (AR 1, 3.7-72.5 M(-1) s(-1)) (pH range 6.3-9.0). The two-compartment first-order model successfully described the chloropicrin (TCNM) formation kinetics, suggesting that both fast- and slow-reacting precursors of TCNM are generated from the chlorination of azo compounds. The ratios between fast and slow formation rate constants for MO and AO were 15.6-5.4 × 10(2), while that of AR 1 was 9.8-19.4 (pH range 6.5-9.0). The fraction of the fast-reacting TCNM precursors decreased with increasing pH for MO and AO; while that for AR 1 decreased when pH increased from 6.5 to 8.0, and then increased when pH increased from 8.0 to 9.0. The impact of pH on TCNM formation was also precursor-specific. The highest molar yields of TCNM predicted from the model in this study were 2.4%, 2.5%, and 1.5% for MO, AO, and AR 1, respectively. The study demonstrates that azo compounds are important HNM precursors, and pose a potential threat to drinking water safety. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Preparation and identification of some metal complexes with new heterocyclic azo dye ligand 2-[2-- (1- Hydroxy -4- Chloro phenyl) azo ]- imidazole and their spectral and thermal studies (United States)

    Al-Adilee, Khalid; Kyhoiesh, Hussein A. K.


    The preparation and spectral identification of metal complexes for Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) ions with new heterocyclic azo dye as ligand 2-[2-- (1- Hydroxy - 4- Chloro phenyl) azo ]- imidazole (HClPAI) were prepared by reacting adizonium chloride salt solution of 2-amino -4- chloro phenol with imidazole in alkaline ethanolic solution. Azo dye ligand and their metal complexes have been characterized by analytical data, 1H NMR, Mass spectrum, Infrared, Electronic spectral data, XRD, SEM, thermal analysis (TG-DSC-DTG), magnetic susceptibility and molar conductance. The elemental analysis of the metal complexes confirm the stoichiometry of the type [M(L)2] Cl where M = Cr(III), Fe(III), Co(II) and [M(L)2] where M = Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and L = azo dye ligand. Molar conductance measurements for prepared metal complexes showed 1:1 electrolyte for Cr(III), Fe(III) and Co(III) ions and non-electrolyte the rest metal complexes. The data show that the azo dye ligand behaves a tridentate and coordinates to the metal ion via nitrogen atom of azo group which is the farthest of imidazole molecule, nitrogen atom of azomethine group of heterocyclic imidazole ring and phenolic oxygen. Octahedral environment is suggested for all metal complexes.

  9. 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.


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    Bambang Purwono


    Full Text Available The synthesis of azo compounds from eugenol has been carried out by diazotation reaction. The diazonium salt was produced by reaction of aniline and sodium nitrite in acid condition at 0-5 °C temperature to yield benzenediazonium chloride salt. The salt was then reacted with eugenol to produce the azo derivatives. The azo product was analyzed by IR, 1H-NMR, dan GC-MS spectrometer. The results showed that the reaction of benzenediazonium chloride with eugenol gave 4-allyl-2-methoxy-6-hydroxyazobenzene in 34.27% yield for 30 minutes reaction. The derivative of azo compound was dissolved in ethanol and then the color changing was observed in range of pH 9.8-11.1 from yellow to red. Application for titration indicator for acetic acid titrated with sodium hydroxide showed error less than 3.20% compared with phenol phtaline indicator.   Keywords: Eugenol, Azo compound, titration indicator

  11. Some heterocyclic azo dyes derived from thiazolyl derivatives; synthesis; substituent effects and solvatochromic studies. (United States)

    Yazdanbakhsh, M R; Mohammadi, A; Abbasnia, M


    A series of azo disperse dyes were synthesized by coupling reaction of N,N-diethylaniline, 2-anilinoethanol and N-phenyl-2,2'-iminodiethanol with diazotized aminothiazolyl derivatives as diazo components. These dyes have been prepared in good yields, and were characterized by UV-Vis, FT-IR and 1H NMR spectroscopic techniques. The effects of solvent polarity and various pH on dyes in the visible absorption spectra were evaluated. All dyes exhibit an excellent correlation coefficient (r>0.92) for the linear solvation energy relationship with π* values calculated by Kamlet et al. The influence of the pH on the dyes with electron-donating group implied that these dyes exist in acid-base equilibrium in acidic environment. The effect of substituents of both coupler and diazo component on the color of dyes was investigated as well. Copyright © 2010 Elsevier B.V. All rights reserved.

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

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    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.



    Bambang Purwono; Catur Mahardiani


    The synthesis of azo compounds from eugenol has been carried out by diazotation reaction. The diazonium salt was produced by reaction of aniline and sodium nitrite in acid condition at 0-5 °C temperature to yield benzenediazonium chloride salt. The salt was then reacted with eugenol to produce the azo derivatives. The azo product was analyzed by IR, 1H-NMR, dan GC-MS spectrometer. The results showed that the reaction of benzenediazonium chloride with eugenol gave 4-allyl-2-methoxy-6-hydroxyaz...

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

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    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.

  15. 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...

  16. 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.

  17. 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.

  18. 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.

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

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    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.

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

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    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.

  1. 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 ...

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

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    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.


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    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.

  4. Some new azole type heterocyclic compounds as antifungal agents

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    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.

  5. Azo group containing compounds: investigation of the decay mechanism

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    Franzke, D.; Kritzenberger, J.; Kunz, T. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    We investigated compounds containing the N=N-X (X=S,P,N{sub 3}) group which are potential candidates for microstructuring by photoresist technology or by photoablation. To elucidate the mechanism of thermal decomposition and photolysis we used infrared and UV spectroscopy, respectively, in solution as well as in the solid state. In this article we describe photolytic and thermolytic properties of one representative molecule for each of three substance classes: diazosulfides, azophosphonates and pentazadienes. (author) 4 figs., 4 refs.

  6. [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.

  7. Sulfur-containing heterocyclic compounds with potential antidiabetic activity

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    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.

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

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    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.

  9. Reduction of azo dyes and nitroaromatic compounds by bacterial enzymes from the human intestinal tract. (United States)

    Rafii, F; Cerniglia, C E


    Several anaerobic bacteria from the human intestinal tract are capable of reducing azo dyes and nitropolycyclic aromatic hydrocarbons to the corresponding aromatic amines with enzymes that have azoreductase and nitroreductase activities. The majority of bacteria with these activities belong to the genera Clostridium and Eubacterium. The azoreductases and nitroreductases from three Clostridium strains and one Eubacterium strain were studied. Both enzymes were produced constitutively in each of the bacteria; the enzymes from various bacteria had different electrophoretic mobilities. The azoreductases from all of the bacteria had immunological homology, as was evident from the cross-reactivity of an antibody raised against the azoreductase of C. perfringens with azoreductases from other bacteria. Comparison of azoreductases and nitroreductases showed that they both had identical electrophoretic mobilities on polyacrylamide gels and reacted with the antibody against the azoreductase from C. perfringens. Furthermore, the nitroaromatic compounds competitively inhibited the azoreductase activity. The data indicate that the reduction of both nitroaromatic compounds and azo dyes may be carried out by the same enzyme, which is possibly a flavin adenine dinucleotide dehydrogenase that is synthesized throughout the cell and not associated with any organized subcellular structure. Images Figure 1. PMID:8565901

  10. Reduction of azo dyes and nitroaromatic compounds by bacterial enzymes from the human intestinal tract

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    Rafii, F.; Cerniglia, C.E. [Food and Drug Administration, Jefferson, AR (United States)


    Several anaerobic bacteria from the human intestinal tract are capable of reducing azo dyes and nitropolycyclic aromatic hydrocarbons to the corresponding aromatic amines with enzymes that have azoreductase and nitroreductase activities. The majority of bacteria with these activities belong to the genera Clostridium and Eubacterium. The azoreductases and nitroreductases from three Clostridium strains and one Eubacterium strain were studied. Both enzymes were produced constitutively in each of the bacteria; the enzymes from various bacteria had different electrophoretic mobilities. The azoreductases from all of the bacteria had immunological homology, as was evident from the cross-reactivity of an antibody raised against the azoreductase of C perfringens with azoreductases from other bacteria. Comparison of azoreductases and nitroreductases showed that they both had identical electrophoretic mobilities on polyacrylamide gels and reacted with the antibody against the azoreductase from C. perfringens. Furthermore, the nitroaromatic compounds competitively inhibited the azoreductase activity. The data indicate that the reduction of both nitroaromatic compounds and azo dyes may be carried out by the same enzyme, which is possibly a flavin adenine dinucleotide dehydrogenase that is synthesized throughout the cell and not associated with any organized subcellular structure. 15 refs., 1 fig., 2 tabs.

  11. 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.

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

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    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.

  13. 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.


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    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.

  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. Structure Modification of an Active Azo-Compound as a Route to New Antimicrobial Compounds

    Directory of Open Access Journals (Sweden)

    Simona Concilio


    Full Text Available Some novel (phenyl-diazenylphenols 3a–g were designed and synthesized to be evaluated for their antimicrobial activity. A previously synthesized molecule, active against bacteria and fungi, was used as lead for modifications and optimization of the structure, by introduction/removal or displacement of hydroxyl groups on the azobenzene rings. The aim of this work was to evaluate the consequent changes of the antimicrobial activity and to validate the hypothesis that, for these compounds, a plausible mechanism could involve an interaction with protein receptors, rather than an interaction with membrane. All newly synthesized compounds were analyzed by 1H-NMR, DSC thermal analysis and UV-Vis spectroscopy. The in vitro minimal inhibitory concentrations (MIC of each compound was determined against Gram-positive and Gram-negative bacteria and Candida albicans. Compounds 3b and 3g showed the highest activity against S. aureus and C. albicans, with remarkable MIC values of 10 µg/mL and 3 µg/mL, respectively. Structure-activity relationship studies were capable to rationalize the effect of different substitutions on the phenyl ring of the azobenzene on antimicrobial activity.

  17. 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.

  18. Anaerobic azo dye reduction

    NARCIS (Netherlands)

    Zee, van der F.P.


    Azo dyes, aromatic moieties linked together by azo (-N=N-) chromophores, represent the largest class of dyes used in textile-processing and other industries. The release of these compounds into the environment is undesirable, not only because of their colour, but also

  19. 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

  20. 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.

  1. Synthesis of azo pyridone dyes

    Directory of Open Access Journals (Sweden)

    Mijin Dušan Ž.


    Full Text Available Over 50% of all colorants which are used nowdays are azo dyes and pigments, and among them arylazo pyridone dyes (and pigments have became of interest in last several decades due to the high molar extinction coefficient, and the medium to high light and wet fastness properties. They find application generally as disperse dyes. The importance of disperse dyes increased in the 1970s and 1980s due to the use of polyester and nylon as the main synthetic fibers. Also, disperse dyes were used rapidly since 1970 in inks for the heat-transfer printing of polyester. The main synthetic route for the preparation of azo dyes is coupling reaction between an aromatic diazo compound and a coupling component. Of all dyes manufactured, about 60% are produced by this reaction. Arylazo pyridone dyes can be prepared from pyridone moiety as a coupling component, where substituent can be on nitrogen, and diazonim salts which can be derived from different substituted anilines or other heterocyclic derivatives. In addition, arylazo dyes containing pyridone ring can be prepared from arylazo diketones or arylazo ketoesters (obtained by coupling β-diketones or β-ketoesters with diazonim salts by condensation with cyanoacetamide. Disazo dyes can be prepared by tetrazotizing a dianiline and coupling it with a pyridone or by diazotizing aniline and coupling it with a dipyridone. Trisazo dyes can be also prepared by diazotizing of aniline and coupling it with a tripyridone or by hexazotizing a trianiline and coupling it with a pyridone. The main goal of this paper is to give a brief review on the synthesis of arylazo pyridone dyes due to the lack of such reviews. In addition, some properties of arylazo pyridone dyes as light fastness and azo-hydrazon tautomerism are disccused.

  2. 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

  3. 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...

  4. 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.

  5. Spectroscopic studies on some azo compounds and their cobalt, copper and nickel complexes (United States)

    Masoud, Mamdouh. S.; Khalil, Ekram A.; Hindawy, Ahmed M.; Ali, Alaa E.; Mohamed, Eman F.


    Synthesis and characterization of [ o-carboxy phenylazo] moiety of barbituric acid, thiobarbituric acid, thiouracil, citrazinic acid, and disodium chromotropate and their complexes derived from cobalt (II), nickel (II), and copper (II) salts were done. The stereochemistry and the mode of bonding of the complexes were achieved based on elemental analysis, NMR, UV-Vis, IR and ESR. The dissociation constants of the free azo ligands are evaluated by spectrophotometric methods.

  6. 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.

  7. 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.

  8. Synthesis and promising properties of a new family of high-nitrogen compounds: polyazido- and polyamino-substituted N,N'-azo-1,2,4-triazoles. (United States)

    Qi, Cai; Li, Sheng-Hua; Li, Yu-Chuan; Wang, Yuan; Zhao, Xiu-Xiu; Pang, Si-Ping


    A new family of high-nitrogen compounds, that is, polyazido- and polyamino-substituted N,N'-azo-1,2,4-triazoles, were synthesized in a safe and convenient manner and fully characterized. The structures of 3,3',5,5'-tetra(azido)-4,4'-azo-1,2,4-triazole (15) and 3,3',5,5'-tetra(amino)-4,4'-azo-1,2,4-triazole (23) were also confirmed by X-ray diffraction. Differential scanning calorimetry (DSC) was performed to determine their thermal stability. Their heats of formation and density, which were calculated by using Gaussian 03, were used to determine the detonation performances of the related compounds (EXPLO 5.05). The heats of formation of the polyazido compounds were also derived by using an additive method. Compound 15 has the highest heat of formation (6933 kJ kg(-1)) reported so far for energetic compounds and a detonation performance that is comparable to that of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), while compound 23 has a decomposition temperature of up to 290 °C. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

  10. 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

  11. 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.

  12. Azo dyes and related compounds as important aquatic contaminants: a ten-year case study (United States)

    Mutagenicity has been found in several aquatic systems in the world; however, this activity usually is not associated with any of the compounds that are currently regulated. Attempting to identify these hazardous compounds, an integrated study was conducted, employing several dif...

  13. 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.

  14. 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.

  15. Influence of the composition of in-vitro azo-reducing systems on the degradation kinetics of the model compound amaranth. (United States)

    Maris, B; Verheyden, L; Samyn, C; Augustijns, P; Kinget, R; Van den Mooter, G


    The purpose of this study was to investigate the influence of the composition of in-vitro azo-reducing systems on the degradation kinetics of the model compound amaranth. The degradation kinetics of amaranth were determined under anaerobic conditions both in rat caecal content (ex-vivo) and in a variety of in-vitro degradation media derived from rat caecal content. It was observed that the reducing activity was highly dependent on the preparation method and composition of the degradation medium. In pure rat caecal content, the degradation of amaranth was apparent first order (k = 0.044 +/- 0.002 min(-1)), while dilution of the rat caecal content resulted in an apparent zero-order degradation. Both apparent zero- and first-order degradations were also observed in media made up of diluted rat caecal content to which cofactors such as NADP, D-glucose-6-phosphate, glucose-6-phosphate dehydrogenase and Bz were added. This study demonstrates that in-vitro azo-reducing kinetics are dependent on the composition and mode of preparation of the in-vitro media used. This has to be taken into account when evaluating the degradability of azo-aromatic drug delivery systems in-vitro.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Synthesis, electrochemical, spectrophotometric and potentiometric studies of two azo-compounds derived from 4-amino-2-methylquinoline in ethanolic-aqueous buffered solutions

    Energy Technology Data Exchange (ETDEWEB)

    El-Attar, Mona A.; Ghoneim, Mohamed M. [Analytical Chemistry Research Unit, Chemistry Department, Tanta University (Egypt); Ismail, Iqbal M., E-mail: [Chemistry Department, Faculty of Science, King Abdul Aziz University, Jeddah (Saudi Arabia)


    Two azo-compounds, 2-methyl-4-(5-amino-2-hydroxy-phenylazo)-quinoline (2) and 2-methyl-4-(2-hydroxy-5-nitrophenylazo)-quinoline, derived from 4-amino-2-methylquinoline were synthesized. Their chemical structures were characterized and confirmed by means of elemental chemical analysis, infrared (IR) spectroscopy, {sup 1}H nuclear magnetic resonance (NMR) and mass spectrometry (MS). The electrochemical behavior of the starting compound (4-amino-2-methylquinoline) and of the two synthesized azo-derivatives was studied at the mercury electrode in the B-R universal buffer at various pH values (2-11.5) containing 40% (v/v) ethanol using dc-polarography, cyclic voltammetry and controlled-potential coulometry. Their electrode reaction pathways were elucidated and discussed. The dissociation constants (pKa) of the examined compounds, stability constants and stoichiometry of their complexes in solution with some transition metal ions (Co(II), Ni(II), Cu(II), La(III) and UO{sup 2+}{sub 2}) were determined. (author)

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

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


    Diels-Alder reactions of benzylidenecyanomethyl-1,3-benzothiazoles 17 and -1,3-benzoxazoles 18 as 1-aza-1,3-butadienes are described. The dienes 17 and 18 featuring stabilized imine moieties in the form of heteroaromatic rings react with both electron-deficient and electron-rich dienophiles to give corresponding cycloadducts regioselectively. The cycloadditions of the intramolecular systems 34c,d and 35c,d proceeded smoothly via the exo-transition state, stereoselectively affording polycyclic compounds 36c,d and 37c,d in good to excellent yields. The diene systems of 17 and 18 were extended to dienes 19a-c with ester groups at diene-4-positions. Dienes 19a-c exhibited high Diels-Alder reactivities with electron-rich alkenes. Dienes 19a-c also reacted with allyl alcohols 55-58 in the presence of stanoxane catalyst 53 to give cycloadducts 59-62 via transesterification and intramolecular cycloaddition. Although alpha-alkoxycarbonylnitrones 64 have been very attractive nitrones for the syntheses of amino acids, the nitrones 64 exist as equilibrating mixtures of (E)-64 and (Z)-64. To solve this problem, three methods were explored: 1) sequential transesterification and intermolecular cycloaddition of nitrones 64 with allyl alcohols; 2) use of chiral and geometry-fixed nitrone 84; and 3) selective activation of (Z)-64 by Eu(fod)3. These methods were applied to syntheses of nikkomycins, clavalanine, and beta-substituted alpha-amino acids. The reactions of photoinduced carbonyl ylides from alpha,beta-unsaturated gamma,delta-epoxy nitriles were studied. Direct irradiation (lambda = 254 nm) of (E)-129 led selectively to products arising from the carbonyl ylide XXV or the carbene intermediate XXVI. The carbonyl ylides generated from (E)-129, (E)-139, and (Z)-143 were trapped with MeOH in the presence of amine, affording the corresponding acetals in moderate yields (Schemes 42 and 43). Photocyclization reactions of delta-hydroxyalkyl epoxy nitriles 148a-e led to spiro acetals

  3. 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.

  4. Azo-hydrazone tautomerism of aryl azo pyridone dyes

    Directory of Open Access Journals (Sweden)

    Mirković Jelena M.


    Full Text Available In the last three or four decades disperse dyes derived from pyridones (in particular azo pyridone dyes have gained in importance, and are widely used in various fields. These compounds have excellent coloration properties, and are suitable for the dyeing of polyester fabrics. Basic features of these dyes are simplicity of their synthesis by diazotation and azo coupling. They generally have high molar extinction coefficient with medium to high light and wet fastness. The absorption maxima of these dyes show their visible absorption wavelength ranging from yellow to orange, which can be attributed to poorly delocalized electrons in the pyridone ring. However, there are several dyes with deep colors such as red or violet. Pyridone dyes with alkyl and aryl groups in ortho position to azo group show 2-pyridone/2-hydroxypyridine tautomerism, while those containing OH and NHR groups conjugated with the azo group show azo-hydrazone tautomerism. Determining azo-hydrazone tautomerism could be therefore interesting, since the tautomers have different physico-chemical properties and most importantly different coloration. The literature on azo-hydrazone tautomerism, determination of equilibrium position, and investigation of substituent and solvent influence on tautomerism has been summarized in the presented review. The general conclusion is that the equilibrium between two tautomers is influenced by the structure of the compounds and by the solvents used. The tautomeric behavior patterns of the arylazo pyridone dyes in the reviewed literature has been studied using various instrumental techniques, including FT-IR, UV-vis, and NMR spectroscopy. The quantum chemical calculations related to the azo-hydrazon tautomerism have also been included. A large number of pyridone dyes exist in hydrazone form in solid state, while in solvents there is a mixture of tautomers. In addition, the X-ray single-crystal diffraction data analysis of some commercial pyridone

  5. Integrated and sequential anaerobic/aerobic biodegradation of azo dyes

    NARCIS (Netherlands)

    Tan, N.G.C.


    Azo dyes constitute a major class of environmental pollutants accounting for 60 to 70% of all dyes and pigments used. These compounds are characterized by aromatic moieties linked together with azo groups (-N=N-). The release of azo dyes into the environment is a concern due to coloration

  6. 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

  7. Characterization of the decolorizing activity of azo dyes by Bacillus subtilis azoreductase AzoR1

    Directory of Open Access Journals (Sweden)

    Montira Leelakriangsak


    Full Text Available The product of the Bacillus subtilis gene azoR1 is annotated as a putative azoreductase, production of which isinduced in response to thiol-reactive compounds. Here we report on the decolorization of four azo dyes by azoreductaseactivity. The ability of overexpressed AzoR1 strain ORB7106 to catalyze decolorization of azo dyes was investigated on agarplates and in liquid cultures. The decolorization efficacy of a mutant, ORB7106, which has lost negative control of azoR1expression, was significantly better than the parental strain (JH642, providing evidence that the azoR1 gene product isan azoreductase with the ability to decolorize azo dyes. ORB7106 showed 40-98% azo dye decolorization within 48 h. Thebacterium exhibited a remarkable color removal capability over a wide range of Methyl Red concentrations (10-200 mg l-1, pH(5-9 and temperatures (25-45°C. A significant increase in the decolorization activity was observed after induction of AzoR1production. The results suggested that AzoR1 production could be induced by Methyl Red. The decolorizing activity isprimarily associated with the cytosolic fraction and requires NADH as a cofactor.

  8. 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)

  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. 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.

  11. 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.

  12. Synthesis and Antimicrobial Studies of New Antibacterial Azo-Compounds Active against Staphylococcus aureus and Listeria monocytogenes. (United States)

    Piotto, Stefano; Concilio, Simona; Sessa, Lucia; Diana, Rosita; Torrens, Gabriel; Juan, Carlos; Caruso, Ugo; Iannelli, Pio


    Some novel (phenyl-diazenyl)phenols (4a-m) were designed and synthesized to be evaluated for their antibacterial activity. Starting from an active previously-synthesized azobenzene chosen as lead compound, we introduced some modifications and optimization of the structure, in order to improve solubility and drug conveyance. Structures of all newly-synthesized compounds were confirmed by ¹H nuclear magnetic resonance (NMR), mass spectrometry, and UV-Vis spectroscopy. Antibacterial activity of the new compounds was tested with the dilution method against the bacteria strains Listeria monocytogenes, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa PAO1. All the compounds were selectively active against Gram-positive bacteria. In particular, compounds 4d, 4h, and 4i showed the highest activity against S. aureus and Listeria monocytogenes, reaching remarkable MIC100 values of 4 μg/mL and 8 μg/mL. The relationship between antimicrobial activity and compound structure has suggested that the presence of hydroxyl groups seems to be essential for antimicrobial activity of phenolic compounds.

  13. Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor. (United States)

    Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A


    Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

  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. 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.

  16. Ab initio calculations on 2-imidazolyl-2-thiazolyl azo compounds - an investigation of potential near-infrared absorbing structures

    DEFF Research Database (Denmark)

    Åstrand, P.-O.; Bak, K.L.; Sauer, S.P.A.


    The two lowest singlet excitation energies of 26 2-imidazolyl-2-thiazolylazo compounds have been investigated by ab initio methods within the second-order polarization propagator approximation (SOPPA). Various combinations of 4- and 5-substituents at both the imidazole and thiazole units have bee...

  17. 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.

  18. 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

  19. 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

  20. Re-evaluation of azo dyes as food additives

    DEFF Research Database (Denmark)

    Pratt, Iona; Larsen, John Christian; Mortensen, Alicja


    Aryl azo compounds are widely used as colorants (azo dyes) in a wide range of products including textiles, leather, paper, cosmetics, pharmaceuticals and food.As part of its systematic re-evaluation of food additives, the European Food Safety Authority (EFSA) has carried out new risk assessments...... of allazo dyes permitted in food. EFSA has also evaluated a number of azo dyes found illegally in food in recent years, including Sudan dyes, Para Red and Orange II. The re-evaluation of all food colours, including the azo dyes,was considered high priority (i) because colorants were among the first...

  1. Effect of cooperative hydrogen bonding in Azo-Hydrazone Tautomerism of Azo Dyes


    Özen, Alimet Sema; Ozen, Alimet Sema; Doruker, Pemra; Aviyente, Viktorya


    Azo-hydrazone tautomerism in azo dyes has been modeled by using density functional theory (DFT) at the B3LYP/6-31+G(d,p) level of theory. The most stable tautomer was determined both for model compounds and for azo dyes Acid Orange 7 and Solvent Yellow 14. The effects of the sulfonate group substitution and the replacement of the phenyl group with naphthyl on the tautomer stability and on the behavior in solvent have been discussed. Intramolecular hydrogen bond energies have been estimated f...

  2. 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.

  3. Efficient synthesis of novel azo compounds based on pyrimido[4,5-e][1,3,4]thiadiazine

    Directory of Open Access Journals (Sweden)

    Mohsen Nikpour


    Full Text Available Some new 5-bromo-2,4-dichloro-6-alkylpyrimidines were prepared by sequential treatment of 6-alkyl-pyrimidin-2,4(1H,3H-diones with bromine and phosphoryl chloride. Condensation of the dithizone with 5-bromo-2,4-dichloro-6-alkylpyrimidines in alkaline acetonitrile achieved 5-alkyl-7-chloro-3-phenylazo-1-phenyl-1H-pyrimido[4,5-e][1,3,4] thiadiazines. 7-chlorine atom of these compounds was replaced by secondary amines in boiling ethanol to afford their 7-amino derivatives. DOI:

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

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    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.

  5. 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.

  6. Toxicological significance of azo dye metabolism by human intestinal microbiota. (United States)

    Feng, Jinhui; Cerniglia, Carl E; Chen, Huizhong


    Approximately 0.7 million tons of azo dyes are synthesized each year. Azo dyes are composed of one or more R₁-N=N-R₂ linkages. Studies have shown that both mammalian and microbial azoreductases cleave the azo bonds of the dyes to form compounds that are potentially genotoxic. The human gastrointestinal tract harbors a diverse microbiota comprised of at least several thousand species. Both water-soluble and water-insoluble azo dyes can be reduced by intestinal bacteria. Some of the metabolites produced by intestinal microbiota have been shown to be carcinogenic to humans although the parent azo dyes may not be classified as being carcinogenic. Azoreductase activity is commonly found in intestinal bacteria. Three types of azoreductases have been characterized in bacteria. They are flavin dependent NADH preferred azoreductase, flavin dependent NADPH preferred azoreductase, and flavin free NADPH preferred azoreductase. This review highlights how azo dyes are metabolized by intestinal bacteria, mechanisms of azo reduction, and the potential contribution in the carcinogenesis/mutagenesis of the reduction of the azo dyes by intestinal microbiota.

  7. 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.

  8. Evaluation of the treatment performance of lab-scaled vertical flow constructed wetlands in removal of organic compounds, color and nutrients in azo dye-containing wastewater. (United States)

    Dogdu, Gamze; Yalcuk, Arda


    The objective of this study is to examine the treatment performance of vertical flow intermittent feeding constructed wetland (VFCW) in removal of organic pollution, nutrients and color in azo-dye containing wastewater. The systems consisted of PVC reactors, some filling materials such as gravel, sand and zeolite and wetland plants including Typha angustifolia and Canna indica. The average treatment efficiency of the systems for COD, color, sulphate, NH4-N, and PO4-P were in the range of 57-63%, 94-99%, 44-48%, 39-44%, and 84-88%, respectively among the VFCW reactors. It is concluded that VFCW reactor system can effectively be used in the treatment of dye-rich wastewater, especially for the removal of color and in the reduction of COD. Biofilm formation and cleavage of azo bonds could be observed by SEM and FTIR results, respectively. Almost similar NH4-N and PO4-P removal were obtained in all reactors by using same amount of zeolite media.

  9. "Protective Effects of Some Azo Derivatives of 5-aminosalicylic Acid and Their Pegylated Prodrugs on Acetic Acid-induced Rat Colitis "

    Directory of Open Access Journals (Sweden)

    Alireza Garjani


    Full Text Available The protective and anti-inflammatory effects of azo and azo-linked polymeric prodrugs of 5-aminosalicylic acid (5-ASA on acetic acid induced colitis in rats were investigated. Three azo prodrugs; 4,4 -dihydroxy-azobenzene-3-carboxilic acid (azo compound I, 4-hydroxy-azobenzene-3,4-dicarboxilic acid (azo compound II, 4,4-dihydroxy-3-formyl-azobenzene-3-carboxylic acid (azo compound III and their polyethylene glycol (PEG 6000 derivatives were synthesized. Rats were pretreated orally (1 hour prior to induction of colitis with sulfasalazin (300 mg/kg, azo compounds I, II, III and polyethylene glycol conjugates of azo compounds II and III in doses which had the same amount of 5-ASA as sulfasalazin contains. The colonic damage was examined 24 hours later and characterized by gross microscopic injury and colonic edema. Among prodrugs only azo compound III (215 mg/kg produced a significant (p<0.01 protective effect against colonic injury comparable with sulfasalazin. Doubling the dose (430 mg/kg showed more anti-colitis effects. Polyethylene glycol conjugate of azo compounds II and III also showed reduction in the extent of the cell death and tissue disorganization similar to sulfasalazin. While neither sulfasalazin, nor azo compound II and its PEG polymer produced anti-edema effects, both azo compound III and its PEG polymer decreased colon edema significantly (p<0.05. Histological examinations also indicated a marked reduction in tissue injury and inhibition in neutrophil infiltration in rats treated with azo compound III and PEG conjugates of azo compounds II and III. Results of this investigation provide experimental evidence supporting new cytoprotective, anti-inflammatory and anti-edema properties of the azo derivatives of 5-ASA and their PEGylated prodrugs.

  10. Novel 2-phenyl-3-{4’-[N-(4”-aminophenylcarbamoyl]-phenyl}-quinazoline-4(3Hone-6-sulphonic acidbased mono azo reactive dyes

    Directory of Open Access Journals (Sweden)



    Full Text Available A series of new heterocyclic mono azo reactive dyes 7a–m were prepared by diazotization of 2-phenyl-3-{4’-[N-(4”-aminophenylcarbamoyl]-phenyl}-quinazoline-4(3H-one-6-sulphonic acid (3 and coupling with various cyanurated coupling components 6a–m and their dyeing performance on silk, wool and cotton fibres was assessed. These dyes were found to give a variety of colour shades with very good depth and levelness on the fibres. All the compounds were identified by conventional method (IR and 1H-NMR and elemental analyses. The percentage dye bath exhaustion on different fibres was reasonably good and acceptable. The dyed fibre showed moderate to very good fastness to light, washing and rubbing.

  11. 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.

  12. 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

  13. The Escherichia coli Azoreductase AzoR Is Involved in Resistance to Thiol-Specific Stress Caused by Electrophilic Quinones ▿ (United States)

    Liu, Guangfei; Zhou, Jiti; Fu, Q. Shiang; Wang, Jing


    The physiological role of Escherichia coli azoreductase AzoR was studied. It was found that AzoR was capable of reducing several benzo-, naphtho-, and anthraquinone compounds, which were better substrates for AzoR than the model azo substrate methyl red. The ΔazoR mutant displayed reduced viability when exposed to electrophilic quinones, which are capable of depleting cellular reduced glutathione (GSH). Externally added GSH can partially restore the impaired growth of the ΔazoR mutant caused by 2-methylhydroquinone. The transcription of azoR was induced by electrophiles, including 2-methylhydroquinone, catechol, menadione, and diamide. A transcription start point was identified 44 bp upstream from the translation start point. These data indicated that AzoR is a quinone reductase providing resistance to thiol-specific stress caused by electrophilic quinones. PMID:19666717

  14. Azo dye reduction by mesophilic and thermophilic anaerobic consortia

    NARCIS (Netherlands)

    Santos, dos A.B.; Madrid, de M.P.; Stams, A.J.M.; Lier, van J.B.; Cervantes, F.J.


    The reduction of the azo dye model compounds Reactive Red 2 (RR2) and Reactive Orange 14 (RO14) by mesophilic (30 C) and thermophilic (55 C) anaerobic consortia was studied in batch assays. The contribution of fermentative and methanogenic microorganisms in both temperatures was evaluated in the

  15. 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.

  16. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong


    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Detection of azo dyes and aromatic amines in women undergarment. (United States)

    Nguyen, Thao; Saleh, Mahmoud A


    Women are exposed to several chemical additives including azo dyes that exist in textile materials, which are a potential health hazard for consumers. Our objective was to analyze suspected carcinogenic azo dyes and their degradation aromatic amines in women underwear panties using a fast and simple method for quantification. Here, we evaluated 120 different samples of women underwear for their potential release of aromatic amines to the skin. Seventy-four samples yielded low level mixtures of aromatic amines; however eighteen samples were found to produce greater than 200 mg/kg (ppm) of aromatic amines. Azo dyes in these 18 samples were extracted from the fabrics and analyzed by reverse phase thin layer chromatography in tandem with atmospheric pressure chemical ionization mass spectrometry. Eleven azo dyes were identified based on their mass spectral data and the chemical structure of the aromatic amine produced from these samples. We demonstrate that planar chromatography and mass spectrometry can be really helpful in confirming the identity of the azo dyes, offering highly relevant molecular information of the responsible compounds in the fabrics. With the growing concern about the consumer goods, analysis of aromatic amines in garments has become a highly important issue.

  19. The Escherichia coli azoreductase AzoR Is involved in resistance to thiol-specific stress caused by electrophilic quinones. (United States)

    Liu, Guangfei; Zhou, Jiti; Fu, Q Shiang; Wang, Jing


    The physiological role of Escherichia coli azoreductase AzoR was studied. It was found that AzoR was capable of reducing several benzo-, naphtho-, and anthraquinone compounds, which were better substrates for AzoR than the model azo substrate methyl red. The DeltaazoR mutant displayed reduced viability when exposed to electrophilic quinones, which are capable of depleting cellular reduced glutathione (GSH). Externally added GSH can partially restore the impaired growth of the DeltaazoR mutant caused by 2-methylhydroquinone. The transcription of azoR was induced by electrophiles, including 2-methylhydroquinone, catechol, menadione, and diamide. A transcription start point was identified 44 bp upstream from the translation start point. These data indicated that AzoR is a quinone reductase providing resistance to thiol-specific stress caused by electrophilic quinones.

  20. 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.

  1. 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.

  2. Azo dyes and human health: A review. (United States)

    Chung, King-Thom


    Synthetic azo dyes are widely used in industries. Gerhardt Domagk discovered that the antimicrobial effect of red azo dye Prontosil was caused by the reductively cleaved (azo reduction) product sulfanilamide. The significance of azo reduction is thus revealed. Azo reduction can be accomplished by human intestinal microflora, skin microflora, environmental microorganisms, to a lesser extent by human liver azoreductase, and by nonbiological means. Some azo dyes can be carcinogenic without being cleaved into aromatic amines. However, the carcinogenicity of many azo dyes is due to their cleaved product such as benzidine. Benzidine induces various human and animal tumors. Another azo dye component, p-phenylenediamine, is a contact allergen. Many azo dyes and their reductively cleaved products as well as chemically related aromatic amines are reported to affect human health, causing allergies and other human maladies.

  3. 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...

  4. 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;.

  5. 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.

  6. Crystal structures, solvatochromisms and DFT computations of three disperse azo dyes having the same azobenzene skeleton (United States)

    Qian, Hui-Fen; Tao, Tao; Feng, Ya-Nan; Wang, Yin-Ge; Huang, Wei


    Three disperse azo dyes having the same 4-nitrobenzene/azo/4-aminobenzene skeleton but different color have been structurally and spectrally characterized and compared in this paper. X-ray single-crystal diffraction analysis of compound 3 reveals that it has a planar molecular conformation between the azo and the nitrobenzene units. However, severely twisted aminoazobenzene structures in compounds 1 and 2 are observed because of the steric hindrance effect of ortho chloro and bromo groups. Electronic spectra of 1-3 are closely related to their molecular structures, which demonstrate that the presence of different substituted groups and the spatial crowding effect in the aminoazobenzene backbone leads to the significant alterations of bathochromic and hypochromatic shifts. In addition, theoretic computational studies as well as solvatochromisms for three azo dyes have been included.

  7. Binding properties of HABA-type azo derivatives to avidin and avidin-related protein 4. (United States)

    Repo, Susanna; Paldanius, Tiina A; Hytönen, Vesa P; Nyholm, Thomas K M; Halling, Katrin K; Huuskonen, Juhani; Pentikäinen, Olli T; Rissanen, Kari; Slotte, J Peter; Airenne, Tomi T; Salminen, Tiina A; Kulomaa, Markku S; Johnson, Mark S


    The chicken genome encodes several biotin-binding proteins, including avidin and avidin-related protein 4 (AVR4). In addition to D-biotin, avidin binds an azo dye compound, 4-hydroxyazobenzene-2-carboxylic acid (HABA), but the HABA-binding properties of AVR4 are not yet known. Differential scanning calorimetry, UV/visible spectroscopy, and molecular modeling were used to analyze the binding of 15 azo molecules to avidin and AVR4. Significant differences are seen in azo compound preferences for the two proteins, emphasizing the importance of the loop between strands beta3 and beta4 for azo ligand recognition; information on these loops is provided by the high-resolution (1.5 A) X-ray structure for avidin reported here. These results may be valuable in designing improved tools for avidin-based life science and nanobiotechnology applications.

  8. 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).

  9. Detoxification of azo dyes by bacterial oxidoreductase enzymes. (United States)

    Mahmood, Shahid; Khalid, Azeem; Arshad, Muhammad; Mahmood, Tariq; Crowley, David E


    Azo dyes and their intermediate degradation products are common contaminants of soil and groundwater in developing countries where textile and leather dye products are produced. The toxicity of azo dyes is primarily associated with their molecular structure, substitution groups and reactivity. To avoid contamination of natural resources and to minimize risk to human health, this wastewater requires treatment in an environmentally safe manner. This manuscript critically reviews biological treatment systems and the role of bacterial reductive and oxidative enzymes/processes in the bioremediation of dye-polluted wastewaters. Many studies have shown that a variety of culturable bacteria have efficient enzymatic systems that can carry out complete mineralization of dye chemicals and their metabolites (aromatic compounds) over a wide range of environmental conditions. Complete mineralization of azo dyes generally involves a two-step process requiring initial anaerobic treatment for decolorization, followed by an oxidative process that results in degradation of the toxic intermediates that are formed during the first step. Molecular studies have revealed that the first reductive process can be carried out by two classes of enzymes involving flavin-dependent and flavin-free azoreductases under anaerobic or low oxygen conditions. The second step that is carried out by oxidative enzymes that primarily involves broad specificity peroxidases, laccases and tyrosinases. This review focuses, in particular, on the characterization of these enzymes with respect to their enzyme kinetics and the environmental conditions that are necessary for bioreactor systems to treat azo dyes contained in wastewater.

  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)

    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:

  13. 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 ...

  14. 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.

  15. 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)

  16. Synthesis and characterization of 5-amino-2-((3-hydroxy-4-((3-hydroxyphenyl phenyl diazenyl phenol and its Cu(II complex – a strategy toward developing azo complexes for reduction of cytotoxicity

    Directory of Open Access Journals (Sweden)

    Durba Ganguly


    Full Text Available A major drawback of azo compounds is their associated toxicity, often carcinogenic, which is related to the reduction of the azo bond. This study intends to re-investigate this behavior by studying 5-amino-2-((3-hydroxy-4-((3-hydroxyphenyl phenyl diazenyl phenol (AHPD, a compound containing two azo bonds. Interaction of AHPD and its dimeric Cu(II complex with bacterial strains Escherichia coli and Staphylococcus aureus revealed the complex was less toxic. Reductive cleavage of the azo bond in AHPD and the complex followed using cytochrome c reductase (a model azo-reductase as well as azo-reductase enzymes obtained from bacterial cell extracts. Degradation of the azo bond was less in the complex allowing us to correlate the observed cytotoxicity. Cyclic voltammetry on AHPD and the complex support observations of enzyme assay experiments. These were particularly useful in realizing the formation of amines as an outcome of the reductive cleavage of azo bonds in AHPD that could not be identified through an enzyme assay. Results suggest that complex formation of azo compounds could be a means to control the formation of amines responsible for cytotoxicity. Studies carried out on bacterial cells for mere simplicity bear significance for multicellular organisms and could be important for human beings involved with the preparation and utilization of azo dyes.

  17. Evaluation of metabolism of azo dyes and their effects on Staphylococcus aureus metabolome. (United States)

    Sun, Jinchun; Jin, Jinshan; Beger, Richard D; Cerniglia, Carl E; Chen, Huizhong


    effects of azo dyes on the bacterial cells and the important role on the toxicity and/or inactivation of these compounds due to microbial metabolism.

  18. Synthesis, spectroscopic and structural studies of new azo dyes metal chelates derivated from 1-phenil-azo-2-naphthol (United States)

    Ferreira, Gilson Rodrigues; de Oliveira, Luiz Fernando C.


    In this study, experimental techniques such as Raman and infrared vibrational analysis and X-ray crystal diffraction were used to characterize three new azo chelate dyes derived from 1-phenyl-azo-2-naphthol (Sudan I) and its analogue 1-(xylylphenylazo)-2-naphthol (Sudan II) with metal ions. The Raman and infrared spectroscopic analysis have also provided useful information concerning the coordination and formation of the molecular complexes through their main bands. In the vibrational spectra, the fingerprint bands, such as the ones at 1369/1368/1359 cm-1 assigned to [ν(CC) + δ(CH)], ν(Cdbnd N)], 1351/1352/1338 cm-1 assigned to [δ(CH)] and 816/824/813 cm-1 assigned to [ω(CH)] respectively for the SD1Cu, SD1Co and SD2Ni, can be used to characterize such compounds.

  19. Examples of reductive azo cleavage and oxidative azo bond formation on Re2(CO)10 template: isolation and characterization of Re(III) complexes of new azo-aromatic ligands. (United States)

    Paul, Nanda D; Samanta, Subhas; Mondal, Tapan K; Goswami, Sreebrata


    A new example of simultaneous reductive azo bond cleavage and oxidative azo bond formation in an azo-aromatic ligand is introduced. The chemical transformation is achieved by the reaction of Re(2)(CO)(10) with the ligand 2-[(2-N-Arylamino)phenylazo]pyridine (HL(1)). A new and unexpected mononuclear rhenium complex [Re(L(1))(L(3))] (1) was isolated from the above reaction. The new azo-aromatic ligand, H(2)L(3) (H(2)L(3) = 2, 2'-dianilinoazobenzene) is formed in situ from HL(1). A similar reaction of Re(2)(CO)(10) and a closely related azo-ligand, 2,4-ditert-butyl-6-(pyridin-2-ylazo)-phenol (HL(2)), resulted in a seven coordinated compound [Re(L(2)){(L(4))(•-)}(2)] (2; HL(4) = 2-amino-4,6-ditert-butyl-phenol) via reductive cleavage of the azo bond. The complexes have been characterized by using a host of physical methods: X-ray crystallography, nuclear magnetic resonance (NMR), cyclic voltammetry, ultraviolet-visible (UV-vis), electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT). The experimental structures are well reproduced by density functional theory calculations and support the overall electronic structures of the above compounds. Complex 1 is a closed shell singlet, while complex 2 exemplifies a singlet diradical complex where the two partially oxidized aminophenoleto ligands are coupled to each other, yielding the observed diamagnetic ground state. Complexes 1 and 2 showed two successive one-electron redox responses. EPR spectral studies in corroboration with DFT results indicated that all of the redox processes occur at the ligand center without affecting the trivalent state of the metal ion. © 2011 American Chemical Society

  20. Voltage-induced switching dynamics based on an AZO/VO2/AZO sandwiched structure (United States)

    Xiao, Han; Li, Yi; Fang, Baoying; Wang, Xiaohua; Liu, Zhimin; Zhang, Jiao; Li, Zhengpeng; Huang, Yaqin; Pei, Jiangheng


    A vanadium dioxide (VO2) thin film was prepared on an Al-doped ZnO (AZO) conductive glass substrate by DC magnetron sputtering and a post-annealing process. The AZO/VO2/AZO sandwiched structure was fabricated on the VO2/AZO composite film using photolithography and a chemical etching process. The composition, microstructure and optical properties of the VO2/AZO composite film were tested. The results showed that the VO2/AZO composite film was poly-crystalline and the AZO layer did not change the preferred growth orientation of VO2. When the voltage was applied on both of the transparent conductive layers of the AZO/VO2/AZO sandwiched structure, an abrupt change in the current was observed at different temperatures. The temperature dependence of I-V characteristic curves for the AZO/VO2/AZO sandwiched structure was analyzed. The phase transition voltage value is 7.5 V at 20 °C and decreases with increasing temperature.

  1. Design, synthesis, and spectroscopic study of some new flavones containing two azo linkages (United States)

    Ayoob, Mzgin Mohammed; Hawaiz, Farouq Emam


    In the present study; 5-(4-chlorophenyl azo) -2-hydroxy acetophenone (1) was prepared by diazotization of 4-chloro aniline and its coupling reaction with 2-hydroxy acetophenone, then reacted with different azo benzyloxy benzaldehydes(3a-i) to give new synthesized 2-hydroxy chalcones(4a-i). The later compounds were subjected to oxidative cyclization by catalytic amount of I2 in DMSO affording the target molecules new flavones bearing two azo-linkages (5a-i). The structures of the newly synthesized compounds were identified on the bases of their FT-IR, 1H-NMR, 13C-NMR and DEPT-135 spectra. The synthesized Flavone derivatives were evaluated against two types of bacteria gram positive (Staphylococcus aurous) and gram negative (Pseudomonas aeruginosa). The results showed that most of the synthesized flavones are more sensitive against (G -ve) bacteria than (G +ve) bacteria.


    Directory of Open Access Journals (Sweden)

    VARZARU Elena


    Full Text Available Toxicology of textiles is a subject of increasing interest, because of the presence of dangerous compounds in clothes generated from dyeing and finishing processes. In order to protect human health, numerous regulations (Oeko Tex Standard 100, REACH Regulation limit the presence of dangerous chemicals, such as aromatic amines, generated by reductive cleavage of azo dyes, by no more than 30 mg/kg of textile material. The objective of this work was to investigate different methods of azo dyes reduction from colored textile specimens, in order to determine the procedure with the highest selectivity and sensibility. Aromatic amines are generated by chemical degradation achieved by the cleavage of the azo linkage using reducing agents.Different alternatives to sodium dithionite, reducing agent recommended by standard method ISO/FDIS 14362-1 were tested, such as: sodium sulfite and tin chloride. Also, xylene extraction, the common procedure for synthetic fibers was also performed for cotton, dyed with azo dye Direct Blue 6, in order to assess the reliability of common simultaneously extraction and reduction of direct dyes from natural fibres. Sodium ditionite remains the popular choice for reducing agent, since it provides efficient cleavage of azo linkage, generating specifically carcinogenic amines. Both liquid and gas chromatography analytical techniques were used for precise quantitative determination of generated compounds.

  3. Structural evolution, electrical and optical properties of AZO films ...

    Indian Academy of Sciences (India)

    Aluminum-doped zinc oxide (AZO) target was fabricated using AZO nanopowders synthesized by co-precipitation method and then the AZO films with different thicknesses were deposited on glass by d.c. magnetron sputtering at room temperature. AZO target is nodules free and shows homogeneous microstructure, ...

  4. Structural evolution, electrical and optical properties of AZO films ...

    Indian Academy of Sciences (India)


    Abstract. Aluminum-doped zinc oxide (AZO) target was fabricated using AZO nanopowders synthesized by co-precipitation method and then the AZO films with different thicknesses were deposited on glass by d.c. magnetron sputtering at room temperature. AZO target is nodules free and shows homogeneous microstruc-.

  5. Design and Synthesis of Novel Antimicrobial Acyclic and Heterocyclic Dyes and Their Precursors for Dyeing and/or Textile Finishing Based on 2-N-Acylamino-4,5,6,7-tetrahydro-benzo[b]thiophene Systems

    Directory of Open Access Journals (Sweden)

    Rafat Milad Mohareb


    Full Text Available A series of novel polyfunctionalized acyclic and heterocyclic dye precursors and their respective azo (hydrazone counterpart dyes and dye precursors based on conjugate enaminones and/or enaminonitrile moieties were synthesized. The dyes and their precursors are based on 2-cyano-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide, 2-ethoxycarbonyl-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide or 2-phenylcarbamoyl-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide systems as precursors. The latter compounds were used to synthesize polyfunctional thiophene-, thiazole-, pyrazole, pyridine-, pyrimidine-, oxazine-, as well as acyclic moieties. The dyes and dye precursors were characterized by elemental analysis and spectral methods. All dyes and their precursors were screened in vitro and evaluated for both their antibacterial and antifungal activities. MIC data of the novel dye systems and their respective precursors showed significant antimicrobial activity against most tested organisms. Some compounds exhibited comparable or even higher efficiency than selected standards. Dyes were applied at 5% depth for disperse dyeing of nylon, acetate and polyester fabrics. Their spectral characteristics and fastness properties were measured and evaluated.

  6. 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.

  7. 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).

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. Syntheses of Azo-Imine Derivatives from Vanillin as an Acid Base Indicator

    Directory of Open Access Journals (Sweden)

    Bambang Purwono


    Full Text Available Preparations of azo, imine and azo-imine derivatives from vanillin as an indicator of acid-base titration have been carried out. The azo derivative of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 was produced by diazotitation reaction of vanillin in 37.04% yield. The azo product was then refluxed with aniline in ethanol to yield azo-imine derivatives, 2-methoxy-6-(phenylazo-4-((phenyliminomethylphenol 1 in 82.21% yield. The imine derivative, 2-methoxy-4-((phenyliminomethyl-phenol 3 was obtained by refluxing of vanillin and aniline mixture in ethanol solvent and produced 82.17% yield. The imine product was then reacted with benzenediazonium chloride salt. However, the products indicated hydrolyzed product of 4-hydroxy-3-methoxy-5-(phenylazobenzaldehyde 2 in 22.15% yield. The 2-methoxy-4-((phenyliminomethylphenol 2 could be used as an indicator for titration of NaOH by H2C2O4 with maximum concentration of H2C2O4 0.1 M while the target compound 1 could be used as titration indicator for titration of NaOH with H2C2O4 with same result using phenolphthalein indicator.

  14. Crystallization and preliminary X-ray analysis of AzoR (azoreductase) from Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Kosuke [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Nakanishi, Masayuki [Department of Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan); Lee, Woo-Cheol; Sasaki, Hiroshi [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan); Zenno, Shuhei; Saigo, Kaoru [Department of Biophysics and Biochemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Kitade, Yukio [Department of Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193 (Japan); Tanokura, Masaru, E-mail: [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657 (Japan)


    The crystallization and preliminary X-ray analysis of AzoR (azoreductase) have been performed. AzoR (azoreductase), an FMN-dependent NADH-azo compound oxidoreductase from Escherichia coli, has been crystallized in the presence of FMN by the sitting-drop vapour-diffusion method using 2-propanol as a precipitant. AzoR catalyzes the reductive cleavage of azo groups. The crystals were found to diffract X-rays to beyond 1.8 Å resolution using a synchrotron-radiation source. The crystals belonged to the tetragonal space group P4{sub 2}2{sub 1}2, with unit-cell parameters a = b = 92.2, c = 51.9 Å. The crystals are expected to contain one subunit of the homodimer in the asymmetric unit (V{sub M} = 2.6 Å{sup 3} Da{sup −1}) and to have a solvent content of 51.6%. Data sets were also collected from heavy-atom derivatives for use in phasing. As a result, crystals soaked in a solution containing K{sub 2}PtCl{sub 4} for 23 d were found to be reasonably isomorphous to the native crystals and the presence of Pt atoms could be confirmed. The data sets from the native crystals and the K{sub 2}PtCl{sub 4}-derivatized crystals are being evaluated for use in structure determination by single isomorphous replacement with anomalous scattering.

  15. Evidence for direct-acting oxidative genotoxicity by reduction products of azo dyes. (United States)

    Sweeney, E A; Chipman, J K; Forsythe, S J


    The intestinal flora forms a complex ecosystem that metabolizes dietary and endogenous nutrients under primarily anaerobic conditions. The ingestion of azo dyes has been proposed as one source of potential genotoxic agents. Many intestinal bacteria are able to reduce the azo bond (termed azofission), which liberates the substituted naphthol compounds. The standard Ames test has not demonstrated mutagenicity either by various common food colorings or by their reduced end products in Salmonella typhimurium strains TA98 and TA100. In contrast, genetic toxicity was demonstrated in the Escherichia coli differential kill assay and in S. typhimurium TA102 for the reduced dyes. The superoxide free radical was produced by the azo dyes only after reduction by the intestinal bacteria Enterococcus faecalis and Bacteroides thetaiotaomicron. PMID:7889833

  16. [Azo dyes, their environmental effects, and defining a strategy for their biodegradation and detoxification]. (United States)

    Gudelj, Ivana; Hrenović, Jasna; Dragičević, Tibela Landeka; Delaš, Frane; Soljan, Vice; Gudelj, Hrvoje


    Intense industrial development has been accompanied by the production of wastewaters of very complex content, which pose a serious hazard to the environment, put at risk sustainable development, and call for new treatment technologies that would more effectively address the issue. One particular challenge in terms of science and technology is how to biodegrade xenobiotics such as azo dyes, which practically do not degrade under natural environmental conditions. These compounds tend to bioaccumulate in the environment, and have allergenic, carcinogenic, mutagenic, and teratogenic properties for humans. Removal of azo dyes from effluents is mostly based on physical-chemical methods. These methods are often very costly and limited, as they accumulate concentrated sludge, which also poses a significant secondary disposal problem, or produce toxic end-products. Biotechnological approach may offer alternative, lowcost biological treatment systems that can completely biodegrade and detoxify even the hard-to-biodegrade azo dyes.

  17. 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.

  18. Chlorine disinfection of dye wastewater: Implications for a commercial azo dye mixture

    Energy Technology Data Exchange (ETDEWEB)

    Vacchi, Francine Inforcato; Albuquerque, Anjaina Fernandes; Vendemiatti, Josiane Aparecida; Morales, Daniel Alexandre [Faculdade de Tecnologia, Universidade Estadual de Campinas, Limeira, SP, 13484-332 (Brazil); Ormond, Alexandra B.; Freeman, Harold S. [Department of Textile Engineering, Chemistry, and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); Zocolo, Guilherme Juliao; Zanoni, Maria Valnice Boldrin [Departamento de Quimica Analitica, Universidade Estadual Paulista Julio de Mesquita Filho, Instituto de Quimica de Araraquara, Araraquara, SP 14801-970 (Brazil); Umbuzeiro, Gisela, E-mail: [Faculdade de Tecnologia, Universidade Estadual de Campinas, Limeira, SP, 13484-332 (Brazil)


    Azo dyes, the most widely used family of synthetic dyes, are often employed as colorants in areas such as textiles, plastics, foods/drugs/cosmetics, and electronics. Following their use in industrial applications, azo dyes have been found in effluents and various receiving waters. Chemical treatment of effluents containing azo dyes includes disinfection using chlorine, which can generate compounds of varying eco/genotoxicity. Among the widely known commercial azo dyes for synthetic fibers is C.I. Disperse Red 1. While this dye is known to exist as a complex mixture, reports of eco/genotoxicity involve the purified form. Bearing in mind the potential for adverse synergistic effects arising from exposures to chemical mixtures, the aim of the present study was to characterize the components of commercial Disperse Red 1 and its chlorine-mediated decoloration products and to evaluate their ecotoxicity and mutagenicity. In conducting the present study, Disperse Red 1 was treated with chlorine gas, and the solution obtained was analyzed with the aid of LC-ESI-MS/MS to identify the components present, and then evaluated for ecotoxicity and mutagenicity, using Daphnia similis and Salmonella/microsome assays, respectively. The results of this study indicated that chlorination of Disperse Red 1 produced four chlorinated aromatic compounds as the main products and that the degradation products were more ecotoxic than the parent dye. These results suggest that a disinfection process using chlorine should be avoided for effluents containing hydrophobic azo dyes such commercial Disperse Red 1. -- Highlights: Black-Right-Pointing-Pointer Aqueous solutions of Disperse Red 1 were treated with chlorine. Black-Right-Pointing-Pointer The chlorination products of Disperse Red 1 were identified using LC-ESI-MS/MS. Black-Right-Pointing-Pointer Daphnia and Salmonella/microsome were employed for eco/genotoxicity testing. Black-Right-Pointing-Pointer The chlorinated dye was more mutagenic

  19. 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

  20. 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.

  1. 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...

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 40 CFR 721.5917 - Phenyl azo dye (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phenyl azo dye (generic). 721.5917... Substances § 721.5917 Phenyl azo dye (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a phenyl azo dye (PMN P-02-17) is subject to...

  11. 40 CFR 721.757 - Polyoxyalkylene substituted aromatic azo colorant. (United States)


    ... azo colorant. 721.757 Section 721.757 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.757 Polyoxyalkylene substituted aromatic azo colorant. (a) Chemical... as polyoxyalkylene substituted aromatic azo colorant (PMN P-92-1131) is subject to reporting under...

  12. 40 CFR 721.4594 - Substituted azo metal complex dye. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal complex...

  13. 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.

  14. 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...

  15. Spectrophotometric determination of persulfate by oxidative decolorization of azo dyes for wastewater treatment. (United States)

    Ding, Yaobin; Zhu, Lihua; Yan, Jingchun; Xiang, Qingqing; Tang, Heqing


    Persulfate can efficiently decolorize azo dyes through oxidizing these compounds, which enabled us to develop a method of rapid spectrophotometric determination of persulfate for monitoring the wastewater treatment on the basis of the oxidation decolorization of azo dyes. Four azo dyes with different molecular structures were investigated as probes, and the influences of operation parameters including reaction time, solution pH, initial dye concentration, and initial concentration of activator Fe(2+) were checked on the determination of persulfate. Under optimum conditions, the decolorization degree of the dyes responded linearly with persulfate concentration for all the four azo dyes, and the linear range and detection limit were found to be 2.0-150 μmol L(-1) and 0.62 μmol L(-1) for rhodamine B, 2.0-100 μmol L(-1) and 0.42 μmol L(-1) for methylene blue, 4.0-150 μmol L(-1) and 0.50 μmol L(-1) for methyl violet, and 20-150 μmol L(-1) and 8.1 μmol L(-1) for orange II. A persulfate treatment of a spiked wastewater sample was satisfactorily monitored with the new method.

  16. Evaluating role of immobilized periphyton in bioremediation of azo dye amaranth. (United States)

    Shabbir, Sadaf; Faheem, Muhammad; Ali, Naeem; Kerr, Philip G; Wu, Yonghong


    The aim of this study was to evaluate the bioremediation capabilities of three kinds of periphyton (i.e. epiphyton, metaphyton and epilithon) immobilized in bioreactors to decolorize and biodegrade the sulphonated azo dye, amaranth. Results showed that periphyton dominated by phyla including Cyanobacteria, Proteobacteria and Bacteroidetes. Complete removal of dye was shown by all the biofilms periphyton (epiphyton showed highest removal efficacy) over a range of initial concentrations (50-500mgL-1) within 84h at pH 7 and 30°C. Biodegradation of amaranth was confirmed through FTIR and HPLC and the biodegradation pathways were detected by GC-MS/MS analysis. The azo bonds in the amaranth were successfully broken by periphyton and amaranth was converted to non-toxic, aliphatic compounds including isobutene, acetyl acetate and ethyl acetate. The results showed the potential application of immobilized periphyton at industrial scale for the removal of azo dyes from wastewater containing azo dye amaranth. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Crystallization and preliminary X-ray analysis of AzoR (azoreductase) from Escherichia coli. (United States)

    Ito, Kosuke; Nakanishi, Masayuki; Lee, Woo-Cheol; Sasaki, Hiroshi; Zenno, Shuhei; Saigo, Kaoru; Kitade, Yukio; Tanokura, Masaru


    AzoR (azoreductase), an FMN-dependent NADH-azo compound oxidoreductase from Escherichia coli, has been crystallized in the presence of FMN by the sitting-drop vapour-diffusion method using 2-propanol as a precipitant. AzoR catalyzes the reductive cleavage of azo groups. The crystals were found to diffract X-rays to beyond 1.8 A resolution using a synchrotron-radiation source. The crystals belonged to the tetragonal space group P4(2)2(1)2, with unit-cell parameters a = b = 92.2, c = 51.9 A. The crystals are expected to contain one subunit of the homodimer in the asymmetric unit (VM = 2.6 A3 Da(-1)) and to have a solvent content of 51.6%. Data sets were also collected from heavy-atom derivatives for use in phasing. As a result, crystals soaked in a solution containing K2PtCl4 for 23 d were found to be reasonably isomorphous to the native crystals and the presence of Pt atoms could be confirmed. The data sets from the native crystals and the K2PtCl4-derivatized crystals are being evaluated for use in structure determination by single isomorphous replacement with anomalous scattering.

  18. Synthesis and structural characterization of new oxovanadium(IV) complexes derived from azo-5-pyrazolone with prospective medical importance (United States)

    Bagdatli, Emine; Altuntas, Eylem; Sayin, Ulku


    Four novel o-hydroxy substituted aryl-(msbnd H, sbnd Cl, sbnd Br, sbnd CH3) azo-5-pyrazolone compounds (2a-d, respectively) were synthesized as azo-group containing ligands by diazotization of aryl amines then coupled with 1-(4-chlorophenyl)-3-isopropyl-1H-pyrazol-5(4H)-one (1) and the structures were confirmed by FTIR, UV-Visible, GC-MS or ESI-LCMS and NMR spectroscopic techniques. As a result, the first synthesis of azo-5-pyrazolone based oxovanadium(IV) complexes (3a-d) was achieved by interaction of 2a-d with half equivalent of vanadyl sulphate pentahydrate in a methanolic medium with moderate to high yields (67, 74, 60, 71 for 3a-d, respectively). The resulting complexes were characterized using FTIR, UV-Visible, ESI-LCMS and EPR spectroscopic techniques as well as with thermogravimetric (TG/DTG) analysis. They have the composition [VO(L)2]·H2O; (3a-c) or [VO(L)2]·CH3OH; (3d) where LH is an azo-5-pyrazolone compound as the ligand (2a-d). The electronic spectra of the complexes are typical of oxovanadium(IV) complexes showing a low intensity band near 500 nm. Spectroscopic results have shown that azo-5-pyrazolone compounds have acted bidendate and the coordination sites are hydroxyl-substituent on the -azo phenyl-aromatic ring and the pyrazolone carbonyl-moiety. The thermal data confirm that the complexes have methanol (3a-c) or water (3d) molecule outside the coordination sphere and the complexes show similar thermogravimetric decomposition fragments which are consistent with the proposed structures. A distorted octahedral geometry has been proposed for these complexes mainly with EPR and the other spectral techniques.

  19. 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...

  20. 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...

  1. Synthesis and evaluation of mutual azo prodrug of 5-aminosalicylic acid linked to 2-phenylbenzoxazole-2-yl-5-acetic acid in ulcerative colitis

    Directory of Open Access Journals (Sweden)

    Jilani JA


    Full Text Available Jamal A Jilani,1 Maha Shomaf,2 Karem H Alzoubi3 1Department of Medicinal Chemistry and Pharmacognosy, Jordan University of Science and Technology, Irbid, Jordan; 2Department of Pathology, Jordan University, Amman, Jordan; 3Department of Clinical Pharmacy, Jordan University of Science and Technology, Irbid, Jordan Abstract: In this study, the syntheses of 4-aminophenylbenzoxazol-2-yl-5-acetic acid, (an analogue of a known nonsteroidal anti-inflammatory drug [NSAID] and 5-[4-(benzoxazol-2-yl-5-acetic acidphenylazo]-2-hydroxybenzoic acid (a novel mutual azo prodrug of 5-aminosalicylic acid [5-ASA] are reported. The structures of the synthesized compounds were confirmed using infrared (IR, hydrogen-1 nuclear magnetic resonance (1H NMR, and mass spectrometry (MS spectroscopy. Incubation of the azo compound with rat cecal contents demonstrated the susceptibility of the prepared azo prodrug to bacterial azoreductase enzyme. The azo compound and the 4-aminophenylbenzoxazol-2-yl-5-acetic acid were evaluated for inflammatory bowel diseases, in trinitrobenzenesulfonic acid (TNB-induced colitis in rats. The synthesized diazo compound and the 4-aminophenylbenzoxazol-2-yl-5-acetic acid were found to be as effective as 5-aminosalicylic acid for ulcerative colitis. The results of this work suggest that the 4-aminophenylbenzoxazol-2-yl-5-acetic acid may represent a new lead for treatment of ulcerative colitis. Keywords: benzoxazole acetic acid, azo prodrug, colon drug delivery

  2. Growth and physiology of Clostridium perfringens wild-type and ΔazoC knockout: an azo dye exposure study. (United States)

    Morrison, Jessica M; John, Gilbert H


    Clostridium perfringens, a strictly anaerobic micro-organism and inhabitant of the human intestine, has been shown to produce the azoreductase enzyme AzoC, an NAD(P)H-dependent flavin oxidoreductase. This enzyme reduces azo dyes to aromatic amines, which are carcinogenic in nature. A significant amount of work has been completed that focuses on the activity of this enzyme; however, few studies have been completed that focus on the physiology of azo dye reduction. Dye reduction studies coupled with C. perfringens growth studies in the presence of ten different azo dyes and in media of varying complexities were completed to compare the growth rates and dye-reducing activity of C. perfringens WT cells, a C. perfringens ΔazoC knockout, and Bifidobacterium infantis, a non-azoreductase-producing control bacterium. The presence of azo dyes significantly increased the generation time of C. perfringens in rich medium, an effect that was not seen in minimal medium. In addition, azo dye reduction studies with the ΔazoC knockout suggested the presence of additional functional azoreductases in this medically important bacterium. Overall, this study addresses a major gap in the literature by providing the first look, to our knowledge, at the complex physiology of C. perfringens upon azo dye exposure and the effect that both azo dyes and the azoreductase enzyme have on growth.

  3. 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.

  4. 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 ...

  5. -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.

  6. 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

  7. 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…

  8. 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

  9. Research on Synthesis of New Azo Calix[4]arene and its Dyeing Properties

    Directory of Open Access Journals (Sweden)

    Tang Jun


    Full Text Available With the raw materials of calix[4]arene, benzocaine, tricaine and procaine hydrochloride, three new azo calix[4]arene derivatives—6a, 6b and 6c are synthesized by diazotization–coupling reaction of an aromatic amine, with its yield of 83%, 81% and 83% respectively. The structural characterization is in a way of IR, 1H NMR and elemental analysis. This paper investigates the spectral properties of azo calix[4]arene derivatives under different solution pH conditions through the UV–visible spectroscopy, and researches the dyeing properties through the dyeing curve, color yield test and fastness test. The results show that, with the increase of pH value, the azo calix[4]arene derivatives—6a, 6b and 6c form azo–hydrazone tautomeric isomers with the maximum absorption peak redshift; the dyeing effect of the compound is good, of which the dye–uptake rate of the compound 6a is as high as 78%; the surface depth of color yield is 2.798, and the dry and wet rubbing fastness and the soaping fastness are respectively 4, which is a better disperse dye.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Degradation of azo dyes by environmental microorganisms and helminths

    Energy Technology Data Exchange (ETDEWEB)

    Kingthom Chung; Stevens, S.E. Jr. (Memphis State Univ., TN (United States). Dept. of Biology)


    The degradation of azo dyes by environmental microorganisms, fungi, and helminths is reviewed. Azo dyes are used in a wide variety of products and can be found in the effluent of most sewage treatment facilities. Substantial quantities of these dyes have been deposited in the environment, particularly in streams and rivers. Azo dyes were shown to affect microbial activities and microbial population sizes in the sediments and in the water columns of aquatic habitats. Only a few aerobic bacteria have been found to reduce azo dyes under aerobic conditions, and little is known about the process. A substantial number of anaerobic bacteria capable of azo dye reduction have been reported. The enzyme responsible for azo dye reduction has been partially purified, and characterization of the enzyme is proceeding. The nematode Ascaris lumbricoides and the cestode Moniezia expanza have been reported to reduce azo dyes anaerobically. Recently the fungus Phanerochaete chrysoporium was reported to mineralize azo dyes via a peroxidation-mediated pathway. A possible degradation pathway for the mineralization of azo dye is proposed and future research needs are discussed.

  15. 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.

  16. 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.

  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. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative (United States)

    Sujamol, M. S.; Athira, C. J.; Sindhu, Y.; Mohanan, K.


    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, 1H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry.

  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. 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.

  1. Synthesis and characterization of textile azo dyes derivatives of methoxyphenols


    Ferreira, Isabel C.F.R.; Queiroz, Maria João R.P.


    Azo dyes are used extensively in the textile and dyestuff industries and effluents from these industrial processes are usually resistant to biological treatment. Textile azo dyes with bioaccessible groups such as guaiacol (2-methoxyphenol) and 2,6--dimethoxyphenol, for lignin-degrading fungus were synthesized using aminobenzoic and aminosulfonic acids as diazocomponents.

  2. Biodegradation of textile Azo Dyes by Phanerochaete chrysosporium


    Ferreira, Isabel C.F.R.; Santos, Isabel M.; Queiroz, Maria João R.P.; Lima, Nelson


    Azo dyes are used extensively in the textile and dyestuff industries and effluents from these industrial processes are usually resistant to biological treatment. Textile azo dyes with bioaccessible groups such as guaiacol and 2,6-dimethoxyphenol, for lignin-degrading fungus as P. chrysosporium were synthesised.

  3. An Interdisciplinary Experiment: Azo-Dye Metabolism by "Staphylococcus Aureus" (United States)

    Brocklesby, Kayleigh; Smith, Robert; Sharp, Duncan


    An interdisciplinary and engaging practical is detailed which offers great versatility in the study of a qualitative and quantitative metabolism of azo-dyes by "Staphylococcus aureus". This practical has broad scope for adaptation in the number and depth of variables to allow a focused practical experiment or small research project. Azo-dyes are…

  4. 40 CFR 721.9717 - Azo monochloro triazine reactive dye. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Azo monochloro triazine reactive dye... Substances § 721.9717 Azo monochloro triazine reactive dye. (a) Chemical substance and significant new uses... reactive dye (PMN P-96-238) is subject to reporting under this section for the significant new uses...

  5. 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).

  6. 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.

  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. 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.

  9. 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.

  10. Preparation and Properties of Flexible AZO@C Nanofibers

    Directory of Open Access Journals (Sweden)

    MA Hui


    Full Text Available A new type of environmental-friendly flexible nanofibers of aluminum doped zinc oxide (AZO coated carbon (AZO@C was successfully prepared by using polyvinyl alcohol (PVA as raw materials. The as-spun PVA nanofibers were prepared via electrospinning and its water resistance was greatly improved after heat-treatment. Then, the PVA nanofibers with a layer of zinc aluminum hydroxide on the surface were synthesized by hydrothermal method. Thereafter, new AZO@C composite nanofibers was produced after sintering at 500℃ to the carbonization of PVA nanofibers and the dehydration of zinc aluminum hydroxide to form AZO nanoparticles. The structure and properties of the samples were characterized by Fourier-transform infrared spectrometer (FT-IR, thermal gravimetric analyzer (TGA and scanning electron microscope (SEM. The average diameter of the AZO@C nanofibers is (320±45nm. The photocatalytic property of the resultant composite fibers is demonstrated by degrading methyl orange under solar light.

  11. Dye-sensitized solar cell based on AZO/Ag/AZO multilayer transparent conductive oxide film

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Jin-He; Li, Ying [School of Materials Science and Engineering, Shanghai University, 149 Yanchang Road, Shanghai 200072 (China); Duong, Thanh-Tung; Choi, Hyung-Jin [Department of Materials Engineering, Chungnam National University, Daeduk Science Town, 305-764 Daejeon (Korea, Republic of); Yoon, Soon-Gil, E-mail: [Department of Materials Engineering, Chungnam National University, Daeduk Science Town, 305-764 Daejeon (Korea, Republic of)


    Highlights: ► AZO/Ag/AZO (AAA) multilayer was used for working electrode of DSSC cell. ► The 100 nm-thick Nb-doped TiO{sub 2} layer showed a good blocking effect. ► The DSSC cell by AAA TCO material showed the highest efficiency of about 3.25%. -- Abstract: Niobium-doped TiO{sub 2} blocking layer and Al-doped ZnO (AZO)/Ag/AZO (AAA) TCO layers were grown onto glass substrate using pulsed laser deposition (PLD) and direct current (dc)/radio-frequency (rf) sputtering at room temperature, respectively for dye-sensitized solar cell (DSSC) applications. The 100 nm-thick NTO layer showed a blocking effect for the oxygen diffusion into AAA layer and for the recombination of the electrons. The DSSC cell composed of the NTO (100 nm)/AAA (400 nm) showed the highest photo-electrical efficiency of about 3.25%. An insertion of aluminum foil between serrated clip and AAA (100 nm) TCO improved a photo-conversion efficiency of the DSSC.

  12. 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 ...

  13. 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...

  14. 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.

  15. Analysis of water-soluble azo dyes in soft drinks by high resolution UPLC-MS. (United States)

    Liu, X; Yang, J L; Li, J H; Li, X L; Li, J; Lu, X Y; Shen, J Z; Wang, Y W; Zhang, Z H


    An UPLC-Orbitrap MS system was exploited to develop and validate a method for the simultaneous determination of 11 water-soluble azo dyes (Acid Yellow 17, Acid Red 14, Acid Red 26, Acid Red 73, Acid Orange 52, Acid Orange 7, Acid Orange 12, Acid Yellow 36, Acid Orange 5, Acid Red 88 and Acid Red 9) in soft drinks. Three pairs of isomers and four disulphonated azo dyes were among a total of 11 water-soluble azo dyes obtained and purified using an SPE cartridge. They were well separated using optimized UPLC conditions with a RP18 column and a MS detector with a compatible mobile phase system. All these dyes were detected by the Orbitrap XL mass spectrometer in negative ion mode. HCD tandem MS fragment ions are first reported in this paper, and these fragment ions can be used for identification of isomers of azo dyes. According to SANCO/10684/2009, one quasi-molecular ion in full scan mode as quantification ion and one or two HCD tandem MS fragment ions as identification ions are required for compound confirmation. Matrix-matched calibration was employed for quantification. The linear matrix-matched calibration for the 11 dyes was in the range 5-200 ng g(-1) with correlation coefficients (r) of 0.9939-0.9988. Recoveries were 68.9-110.8% with coefficients of variation of 0.9-12.0%. Depending on the dye and matrix involved, the LODs were between 1.0 and 3.2 ng g(-1) and LOQs were between 5.2 and 9.8 ng g(-1).

  16. Decolorization of azo dyes by Geobacter metallireducens. (United States)

    Liu, Guangfei; Zhou, Jiti; Chen, Congcong; Wang, Jing; Jin, Ruofei; Lv, Hong


    Geobacter metallireducens was found to be capable of decolorizing several azo dyes with different structures to various extents. Pyruvate, ethanol, acetate, propionate, and benzoate could support 66.3 ± 2.6-93.7 ± 2.1 % decolorization of 0.1 mM acid red 27 (AR27) in 40 h. The dependence of the specific decolorization rate on AR27 concentration (25 to 800 μM) followed Michaelis-Menten kinetics (K m = 186.9 ± 1.4 μΜ, V max = 0.65 ± 0.02 μmol mg protein(-1) h(-1)). Enhanced AR27 decolorization was observed with the increase of cell concentrations ranging from 7.5 to 45 mgL(-1). AR27 decolorization by G. metallireducens was retarded by the presence of goethite, which competed electrons with AR27 and was reduced to Fe(II). The addition of low concentrations of humic acid (1-100 mgL(-1)) or 2-hydroxy-1,4-naphthoquinone (0.5-50 μM) could improve the decolorization performance of G. metallireducens. High-performance liquid chromatography analysis suggested reductive pathway to be responsible for decolorization. This was the first study on azo dye decolorization by Geobacter strain and might improve our understanding of natural attenuation and bioremediation of environments polluted by azo dyes.

  17. Azo-derivatives thin films grown by matrix-assisted pulsed laser evaporation for non-linear optical applications

    Energy Technology Data Exchange (ETDEWEB)

    Constantinescu, C. [INFLPR – National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); Matei, A., E-mail: [INFLPR – National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); Ionita, I. [INFLPR – National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); UB – University of Bucharest, Faculty of Physics, 405 Atomistilor Street, Magurele RO-077125, Bucharest (Romania); Ion, V.; Marascu, V.; Dinescu, M. [INFLPR – National Institute for Laser, Plasma and Radiation Physics, 409 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); Vasiliu, C. [INOE2000 – National Institute for Optoelectronics 2000, 1 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); Emandi, A. [INOE2000 – National Institute for Optoelectronics 2000, 1 Atomistilor Street, Magurele, RO-077125 Bucharest (Romania); UB – University of Bucharest, Faculty of Chemistry, Department of Inorganic Chemistry, 90-92 Panduri Street, RO-050663 Bucharest (Romania)


    Azo-dye compounds, in bulk or as thin films, are extensively studied due to their particular optical properties. These properties include non-linear interaction, e.g. two-photon absorption, optical limiting and all-optical poling, with potential applications in optoelectronics and sensors development. Herein, we report on the deposition of pyrazolone derivatives, namely 1-phenyl-3-methyl-4-(1′-azo-2′-sodium carboxylate)-pyrazole-5-one thin films, for applications in second harmonic generation. Matrix-assisted pulsed laser evaporation was employed for layers growth, using a Nd:YAG device operating at 266 nm (4ω). The structure and surface morphology of the deposited films were examined by Fourier transform infrared spectroscopy, atomic force microscopy, and scanning electron microscopy. Spectroscopic-ellipsometry was employed to investigate thin film optical properties. Significant second harmonic generation capabilities of the compound were pointed out by using a femtosecond Ti:sapphire laser.

  18. A new Organopalladium compound containing four Iron (III ...

    Indian Academy of Sciences (India)

    Abstract. Two iron(III) tetraphenyl porphyrin catalytic units are connected by an azo-link to form the dimeric compound A. The compound A was then reacted with Pd2+ to make a tetrameric iron(III) porphyrin complex B with all four iron(III) catalytic sites open to the substrates and reactants. Both the compounds were character ...

  19. 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.

  20. 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

  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. 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.

  3. 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

  4. 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.

  5. Adsorption of azo dyes on polymer materials

    Directory of Open Access Journals (Sweden)

    Panić Vesna V.


    Full Text Available The use of polymeric adsorbents for the removal of azo dyes from solution has been reviewed. Adsorption techniques are widely used to remove certain classes of pollutants from waters, especially those which are not easily biodegradable. The removal of azo dyes as pollutants from wastewaters of textile, paper, printing, leather, pharmaceutical and other industries has been addressed by the researchers. The wider use of already available adsorbents is restricted due to their high costs which lead to investigation and development of new materials that can be cheaper, eficient and easy regenerated. The aim of this article is to present to the readers the widespread investigations in recent years of synthetic and natural polymers as adsorbents and potential replacement of conventional adsorbents. This review presents only the data obtained using raw, hydrogel, grafted and crosslinked forms of synthetic and nature based polymers, and the discussion is limited to these polymer-based materials and their adsorption properties. [Projekat Ministarstva nauke Republike Srbije, br. 43009 i br. 172062.

  6. Biodegradation of azo dyes by genetically engineered azoreductase. (United States)

    Wang, Jing; Yan, Bin; Zhou, Ji-Ti; Bao, Yong-Ming; Lu, Hong; Yuan, Xiao-Dong


    A azoreductase gene with 537 bp was obtained by PCR amplification from Rhodobacter sphaeroides AS1.1737. The enzyme, with a molecular weight of 18.7 kD, was efficiently expressed in Escherichia coli and its biodegradation characteristics for azo dyes were investigated. Furthermore, the reaction kinetics and mechanism of azo dyes catalyzed by the genetically engineered azoreductase were studied in detail. The presence of a hydrazo-intermediate was identified, which provided a convincing evidence for the assumption that azo dyes were degraded via an incomplete reduction stage.

  7. Effects of reduction products of ortho-hydroxyl substituted azo dyes on biodecolorization of azo dyes

    Energy Technology Data Exchange (ETDEWEB)

    Liu Guangfei [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China); Wang Jing, E-mail: [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China); Lu Hong; Jin Ruofei; Zhou Jiti; Zhang Long [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, School of Environmental and Biological Science and Technology, Dalian University of Technology, Linggong Road No. 2, Dalian 116024 (China)


    The mediated effects of reduction products of some ortho-hydroxyl substituted azo dyes on biodecolorization were investigated. The results indicated that the addition of reduction products could effectively accelerate dye decolorization by Shigella sp. QRZ-1. The best accelerating effect was obtained with the addition of reduction products of Acid Red 14 (AR14), resulting in an over 3-fold increase in decolorization efficiency of many azo dyes. In sequencing batch reactor experiments, the accelerating effect of reduction products of AR14 was more obvious (1.5-fold) during the startup of the system. When the dye concentration was increased to 500 mg L{sup -1}, the accelerated decolorization efficiency was still maintained around 95%. The presence of AR14 in the feed enhanced the decolorization performance of anaerobic sludge, indicating that the strategy may be beneficial for practical application. 1-Naphthol-2-amino-4-sulfonic acid, which is one of the reduction products of AR14, may function as redox mediator to speed up azo dye biodecolorization.

  8. Antimicrobial azobenzene compounds and their potential use in biomaterials (United States)

    Sessa, L.; Concilio, S.; Iannelli, P.; De Santis, F.; Porta, A.; Piotto, S.


    We recently synthesized a class of active compounds with azobenzene structure [1] and lowest in silico toxicity values. The antimicrobial activity of these molecules and their thermal stability are very promising and indicate that they may have interesting and therapeutically significant applications. This work aims to develop new materials with antibacterial and antifungal activity inserting different percentages of synthetic antimicrobial azo compounds in commercial polymer matrices. We realized thin films using solvent casting and melt compounding techniques. The obtained materials retained the proprieties of the pure matrices. This means that azo dye dissolved in the matrix does not influence the thermal behavior and the morphology of the material. Tested films exhibited the capability to inhibit biofilms formation of S. aureus and C. albicans. Spectrophotometric investigation of the azo compound released from the polymer matrices confirmed that the realized materials might be interesting for biomedical tools, antibacterial surfaces, and films for active packaging.

  9. (azo anils and oxalate ion) copper(ii) complexes

    African Journals Online (AJOL)

    B. S. Chandravanshi

    54890, Pakistan. 2Nano Science and Catalysis Division, National Centre for Physics, Islamabad-45320, Pakistan. (Received October ... Antibacterial activities of free ligands (azo anils and oxalate) and Cu(II) complexes were determined. Gram.

  10. 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.

  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. A New Generation of Glycoconjugated Azo Dyes Based on Aminosugars


    Guazzelli, Lorenzo; Catelani, Giorgio; D’Andrea, Felicia


    The third generation of glycoconjugated azo dyes (GADs) was prepared linking monoazo dyes to 6-amino-6-deoxy-d-galactose or 6′amino-6′-deoxylactose through mixed amido-ester connections. The complementary conjugation reactions were studied using the succinyl derivative of either the acetal protected aminosugar or the azo dye. Target “naturalized” GADs were obtained after acid hydrolysis of the acetal protecting groups present on the sugar moiety.

  16. A New Generation of Glycoconjugated Azo Dyes Based on Aminosugars

    Directory of Open Access Journals (Sweden)

    Lorenzo Guazzelli


    Full Text Available The third generation of glycoconjugated azo dyes (GADs was prepared linking monoazo dyes to 6-amino-6-deoxy-d-galactose or 6′amino-6′-deoxylactose through mixed amido-ester connections. The complementary conjugation reactions were studied using the succinyl derivative of either the acetal protected aminosugar or the azo dye. Target “naturalized” GADs were obtained after acid hydrolysis of the acetal protecting groups present on the sugar moiety.

  17. Ion irradiation of AZO thin films for flexible electronics

    Energy Technology Data Exchange (ETDEWEB)

    Boscarino, Stefano; Torrisi, Giacomo; Crupi, Isodiana [IMM-CNR and Dipartimento di Fisica e Astronomia, Università di Catania, via S. Sofia 64, 95123 Catania (Italy); Alberti, Alessandra [CNR-IMM, via Strada VIII 5, 95121 Catania (Italy); Mirabella, Salvatore; Ruffino, Francesco [IMM-CNR and Dipartimento di Fisica e Astronomia, Università di Catania, via S. Sofia 64, 95123 Catania (Italy); Terrasi, Antonio, E-mail: [IMM-CNR and Dipartimento di Fisica e Astronomia, Università di Catania, via S. Sofia 64, 95123 Catania (Italy)


    Highlights: • Evidence of electrical good quality AZO ultra thin films without thermal annealing. • Evidence of the main role of Oxygen vs. structural parameters in controlling the electrical performances of AZO. • Evidence of the role of the ion irradiation in improving the electrical properties of AZO ultra thin films. • Synthesis of AZO thin films on flexible/plastic substrates with good electrical properties without thermal processes. - Abstract: Aluminum doped Zinc oxide (AZO) is a promising transparent conductor for solar cells, displays and touch-screen technologies. The resistivity of AZO is typically improved by thermal annealing at temperatures not suitable for plastic substrates. Here we present a non-thermal route to improve the electrical and structural properties of AZO by irradiating the TCO films with O{sup +} or Ar{sup +} ion beams (30–350 keV, 3 × 10{sup 15}–3 × 10{sup 16} ions/cm{sup 2}) after the deposition on glass and flexible polyethylene naphthalate (PEN). X-ray diffraction, optical absorption, electrical measurements, Rutherford Backscattering Spectrometry and Atomic Force Microscopy evidenced an increase of the crystalline grain size and a complete relief of the lattice strain upon ion beam irradiation. Indeed, the resistivity of thin AZO films irradiated at room temperature decreased of two orders of magnitude, similarly to a thermal annealing at 400 °C. We also show that the improvement of the electrical properties does not simply depend on the strain or polycrystalline domain size, as often stated in the literature.

  18. Decolorization and biogas production by an anaerobic consortium: effect of different azo dyes and quinoid redox mediators. (United States)

    Alvarez, L H; Valdez-Espinoza, R; García-Reyes, R B; Olivo-Alanis, D; Garza-González, M T; Meza-Escalante, E R; Gortáres-Moroyoqui, P


    The inhibitory effect of azo dyes and quinoid compounds on an anaerobic consortium was evaluated during a decolorization process and biogas production. In addition, the impact of quinoid compounds such as lawsone (LAW) and anthraquinone-2,6-disulfonate (AQDS) on the rate of decolorization of Direct Blue 71 (DB71) was assessed. The anaerobic consortium was not completely inhibited under all tested dye concentrations (0.1-2 mmol l(-1)), evidenced by an active decolorization process and biogas production. The presence of quinoid compounds at different concentrations (4, 8, and 12 mmol l(-1)) also inhibited biogas production compared to the control incubated without the quinoid compounds. In summary, the anaerobic consortium was affected to a greater extent by increasing the quantity of azo dyes or quinoid compounds. Nevertheless, at a lower concentration (1 mmol l(-1)) of quinoid compounds, the anaerobic consortium effectively decolorized 2 mmol l(-1) of DB71, increasing up to 5.2- and 20.4-fold the rate of decolorization with AQDS and LAW, respectively, compared to the control lacking quinoid compounds.

  19. 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

  20. 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

  1. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)


    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  2. Modification of azo dyes by lactic acid bacteria. (United States)

    Pérez-Díaz, I M; McFeeters, R F


    The ability of Lactobacillus casei and Lactobacillus paracasei to modify the azo dye, tartrazine, was recently documented as the result of the investigation on red coloured spoilage in acidified cucumbers. Fourteen other lactic acid bacteria (LAB) were screened for their capability to modify the food colouring tartrazine and other azo dyes of relevance for the textile industry. Most LAB modified tartrazine under anaerobic conditions, but not under aerobic conditions in modified chemically defined media. Microbial growth was not affected by the presence of the azo dyes in the culture medium. The product of the tartrazine modification by LAB was identified as a molecule 111 daltons larger than its precursor by liquid chromatography-mass spectrometry. This product had a purple colour under aerobic conditions and was colourless under anaerobic conditions. It absorbed light at 361 and 553 nm. LAB are capable of anabolizing azo dyes only under anaerobic conditions. IMPACT AND SIGNIFICANCE OF THE STUDY: Although micro-organisms capable of reducing the azo bond on multiple dyes have been known for decades, this is the first report of anabolism of azo dyes by food related micro-organisms, such as LAB.

  3. 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.

  4. 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...

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Diaminomaleonitrile-based azo receptors: Synthesis, DFT studies and their antibacterial activities (United States)

    Khanmohammadi, Hamid; Arab, Vajihe; Rezaeian, Khatereh; Talei, Gholam Reza; Pass, Maryam; Shabani, Nafiseh


    New unsymmetric diaminomaleonitrile-based azo receptors (H3Ln, n = 1-3) have been synthesized via condensation reaction of 5-(4-X-phenyl)-azo-salicyladehyde (X = NO2, OMe and CH3) with 2-amino-3-(5-bromo-2-hydroxybenzylamino)maleonitrile. The solvatochromic behaviors of the molecules were probed by studying their UV-Vis spectra in five pure organic solvents of different polarities. The p-NO2 substituted receptor shows a dramatic color change from yellow to blue upon the addition of fluoride ion in CH3CN. This capability was studied by systematic TD-DFT calculations. These compounds were assayed for their in vitro antibacterial activities against Gram-positive (S. aureus, S. epidermidis and L. monocytogenes) and Gram-negative (E. coli, P. aeruginosa and K. pneumonia.) bacteria by disc diffusion method. The results indicated that the compounds show good inhibition against Gram positive bacteria namely L. monocytogenes as compared to standard drugs.

  14. 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.

  15. 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.

  16. Novel azo-peresters radical initiators used for the synthesis of acrylic pressure-sensitive adhesives

    Directory of Open Access Journals (Sweden)


    Full Text Available Acrylic pressure-sensitive adhesives (PSA based on two monomers: 2-ethylhexyl acrylate and acrylic acid were synthesized in organic solvent ethyl acetate using AIBN (2, 2'-azo-diisobutyronitrile and new synthesized azo-peresters as radical initiators. After polymerization the viscosity, molecular weight and polydispersity of synthesized acrylic PSA were evaluated. The novel synthesized radical azo-perester initiators were synthesized, isolated and compared with industrial predominant usable azo-initiator AIBN.

  17. 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.

  18. Novel zinc(II)phthalocyanines bearing azo-containing schiff base: Determination of pKa values, absorption, emission, enzyme inhibition and photochemical properties (United States)

    Kantar, Cihan; Mavi, Vildan; Baltaş, Nimet; İslamoğlu, Fatih; Şaşmaz, Selami


    Azo-containing schiff bases are well known and there are many studies about their various properties in literature. However, phthalocyanines bearing azo-containing schiff bases, their spectral, analytical and biological properties are unknown. Therefore, new zinc (II) phthalocyanines bearing azo-containing schiff base were synthesized and investigated to determine pKa values, absorption, emission, enzyme inhibition and photochemical properties. Emission spectra were reported and large Stokes shift values were determined for all compounds, indicating that all molecules exhibit excited state intramolecular proton transfer. These phthalocyanines were the first examples of phthalocyanine showing excited state intramolecular proton transfer. Singlet oxygen quantum yields of zinc (II) phthalocyanines were determined. pKa values and indicator properties of all compounds were investigated by potentiometry. All compounds were assayed for inhibitory activity against bovine milk xanthine oxidase and acetylcholinesterase enzyme in vitro. Compound 2 showed the high inhibitory effect against xanthine oxidase (IC50 = 0.24 ± 0.01 μM). However, phthalocyanine compounds did not show enzyme inhibitor behavior.

  19. 40 CFR 721.980 - Sodium salt of azo acid dye. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sodium salt of azo acid dye. 721.980... Substances § 721.980 Sodium salt of azo acid dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a sodium salt of azo acid dye (PMN P-95-633...

  20. Reduction of the azo dye Mordant Orange 1 by methanogenic granular sludge exposed to oxygen

    NARCIS (Netherlands)

    Tan, N.C.G.; Lettinga, G.; Field, J.A.


    Integration of anaerobic and aerobic conditions in a single bioreactor is a good strategy for the complete mineralization of azo dyes. In order for this strategy to work, azo dye reduction should occur in biofilms exposed to oxygen. Therefore, the effect of oxygen on the azo dye reduction by

  1. 40 CFR 721.2097 - Azo chromium complex dyestuff preparation (generic name). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Azo chromium complex dyestuff... New Uses for Specific Chemical Substances § 721.2097 Azo chromium complex dyestuff preparation... substance identified generically as an azo chromium complex dyestuff preparation (PMN P-95-240) is subject...

  2. Microbial fuel cell with an azo-dye-feeding cathode

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Liang [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Geochemistry; Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou (China). Guangdon Key Lab. of Agricultural Environment Pollution Integrated Control; Graduate Univ. of Chinese Academy of Sciences, Beijing (China); Li, Fang-bai [Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou (China). Guangdon Key Lab. of Agricultural Environment Pollution Integrated Control; Feng, Chun-hua [South China Univ. of Technology, Guangzhou (China). School of Chemistry and Chemical Engineering; Li, Xiang-zhong [Hong Kong Polytechnic Univ., Hong Kong (China). Dept. of Civil and Structural Engineering


    Microbial fuel cells (MFCs) were constructed using azo dyes as the cathode oxidants to accept the electrons produced from the respiration of Klebsiella pneumoniae strain L17 in the anode. Experimental results showed that a methyl orange (MO)-feeding MFC produced a comparable performance against that of an air-based one at pH 3.0 and that azo dyes including MO, Orange I, and Orange II could be successfully degraded in such cathodes. The reaction rate constant ({kappa}) of azo dye reduction was positively correlated with the power output which was highly dependent on the catholyte pH and the dye molecular structure. When pH was varied from 3.0 to 9.0, the k value in relation to MO degradation decreased from 0.298 to 0.016 {mu}mol min{sup -1}, and the maximum power density decreased from 34.77 to 1.51 mW m{sup -2}. The performances of the MFC fed with different azo dyes can be ranked from good to poor as MO > Orange I > Orange II. Furthermore, the cyclic voltammograms of azo dyes disclosed that the pH and the dye structure determined their redox potentials. A higher redox potential corresponded to a higher reaction rate. (orig.)

  3. 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

  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. Yeast extract promotes decolorization of azo dyes by stimulating azoreductase activity in Shewanella sp. strain IFN4. (United States)

    Imran, Muhammad; Arshad, Muhammad; Negm, Fayek; Khalid, Azeem; Shaharoona, Baby; Hussain, Sabir; Mahmood Nadeem, Sajid; Crowley, David E


    Biological treatment of azo dyes commonly requires a combined anaerobic-aerobic process in which initial decolorization is achieved by reductive cleavage of azo bonds on the parent molecule. The present study was conducted to examine the relative importance of co-substrates for driving reductive decolorization of azo dyes by Shewanella sp. strain IFN4 using whole cells and enzyme assays. Results showed that the dye decolorization by strain IFN4 was faster in medium containing 1gL(-1) yeast extract (YE) as compared to nine other co-substrates. Moreover, only YE stimulated azoreductase activity (increased from 1.32 to 4.19U/mg protein). Increasing the level of YE up to 8gL(-)(1) resulted into 81% decolorization of the dye in 1h along with an increase in azoreductase activity up to 6.16U/mg protein. Among the components of YE, only riboflavin stimulated the decolorization process as well as enzyme activity. Moreover, strain IFN4 demonstrated flavin reductase activity, and a significant correlation (r(2)=0.98) between flavin reduction and dye reduction by this strain emphasized the involvement of flavin compounds in the decolorization process. The results of this study show that YE serves both as a source of reducing equivalents and an electron shuttle for catalyzing dye reduction. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. New tridentate azo-azomethines and their copper(II) complexes: Synthesis, solvent effect on tautomerism, electrochemical and biological studies (United States)

    Sarigul, Munire; Deveci, Pervin; Kose, Muhammet; Arslan, Ugur; Türk Dagi, Hatice; Kurtoglu, Mukerrem


    In this study, three azo-azomethines and their copper(II) complexes were prepared and characterized by analytical and spectroscopic methods. The complexes prepared were found to be mononuclear and the chelation of the ligands to the copper(II) ions occurs through two phenolic oxygens and a nitrogen atom of the azomethine group of the ligand. The tautomeric behaviors of the azo-azomethines in solution were studied by UV-Vis. spectra in three organic solvents with different polarity (CHCl3, DMSO and DMF) at room temperature. The redox behaviors of the azo-azomethines and their Cu(II) complexes were investigated by cyclic voltammetry (CV) in DMSO solution containing 0.1 M tetrabutylammonium tetrafluoroborate (TBATFB) as supporting electrolyte. Additionally, the antibacterial activity was also evaluated by the broth microdilution methods against Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. The compounds were found to be less effective against all bacteria tested than two reference antibiotics (ampicillin and gentamicin).

  7. AZO/Ag/AZO anode for resonant cavity red, blue, and yellow organic light emitting diodes

    Energy Technology Data Exchange (ETDEWEB)

    Gentle, A. R., E-mail:; Smith, G. B. [School of Mathematical and Physical Sciences and Institute of Nanoscale Technology, University of Technology Sydney, P.O. Box 123, Broadway, New South Wales 2007 (Australia); Yambem, S. D.; Burn, P. L.; Meredith, P. [Centre for Organic Photonics and Electronics, School of Chemistry and Molecular Biosciences and School of Mathematics and Physics, The University of Queensland, St Lucia, Queensland 4072 (Australia)


    Indium tin oxide (ITO) is the transparent electrode of choice for organic light-emitting diodes (OLEDs). Replacing ITO for cost and performance reasons is a major drive across optoelectronics. In this work, we show that changing the transparent electrode on red, blue, and yellow OLEDs from ITO to a multilayer buffered aluminium zinc oxide/silver/aluminium zinc oxide (AZO/Ag/AZO) substantially enhances total output intensity, with better control of colour, its constancy, and intensity over the full exit hemisphere. The thin Ag containing layer induces a resonant cavity optical response of the complete device. This is tuned to the emission spectra of the emissive material while minimizing internally trapped light. A complete set of spectral intensity data is presented across the full exit hemisphere for each electrode type and each OLED colour. Emission zone modelling of output spectra at a wide range of exit angles to the normal was in excellent agreement with the experimental data and hence could, in principle, be used to check and adjust production settings. These multilayer transparent electrodes show significant potential for both eliminating indium from OLEDs and spectrally shaping the emission.

  8. Effect of molecular structure and packing density of an azo self-assembled monolayer on liquid crystal alignment. (United States)

    Vengatesan, M R; Lee, Seung-Ho; Son, Jong-Ho; Lim, Jeong-Ku; Song, Jang Kun


    We studied the alignment of liquid crystals (LCs) on a photo-switchable azo-containing self-assembled monolayer (azo-SAM) with different packing densities and molecular structures. The packing density of the azo-SAM substrates was varied by changing the dipping time of the substrate in azosilane monomers solution (2mM in toluene). The thickness of the monolayer on the silicon substrate increased as the dipping time was increased. The relative surface packing density on the glass substrates was estimated from the surface energies of the azo-SAM. The photo-induced dynamics of liquid crystal alignment on the azo-SAM significantly varied according to the packing density of the azo-SAM and the structure of the azo-SAM molecules. The azo-SAM from long octyloxy chain-terminated azosilane (azo-S1) possessed stable homeotropic alignment even after photobuffing, while the azo-SAM from short methyl group-terminated azosilane monomer (azo-S2) showed photo-switchable homeotropic and planar alignments. However, when the packing density was increased to an excessive degree, even the azo-SAM from azo-S2 exhibited stable homeotropic alignment regardless of photobuffing. Copyright © 2013 Elsevier Inc. All rights reserved.

  9. 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.

  10. Synthesis, Characterization, and Biological Activity of 5-Phenyl-1,3,4-thiadiazole-2-amine Incorporated Azo Dye Derivatives

    Directory of Open Access Journals (Sweden)

    Chinnagiri T. Keerthi Kumar


    Full Text Available 5-Phenyl-1,3,4-thiadiazole-2-amine has been synthesized by single step reaction. A series of heterocyclic azodyes were synthesized by diazotisation of 5-phenyl-1,3,4-thiadiazole-2-amine by nitrosyl sulphuric acid followed by coupling with different coupling compounds such as 8-hydroxyquinoline, 2,6-diaminopyridine, 2-naphthol, N,N-dimethyl aniline, resorcinol, and 4,6-dihydroxypyrimidine. The dyes were characterized by UV-Vis, IR, 1H-NMR, 13C NMR, and elemental analysis. The synthesized compounds were also screened for biological activity.

  11. Synthesis, Characterization and Reactivity of Nanostructured Zero-Valent Iron Particles for Degradation of Azo Dyes (United States)

    Mikhailov, Ivan; Levina, Vera; Leybo, Denis; Masov, Vsevolod; Tagirov, Marat; Kuznetsov, Denis

    Nanostructured zero-valent iron (NSZVI) particles were synthesized by the method of ferric ion reduction with sodium borohydride with subsequent drying and passivation at room temperature in technical grade nitrogen. The obtained sample was characterized by means of X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering studies. The prepared NSZVI particles represent 100-200nm aggregates, which consist of 20-30nm iron nanoparticles in zero-valent oxidation state covered by thin oxide shell. The reactivity of the NSZVI sample, as the removal efficiency of refractory azo dyes, was investigated in this study. Two azo dye compounds, namely, orange G and methyl orange, are commonly detected in waste water of textile production. Experimental variables such as NSZVI dosage, initial dye concentration and solution pH were investigated. The kinetic rates of degradation of both dyes by NSZVI increased with the decrease of solution pH from 10 to 3 and with the increase of NSZVI dosage, but decreased with the increase of initial dye concentration. The removal efficiencies achieved for both orange G and methyl orange were higher than 90% after 80min of treatment.

  12. Metabolism of the benzidine-based azo dye Direct Black 38 by human intestinal microbiota

    Energy Technology Data Exchange (ETDEWEB)

    Manning, B.W.; Cerniglia, C.E.; Federle, T.W.


    Benzidine-based azo dyes are proven mutagens and have been linked to bladder cancer. Previous studies have indicated that their initial reduction is the result of the azo reductase activity of the intestinal microbiota. Metabolism of the benzidine-based dye Direct Black 38 was examined by using a semicontinuous culture system that simulates the lumen of the human large intestine. The system was inoculated with freshly voided feces, and an active flora was maintained as evidenced by volatile fatty acid and gas production. Within 7 days after exposure to the dye, the following metabolites were isolated and identified by gas chromatography - mass spectrometry: benzidine, 4-aminobiphenyl, monoacetylbenzidine, and acetylaminobiphenyl. Benzidine reached its peak level after 24 h, accounting for 39.1% of the added dye. Its level began to decline, and by day 7 the predominant metabolite was acetylaminobiphenyl, which accounted for 51.1% of the parent compound. Formation of the deaminated and N-acetylated analogs of benzidine, which have enhanced mutagenicity and lipophilicity, previously has not been attributed to the intestinal microbiota.

  13. Synthesis and characterization of high wash fastness novel azo reactive dyes incorporating aromatic bridged diamines

    Directory of Open Access Journals (Sweden)

    Aamer Saeed


    Full Text Available A new series of azo reactive dyes containing free chlorine atoms have been synthesized. The synthetic methodology involves the diazotization of 4′4-diamino diphenylamine-2-sulfonic acid (2 followed by azo coupling with 1-amino-8-naphthol-3,6-disulfonic acid (3 in alkaline medium to yield intermediate dye (4. Condensation of the latter with 1,3,5-trichlorotriazine afforded the cyanurated dye (5. A number of novel bis aromatic diamines (1a–j were separately synthesized as bridging groups and were coupled with cyanurated dye (5 at room temperature to provide the target dyes designated as S1–S10 containing triazine and linker in a single molecule. The structures of newly synthesized compounds were confirmed by analytical data and spectroscopic techniques. The synthesized dyes were applied on cotton fibers to assess their light fastness, wash fastness and rubbing fastness and were found to possess medium to high fastness values in different dyes.

  14. Cyclodepsipeptides and Other O-Containing Heterocyclic Metabolites from Beauveria felina EN-135, a Marine-Derived Entomopathogenic Fungus

    Directory of Open Access Journals (Sweden)

    Feng-Yu Du


    Full Text Available Bioassay-guided fractionation of a culture extract of Beauveria felina EN-135, an entomopathogenic fungus isolated from a marine bryozoan, led to the isolation of a new cyclodepsipeptide, iso-isariin D (1; two new O-containing heterocyclic compounds that we have named felinones A and B (2 and 3; and four known cyclodepsipeptides (4–7. The structures were elucidated via spectroscopic analysis, and the absolute configurations of 1 and 2 were determined using single-crystal X-ray diffraction and CD, respectively. All isolated compounds were evaluated for antimicrobial activity and brine-shrimp (Artemia salina lethality.

  15. Discovery of Novel Tricyclic Heterocycles as Potent and Selective DPP-4 Inhibitors for the Treatment of Type 2 Diabetes

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wen-Lian; Hao, Jinsong; Domalski, Martin; Burnett, Duane A.; Pissarnitski, Dmitri; Zhao, Zhiqiang; Stamford, Andrew; Scapin, Giovanna; Gao, Ying-Duo; Soriano, Aileen; Kelly, Terri M.; Yao, Zuliang; Powles, Mary Ann; Chen, Shiying; Mei, Hong; Hwa, Joyce (Merck)


    In our efforts to develop second generation DPP-4 inhibitors, we endeavored to identify distinct structures with long-acting (once weekly) potential. Taking advantage of X-ray cocrystal structures of sitagliptin and other DPP-4 inhibitors, such as alogliptin and linagliptin bound to DPP-4, and aided by molecular modeling, we designed several series of heterocyclic compounds as initial targets. During their synthesis, an unexpected chemical transformation provided a novel tricyclic scaffold that was beyond our original design. Capitalizing on this serendipitous discovery, we have elaborated this scaffold into a very potent and selective DPP-4 inhibitor lead series, as highlighted by compound 17c.

  16. Microwave-induced and conventional heterocyclic synthesis: An antimicrobial entites of newer quinazolinyl-Δ2-pyrazolines

    Directory of Open Access Journals (Sweden)

    Krunal G. Desai


    Full Text Available Heterocyclic compounds containing pyrazolines were reported to possess significant biological activity. Synthesis of 2-(ω-chloroacetonyl-3-p-fluorophenyl-6-bromoquinazoline-4(3H-ones (2, 2-(ω-hydrazinoacetonyl-3-p-fluorophenyl-6-bromoquinazoline-4(3H-ones (3 and 1′-[3H-3-p-fluorophenyl-4-oxo-6-bromoquinazoline-2-acetonyl]-3′-[1-o-chlorophenyl-3-methyl-5-azomethine-2-pyrazolidene]-5′-(substituted phenyl-Δ2-pyrazolines (4a–j have been described. Some of the new compounds were tested against bacteria (Gram –ve and Gram +ve and fungi.

  17. Laser prepared organic heterostuctures on glass/AZO substrates (United States)

    Stanculescu, Anca; Socol, Marcela; Rasoga, Oana; Mihailescu, Ion N.; Socol, Gabriel; Preda, Nicoleta; Breazu, Carmen; Stanculescu, Florin


    This paper presents some studies about the bi-layer organic heterostructures realized with zinc phthalocyanine (ZnPc) as donor layer and 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) as acceptor layer, on substrate of glass covered by Al doped ZnO (AZO) layer. These heterostructures have been prepared using laser techniques: pulsed laser deposition (PLD) in an atmosphere of oxygen for AZO films deposition and matrix assisted pulsed laser evaporation (MAPLE) for organic films deposition. The influence of the deposition conditions on the transmission of the organic films has been analysed. The effect of the oxygen plasma treatment, with duration of 5 min and 10 min, on the surface topography, structural and optical properties of AZO layers deposited by PLD and, as consequence, on the optical and electrical properties of the single layer (ZnPc) and bi-layer (ZnPc/NTCDA) organic heterostructure, deposited by MAPLE, was investigated.



    Dian Windy Dwiasi; Mardiyah Kurniasih


    Synthesis of ferrate and its application to azo dyes degradation have been investigated. The synthesis was carried out by reacting Fe(NO3)3 solution with NaOCl in alkaline condition. Oxidation reaction of azo dyes was carried out by adjusting the molar ratio of ferrate to azo dyes. When ferrate reacted with azo dyes, its absorbance was monitored using UV-Vis spectrophotometer at pH condition that had been optimized. Kinetics study for azo dyes degradation was carried out at the absorbance max...

  19. Metal complex modified azo polymers for multilevel organic memories (United States)

    Ma, Yong; Chen, Hong-Xia; Zhou, Feng; Li, Hua; Dong, Huilong; Li, You-Yong; Hu, Zhi-Jun; Xu, Qing-Feng; Lu, Jian-Mei


    Multilevel organic memories have attracted considerable interest due to their high capacity of data storage. Despite advances, the search for multilevel memory materials still remains a formidable challenge. Herein, we present a rational design and synthesis of a class of polymers containing an azobenzene-pyridine group (PAzo-py) and its derivatives, for multilevel organic memory storage. In this design, a metal complex (M(Phen)Cl2, M = Cu, Pd) is employed to modify the HOMO-LUMO energy levels of azo polymers, thereby converting the memory state from binary to ternary. More importantly, this approach enables modulating the energy levels of azo polymers by varying the coordination metal ions. This makes the achievement of high performance multilevel memories possible. The ability to tune the bandgap energy of azo polymers provides new exciting opportunities to develop new materials for high-density data storage.Multilevel organic memories have attracted considerable interest due to their high capacity of data storage. Despite advances, the search for multilevel memory materials still remains a formidable challenge. Herein, we present a rational design and synthesis of a class of polymers containing an azobenzene-pyridine group (PAzo-py) and its derivatives, for multilevel organic memory storage. In this design, a metal complex (M(Phen)Cl2, M = Cu, Pd) is employed to modify the HOMO-LUMO energy levels of azo polymers, thereby converting the memory state from binary to ternary. More importantly, this approach enables modulating the energy levels of azo polymers by varying the coordination metal ions. This makes the achievement of high performance multilevel memories possible. The ability to tune the bandgap energy of azo polymers provides new exciting opportunities to develop new materials for high-density data storage. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00871a

  20. A highly efficient single chambered up-flow membrane-less microbial fuel cell for treatment of azo dye Acid Orange 7-containing wastewater. (United States)

    Thung, Wei-Eng; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Ridwan, Fahmi; Oon, Yoong-Ling; Oon, Yoong-Sin; Lehl, Harvinder Kaur


    Single chambered up-flow membrane-less microbial fuel cell (UFML MFC) was developed to study the feasibility of the bioreactor for decolorization of Acid Orange 7 (AO7) and electricity generation simultaneously. The performance of UFML MFC was evaluated in terms of voltage output, chemical oxygen demand (COD) and color removal efficiency by varying the concentration of AO7 in synthetic wastewater. The results shown the voltage generation and COD removal efficiency decreased as the initial AO7 concentration increased; this indicates there is electron competition between anode and azo dye. Furthermore, there was a phenomenon of further decolorization at cathode region which indicates the oxygen and azo dye are both compete as electron acceptor. Based on the UV-visible spectra analysis, the breakdown of the azo bond and naphthalene compound in AO7 were confirmed. These findings show the capability of integrated UFML MFC in azo dye wastewater treatment and simultaneous electricity generation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. [Determination of carcinogenic aromatic amines derived from azo colorants in plastic components of electrical and electronic products by high performance liquid chromatography-mass spectrometry]. (United States)

    Niu, Zengyuan; Luo, Xin; Ye, Xiwen; Wang, Huihui; Li, Jingying


    A study for the simultaneous determination of 21 primary aromatic amines derived from the reduction of the azo colorants in plastic components of electrical and electronic products was conducted. Organic solvents were used to dissolve or swell the plastics to release the azo dyes existing in the plastic components. The azo colorants were reduced to aromatic amines under strong reducing condition of dithionite. Aromatic amines were extracted with methyl tert-butyl ether. Methanol-water (1: 1, v/v) was used to concentrate the extract to constant-volume for HPLC-MS analysis. The analytes were separated on a ZORBAX Eclipse XDB C18 column using the gradient elution with acetonitrile and 0.1% (v/v) formic acid aqueous solution at a flow rate of 0.6 mL/min. The analyte confirmation was performed using retention time and characteristic ions in selected ion monitoring (SIM) mode. The correlation coefficients (r) of all the standard curves were more than 0.998, and the limits of quantification of the analytes were 0.5 mg/kg. The recoveries were 60.1% - 129.5% for the 21 aromatic amines with the RSDs not more than 14.0% except for a few compounds. The results showed that the banned azo colorants in the plastic products can be analyzed qualitatively and quantitatively through reductive conversion into aromatic amines. In addition, this method has high accuracy and good precision.

  2. Assessment of Environmental Effects of Ordnance Compounds and their Transformation Products in Coastal Ecosystems (United States)


    including some compounds of environmental concern such as substituted azobenzenes or phenazines (Haderlein and Schwarzenbach 1995). Aminonitrotoluenes...degradation only occurred under laboratory conditions in waters from sites with previous history of pollution by munition compounds, suggesting that...products were tentatively identified, including azoxy- and azobenzenes , in addition to 2,6-dinitrobenzaldehyde and 6-nitroanthranil. Azo compounds

  3. Non-classical azoreductase secretion in Clostridium perfringens in response to sulfonated azo dye exposure. (United States)

    Morrison, Jessica M; John, Gilbert H


    Clostridium perfringens, a strictly anaerobic microorganism and inhabitant of the human intestine, has been shown to produce an azoreductase enzyme (AzoC), an NADH-dependent flavin oxidoreductase. This enzyme reduces azo dyes into aromatic amines, which can be carcinogenic. A significant amount of work has been completed on the activity of AzoC. Despite this, much is still unknown, including whether azoreduction of these dyes occurs intracellularly or extracellulary. A physiological study of C. perfringens involving the effect of azo dye exposure was completed to answer this question. Through exposure studies, azo dyes were found to cause cytoplasmic protein release, including AzoC, from C. perfringens in dividing and non-dividing cells. Sulfonation (negative charge) of azo dyes proved to be the key to facilitating protein release of AzoC and was found to be azo-dye-concentration-dependent. Additionally, AzoC was found to localize to the Gram-positive periplasmic region. Using a ΔazoC knockout mutant, the presence of additional azoreductases in C. perfringens was suggested. These results support the notion that the azoreduction of these dyes may occur extracellularly for the commensal C. perfringens in the intestine. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Synthesis, characterization and biological evaluation of some novel nitrogen and sulphur containing organometallic heterocycles

    Directory of Open Access Journals (Sweden)

    Humaira Parveen


    Full Text Available 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 dubliniensis, Candida glabrata, Candida parapsilosis, Candida tropicalis, Candida kefyr and Candida krusei strains. The results clearly depict that the compounds (1–12 gave an average antimicrobial activity against the tested strains with an exception of compound 12 which stood out in terms of its activity against the tested organisms. All these compounds gave a range of MIC value between 32–64 μg/ml against S. bovis, E. coli and C. tropicalis except compound 12 which gave a MIC of 16 μg/ml against each of them. The MIC values of all these compounds against biofilm forming P. aeruginosa and S. mutans were 64–256 μg/ml and 64–128 μg/ml respectively which is apparently high, concluding that these compounds hold immense potential to be employed as a two in one formulation of antibacterial as well as antifungal agents.

  5. The Phosphinoboration of N-Heterocycles. (United States)

    Geier, Stephen J; Vogels, Christopher M; Mellonie, Niall R; Daley, Erika N; Decken, Andreas; Doherty, Simon; Westcott, Stephen A


    The addition of phosphinoboronate ester Ph2 PBpin (pin=1,2-O2 C2 Me4 ) (1) to a number of different N-heterocycles has been investigated. Reaction of 1 with pyridine resulted in highly selective formation of the corresponding 1,4-addition product, with addition of the electron-deficient Bpin group to the pyridine nitrogen atom and the phosphido group to the para carbon atom. Conversely, reactions of para-substituted pyridine derivatives occurred predominately to afford 1,2-addition products while quinoline reacted to afford the 1,2-adduct which ultimately isomerized to afford the corresponding 1,4-addition product. Preliminary computational studies have been undertaken to explore possible pathways for these transformations including transfer of the PPh2- anion from [B(PPh2 )2 pin]- to the 4-position of a borenium/boronium activated pyridine and concerted pathways for 1,2-addition via intramolecular nucleophilic attack of PPh2 at C2 of a Ph2 PBpin-coordinated pyridine via a four-centered transition state and intramolecular transfer of PPh2 to the 2-position of a boron-activated pyridine in a phosphido-bridged dimer involving a six-centered transition state. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed


    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  7. Heterocyclic Schiff bases as non toxic antioxidants: Solvent effect, structure activity relationship and mechanism of action. (United States)

    Shanty, Angamaly Antony; Mohanan, Puzhavoorparambil Velayudhan


    Phenolic heterocyclic imine based Schiff bases from Thiophene-2-carboxaldehyde and Pyrrole-2-carboxaldehyde were synthesized and characterized as novel antioxidants. The solvent effects of these Schiff bases were determined and compared with standard antioxidants, BHA employing DPPH assay and ABTS assay. Fixed reaction time and Steady state measurement were used for study. IC50 and EC50 were calculated. Structure-activity relationship revealed that the electron donating group in the phenolic ring increases the activity where as the electron withdrawing moiety decreases the activity. The Schiff base derivatives showed antioxidant property by two different pathways namely SPLET and HAT mechanisms in DPPH assay. While in ABTS method, the reaction between ABTS radical and Schiff bases involves electron transfer followed by proton transfer (ET-PT) mechanism. The cytotoxicity of these compounds has been evaluated by MTT assay. The results showed that all these compounds are non toxic in nature. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Probing the structure of DNA aptamers with a classic heterocycle. (United States)

    Wood, Arthur E; Bishop, G Reid


    DNA aptamers are synthetic, single-stranded DNA oligonucleotides selected by SELEX methods for their binding with specific ligands. Here we present ethidium binding results for three related DNA aptamers (PDB code: 1OLD, 1DB6, and 2ARG)that bind L-argininamide (L-Arm). The ligand bound form of each aptamer's structure has been reported and each are found to be composed primarily of two domains consisting of a stem helical region and a loop domain that forms a binding pocket for the cognate ligand. Previous thermodynamic experiments demonstrated that the DNA aptamer 1OLD undergoes a large conformational ordering upon binding to L-Arm. Here we extend those linkage binding studies by examining the binding of the heterocyclic intercalator ethidium to each of the three aptamers by fluorescence and absorption spectrophotometric titrations. Our results reveal that ethidium binds to each aptamer with DeltaG degree's in the range of -8.7 to -9.4 kcal/mol. The stoichiometry of binding is 2:1 for each aptamer and is quantitatively diminished in the presence of L-Arm as is the overall fluorescence intensity of ethidium. Together, these results demonstrate that a portion of the bound ethidium is excluded from the aptamer in the presence of a saturating amount of L-Arm. These results demonstrate the utility of ethidium and related compounds for the probing of non-conventional DNA structures and reveal an interesting fundamental thermodynamic linkage in DNA aptamers. Results are discussed in the context of the thermodynamic stability and structure of each of the aptamers examined.

  9. Effect of different redox mediators during thermophilic azo dye reduction by anaerobic granular sludge and comparative study between mesophilic (30C) and thermophilic (55C) treatments for decolourisation of textile wastewaters

    NARCIS (Netherlands)

    Bezerra Dos Santos, A.; Bisschops, I.A.E.; Cervantes, F.J.; Lier, van J.B.


    The impact of different redox mediators on colour removal of azo dye model compounds and textile wastewater by thermophilic anaerobic granular sludge (55 C) was investigated in batch assays. Additionally, a comparative study between mesophilic (30 C) and thermophilic (55 C) colour removal was

  10. Diphenyl (4′-(Aryldiazenylbiphenyl-4-ylamino(pyridin-3-ylmethylphosphonates as Azo Disperse Dyes for Dyeing Polyester Fabrics

    Directory of Open Access Journals (Sweden)

    Mohamed F. Abdel-Megeed


    Full Text Available Diphenyl (4′-aminobiphenyl-4-ylamino(pyridin-3-ylmethylphosphonate (1 was synthesized in 88% yield from reaction of pyridine-3-carboxaldehyde with benzidine and triphenylphosphite in the presence of titanium tetrachloride as a catalyst. Diazotization of 1 gave the corresponding diazonium salt 2 which was coupled with several hydroxyl or amino compounds to give the corresponding azo dyes 3–8 in 82–88% yields after crystallization. The dyes produced were applied to polyesters as disperse dyes and their fastness properties were elevated.

  11. Aerobic decolourization of two reactive azo dyes under varying ...

    African Journals Online (AJOL)

    Bacillus cereus isolated from dye industrial waste, that is, effluent and soil samples was screened for its ability to decolourize two reactive azo dye – cibacron black PSG and cibacron red P4B under aerobic conditions at pH 7 and incubated at 35°C over a five day period. Different carbon and nitrogen sources were used for ...

  12. Decolorization of Azo Dyes by Pycnoporus sanguineus and ...

    African Journals Online (AJOL)


    Decolorization of azo dyes by Pycnoporus sanguineus and Trametes membranacea. Da Paz, E. S. L.1*, Paz Júnior, F. B.2, Neto, B. B.3 and Cavalcanti, M. A. Q.4. 1School of Dentistry, Federal University of Pernambuco, Recife, Brazil. 2Federal Institute of Education, Science and Technology, Pernambuco, Recife, Brazil.

  13. Decolorization of the azo dye reactive black 5 using laccase ...

    African Journals Online (AJOL)

    Laccase mediator system (LMS) has been widely used in various fields. In this study, we tested the capacity of LMS in the decolorization of a recalcitrant azo dye Reactive Black 5 (RB5). Both acetosyringone and syringaldehyde demonstrated high mediating ability for RB5 decolorization and acetosyringone was proved to ...

  14. Azo-polysiloxanes as new supports for cell cultures

    Energy Technology Data Exchange (ETDEWEB)

    Hurduc, Nicolae, E-mail: [“Gheorghe Asachi” Technical University of Iasi, Department of Natural and Synthetic Polymers, Prof. Dimitrie, Mangeron Street, 73, 700050-Iasi (Romania); Macovei, Alina [Institute of Biochemistry of the Romanian Academy, Department of Viral Glycoproteins, Splaiul Independentei 296, Sector 6, 060041-Bucuresti (Romania); Paius, Cristina; Raicu, Alina [“Gheorghe Asachi” Technical University of Iasi, Department of Natural and Synthetic Polymers, Prof. Dimitrie, Mangeron Street, 73, 700050-Iasi (Romania); Moleavin, Ioana [CEA, LIST Saclay, Laboratoire Capteurs et Architectures Électroniques, F-91191 Gif-sur-Yvette, Cedex (France); Branza-Nichita, Norica, E-mail: [Institute of Biochemistry of the Romanian Academy, Department of Viral Glycoproteins, Splaiul Independentei 296, Sector 6, 060041-Bucuresti (Romania); Hamel, Matthieu [CEA, LIST Saclay, Laboratoire Capteurs et Architectures Électroniques, F-91191 Gif-sur-Yvette, Cedex (France); Rocha, Licinio, E-mail: [CEA, LIST Saclay, Laboratoire Capteurs et Architectures Électroniques, F-91191 Gif-sur-Yvette, Cedex (France)


    The paper introduces a new class of materials with azo-polysiloxanic structure bearing the property to generate nano-structured surfaces by laser irradiation. The ability to modulate the optical response of the film, through a modification of the polymer chemical structure, has been investigated. The azo-materials were tested for their ability to support cell adhesion and growth, with very promising results. A future use of these materials as growth support in cell cultures is of great interest, due to an easy, one step-method to generate the surface relief grating and to the possibility to introduce a large range of chemical modifications due to the presence of the chlorobenzyl groups in the polymeric side-chain. - Graphical abstract: Cell development on a nano-structured surface obtained from an azo-polysiloxanic film. Highlights: ► New azo-polysiloxanic films for biological applications were reported. ► Nanostructured surfaces with controllable geometry are obtained by laser irradiation. ► Cells are very sensitive to the chemical and physical properties of the polymeric substrate.


    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. Nano-silica supported periodic acid (nano-SPIA) has been utilized as a heterogeneous reagent for a highly efficient and one pot synthesis of azo dyes based on 1-naphthol under solvent-free conditions at room temperature. This method has some advantages, the reaction workup is very easy and the catalyst ...

  16. Textile azo dye degradation by Candida rugosa INCQS 71011 ...

    African Journals Online (AJOL)

    Textile azo dye degradation by Candida rugosa INCQS 71011 isolated from a non-impacted area in Semi-Arid Region of Brazilian Northeast. Carlos Roberto S. do Nascimento, Marília M. Nishikawa, Aline B. M. Vaz, Carlos Augusto Rosa, Manuela da Silva ...

  17. Optimization of AZO films prepared on flexible substrates

    Indian Academy of Sciences (India)


    grey relational analysis, the optimization of these deposition process parameters for AZO thin films with multiple characteristics was ... Keywords. Flexible substrates; Al2O3-doped zinc oxide; magnetron sputtering; grey relational analysis. 1. Introduction ..... visible range of around 81∙3% (figure 5c). Figure 6(a) shows XRD ...

  18. Mutagenic activity and heterocyclic amine content of the human diet

    Energy Technology Data Exchange (ETDEWEB)

    Knize, M.G.; Dolbeare, F.A.; Cunningham, P.L.; Felton, J.S.


    The mutagenic activity and the mass amount of heterocyclic amines responsible for the mutagenic activity have been measured in some cooked foods. Cooked meats are the predominant source of mutagenic activity in the diet with values ranging from 0 to 10,000 revertants per gram reported in the Ames/Salmonelia test with strain TA98. Several heterocyclic amines are present and have been quantified using solid-phase extraction followed by HPLC. Frying at higher temperatures and for longer times produces the greatest mutagenic response, and concomitantly, the largest amounts of heterocyclic amines. Most of the mutagenic activity in fried meat samples can be accounted for by MelQx, DiMelQx and IQ, although other heterocylic amines are present and PHIP mutagenic activity becomes significant at higher temperatures. Non-meat products such as baked breads can also form significant mutagenic activity, particularly when overcooked. Commercially prepared hamburgers made from meat substitutes such as tofu, wheat gluten or tempeh and fried at 210{degrees}C have up to 10% of the mutagenic activity of a fried beef patty cooked under the same conditions. When detected, amounts of heterocyclic amines in fried beef patties range from a total of 0.35 ng/g for commercial beef hamburgers to 142 ng/g for a beef patty cooked over a barbecue. Dietary intake is expected to have a large range, from less than one microgram per day to over 50 micrograms per day based on current knowledge of known heterocyclic amine chemicals and heterocyclic amine-containing foods.

  19. Synthesis and antitumor evaluation of thiophene based azo dyes incorporating pyrazolone moiety

    Directory of Open Access Journals (Sweden)

    Moustafa A. Gouda


    Full Text Available A series of thiophene incorporating pyrazolone moieties 5a–f and 6a–c were synthesized via diazo coupling of diazonium salt of 3-substituted-2-amino-4,5,6,7-tetrahydrobenzo[b]thiophenes 1a–c with 3-methyl-1H-pyrazol-5(4H-one, 3-methyl-1-phenyl-1H-pyrazol-5(4H-one or 3-amino-1H-pyrazol-5(4H-one, respectively. Newly synthesized dyes were applied to polyester fabric as disperse dyes in which their color measurements and fastness properties were evaluated. These dyes showed generally red to blue shifted color with high extinction coefficient in comparison with aniline-based azo dyes. The antitumor activity of the synthesized dyes was evaluated. The results showed clearly that most of them exhibited good activity and compounds 5c and 5d exhibited moderate activity.

  20. Spectroscopic, thermal, catalytic and biological studies of Cu(II) azo dye complexes (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Shoair, A. F.; Hussein, M. A.; El-Boz, R. A.


    New complexes of copper(II) with azo compounds of 5-amino-2-(aryl diazenyl)phenol (HLn) are prepared and investigated by elemental analyses, molar conductance, IR, 1H NMR, UV-Visible, mass, ESR spectra, magnetic susceptibility measurements and thermal analyses. The complexes have a square planar structure and general formula [Cu(Ln)(OAc)]H2O. Study the catalytic activities of Cu(II) complexes toward oxidation of benzyl alcohol derivatives to carbonyl compounds were tested using H2O2 as the oxidant. The intrinsic binding constants (Kb) of the ligands (HLn) and Cu(II) complexes (1-4) with CT-DNA are determined. The formed compounds have been tested for biological activity of antioxidants, antibacterial against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and yeast Candida albicans. Antibiotic (Ampicillin) and antifungal against (Colitrimazole) and cytotoxic compounds HL1, HL2, HL3 and complex (1) showed moderate to good activity against S. aureus, E. coli and Candida albicans, and also to be moderate on antioxidants and toxic substances. Molecular docking is used to predict the binding between the ligands with the receptor of breast cancer (2a91).

  1. Synthesis of different heterocycles-linked chalcone conjugates as cytotoxic agents and tubulin polymerization inhibitors. (United States)

    Shankaraiah, Nagula; Nekkanti, Shalini; Brahma, Uma Rani; Praveen Kumar, Niggula; Deshpande, Namrata; Prasanna, Daasi; Senwar, Kishna Ram; Jaya Lakshmi, Uppu


    A series of new heterocycles-linked chalcone conjugates has been designed and synthesized by varying different alkane spacers. These conjugates were tested for their in vitro cytotoxic potential against a panel of selected human cancer cell lines namely, lung (A549 and NCI-H460), prostate (DU-145 and PC-3), colon (HCT-15 and HCT-116), and brain (U-87 glioblastoma) by MTT assay. Notably, among all the tested compounds, 4a exhibited potent cytotoxicity on NCI-H460 (lung cancer) cells with IC50 of 1.48±0.19µM. The compound 4a showed significant inhibition of tubulin polymerization and disruption of the formation of microtubules (IC50 of 9.66±0.06μM). Moreover, phase contrast microscopy and DAPI staining studies indicated that compound 4a can induce apoptosis in NCI-H460 cells. Further, the flow-cytometry analysis revealed that compound 4a arrests NCI-H460 cells in the G2/M phase of the cell cycle. In addition, molecular docking studies of the most active compounds 4a and 4b into the colchicine site of the tubulin, revealed the possible mode of interaction by these new conjugates. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Quantitative Structure-Cytotoxicity Relationship of Bioactive Heterocycles by the Semi-empirical Molecular Orbital Method with the Concept of Absolute Hardness (United States)

    Ishihara, Mariko; Sakagami, Hiroshi; Kawase, Masami; Motohashi, Noboru

    The relationship between the cytotoxicity of N-heterocycles (13 4-trifluoromethylimidazole, 15 phenoxazine and 12 5-trifluoromethyloxazole derivatives), O-heterocycles (11 3-formylchromone and 20 coumarin derivatives) and seven vitamin K2 derivatives against eight tumor cell lines (HSC-2, HSC-3, HSC-4, T98G, HSG, HepG2, HL-60, MT-4) and a maximum of 15 chemical descriptors was investigated using CAChe Worksystem 4.9 project reader. After determination of the conformation of these compounds and approximation to the molecular form present in vivo (biomimetic) by CONFLEX5, the most stable structure was determined by CAChe Worksystem 4.9 MOPAC (PM3). The present study demonstrates the best relationship between the cytotoxic activity and molecular shape or molecular weight of these compounds. Their biological activities can be estimated by hardness and softness, and by using η-χ activity diagrams.

  3. Novel Strategy for Tracking the Microbial Degradation of Azo Dyes with Different Polarities in Living Cells. (United States)

    Liu, Fei; Xu, Meiying; Chen, Xingjuan; Yang, Yonggang; Wang, Haiji; Sun, Guoping


    Direct visualization evidence is important for understanding the microbial degradation mechanisms. To track the microbial degradation pathways of azo dyes with different polar characterizations, sensors based on the fluorescence resonance energy transfer (FRET) from 1,8-naphthalimide to azo dyes were synthesized, in which the quenched fluorescence will recover when the azo bond was cleaved. In living cells, the sensor-tracking experiment showed that the low polarity and hydrophobic azo dye can be taken up into the cells and reduced inside the cells, whereas the high polarity and hydrophilic azo dye can be reduced only outside the cells because of the selective permeability of the cell membranes. These results indicated that there were two different bacterial degradation pathways available for different polarity azo dyes. To our knowledge, no fluorescent sensor has yet been designed for illuminating the microbial degradation mechanisms of organic pollutants with different characteristics.

  4. Synthesis, Characterization and Photoinduction of Optical Anisotropy in Liquid Crystalline Diblock Azo-Copolymers

    DEFF Research Database (Denmark)

    Forcén, P; Oriol, L; Sánchez, C


    behavior similar to that of the azo homopolymers. Thin films of these copolymers were characterized by transmission elevtron microscopy (TEM). A lamellar nanostructure was observed for azo content down to 20 wt %, while no structure is observed for the copolymer with a 7% azo content. The optical......Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline WC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobeazene content in these copolymers ranges from 52 to 7 wt %. For an azo conteat dowri to 20% they exhibit a LC...... the homopolymer to the copolymers. Photoinduced azo orientation perpendicular to the 488 nm light polarization was found in aH the polymers. The orientational order parameter is very similar in the homopolymer and in the block copolymers with an azo content down to 20 wt %, while it is much lower in the random...

  5. Facile Synthesis of Electroconductive AZO@TiO2 Whiskers and Their Application in Textiles

    Directory of Open Access Journals (Sweden)

    Hui Ma


    Full Text Available The electroconductive AZO@TiO2 whiskers have been successfully prepared via coating Al doped ZnO onto TiO2 whisker. The orthogonal tests were employed to optimize the synthetic conditions. The crystallographic structure and the morphology of the AZO@TiO2 whiskers and the polypropylene nonwoven fabrics modified with AZO@TiO2 whiskers were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope, four-probe meter, and electrometer. The results showed the AZO@TiO2 whiskers exhibited good electroconductive performance. Moreover, the polypropylene nonwoven fabrics modified with AZO@TiO2 whiskers revealed excellent antistatic performance indicating wide application of AZO@TiO2 whiskers in the antistatic textiles.

  6. Highly transparent conductive AZO/Zr50Cu50/AZO films in wide range of visible and near infrared wavelength grown by pulsed laser deposition

    Directory of Open Access Journals (Sweden)

    Jingyun Cheng

    Full Text Available Novel AZO/Zr50Cu50/AZO tri-layer transparent conductive films with excellent transmittance in both visible and near infrared region were successfully prepared by pulsed laser deposition on glass substrates. The electrical and optical properties were investigated at various Zr50Cu50 thicknesses. As the AZO thickness was fixed at 50 nm and Zr50Cu50 thickness was varied between 1 and 18 nm, it was found that AZO (50 nm/Zr50Cu50/AZO (50 nm tri-layer films exhibited good conductivity and high transmittance in both visible and near infrared wavelength. Additionally, both the electrical and optical properties of AZO (50 nm/Zr50Cu50 (2 nm/AZO (50 nm tri-layer films were found to be sensitive to the growth temperature. In this work, the lowest sheet resistance (43 Ω/□ and relatively high transmittance (∼80% in the range of 400–2000 nm were achieved while the growth temperature was 350 °C. Furthermore, the AZO (50 nm/Zr50Cu50 (2 nm/AZO (50 nm thin film deposited at 350 °C exhibits the highest figure of merit of 1.42 × 10−3 Ω−1, indicating that the multilayer is promising for coated glasses and thin film solar cells. Keywords: Transparent conductive oxide, AZO, Zr50Cu50, Electrical and optical properties, Visible and near infrared transmittance

  7. Application of chalcones in heterocycles synthesis: Synthesis of 2 ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 3. Application of chalcones in heterocycles synthesis: Synthesis of 2-(isoxazolo, pyrazolo and pyrimido) substituted analogues of 1,4-benzodiazepin-5-carboxamides linked through an oxyphenyl bridge. N Kaur D Kishore. Volume 125 Issue 3 May 2013 pp ...

  8. Synthesis, Characterization, and Biological Activity of 5-Phenyl-1,3,4-thiadiazole-2-amine Incorporated Azo Dye Derivatives


    Chinnagiri T. Keerthi Kumar; Jathi Keshavayya; Tantry N. Rajesh; Sanehalli K. Peethambar; Angadi R. Shoukat Ali


    5-Phenyl-1,3,4-thiadiazole-2-amine has been synthesized by single step reaction. A series of heterocyclic azodyes were synthesized by diazotisation of 5-phenyl-1,3,4-thiadiazole-2-amine by nitrosyl sulphuric acid followed by coupling with different coupling compounds such as 8-hydroxyquinoline, 2,6-diaminopyridine, 2-naphthol, N,N-dimethyl aniline, resorcinol, and 4,6-dihydroxypyrimidine. The dyes were characterized by UV-Vis, IR, 1H-NMR, 13C NMR, and elemental analysis. The synthesized compo...

  9. Synthesis of 1-(4-Trifluoromethoxyphenyl-2,5-dimethyl-3-(2-R-thiazol-4-yl-1H-pyrroles via Chain Heterocyclization

    Directory of Open Access Journals (Sweden)

    Andrij O. Tolmachov


    Full Text Available The title compounds, (4-trifluoromethoxyphenyl-2,5-dimethyl-3-(2-R-thiazol-4-yl-1H-pyrroles, were prepared in four steps starting from commercially available 4-trifluoromethoxyaniline. The pyrrole (second ring was added in one step using the Paal-Knorr method. The thiazole (third ring was added in three steps using chloroacylation with chloroacetonitrile followed by heterocyclization with thioamides/thioureas.

  10. UV-visible-DAD and 1H-NMR spectroscopy data fusion for studying the photodegradation process of azo-dyes using MCR-ALS. (United States)

    Fernández, Cristina; Pilar Callao, M; Larrechi, M Soledad


    The photodegradation process of three azo-dyes - Acid Orange 61, Acid Red 97 and Acid Brown 425 - was monitored simultaneously by ultraviolet-visible spectroscopy with diode array detector (UV-vis-DAD) and (1)H-nuclear magnetic resonance ((1)H-NMR). Multivariate curve resolution-alternating least squares (MCR-ALS) was applied to obtain the concentration and spectral profile of the chemical compounds involved in the process. The analysis of the H-NMR data suggests there are more intermediate compounds than those obtained with the UV-vis-DAD data. The fusion of UV-vis-DAD and the (1)H-NMR signal before the multivariate analysis provides better results than when only one of the two detector signals was used. It was concluded that three degradation products were present in the medium when the three azo-dyes had practically degraded. This study is the first application of UV-vis-DAD and (1)H-NMR spectroscopy data fusion in this field and illustrates its potential as a quick method for evaluating the evolution of the azo-dye photodegradation process. © 2013 Elsevier B.V. All rights reserved.

  11. Periphyton biofilms: A novel and natural biological system for the effective removal of sulphonated azo dye methyl orange by synergistic mechanism. (United States)

    Shabbir, Sadaf; Faheem, Muhammad; Ali, Naeem; Kerr, Philip G; Wu, Yonghong


    Due to their large scale use, azo dyes are adversely affecting aquatic fauna and flora as well as humans. The persistent nature of sulphonated azo dyes makes them potential ecotoxic hazards. The aim of the present study was to employ a proficient, locally available biomaterial, viz. periphyton (i.e. epiphyton, epilithon or metaphyton), for removal of the azo dye, methyl orange (MO). Results showed that the periphytic biofilms are capable of completely removing comparatively high concentrations (up to 500 mg L -1 ) of MO from wastewater. The removal of MO occurs by a synergistic mechanism involving bioadsorption and biodegradation processes. The adsorption of MO by periphyton can be described by pseudo-second order kinetics. Elovich and intraparticle diffusion models as well as Langmuir equations fit well to the MO adsorption process. FTIR analysis of MO and its metabolites demonstrated biotransformation into simpler compounds within 72 h. GC-MS/MS analysis showed the conversion of MO into simpler compounds such as phenol, ethyl acetate and acetyl acetate. The results indicated that periphyton is a promising biomaterial for the complete removal of MO from wastewater and that the treatment process has the potential for in situ removal of MO at contaminated sites. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Synthesis, Structural Analysis and Antimicrobial Activities of Novel Water Soluble Ionic Liquids Derived from N-Heterocyclic Carbene Salts

    Directory of Open Access Journals (Sweden)

    Ahmet Kunduracıoğlu


    Full Text Available Six N-heterocyclic Carbene based Ionic Liquids (ILs have been synthesized by conventional methods. The ILs were spectroscopically characterized by NMR and FT-IR techniques. Their in vitro antimicrobial activities were determined towards gram-positive and gram-negative bacterias and yeast strains using minimum inhibition concentration (MIC assay. The best inhibition performances were obtained with compound 1 due to its more hydrophilic nature compared with the others. It exhibited 1 mg L–1 MIC value against to the most bacteria while the others showed 4 mg L–1. This work is licensed under a Creative Commons Attribution 4.0 International License.

  13. Synthesis and characterization of an iron complex bearing a cyclic tetra-N-heterocyclic carbene ligand: An artifical heme analogue?

    KAUST Repository

    Anneser, Markus R.


    An iron(II) complex with a cyclic tetradentate ligand containing four N-heterocyclic carbenes was synthesized and characterized by means of NMR and IR spectroscopies, as well as by single-crystal X-ray structure analysis. The iron center exhibits an octahedral coordination geometry with two acetonitrile ligands in axial positions, showing structural analogies with porphyrine-ligated iron complexes. The acetonitrile ligands can readily be substituted by other ligands, for instance, dimethyl sulfoxide, carbon monoxide, and nitric oxide. Cyclic voltammetry was used to examine the electronic properties of the synthesized compounds. © 2015 American Chemical Society.

  14. 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.

  15. Susceptibility to Exposure to Heterocyclic Amines from Cooked Food: Role of UDP-glucuronosyltransferases

    Energy Technology Data Exchange (ETDEWEB)

    Malfatti, M A; Felton, J S


    A number of carcinogenic heterocyclic amines (PhIP, MeIQx, and DiMeIQx) are produced from the condensation of creatinine, hexoses and amino acids during the cooking of meat (1). There are many variables that impact the production and subsequent ingestion of these compounds in our diet. Temperature, type of meat product, cooking method, doneness, and other factors affect the quantity of these carcinogens consumed by humans. Estimates of ingestion of these carcinogens are 1-20 ng/kg body weight per day (2). Human case control studies that correlate meat consumption from well-done cooking practices with cancer incidence indicate excess tumors for breast, colon, stomach, esophagus, and possibly prostate (3-5).

  16. Synthesis, Singlet Oxygen Photogeneration and DNA Photocleavage of Porphyrins with Nitrogen Heterocycle Tails

    Directory of Open Access Journals (Sweden)

    Xiu-Lan Zhang


    Full Text Available Eight novel compounds were prepared by reaction of 5-(bromo- propoxyphenyl-10,15,20-triphenylporphyrin with oxazole thiols, 1,3,4-oxadiazole thiols and 1,3,4-thiadiazole thiols, and their structures confirmed by UV-vis, IR, 1H-NMR, MS and elemental analysis. The assessment of indirectly measured 1O2 production rates against 5,10,15,20-tetraphenyl porphyrin (H2TPP were described and the relative singlet oxygen production yields were:porphyrin 5 > porphyrins 1, 3, 4, 6-8, H2TPP > porphyrin 2. Porphyrin 4 and porphyrin 7 showed substantial photocleavage activities toward DNA, with over 75% cleavage observed at 40 µM. It suggested that these those porphyrins with nitrogen heterocycle tails are potential photosensitive agents.

  17. Synthesis, structural characterization and tautomeric properties of some novel bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone. (United States)

    Mohammadi, Asadollah; Safarnejad, Mastaneh


    Nine new bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone have been synthesized in two steps using Knoevenagel condensation and diazotization-coupling reaction. The structures of the compounds were confirmed by UV-vis, IR, (1)H NMR and (13)C NMR spectroscopic techniques. The spectral characterizations demonstrate that there is an equilibrium between the azo (T1) and hydrazine (T2 and T3) tautomers for all prepared dyes in solutions. In addition, the solvatochromic behavior of the prepared dyes was evaluated using polarity/polarizability parameter (π(*)) in various solvents. The UV-vis absorption spectra of dyes show a bathochromic shift with increasing polarity and base strength of the solvents. Finally, the effects of acid and base on the UV-vis absorption spectra of the dyes with different substituent in diazo component are reported. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. CYP-450 isoenzymes catalyze the generation of hazardous aromatic amines after reaction with the azo dye Sudan III. (United States)

    Zanoni, Thalita Boldrin; Lizier, Thiago M; Assis, Marilda das Dores; Zanoni, Maria Valnice B; de Oliveira, Danielle Palma


    This work describes the mutagenic response of Sudan III, an adulterant food dye, using Salmonella typhimurium assay and the generation of hazardous aromatic amines after different oxidation methods of this azo dye. For that, we used metabolic activation by S9, catalytic oxidation by ironporphyrin and electrochemistry oxidation in order to simulate endogenous oxidation conditions. The oxidation reactions promoted discoloration from 65% to 95% of Sudan III at 1 × 10(-4)molL(-1) and generation of 7.6 × 10(-7)molL(-1) to 0.31 × 10(-4)molL(-1) of aniline, o-anisidine, 2-methoxi-5-methylaniline, 4-aminobiphenyl, 4,4'-oxydianiline; 4,4'-diaminodiphenylmethane and 2,6-dimethylaniline. The results were confirmed by LC-MS-MS experiments. We also correlate the mutagenic effects of Sudan III using S. typhimurium with the strain TA1535 in the presence of exogenous metabolic activation (S9) with the metabolization products of this compound. Our findings clearly indicate that aromatic amines are formed due to oxidative reactions that can be promoted by hepatic cells, after the ingestion of Sudan III. Considering that, the use of azo compounds as food dyestuffs should be carefully controlled. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Decolouration of azo dyes by Phanerochaete chrysosporium immobilised into alginate beads. (United States)

    Enayatzamir, Kheirghadam; Alikhani, Hossein A; Yakhchali, Bagher; Tabandeh, Fatemeh; Rodríguez-Couto, Susana


    Because of high discharged volumes and effluent composition, wastewater from the textile industry can be considered as the most polluting amongst all industrial sectors, thus greatly requiring appropriate treatment technologies. Although some abiotic methods for the reduction of several dyes exist, these require highly expensive catalysts and reagents. Biotechnological approaches were proven to be potentially effective in the treatment of this pollution source in an eco-efficient manner. The white-rot fungi are, so far, the most efficient microorganisms in degrading synthetic dyes. This white-rot fungi's property is due to the production of extracellular lignin-modifying enzymes, which are able to degrade a wide range of xenobiotic compounds because of their low substrate specificity. In this paper, we studied the ability of the white-rot fungus Phanerochaete chrysosporium immobilised into Ca-alginate beads to decolourise different recalcitrant azo dyes such as Direct Violet 51 (DV), Reactive Black 5 (RB), Ponceau Xylidine (PX) and Bismark Brown R (BB) in successive batch cultures. To the best of our knowledge, this is the first study on the immobilisation of P. chrysosporium into Ca-alginate beads for its application in dye decolouration. P. chrysosporium was immobilised into Ca-alginate beads using a method of gel recoating to minimise cellular leaking. The immobilised fungus was transferred to 250-ml Erlenmeyer flasks containing 50 ml of growth medium and incubated on an orbital shaker at 150 rpm and 30 degrees C for 7 days. The ratio of beads/medium used was 10% (w/v). The dyes were added into the culture flasks when MnP production started (50 U l(-1)), which corresponded with the seventh cultivation day. MnP activity and dye decolouration were measured spectrophotometrically. The dyes DV, RB and PX were almost totally decolourised at the end of each batch during the course of three successive batches. However, the dye BB was more resistant to decolouration and

  20. Prenylated flavanones isolated from flowers of Azadirachta indica (the neem tree) as antimutagenic constituents against heterocyclic amines. (United States)

    Nakahara, Kazuhiko; Roy, Molay Kumar; Ono, Hiroshi; Maeda, Ikuko; Ohnishi-Kameyama, Mayumi; Yoshida, Mitsuru; Trakoontivakorn, Gassinee


    Four prenylated flavanones were isolated from the methanol extract of the flowers of Azadirachta indica (the neem tree) as potent antimutagens against Trp-P-1 (3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole) in the Salmonella typhimurium TA98 assay by activity-guided fractionation. Spectroscopic properties revealed that those compounds were 5,7,4'-trihydroxy-8-prenylflavanone (1), 5,4'-dihydroxy-7-methoxy-8-prenylflavanone (2), 5,7,4'-trihydroxy-3',8-diprenylflavanone (3), and 5,7,4'-trihydroxy-3',5'-diprenylflavanone (4). All isolated compounds were found for the first time in this plant. The antimutagenic IC(50) values of compounds 1-4 were 2.7 +/- 0.1, 3.7 +/- 0.1, 11.1 +/- 0.1, and 18.6 +/- 0.1 microM in the preincubation mixture, respectively. These compounds also similarly inhibited the mutagenicity of Trp-P-2 (3-amino-1-methyl-5H-pyrido[4,3-b]indole) and PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine). All of the compounds 1-4 strongly inhibited ethoxyresorufin O-dealkylation activity of cytochrome P450 1A isoforms, which catalyze N-hydroxylation of heterocyclic amines. However, compounds 1-4 did not show significant inhibition against the direct-acting mutagen NaN(3). Thus, the antimutagenic effect of compounds 1-4 would be mainly based on the inhibition of the enzymatic activation of heterocyclic amines.

  1. Mg-based amorphous alloys for decolorization of azo dyes (United States)

    Zhang, Changqin; Zhu, Zhengwang; Zhang, Haifeng

    The authors recently found that Mg-based amorphous ribbons had a prominent effect on the decolorization of azo dyes. Direct Blue 2B and Acid Orange II solutions of 100 mg/L could be decolorized nearly completely by the ribbons within 30 min. Decolorization mechanism was discussed briefly, and kinetic analysis based on the experimental data indicated that physical adsorption and reductive degradation for the azo dye solutions mediated by Mg63Cu16.8Ag11.2Er9 amorphous ribbons could proceed in an elegant and rapid manner. This new finding seems attractive, valuable and promising for the raw effluent generated by textile dye manufacturing company in the future.

  2. Organocatalytic asymmetric arylation of indoles enabled by azo groups (United States)

    Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin


    Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

  3. Biosorption of Azo dyes by spent Rhizopus arrhizus biomass (United States)

    Salvi, Neeta A.; Chattopadhyay, S.


    In the present study, spent Rhizopus arrhizus biomass was used for the removal of six azo dyes from aqueous solutions. The dye removal capacity of the biomass was evaluated by conducting batch tests as a function of contact time, biomass dosage, pH and initial dye concentrations. The pseudo-second-order kinetic model fitted well with the experimental data with correlation coefficients greater than 0.999, suggesting that chemisorptions might be the rate limiting step. The equilibrium sorption data showed good fit to the Langmuir isotherm model. Among the six dyes tested, the maximum monolayer adsorption capacity for fast red A and metanil yellow was found to be 108.8 and 128.5 mg/g, respectively. These encouraging results suggest that dead Rhizopus arrhizus biomass could be a potential biomaterial for the removal of azo dyes from aqueous dye solution.

  4. Synthesis and characterization of azo-guanidine based alcoholic media naked eye DNA sensor. (United States)

    Altaf, Ataf Ali; Hashmat, Uzma; Yousaf, Muhammad; Lal, Bhajan; Ullah, Shafiq; Holder, Alvin A; Badshah, Amin


    DNA sensing always has an open meadow of curiosity for biotechnologists and other researchers. Recently, in this field, we have introduced an emerging class of molecules containing azo and guanidine functionalities. In this study, we have synthesized three new compounds (UA1, UA6 and UA7) for potential application in DNA sensing in alcoholic medium. The synthesized materials were characterized by elemental analysis, FTIR, UV-visible, (1)H NMR and (13)C NMR spectroscopies. Their DNA sensing potential were investigated by UV-visible spectroscopy. The insight of interaction with DNA was further investigated by electrochemical (cyclic voltammetry) and hydrodynamic (viscosity) studies. The results showed that compounds have moderate DNA binding properties, with the binding constants range being 7.2 × 10(3), 2.4 × 10(3) and 0.2 × 10(3) M(-1), for UA1, UA6 and UA7, respectively. Upon binding with DNA, there was a change in colour (a blue shift in the λmax value) which was observable with a naked eye. These results indicated the potential of synthesized compounds as DNA sensors with detection limit 1.8, 5.8 and 4.0 ng µl(-1) for UA1, UA6 and UA7, respectively.

  5. The Hydractinia echinata Test-System. III: Structure-Toxicity Relationship Study of Some Azo-, Azo-Anilide, and Diazonium Salt Derivatives

    Directory of Open Access Journals (Sweden)

    Sergiu Adrian Chicu


    Full Text Available Structure-toxicity relationships for a series of 75 azo and azo-anilide dyes and five diazonium salts were developed using Hydractinia echinata (H. echinata as model species. In addition, based on these relationships, predictions for 58 other azo-dyes were made. The experimental results showed that the measured effectiveness Mlog(1/MRC50 does not depend on the number of azo groups or the ones corresponding to metobolites, but it is influenced by the number of anilide groups, as well as by the substituents’ positions within molecules. The conformational analysis pointed out the intramolecular hydrogen bonds, especially the simple tautomerization of quinoidic (STOH or aminoidic (STNH2 type. The effectiveness is strongly influenced by the “push-pull” electronic effect, specific to two hydroxy or amino groups separated by an azo moiety (double alternate tautomery, (DAT, to the –COOH or –SO3H groups which are located in ortho or para position with respect to the azo group. The levels of the lipophylic/hydrophilic, electronic and steric equilibriums, pointed out by the Mlog(1/MRC50 values, enabled the calculation of their average values Clog(1/MRC50 (“Köln model”, characteristic to one derivative class (class isotoxicity. The azo group reduction and the hydrolysis of the amido/peptidic group are two concurrent enzymatic reactions, which occur with different reaction rates and mechanisms. The products of the partial biodegradation are aromatic amines. No additive or synergic effects are noticed among them.

  6. Organic heterostructures deposited by MAPLE on AZO substrate (United States)

    Socol, M.; Preda, N.; Stanculescu, A.; Breazu, C.; Florica, C.; Stanculescu, F.; Iftimie, S.; Girtan, M.; Popescu-Pelin, G.; Socol, G.


    Organic heterostructures based on poly(3-hexylthiophene) (P3HT) and fullerene (C60) as blends or multilayer were deposited on Al:ZnO (AZO) by Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. The AZO layers were obtained by Pulsed Laser Deposition (PLD) on glass substrate, the high quality of the films being reflected by the calculated figure of merit. The organic heterostructures were investigated from morphological, optical and electrical point of view by atomic force microscopy (AFM), UV-vis spectroscopy, photoluminescence (PL) and current-voltage (I-V) measurements, respectively. The increase of the C60 content in the blend heterostructure has as result a high roughness. Compared with the multilayer heterostructure, those based on blends present an improvement in the electrical properties. Under illumination, the highest current value was recorded for the heterostructure based on the blend with the higher C60 amount. The obtained results showed that MAPLE is a useful technique for the deposition of the organic heterostructures on AZO as transparent conductor electrode.

  7. Statistical and fractal features of nanocrystalline AZO thin films (United States)

    Hosseinabadi, S.; Abrinaei, F.; Shirazi, M.


    In this paper, We investigate the morphology effect of Aluminum-doped zinc oxide (AZO) thin films on the physical properties such as conductivity and grain size. The AZO thin films are prepared by spray pyrolysis at different thicknesses in the range 100-400 nm. Height fluctuations obtained from atomic force microscopy (AFM) analysis are applied to the statistical and fractal analysis of thin films. We show that the conductivity of thin films is proportional to the roughness parameter as σ ∼Wm which m = 6 . 42 ± 0 . 50. Calculating the nonlinear measures (skewness and kurtosis) of height fluctuations demonstrates the isotropic nature of AZO rough surfaces. Fractal analysis of the mentioned thin films using two dimensional multifractal detrended fluctuation analysis illustrates the multifractality scaling and the strength of multifractality increases with thickness. Our results show that the reason for the multi-affinity is the existence of different correlations in the height fluctuations of the thin films. Calculating the contour loops features of the height fluctuations reveals that the radius, length, and area of loops increase with thickness enhancement and the radius of contour loops is introduced as a new statistical parameter which is linearly related to the grain size and could be useful to calculate it.

  8. Evaluation of the Effect of Azo Group on the Biological Activity of 1-(4-Methylphenylazo-2-naphthol

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    V. Mkpenie


    Full Text Available Azo-2-naphthol and 2-naphthol were tested against five microorganisms: Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa and Streptococcus faecalis. 2-Naphthol was slightly active while azo-2-naphthol was highly active against all the bacteria species tested. The presence of azo group contributed more than 60% of the antibacterial activities exhibited by azo-2-naphthol on all the bacteria tested.

  9. Effect of Ag nanostructures and annealing process on the localized surface plasmon resonance properties of Ag-based AZO films (United States)

    Jin, Jing; Hui, Chaoxian; Liu, Can; Shi, Weimin


    Ag nanoparticles were obtained in Ag/AZO and AZO/Ag/AZO films by magnetron sputtering method at room temperature with different deposition time. The morphology of Ag nanoparticles is strongly affected by the particle size, shape and distribution as well as annealing temperatures, which determine the optical response of films. The high quality of AZO film with better crystallinity can enhance the optical transmittance and a good coverage by AZO as top layer on Ag nanoparticles can also enhance the surface plasmon resonance (SPR) absorption of Ag in long wavelengths. The mechanisms involved in shifts and broadening of SPR peaks have been explained detailedly. The effect of annealing process on SPR of Ag and photoelectric properties of AZO/Ag/AZO films can be also discussed. It is shown that the SPR peak of 664 nm only appears in AZO/Ag (5 s)/AZO film and no SPR peaks are found in annealed AZO/Ag/AZO films. The AZO/Ag (20 s)/AZO film annealed at 300 °C shows a great figure of merit (F_{{TC}}) of 4.8 × 10-2 Ω-1 because of high visible optical average transmittance of 85% and low sheet resistance (R_{{S}}) of 4.1 Ω/sq. The overall results reveal that annealing process can improve the electrical property of film and may not be able to promote the SPR of Ag nanoparticles, especially when AZO top layer is added. The introduction of Ag nanoparticles in AZO/Ag/AZO films should be very effective for improving the SPR or photoelectric properties of films depending on deposition conditions and annealing process.

  10. Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities (United States)

    McLeod, David Charles

    compositions, architectures, and thermal stabilities of the resulting ?-hydroxy ether-functionalized homopolymers were evaluated using NMR and FTIR spectroscopy, size exclusion chromatography, and thermal gravimetric analysis. Aziridines and thiiranes (saturated, three-membered heterocycles containing either a single nitrogen or sulfur atom, respectively) are also susceptible to nucleophilic ring-opening reactions, and functional materials derived from aziridine- or thiirane-containing polymers could potentially have many interesting properties as a result of their high amine or thiol content, such as the ability to form pH- or redox-responsive structures. The synthesis of polymers containing aziridines that are activated towards nucleophilic ring-opening by C-aryl and/or N-sulfonyl substituents is unprecedented in the literature. Efficient methods for synthesizing styrenic monomers that contain these highly-reactive functionalities, namely 2-(4-vinylphenyl)aziridine (VPA) and its sulfonyl-activated derivative, N-mesyl-2-(4-vinylphenyl)aziridine (NMVPA), were developed utilizing 4VPO as a starting material. VPA was polymerized under LCC ATRP and RAFT conditions, but these methods were ineffective at producing well-defined polymers due to side reactions between the aziridine groups and the polymerization mediating compounds. Nitroxide-mediated radical polymerization (NMRP) produced well-defined polyVPA at low to moderate conversions of monomer, but cross-linking side reactions were evident at higher monomer conversions. Nearly all undesirable side reactions were prevented by attaching a mesyl group to the aziridine nitrogen atom, and well-defined polyNMVPA was realized under RAFT and NMRP conditions. Under ATRP conditions, reactions between the aziridine groups and catalyst still occurred, so the polymerization of NMVPA was not controlled using this technique. The synthesis of thiirane-containing styrenic polymers from either 2-(4-vinylphenyl)thiirane (VPT) or 2

  11. Synthesis and antimycobacterial activity of novel heterocycles

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    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.

  12. Heterocyclic methacrylates for clinical applications. I. Mechanical properties. (United States)

    Patel, M P; Braden, M


    The mechanical properties of a number of heterocyclic and one cyclic methacrylate have been studied for their potential in low polymerization shrinkage systems. This study included both homopolymers and room temperature polymerizing systems using poly(ethyl methacrylate) powder with a heterocyclic methacrylate monomer. The one cyclic methacrylate studied, isobornyl methacrylate, gave an extremely brittle polymer; furthermore, it would not form a dough with poly(ethyl methacrylate). The homopolymers gave Young's moduli in the range 1.38-2.19 GN/m2, i.e. lower than poly(methyl methacrylate). The moduli of poly(ethyl methacrylate)/monomer systems are theoretically predictable from the moduli of the homopolymers involved. The above materials were generally ductile and the mechanical properties indicated a useful class of materials for clinical use.

  13. Coordination chemistry of N-heterocyclic nitrenium-based ligands. (United States)

    Tulchinsky, Yuri; Kozuch, Sebastian; Saha, Prasenjit; Mauda, Assaf; Nisnevich, Gennady; Botoshansky, Mark; Shimon, Linda J W; Gandelman, Mark


    Comprehensive studies on the coordination properties of tridentate nitrenium-based ligands are presented. N-heterocyclic nitrenium ions demonstrate general and versatile binding abilities to various transition metals, as exemplified by the synthesis and characterization of Rh(I) , Rh(III) , Mo(0) , Ru(0) , Ru(II) , Pd(II) , Pt(II) , Pt(IV) , and Ag(I) complexes based on these unusual ligands. Formation of nitrenium-metal bonds is unambiguously confirmed both in solution by selective (15) N-labeling experiments and in the solid state by X-ray crystallography. The generality of N-heterocyclic nitrenium as a ligand is also validated by a systematic DFT study of its affinity towards all second-row transition and post-transition metals (Y-Cd) in terms of the corresponding bond-dissociation energies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Tetrazolium Compounds: Synthesis and Applications in Medicine

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    Cheng-Xi Wei


    Full Text Available Tetrazoles represent a class of five-membered heterocyclic compounds with polynitrogen electron-rich planar structural features. This special structure makes tetrazole derivatives useful drugs, explosives, and other functional materials with a wide range of applications in many fields of medicine, agriculture, material science, etc. Based on our research works on azoles and other references in recent years, this review covers reported work on the synthesis and biological activities of tetrazole derivatives.

  15. Fabrication of AZO TCO Films by RF-sputtering and Their Physical Properties

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    Jang T.S.


    Full Text Available We report on the fabrication of Al-doped ZnO (AZO transparent-conductive oxide (TCO films on glass substrates by RF-sputtering, their physical properties, and the effect of thermal annealing on the AZO TCO films. The AZO films on glass substrates have a preferred orientation of the c-axis, irrespective of deposition conditions, which means that the AZO films have textured structures along the c-axis. The film thickness and surface roughness in the AZO films are proportional to plasma power and deposition time, while they are inverse-proportional to working gas ratio and working pressure. The AZO films have the optical transmittance over 80 % in the wavelength range of 400 – 1000 nm, irrespective of deposition conditions. The plasma power and the deposition time relatively give a large influence on the optical transmittance, compared to the working gas ratio and the working pressure. The AZO films deposited at room temperature have poor electrical properties, while the thermal annealing under Ar ambient significantly improves the electrical conductivity of the AZO films: an as-deposited sample has an electrical resistivity of 87 Wcm and an electron concentration of 1.3´1017 cm−3, while the annealed sample has an electrical resistivity of 3.7´10-2 Wcm and an electron concentration of 1.2´1020 cm−3.


    The objective of this study was to determine the partitioning of water soluble azo dyes in the activated sludge process (ASP). Azo dyes are of concern because some of the dyes, dye precursors , and/or their degradation products such as aromatic amines (which are also dye precurso...


    The reduction of azo dyes by zero-valent iron metal (Fe0) at pH 7.0 in 10 mM HEPES buffer was studied in aqueous, anaerobic batch systems. Orange II was reduced by cleavage of the azo linkage, as evidenced by the production of sulfanilic acid (a substituted ani...


    The mutagenicity of metallized and unmetallized azo and formazan dyes in the Salmonella mutagenicityLaura. C. Edwards', Harold S. Freeman'*, and Larry D. Claxton2AbstractIn previous papers, the synthesis and chemical properties of iron complexed azo and formazan d...

  19. The contribution of biotic and abiotic processes during azo dye reduction in anaerobic sludge

    NARCIS (Netherlands)

    Zee, van der F.P.; Bisschops, I.A.E.; Blanchard, V.G.; Bouwman, R.H.M.; Lettinga, G.; Field, J.A.


    Azo dye reduction results from a combination of biotic and abiotic processes during the anaerobic treatment of dye containing effluents. Biotic processes are due to enzymatic reactions whereas the chemical reaction is due to sulfide. In this research, the relative impact of the different azo dye

  20. Evaluation of biodecolorization of the textile azo dye by halophilic archaea

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    Masoomeh Selseleh Hassan-Kiadehi


    Discussion and conclusion: In conclusion, our results indicate that halophilic archaea have very high potential to decolorize azo dyes. Regarding high amounts of salts in textile wastewaters, using such microorganisms which can tolerate the harsh environment in order to decolorize azo dyes, could be a new approach in this field.

  1. Selective Functionalization of Pyridines via Heterocyclic Phosphonium Salts. (United States)

    Hilton, Michael C; Dolewski, Ryan D; McNally, Andrew


    Methods that directly functionalize pyridines are in high demand due to their presence in pharmaceuticals, agrochemicals and materials. A reaction that selectively transforms the 4-position C-H bonds in pyridines into C-PPh3+ groups that are subsequently converted into heteroaryl ethers is presented. The two step sequence is effective on complex pyridines, pharmaceutical molecules and other classes of heterocycles. Initial studies show that C-C, C-N and C-S bond formations are also amenable.

  2. Solid Phase versus Solution Phase Synthesis of Heterocyclic Macrocycles


    McAlpine, Shelli R.; Seong Jong Kim


    Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A) confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved...

  3. Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures (United States)

    Smith, Karen E.; Callahan, Michael P.; Cleaves, Henderson J.; Dworkin, Jason P.; House, Christopher H.


    A long standing question in the field of prebiotic chemistry is the origin of the genetic macromolecules DNA and RNA. DNA and RNA have very complex structures with repeating subunits of nucleotides, which are composed of nucleobases (nitrogen heterocycles) connected to sugar-phosphate. Due to the instability of some nucleobases (e.g. cytosine), difficulty of synthesis and instability of D-ribose, and the likely scarcity of polyphosphates necessary for the modern nucleotides, alternative nucleotides have been proposed for constructing the first genetic material. Thus, we have begun to investigate the chemistry of nitrogen heterocycles in plausible, complex prebiotic mixtures in an effort to identify robust reactions and potential alternative nucleotides. We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2, and reacted it with four nitrogen heterocycles: uracil, 5-hydroxymethyluracil, guanine, and isoxanthopterin (2-amino-4,7-dihydroxypteridine). The products of the reaction between the spark mixture and each nitrogen heterocycle were characterized by liquid chromatography coupled to UV spectroscopy and Orbitrap mass spectrometry. We found that the reaction between the spark mixtUl'e and isoxanthopterin formed one major product, which was a cyanide adduct. 5-hydroxymethyluracil also reacted with the spark mixture to form a cyanide adduct, uracil-5-acetonitrile, which has been synthesized previously by reacting HCN with S-hydroxymethyluracil. Unlike isoxanthopterin, the chromatogram of the 5-hydroxymethyluracil reaction was much more complex with multiple products including spark-modified dimers. Additionally, we observed that HMU readily self-polymerizes in solution to a variety of oligomers consistent with those suggested by Cleaves. Guanine and uracil, the biological nucleobases, did not react with the spark mixture, even at high temperature (100 C). This suggests that there are alternative

  4. Redox-Active N-Heterocyclic Germylenes and Stannylenes with a Ferrocene-1,1'-diyl Backbone. (United States)

    Oetzel, Jan; Weyer, Nadine; Bruhn, Clemens; Leibold, Michael; Gerke, Birgit; Pöttgen, Rainer; Maier, Markus; Winter, Rainer F; Holthausen, Max C; Siemeling, Ulrich


    We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η5 -C5 H4 )NR}2 E:] (1 RE; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox-functionalised N-heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X-ray diffraction studies, except for the neopentyl-substituted stannylene 1 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH2 tBu)(N=CHtBu)] (2) and the spiro tin(IV) compound (1 Np)2 Sn (3). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one-electron oxidation process affords ions of the type 1 RE+. . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE+. . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis, Molecular Structure and Spectroscopic Investigations of Novel Fluorinated Spiro Heterocycles

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    Mohammad Shahidul Islam


    Full Text Available This paper describes an efficient and regioselective method for the synthesis of novel fluorinated spiro-heterocycles in excellent yield by cascade [5+1] double Michael addition reactions. The compounds 7,11-bis(4-fluorophenyl-2,4-dimethyl- 2,4-diazaspiro[5.5] undecane-1,3,5,9-tetraone (3a and 2,4-dimethyl-7,11-bis (4-(trifluoromethylphenyl-2,4-diazaspiro[5.5]undecane-1,3,5,9-tetraone (3b were characterized by single-crystal X-ray diffraction, FT-IR and NMR techniques. The optimized geometrical parameters, infrared vibrational frequencies and NMR chemical shifts of the studied compounds have also been calculated using the density functional theory (DFT method, using Becke-3-Lee-Yang-Parr functional and the 6-311G(d,p basis set. There is good agreement between the experimentally determined structural parameters, vibrational frequencies and NMR chemical shifts of the studied compounds and those predicted theoretically. The calculated natural atomic charges using NBO method showed higher polarity of 3a compared to 3b.The calculated electronic spectra are also discussed based on the TD-DFT calculations.

  6. Synthesis and antimicrobial study of linked heterocyclics containing Pyrazole-pyrimidine-thiazolidin-4-one. (United States)

    Sanjeeva Reddy, Cherkupally; Vani Devi, Macherla; Sunitha, Malladi; Nagaraj, Adki


    A new series of linked heterocyclics, 3-[4-(4-chlorophenyl)-6-(3,5-dimethyl-1-phenyl-1H-4-pyrazolyl)-2-pyrimidinyl]-2-(aryl/heteryl)-1,3-thiazolan-4-ones (6a-j), has been synthesized by the one-pot cyclo-condensation of 4-(4-chlorophenyl)-6-(3,5-dimethyl-1-phenyl-1H-4-pyrazolyl)-2-pyrimidinamine (5), aryl/heteroaryl aldehyde and thioglycolic acid. The structures of the synthesized compounds have been confirmed via IR, (1)H-NMR, (13)C-NMR, MS and elemental analyses. Further, all the newly synthesized compounds 6a-j have been assayed for their antimicrobial activity against Gram-positive and Gram-negative bacteria and fungi. The compounds containing moieties like 4-nitrophenyl (6c), 3-nitrophenyl (6d), 4-dimethylaminophenyl (6g), 2-furyl (6i) and 1,3-benzodioxole (6j), at 2-position of thiazolidin-4-one ring exhibited good inhibitory activity against all the tested organisms.

  7. Heterocyclic energetic materials: Synthesis, characterization and computational design (United States)

    Tsyshevsky, Roman; Pagoria, Philip; Smirnov, Aleksander; Kuklja, Maija


    Achievement of the tailored properties (high performance, low sensitivity, etc.) in targeted new energetic materials (EM) remains a great challenge. Recently, attention of researchers has shifted from conventional nitroester-, nitramine-, and nitroaromatic-based explosives to new heterocyclic EM with oxygen- and nitrogenrich molecular structures. They have increased densities and formation enthalpies complemented by attractive performance and high stability to external stimuli. We will demonstrate that oxadiazol-containing heterocycles offer a convenient playground to probe specific chemical functional groups as building blocks for design of EM. We discuss a joint experimental and computational approach for design, characterization, synthesis, and modeling of novel heterocyclic EM. Combinatorically, we comprehensively analyzed how overall stability and performance of each material in the family (BNFF, LLM-172, LLM-175, LLM-191, LLM-192, LLM-200) depends upon their chemical composition and details of the molecular structure (such as a substitution of a nitro group by an amino group and 1,2,5-oxadiazole fragment by 1,2,3- or 1,2,4-oxadiazol ring). We will also discuss proposed new EM with predicted superior chemical and physical properties. P. Pagoria, R. Tsyshevsky, A. Smirnov.

  8. Synthesis and anticancer activity of silver(I)-N-heterocyclic carbene complexes derived from the natural xanthine products caffeine, theophylline and theobromine. (United States)

    Mohamed, Heba A; Lake, Benjamin R M; Laing, Thomas; Phillips, Roger M; Willans, Charlotte E


    A new library of silver(I)-N-heterocyclic carbene complexes prepared from the natural products caffeine, theophylline and theobromine is reported. The complexes have been fully characterised using a combination of NMR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction analysis. Furthermore, the hydrophobicity of the complexes has been measured. The silver(I)-N-heterocyclic carbenes have been evaluated for their antiproliferative properties against a range of cancer cell lines of different histological types, and compared to cisplatin. The data shows different profiles of response when compared to cisplatin in the same panel of cells, indicating a different mechanism of action. Furthermore, it appears that the steric effect of the ligand and the hydrophobicity of the complex both play a role in the chemosensitivity of these compounds, with greater steric bulk and greater hydrophilicity delivering higher cytotoxicity.

  9. The [3 + 3]-cycloaddition alternative for heterocycle syntheses: catalytically generated metalloenolcarbenes as dipolar adducts. (United States)

    Xu, Xinfang; Doyle, Michael P


    The combination of two or more unsaturated structural units to form cyclic organic compounds is commonly referred to as cycloaddition, and the combination of two unsaturated structural units that forms a six-membered ring is formally either a [5 + 1]-, [4 + 2]-, [2 + 2 + 2]-, or [3 + 3]-cycloaddition. Occurring as concerted or stepwise processes, cycloaddition reactions are among the most useful synthetic constructions in organic chemistry. Of these transformations, the concerted [4 + 2]-cycloaddition, the Diels-Alder reaction, is by far the best known and most widely applied. However, although symmetry disallowed as a concerted process and lacking certifiable examples until recently, stepwise [3 + 3]-cycloadditions offer advantages for the synthesis of a substantial variety of heterocyclic compounds, and they are receiving considerable attention. In this Account, we present the development of stepwise [3 + 3]-cycloaddition reactions from virtual invisibility in the 1990s to a rapidly growing synthetic methodology today, involving organocatalysis or transition metal catalysis. With origins in organometallic or vinyliminium ion chemistry, this area has blossomed into a viable synthetic transformation for the construction of six-membered heterocyclic compounds containing one or more heteroatoms. The development of [3 + 3]-cycloaddition transformations has been achieved through identification of suitable and compatible reactive dipolar adducts and stable dipoles. The reactive dipolar species is an energetic dipolar intermediate that is optimally formed catalytically in the reaction. The stepwise process occurs with the reactive dipolar adduct reacting as an electrophile or as a nucleophile to form the first covalent bond, and this association provides entropic assistance for the construction of the second covalent bond and the overall formal [3 + 3]-cycloaddition. Organocatalysis is well developed for both inter- and intramolecular synthetic transformations, but the

  10. Mineralization of reactive azo dyes present in simulated textile waste water using down flow microaerophilic fixed film bioreactor. (United States)

    Balapure, Kshama; Bhatt, Nikhil; Madamwar, Datta


    The present research emphasizes on degradation of azo dyes from simulated textile wastewater using down flow microaerophilic fixed film reactor. Degradation of simulated textile wastewater (COD 7200mg/L and dye concentration 300mg/L) was studied in a microaerophilic fixed film reactor using pumice stone as a support material under varying hydraulic retention time (HRT) and organic loading rate (OLR). The intense metabolic activity of the inoculated bacterial consortium in the reactor led to 97.5% COD reduction and 99.5% decolorization of simulated wastewater operated under OLR of 7.2kgCODm(3)/d and 24h of HRT. FTIR, (1)H NMR and GC-MS studies revealed the formation of lower molecular weight aliphatic compounds under 24h of HRT, leading to complete mineralization of simulated wastewater. The detection of oxido-reductive enzyme activities suggested the enzymatic reduction of azo bonds prior to mineralization. Toxicity studies indicated that microbial treatment favors detoxification of simulated wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Time-dependent density functional theory calculations of the solvatochromism of some azo sulfonamide fluorochromes. (United States)

    Krawczyk, Przemysław


    The absorption and emission spectra of three azo sulfonamide compounds in different solvents were investigated theoretically by using response functions combined with density functional theory (DFT), while the solvent effect on the structure and the electronic transitions was determined using the integral equation formalism for the polarizable continuum model (IEF-PCM). The results show that the applied different exchange-correlation functionals can reproduce the experimental values well. DFT calculations of the title compounds showed that the H-bond formed between the solute and solvent molecules is one of the major causes of the reversible solvatochromism observed in measured spectra. This is due to a better stabilization of the neutral form than the zwitterionic form in the polar protic solvents, which is characteristic of the hypsochromic shift. On the other hand, the molecules considered exhibit a monotonic behavior regarding the polarity of the low-lying excited state (Δμg-CT) as a function of the solvent polarity. This dependence occurs in the case of the positive solvatochromism and confirms the thesis regarding the H-bond solute-solvent interactions. Theoretically determined values of the two-photon cross section revealed that the (σOF(2)) shows similar trends with changes in λabs, in contrast to values. In conclusion, the results demonstrate that the investigated molecules can be used successfully as fluorochromes in bioimaging.

  12. Utility of 4-formylantipyrine in heterocyclic synthesis

    Directory of Open Access Journals (Sweden)

    Abdou O. Abdelhamid


    Full Text Available Pyrrolo[3,4-c]pyrazole-4,6(1H,5H-dione, pyrano[2,3-c]pyrazole-5-carbonitrile, pyrano[2,3-d]4-imidazolines, pyrido[2,1-b]benzimidazole, pyrido[2,1-b][1,3]benzoxazole, pyrido[2,1-b][1,3]benzothiazole and pyrido[2,1-b]quinazoline were synthesised from antipyrine derivatives with appropriate reagents such as maleimides, malononitrile, ethyl cyanoacetate, benzimidazole-2-acetonitrile, benzothiazole-2-acetonitrile, benzoxazol-2-acetonitrile, benzoylacetonitrile and other reagents. The newly synthesised compounds were established by elemental analysis, spectral data, and alternative synthetic routes whenever possible.

  13. Reaction of uranocenes with nitro compounds

    Energy Technology Data Exchange (ETDEWEB)

    Grant, C.B.; Streitwieser, A. Jr.


    Uranocenes (di-eta/sup 8/-cyclooctatetraeneuranium) are relatively stable to many neutral oxygen-containing organic compounds but react rapidly with aromatic and aliphatic nitro compounds to liberate the cyclooctatetraene ligand in quantitative yield and form azo compounds, often in good yield but in some cases with formation also of the corresponding amines. p-Nitrotoluene reacts more slowly than nitrobenzene. Additional studies of reaction mechanism show that free nitro radical anions or nitrenes do not appear to be involved, but free nitroso compounds are probable intermediates. Azoxy compounds react more slowly with uranocenes and cannot be intermediates in the reactions of nitro compounds. The reaction has few analogies. 67 references, 3 tables.

  14. Evidence for significantly enhancing reduction of Azo dyes in Escherichia coli by expressed cytoplasmic Azoreductase (AzoA) of Enterococcus faecalis. (United States)

    Feng, J; Heinze, T M; Xu, H; Cerniglia, C E; Chen, H


    Although cytoplasmic azoreductases have been purified and characterized from various bacteria, little evidence demonstrating that these azoreductases are directly involved in azo dye reduction in vivo is known. In order to evaluate the contribution of the enzyme to azo dye reduction in vivo, experiments were conducted to determine the effect of a recombinant cytoplasmic azoreductase (AzoA) from Enterococcus faecalis expressed in Escherichia coli on the rate of metabolism of Methyl Red, Ponceau BS and Orange II. The intact cells that contained IPTG induced AzoA had a higher rate of dye reduction with increases of 2 (Methyl Red), 4 (Ponceau BS) and 2.6 (Orange II)-fold compared to noninduced cells, respectively. Metabolites of Methyl Red isolated from induced cultures were identified as N,N-dimethyl-p-phenylenediamine and 2-aminobenzoic acid through liquid chromatography electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) analyses. In conclusion, our data demonstrate that AzoA from Ent. faecalis is capable of increasing the reduction of azo dyes in intact E. coli cells and that cytoplasmic azoreductase is involved in bacterial dye degradation in vivo.

  15. Anaerobic/aerobic treatment of selected azo dyes in wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Seshadri, S.; Bishop, P.L. (Univ. of Cincinnati, OH (United States). Dept. of Civil and Environmental Engineering); Agha, A.M. (Univ. of Aleppo (Syrian Arab Republic). Faculty of Civil Engineering)


    Azo dyes represent the largest class of dyes in use today. Current environmental concern with these dyes revolves around the potential carcinogenic health risk presented by these dyes or their intermediate biodegradation products when exposed to microflora in the human digestive tract. These dyes may build up in the environment, since many wastewater treatment plants allow these dyes to pass through the system virtually untreated. The initial step in the degradation of these dyes is the cleavage of the Azo bond. This cleavage is often impossible under aerobic conditions, but has been readily demonstrated under anaerobic conditions. The focus of the study was to determine the feasibility of using an anaerobic fluidized-bed reactor to accomplish this cleavage. The effects of typical process variables such as hydraulic retention time (HRT), influent dye concentration levels, and degree of bed fluidization on removal efficiencies were also studied. The four dyes selected for this study were Acid-Orange 7, Acid-Orange 8, Acid-Orange 10, and Acid-Red 14. The effectiveness of using a bench-scale-activated sludge reactor as a sequenced second stage was also examined. Results indicate that nearly complete cleavage of the Azo bond is easily accomplished for each of the four dyes under hydraulic retention times of either 12 or 24 h. Initial results indicate, though, that aromatic amine by-products remain. The sequenced second stage was able to remove the remaining Chemical Oxygen Demand (COD) load to acceptable levels. Work is presently underway to determine the face of the anaerobic by-products in the aerobic second stage.

  16. Mode of action of nifurtimox and N-oxide-containing heterocycles against Trypanosoma cruzi: is oxidative stress involved? (United States)

    Boiani, Mariana; Piacenza, Lucia; Hernández, Paola; Boiani, Lucia; Cerecetto, Hugo; González, Mercedes; Denicola, Ana


    Chagas disease is caused by the trypanosomatid parasite Trypanosoma cruzi and threatens millions of lives in South America. As other neglected diseases there is almost no research and development effort by the pharmaceutical industry and the treatment relies on two drugs, Nifurtimox and Benznidazole, discovered empirically more than three decades ago. Nifurtimox, a nitrofurane derivative, is believed to exert its biological activity through the bioreduction of the nitro-group to a nitro-anion radical which undergoes redox-cycling with molecular oxygen. This hypothesis is generally accepted, although arguments against it have been presented. In the present work we studied the ability of Nifurtimox and five N-oxide-containing heterocycles to induce oxidative stress in T. cruzi. N-Oxide-containing heterocycles represent a promising group of new trypanosomicidal agents and their mode of action is not completely elucidated. The results here obtained argue against the oxidative stress hypothesis almost for all the studied compounds, including Nifurtimox. A significant reduction in the level of parasitic low-molecular-weight thiols was observed after Nifurtimox treatment; however, it was not linked to the production of reactive oxidant species. Besides, redox-cycling is only observed at high Nifurtimox concentrations (>400microM), two orders of magnitude higher than the concentration required for anti-proliferative activity (5microM). Our results indicate that an increase in oxidative stress is not the main mechanism of action of Nifurtimox. Among the studied N-oxide-containing heterocycles, benzofuroxan derivatives strongly inhibited parasite dehydrogenase activity and affected mitochondrial membrane potential. The indazole derivative raised intracellular oxidants production, but it was the least effective as anti-T. cruzi. Copyright 2010 Elsevier Inc. All rights reserved.

  17. Toxicity of the azo dyes Acid Red 97 and Bismarck Brown Y to Western clawed frog (Silurana tropicalis). (United States)

    Soriano, Jeriel J; Mathieu-Denoncourt, Justine; Norman, Grant; de Solla, Shane R; Langlois, Valérie S


    Azo compounds are used in a variety of industrial applications, such as textile colorant. Azo dyes have been found to contaminate aquatic environments and it has been shown that these compounds could potentially be toxic or induce endocrine disruption in aquatic organisms. However, there are few data available on the toxicity of these dyes, specifically Acid Red 97 (AR97) and Bismarck Brown Y (BBY). The aim of this study was to determine the toxicity and the endocrine-disrupting properties of AR97 and BBY in frogs. As fugacity modeling predicted that both compounds would sorb to sediment, sediment exposures were performed using a geometric range of concentrations (0, 1, 10, 100 and 1,000 ppm). Both AR97 and BBY dyes were not lethal to Silurana tropicalis embryos; however, BBY significantly induced malformations. Gene expression analysis of oxidative stress and mutagen-related genes was performed in BBY-treated larvae. There were significant two-fold increases of the tumor-suppressing protein p53 and heat shock protein 70 mRNA at 1,000 ppm suggesting that BBY induces cellular stress in early S. tropicalis development. Transcripts of the heat shock protein 90 did not change. Furthermore, reproductive-related genes were assessed and a 2.1-fold change was observed in the mRNA of the steroidogenic acute regulatory protein while steroid 5 alpha-reductase type 2 and androgen receptor transcript levels did not vary among treatments. In conclusion, high concentrations of BBY lead to increased developmental defects in frog embryogenesis and early larval development.

  18. Static and dynamic first hyperpolarizabilities of azo-enaminone isomers (United States)

    Fonseca, T. L.; Castro, M. A.; de Oliveira, H. C. B.; Cunha, S.


    The linear polarizabilities and first hyperpolarizabilities of two geometrical isomers ( Z, E) of donor-acceptor azo-enaminones have been calculated, taking into account frequency dispersion effects, through CPHF method. Static results were also obtained at the MP2 level and correlated dynamic values were estimated using the multiplicative correction scheme. Our results show that the diagonal component of the first hypepolarizability of E isomers is enhanced with increasing donor strength. Dispersion effects have a marked influence for the standard frequencies considered here ( ω = 0.0239 and 0.0428 a.u), specially for second harmonic generation.

  19. A novel one-pot synthesis of heterocyclic compound (4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one): structural (X-ray and DFT) and spectroscopic (FT-IR, NMR, UV-Vis and Mass) characterization studies. (United States)

    Özdemir, Mecit; Sönmez, Mehmet; Şen, Fatih; Dinçer, Muharrem; Özdemir, Namık


    In this study, the title compound named as 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one (C24H18N4O2) was both experimentally and theoretically investigated. The compound was synthesized and characterized by FT-IR, NMR ((1)H NMR, (13)C NMR and HETCOR-NMR), Mass spectroscopies and single-crystal X-ray diffraction methods. The compound crystallizes in the monoclinic space group P2(1)/n with a=6.1402 (3) Å, b=21.4470 (15) Å, c=15.0049 (8) Å and β=97.407 (4)°. The molecular geometry was obtained from the X-ray structure determination optimized using density functional theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. From the optimized structure, geometric parameters, vibrational wavenumbers and chemical shifts of molecule were obtained. Experimental measurements were compared with its corresponding the calculated data. An excellent harmony between the two data was ascertained. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title molecule were investigated by theoretical calculations at the B3LYP/6-31+G(d, p) level. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Association between photodynamic and carcinogenic activities in polycyclic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, S.S.; Small, M.; Falk, H.L.; Mantel, N.


    The photodynamic activities of 157 polycyclic compounds of wide structural range were determined, with the use of Paramecium caudatum. High photodynamic activity was largely confined to polycyclic compounds, either homocyclic or heterocyclic, with four or five fused rings. Significant absorption of light was shown to be prerequisite but not sufficient for high photodynamic activity. A significant statistical association between photodynamic activity and carcinogenicity was demonstrated. It was shown that compounds with high photodynamic activity had 4 times greater odds of being carcinogenic than compounds with low activity. However, the photodynamic assay cannot identify a particular polycyclic compound as being carcinogenic or noncarcinogenic.

  1. Differential catalytic action of Brevibacillus laterosporus on two dissimilar azo dyes Remazol red and Rubine GFL. (United States)

    Kurade, Mayur B; Waghmode, Tatoba R; Tamboli, Dhawal P; Govindwar, Sanjay P


    This comparative study disclosed the diverse catalytic activities of Brevibacillus laterosporus on two different azo dyes. It decolorized 100% of Remazol red and 95% of Rubine GFL within 30 and 48 h respectively, under static condition at 50 mg l⁻¹ dye concentration. Significant increase was observed in azo reductase, NADH-DCIP reductase, veratryl alcohol oxidase and tyrosinase in cells obtained after decolorization of Remazol red; whereas these values were much different with complete inhibition of azo reductase during decolorization of Rubine GFL. The plausible pathway of dye degradation obtained from Gas chromatography-Mass spectroscopy (GC-MS) data confirmed the different metabolic fate of these structurally unidentical dyes. FTIR and HPTLC analysis of extracted metabolites confirmed the biodegradation, while phytotoxicity study assured the detoxification of both the dyes studied. The results obtained in this study suggests, i) sulpho and hydroxyl group present at ortho position to azo group stimulated reduction of azo bond by azo reductase in Remazol red, ii) the same reduction was totally hampered due to presence of ethyl-amino propanenitrile group at para position to azo group in Rubine GFL. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Study on the photoreductive decolorization of azo dyes by sulfite aqua (United States)

    Liu, Wei; Hu, Wenna; Liu, Jian


    In this paper, the decolorization of a series of azo dyes by sulfite aqua was studied under UV light irradiation and in the dark, respectively. Soluble azo dyes were easily decolorized with high decolorization efficiency under UV light irradiation, while their decolorization efficiency was much lower in the dark. The ultraviolet light is of the utmost importance for the rapid decolorization of azo dyes. As for the 10 mg/L Methyl Orange and Congo Red exposed to UV light, the decolorization efficiency reaches up to 95.9% in 10 min and 95.8% in 20 min, using 1.0 g/L and 8.0 g/L sodium sulfite, respectively. Whereas, for the same concentration of azo dyes and sodium sulfite, the decolorization efficiency of Methyl Orange and Congo Red is only 13.8% and 25.6%, respectively, even if they are laid in the dark with sodium sulfite for 48 h. The decolorization process of Methyl Orange and Congo Red follows the first order rate kinetics. The location of absorption peak in the visible region is blue-shifted in the course of the reaction. It is proposed that the decolorization of azo dyes is a reduction reaction. The chromophore of azo dye reacts with hydrogen and results in their decolorization. The possible mechanisms of the reductive decolorization of azo dyes were also discussed.

  3. Crystal structure of an aerobic FMN-dependent azoreductase (AzoA) from Enterococcus faecalis. (United States)

    Liu, Zhi-Jie; Chen, Huizhong; Shaw, Neil; Hopper, Sherryll L; Chen, Lirong; Chen, Siwei; Cerniglia, Carl E; Wang, Bi-Cheng


    The initial critical step of reduction of the azo bond during the metabolism of azo dyes is catalyzed by a group of NAD(P)H dependant enzymes called azoreductases. Although several azoreductases have been identified from microorganisms and partially characterized, very little is known about the structural basis for substrate specificity and the nature of catalysis. Enterococcus faecalis azoreductase A (AzoA) is a highly active azoreductase with a broad spectrum of substrate specificity and is capable of degrading a wide variety of azo dyes. Here, we report the crystal structure of the AzoA from E. faecalis determined at 2.07 A resolution with bound FMN ligand. Phases were obtained by single wavelength anomalous scattering of selenomethionine labeled protein crystals. The asymmetric unit consisted of two dimers with one FMN molecule bound to each monomer. The AzoA monomer takes a typical NAD(P)-binding Rossmann fold with a highly conserved FMN binding pocket. A salt bridge between Arg18 and Asp184 restricts the size of the flavin binding pocket such that only FMN can bind. A putative NADH binding site could be identified and a plausible mechanism for substrate reduction is proposed. Expression studies revealed azoA gene to be expressed constitutively in E. faecalis.

  4. Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

    Directory of Open Access Journals (Sweden)

    Pedro Almendros


    Full Text Available New gold-catalyzed methods using the β-lactam scaffold have been recently developed for the synthesis of different sized heterocycles. This overview focuses on heterocyclization reactions of allenic and alkynic β-lactams which rely on the activation of the allene and alkyne component. The mechanism as well as the regio- and stereoselectivity of the cyclizations are also discussed.

  5. Palladium complexes of a new type of N-heterocyclic carbene ligand ...

    Indian Academy of Sciences (India)

    23−25% yield. The new tricyclic triazolooxazine derived N-heterocyclic carbene moiety, as stabilized upon binding to palladium in the (1−2)b complexes, was structurally characterized by the X-ray single crystal diffraction studies. Keywords. Palladium; tricyclic triazolooxazine derived N-heterocyclic carbene (NHC); PEPPSI.

  6. Microwave-assisted synthesis of bio-active heterocycles in aqueous media

    KAUST Repository

    Polshettiwar, Vivek


    Synthesis of bio-active heterocycles and fine chemicals in aqueous media are one of the best solutions for the development of green and sustainable protocols. To illustrate the advantages of aqueous MW chemistry in heterocycle synthesis, in this chapter, various synthetic pathways developed in recent years in aqueous reaction media using microwave irradiation are described.

  7. N-heterocyclic carbene catalyzed synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol


    Du, Guang-Fen; Guo, Hao; Wang, Ying; Li, Wen-Juan; Shi, Wei-Jie; Dai, Bin


    An organocatalytic protocol for the synthesis of dimethyl carbonate has been developed. Under the catalysis of 5 mol% N-heterocyclic carbenes, ethylene carbonate undergoes transesterification reaction with methanol under very mild reaction conditions, producing dimethyl carbonate with high efficiency. Furthermore, this N-heterocyclic carbene promoted transesterification can be scaled-up easily without lose of the conversion of dimethyl carbonate.

  8. The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids (United States)

    Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.


    The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

  9. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    KAUST Repository

    Novak, Maria S.


    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

  10. Azo Dye Biodecolorization Enhanced by Echinodontium taxodii Cultured with Lignin (United States)

    Meng, Jing; Yu, Hongbo; Zhang, Xiaoyu


    Lignocellulose facilitates the fungal oxidization of recalcitrant organic pollutants through the extracellular ligninolytic enzymes induced by lignin in wood or other plant tissues. However, available information on this phenomenon is insufficient. Free radical chain reactions during lignin metabolism are important in xenobiotic removal. Thus, the effect of lignin on azo dye decolorization in vivo by Echinodontium taxodii was evaluated. In the presence of lignin, optimum decolorization percentages for Remazol Brilliant Violet 5R, Direct Red 5B, Direct Black 38, and Direct Black 22 were 91.75% (control, 65.96%), 76.89% (control, 43.78%), 43.44% (control, 17.02%), and 44.75% (control, 12.16%), respectively, in the submerged cultures. Laccase was the most important enzyme during biodecolorization. Aside from the stimulating of laccase activity, lignin might be degraded by E. taxodii, and then these degraded low-molecular-weight metabolites could act as redox mediators promoting decolorization of azo dyes. The relationship between laccase and lignin degradation was investigated through decolorization tests in vitro with purified enzyme and dozens of aromatics, which can be derivatives of lignin and can function as laccase mediators or inducers. Dyes were decolorized at triple or even higher rates in certain laccase–aromatic systems at chemical concentrations as low as 10 µM. PMID:25285777

  11. Abatement of Azo Dye from Wastewater Using Bimetal-Chitosan (United States)

    Asgari, Ghorban; Farjadfard, Sima


    We introduce a new adsorbent, bimetallic chitosan particle (BCP) that is successfully synthesized and applied to remove the orange II dye from wastewater. The effects of pH, BCP quantity, and contact time are initially verified on the basis of the percentage of orange II removed from the wastewater. Experimental data reveal that the Cu/Mg bimetal and chitosan have a synergistic effect on the adsorption process of the adsorbate, where the dye adsorption by Cu/Mg bimetal, chitosan alone, and bimetal-chitosan is 10, 49, and 99.5%, respectively. The time required for the complete decolorization of orange II by 1 mg/L of BCP is 10 min. The Langmuir model is the best fit for the experimental data, which attains a maximum adsorption capacity of 384.6 mg/g. The consideration of the kinetic behavior indicates that the adsorption of orange II onto the BCP fits best with the pseudo-second-order and Elovich models. Further, the simulated azo dye wastewater can be effectively treated using a relatively low quantity of the adsorbent, 1 mg/L, within a short reaction time of 20 min. Overall, the use of BCP can be considered a promising method for eliminating the azo dye from wastewater effectively. PMID:24348163

  12. Effect of nitrate on anaerobic azo dye reduction. (United States)

    Cirik, Kevser; Kitiş, Mehmet; Çinar, Özer


    The aim of the study was to investigate the effect of nitrate on anaerobic color removal efficiencies. For this aim, anaerobic-aerobic sequencing batch reactor (SBR) fed with a simulated textile effluent including Remazol Brilliant Violet 5R azo dye was operated with a total cycle time of 12 h, including anaerobic (6 h) and aerobic cycles (6 h). Microorganism grown under anaerobic phase of the reactor was exposed to different amounts of competitive electron acceptor (nitrate) and performance of the system was determined by monitoring color removal efficiency, nitrate removal, nitrite formation and removal, oxidation reduction potential, color removal rate, chemical oxygen demand (COD), specific anaerobic enzyme (azo reductase) and aerobic enzyme (catechol 1,2 dioxygenase), and formation and removal of aromatic amines. Variations of population dynamics of microorganisms exposed to various amount of nitrate were identified by denaturing gradient gel electrophoresis (DGGE). It was found that nitrate has adverse effect on anaerobic color removal efficiency and color removal was achieved after denitrification process was completed. It was found that nitrate stimulates the COD removal efficiency and accelerates the COD removal in the first hour of anaerobic phase. About 90 % total COD removal efficiencies were achieved in which microorganism exposed to increasing amount of nitrate. Population dynamics of microorganisms exposed to various amount of nitrate were changed and diversity was increased.

  13. Abatement of Azo Dye from Wastewater Using Bimetal-Chitosan

    Directory of Open Access Journals (Sweden)

    Ghorban Asgari


    Full Text Available We introduce a new adsorbent, bimetallic chitosan particle (BCP that is successfully synthesized and applied to remove the orange II dye from wastewater. The effects of pH, BCP quantity, and contact time are initially verified on the basis of the percentage of orange II removed from the wastewater. Experimental data reveal that the Cu/Mg bimetal and chitosan have a synergistic effect on the adsorption process of the adsorbate, where the dye adsorption by Cu/Mg bimetal, chitosan alone, and bimetal-chitosan is 10, 49, and 99.5%, respectively. The time required for the complete decolorization of orange II by 1 mg/L of BCP is 10 min. The Langmuir model is the best fit for the experimental data, which attains a maximum adsorption capacity of 384.6 mg/g. The consideration of the kinetic behavior indicates that the adsorption of orange II onto the BCP fits best with the pseudo-second-order and Elovich models. Further, the simulated azo dye wastewater can be effectively treated using a relatively low quantity of the adsorbent, 1 mg/L, within a short reaction time of 20 min. Overall, the use of BCP can be considered a promising method for eliminating the azo dye from wastewater effectively.

  14. Synthesis, anticancer activity and molecular docking studies on a series of heterocyclic trans-cyanocombretastatin analogues as antitubulin agents. (United States)

    Penthala, Narsimha Reddy; Zong, Hongliang; Ketkar, Amit; Madadi, Nikhil Reddy; Janganati, Venumadav; Eoff, Robert L; Guzman, Monica L; Crooks, Peter A


    A series of heterocyclic combretastatin analogues have been synthesized and evaluated for their anticancer activity against a panel of 60 human cancer cell lines. The most potent compounds were two 3,4,5-trimethoxy phenyl analogues containing either an (Z)-indol-2-yl (8) or (Z)-benzo[b]furan-2-yl (12) moiety; these compounds exhibited GI50 values of 50%. The binding modes of the three most active compounds (8, 12 and 29) to tubulin were also investigated utilizing molecular docking studies. All three molecules were observed to bind in the same hydrophobic pocket at the interface of α- and β-tubulin that is occupied by colchicine, and were stabilized by van der Waals' interactions with surrounding tubulin residues. The results from the tubulin polymerization and molecular docking studies indicate that compounds 8 and 29 are the most potent anti-leukemic compounds in this structural class, and are considered lead compounds for further development as anti-leukemic drugs. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  15. Effect of dye structure and redox mediators on anaerobic azo and anthraquinone dye reduction

    Directory of Open Access Journals (Sweden)

    Mayara Carantino Costa


    Full Text Available We investigated the biological decolourisation of dyes with different molecular structures. The kinetic constant values (k1 achieved with azo dye Reactive Red 120 were 7.6 and 10.1 times higher in the presence of RM (redox mediators AQDS and riboflavin, respectively, than the assays lacking RM. The kinetic constant achieved with the azo dye Congo Red was 42 times higher than that obtained with the anthraquinone dye Reactive Blue 4. The effect of RM on dye reduction was more evident for azo dyes resistant to reductive processes, and ineffective for anthraquinone dyes because of the structural stability of the latter.

  16. Heterocyclic methacrylates for clinical applications. III. Water absorption characteristics. (United States)

    Patel, M P; Braden, M


    The water absorption and desorption behaviour of poly(isobornyl methacrylate) and poly(tetrahydropyran-2-ylmethyl methacrylate) obeyed diffusion laws on repeated absorption/desorption cycles. However, the polymers of 2,3-epoxypropyl, tetrahydrofurfuryl and tetrahydropyranyl methacrylates did not obey diffusion laws, did not equilibrate after 2 yr immersion in water and exhibited very high uptake values (30-90%). For 2,3-epoxypropyl methacrylate, the sample disintegrated. A clearly detailed structure of the heterocyclic ring is critical. The use of these monomers in room temperature polymerizing poly(ethyl methacrylate)/monomer systems generally reflected the behaviour of the related homopolymers.

  17. Solid Phase versus Solution Phase Synthesis of Heterocyclic Macrocycles

    Directory of Open Access Journals (Sweden)

    Shelli R. McAlpine


    Full Text Available Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved relatively straightforward. Given the ease with which the oxazole Ustat A precursor is formed via our solid phase approach, this route is amenable to rapid analog synthesis.

  18. Solid phase versus solution phase synthesis of heterocyclic macrocycles. (United States)

    Kim, Seong Jong; McAlpine, Shelli R


    Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A) confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved relatively straightforward. Given the ease with which the oxazole Ustat A precursor is formed via our solid phase approach, this route is amenable to rapid analog synthesis.

  19. Laterally azo-bridged h-shaped ferroelectric dimesogens for second-order nonlinear optics: ferroelectricity and second harmonic generation. (United States)

    Zhang, Yongqiang; Martinez-Perdiguero, Josu; Baumeister, Ute; Walker, Christopher; Etxebarria, Jesus; Prehm, Marko; Ortega, Josu; Tschierske, Carsten; O'Callaghan, Michael J; Harant, Adam; Handschy, Mark


    Two classes of laterally azo-bridged H-shaped ferroelectric liquid crystals (FLCs), incorporating azobenzene and disperse red 1 (DR-1) chromophores along the FLC polar axes, were synthesized and characterized by polarized light microscopy, differential scanning calorimetry, 2D X-ray diffraction analysis, and electro-optical investigations. They represent the first H-shaped FLC materials exhibiting the ground-state, thermodynamically stable enantiotropic SmC* phase, i.e., ground-state ferroelectricity. Second harmonic generation measurements of one compound incorporating a DR-1 chromophore at the incident wavelength of 1064 nm give a nonlinear coefficient of d(22) = 17 pm/V, the largest nonlinear optics coefficient reported to date for calamitic FLCs. This value enables viable applications of FLCs in nonlinear optics.

  20. Genotoxic and carcinogenic products arising from reductive transformations of the azo dye, Disperse Yellow 7. (United States)

    Balakrishnan, Vimal K; Shirin, Salma; Aman, Ahmed M; de Solla, Shane R; Mathieu-Denoncourt, Justine; Langlois, Valerie S


    Selected aromatic azo and benzidine based dyes are priority compounds under the Government of Canada's Chemical Management Plan (CMP) for environmental risk assessments. Organic compounds undergo chemical and biological transformations when they interact with environmental matrices and biotic species; identifying the transformation products is thus a critical component of the risk assessment process. Here, we used zero valent iron (ZVI) to initiate the reduction of the diazo compound dye Disperse Yellow 7 (DY 7). Using state-of-the-art accurate mass Liquid Chromatography-Quadrupole Time of Flight-Mass Spectroscopy (LC-QToF-MS), four transformation products were conclusively identified, while a fifth product was tentatively ascertained. The conclusively established transformation products included p-phenylenediamine (p-PDA, a known genotoxin), 4-aminoazobenzene (4-AAB, a category 2 carcinogen) and 4-aminobiphenyl (4-ABP, a category 1 human carcinogen). 4-ABP is thought to form via a benzidine rearrangement; this is the first report of DY 7 undergoing a benzidine rearrangement. Given the importance of reduction processes in the metabolism of organic contaminants by aquatic species, we used LC-MS/MS to analyze sediment samples that had been generated previously upon exposure of Western clawed frogs (Silurana tropicalis) to DY 7 (at exposure levels where cellular stress was observed in S. tropicalis). We found p-PDA, 4-AAB, and 4-ABP were present in all exposures, but not in any of the sediment controls, demonstrating that upon release of DY 7 to the aquatic environment, sediment dwelling organisms will metabolize DY 7 to generate known (and suspected) human carcinogens, including through a previously unreported in vivo benzidine rearrangement to produce 4-ABP. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

  1. Reações de inserção intramolecular de diazo compostos polifuncionais catalisadas por ródio(II: síntese de oxetan-3-ona-2-carboxilato e outros heterociclos funcionalizados Rhodium(II-catalysed intramolecular insertion reaction of multifunctional diazo compounds: synthesis of oxetan-3-one-2-carboxilate and other heterocycles

    Directory of Open Access Journals (Sweden)

    Albert Padwa


    Full Text Available gamma-Hydroxy-alpha-diazo-beta-ketoesters are key intermediates in the chemistry of penicilin-based antibiotics and natural products. The method developed here for the synthesis of ethyl 2-diazo-4-hydroxy-3-oxo-butanoate 17 (in two steps from the diazo mercurial 2 compares very favorably with those reported in the literature for similar compounds. The Rh2(OAc4-mediated intramolecular OH-insertion reaction of the diazo hydroxy ester 17 was investigated, furnishing the oxetan-3-one-2-carboxilate 18 in good yield. When the diazo ester lacks a free hydroxyl group as in the case of the phenoxy diazo ester 11 an intramolecular CH-insertion takes place, affording the 2H-chromene 20 in almost quantitative yield. The behavior of other functionalized diazo esters towards Rh2(OAc4 was also investigated.

  2. Simultaneous chromate reduction and azo dye decolourization by Brevibacterium casei: azo dye as electron donor for chromate reduction. (United States)

    Ng, Tsz Wai; Cai, Qinhong; Wong, Chong-Kim; Chow, Alex T; Wong, Po-Keung


    Chromate [Cr(VI)] and azo dyes are common pollutants which may co-exist in some industrial effluents. Hence studies of biological treatment of industrial wastewater should include investigation of the co-removal of these two pollutants. Brevibacterium casei, which can reduce Cr(VI) in the presence of the azo dye Acid Orange 7 (AO7) under nutrient-limiting condition, was isolated from a sewage sludge sample of a dyeing factory. Response surface methodology, which is commonly used to optimize growth conditions for food microorganisms to maximize product(s) yield, was used to determine the optimal conditions for chromate reduction and dye decolourization by B. casei. The optimal conditions were 0.24 g/L glucose, 3.0 g/L (NH(4))(2)SO(4) and 0.2 g/L peptone at pH 7 and 35 degrees C. The predicted maximum chromate reduction efficiencies and dye decolourization were 83.4+/-0.6 and 40.7+/-1.7%, respectively. A new mechanism was proposed for chromate reduction coupling with AO7 decolourization by B. casei. Under nutrient-limiting condition, AO7 was used as an e(-) donor by the reduction enzyme(s) of B. casei for the reduction of Cr(VI). The resulted Cr(III) then complexed with the oxidized AO7 to form a purple coloured intermediate. 2010 Elsevier B.V. All rights reserved.

  3. Simultaneous chromate reduction and azo dye decolourization by Brevibacterium casei: Azo dye as electron donor for chromate reduction

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Tsz Wai; Cai Qinhong [Department of Biology, Chinese University of Hong Kong, Shatin, N.T. (Hong Kong); Wong, Chong-Kim [Department of Biology, Chinese University of Hong Kong, Shatin, N.T. (Hong Kong); Environmental Science Programme, Chinese University of Hong Kong, Shatin, N.T. (Hong Kong); Chow, Alex T. [Department of Biosystems Engineering, Clemson University, SC 29634 (United States); Department of Forestry and Natural Resources, Clemson University, SC 29634 (United States); Wong, Po-Keung, E-mail: [Department of Biology, Chinese University of Hong Kong, Shatin, N.T. (Hong Kong); Environmental Science Programme, Chinese University of Hong Kong, Shatin, N.T. (Hong Kong)


    Chromate [Cr(VI)] and azo dyes are common pollutants which may co-exist in some industrial effluents. Hence studies of biological treatment of industrial wastewater should include investigation of the co-removal of these two pollutants. Brevibacterium casei, which can reduce Cr(VI) in the presence of the azo dye Acid Orange 7 (AO7) under nutrient-limiting condition, was isolated from a sewage sludge sample of a dyeing factory. Response surface methodology, which is commonly used to optimize growth conditions for food microorganisms to maximize product(s) yield, was used to determine the optimal conditions for chromate reduction and dye decolourization by B. casei. The optimal conditions were 0.24 g/L glucose, 3.0 g/L (NH{sub 4}){sub 2}SO{sub 4} and 0.2 g/L peptone at pH 7 and 35 deg. C. The predicted maximum chromate reduction efficiencies and dye decolourization were 83.4 {+-} 0.6 and 40.7 {+-} 1.7%, respectively. A new mechanism was proposed for chromate reduction coupling with AO7 decolourization by B. casei. Under nutrient-limiting condition, AO7 was used as an e{sup -} donor by the reduction enzyme(s) of B. casei for the reduction of Cr(VI). The resulted Cr(III) then complexed with the oxidized AO7 to form a purple coloured intermediate.

  4. Preparation, spectral, X-ray powder diffraction and computational studies and genotoxic properties of new azo-azomethine metal chelates (United States)

    Bitmez, Şirin; Sayin, Koray; Avar, Bariş; Köse, Muhammet; Kayraldız, Ahmet; Kurtoğlu, Mükerrem


    A new tridentate azo-azomethine ligand, N‧-[{2-hydroxy-5-[(4-nitrophenyl)diazenyl]phenyl}methylidene]benzohydrazidemonohydrate, (sbH·H2O) (1), is prepared by condensation of benzohydrazide and 2-hydroxy-5-[(4-nitrophenyl)diazenyl]benzaldehyde (a) with treatment of a solution of diazonium salt of p-nitroaniline and 2-hydroxybenzaldehyde in EtOH. The five coordination compounds, [Co(sb)2]·4H2O (2), [Ni(sb)2]·H2O (3), [Cu(sb)2]·4H2O (4), [Zn(sb)2]·H2O (5) and [Cd(sb)2]·H2O (6) are prepared by reacting the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with the ligand. The structures of the compounds are elucidated from the elemental analyses data and spectroscopic studies. It is found the ligand acts as a tridentate bending through phenolic and carbonyl oxygens and nitrogen atom of the Cdbnd Nsbnd group similar to the most of salicylaldimines. Comparison of the infrared spectra of the ligand and its metal complexes confirm that azo-Schiff base behaves as a monobasic tridentate ligand towards the central metal ion with an ONO donor sequence. Upon complexation with the ligand, the Cd(II), and Zn(II) ions form monoclinic structures, while Co(II), Cu(II) and Ni(II) ions form orthorhombic structures. Quantum chemical calculations are performed on tautomers and its metal chelates by using DFT/B3LYP method. Most stable tautomer is determined as tautomer (1a). The geometrical parameters of its metal chelates are obtained as theoretically. The NLO properties of tautomer (1a) and its metal complexes are investigated. Finally, the ligand and its metal complexes are assessed for their genotoxicity.

  5. Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation. (United States)

    Augugliaro, Vincenzo; Baiocchi, Claudio; Prevot, Alessandra Bianco; García-López, Elisa; Loddo, Vittorio; Malato, Sixto; Marcí, Giuseppe; Palmisano, Leonardo; Pazzi, Marco; Pramauro, Edmondo


    The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the "Plataforma Solar de Almería" (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H2O2, S2O8(2-)) and some ions (Cl-, SO4(2-)) on the process was also studied.

  6. Photolytic degradation of organic azo dye in aqueous solution using Xe-excimer lamp. (United States)

    Feng, X; Zhu, S; Hou, H


    The photodegradation of organic azo dye C.I. Food Yellow 4 (FY-4) in aqueous solution was achieved, without the addition of oxidants, by 172 nm vacuum ultraviolet (VUV) radiation emitted from the planar Xe-excimer lamp. The degradation was mainly attributed to the impact of HO radicals produced by water absorbing VUV radiation. The dye decolorization followed pseudo-first order kinetics. The initial quantum yields of FY-4 decolorization in O2-saturated solution and N2-saturated solution were respectively 0.151 +/- 0.003 and 0.103 +/- 0.002. Dissolved oxygen in the solution contributed to the increase of the decolorization rate and chemical oxygen demand (COD) removal rate while KCI added as HO radical scavenger decreased the efficiency of the decolorization and COD removal. It was found from the change of the UV-Vis spectra that the degradation of FY-4 was accompanied by both the cleavage of chromophoric group and the opening of aromatic ring. Major intermediates detected were aromatic compounds, some low molecular weight by-products and several organic acids and inorganic ions.

  7. Case study of the sonochemical decolouration of textile azo dye Reactive Black 5

    Energy Technology Data Exchange (ETDEWEB)

    Vajnhandl, Simona [University of Maribor, Faculty of Mechanical Engineering, Smetanova 17, 2000 Maribor (Slovenia)]. E-mail:; Le Marechal, Alenka Majcen [University of Maribor, Faculty of Mechanical Engineering, Smetanova 17, 2000 Maribor (Slovenia)


    The decolouration and mineralization of reactive dye C.I. Reactive Black 5, a well-known representative of non-biodegradable azo dyes, by means of ultrasonic irradiation at 20, 279 and 817 kHz has been investigated with emphasis on the effect of various parameters on decolouration and degradation efficiency. Characterization of the used ultrasound systems was performed using calorimetric measurements and oxidative species monitoring using Fricke and iodine dosimeter. Experiments were carried out with low frequency probe type, and a high-frequency plate type transducer at 50, 100 and 150 W of acoustic power and within the 5-300 mg/L initial dye concentration range. Decolouration, as well as radical production, increased with increasing frequency, acoustic power, and irradiation time. Any increase in initial dye concentration results in decreased decolouration rates. Sonochemical decolouration was substantially depressed by the addition of 2-methyl-2-propanol as a radical scavenger, which suggests radical-induced reactions in the solution. Acute toxicity to marine bacteria Vibrio fischeri was tested before and after ultrasound irradiation. Under the conditions employed in this study, no toxic compounds were detected after 6 h of irradiation. Mineralization of the dye was followed by TOC measurements. Relatively low degradation efficiency (50% after 6 h of treatment) indicates that ultrasound is rather inefficient in overall degradation, when used alone.

  8. Design and synthesis of heterocyclic cations for specific DNA recognition: from AT-rich to mixed-base-pair DNA sequences. (United States)

    Chai, Yun; Paul, Ananya; Rettig, Michael; Wilson, W David; Boykin, David W


    The compounds synthesized in this research were designed with the goal of establishing a new paradigm for mixed-base-pair DNA sequence-specific recognition. The design scheme starts with a cell-permeable heterocyclic cation that binds to AT base pair sites in the DNA minor groove. Modifications were introduced in the original compound to include an H-bond accepting group to specifically recognize the G-NH that projects into the minor groove. Therefore, a series of heterocyclic cations substituted with an azabenzimidazole ring has been designed and synthesized for mixed-base-pair DNA recognition. The most successful compound, 12a, had an azabenzimidazole to recognize G and additional modifications for general minor groove interactions. It binds to the DNA site -AAAGTTT- more strongly than the -AAATTT- site without GC and indicates the design success. Structural modifications of 12a generally weakened binding. The interactions of the new compound with a variety of DNA sequences with and without GC base pairs were evaluated by thermal melting analysis, circular dichroism, fluorescence emission spectroscopy, surface plasmon resonance, and molecular modeling.

  9. Theoretical study on benzoheterocycle based energetic materials, effect of heterocyclic-fused, conjugation, hydrogen bond, and substitutional group on the detonation performance. (United States)

    Shen, Cheng; Wang, Pengcheng; Lu, Ming


    In this paper, four series of benzoheterocycle based energetic materials (EMs) have been designed to plan out a strategy to improve the density and safety of EMs, such as combining the insensitive group with aminobenzene ring and the high energetic nitramine explosives, benzo-heterocycle mother ring, designing multi-nitrogen heterocycles with a conjugated system containing N-N and C-N high energy bonds, and hydrogen bonding. Their optimized structure and detonation properties were first calculated and discussed using DFT methods. After calculation, these designed explosives all showed good detonation from 7352 m/s to 8788 m/s. Among them, the compounds with six nitro groups, 1c, 2c, 3c, and 4c, exhibit better performance and rather poor impact sensitivity. However, we found that the compounds with five nitro groups and one amino group have a limited performance reduction and a rapid stability improvement. These four compounds, 1b, 2b, 3b, and 4b, have good detonation performance and better stability. Moreover, the synthesis routes for these four compounds were also designed. The precursor 4-0 and mononitro product 4-1 were successfully synthesized. Their 1H NMR, single crystal, and elemental analysis were also done to verify the structures.

  10. Conductive Supramolecular Architecture Constructed from Polyoxovanadate Cluster and Heterocyclic Surfactant

    Directory of Open Access Journals (Sweden)

    Toshiyuki Misawa


    Full Text Available Proton-conductive solid electrolytes are significant for fuel-cell battery technology. Especially for use in motor vehicles, proton conductors which work at intermediate temperatures (373–673 K under an anhydrous atmosphere are desired to improve the fuel cell stability and efficiency. Inorganic–organic hybrid supramolecular architectures are a promising option for the realization of highly conductive proton conductors. Here, a hybrid layered crystal was synthesized for the first time by using an proton-containing decavanadate (V10 anion and a heterocyclic surfactant cation. A simple ion-exchange reaction led to the formation of an inorganic–organic hybrid of V10 by using dodecylpyridazinium (C12pda as the heterocyclic surfactant. Single crystal X-ray analyses revealed that four C12pda cations were associated with one V10 anion, which was a diprotonated species forming a one-dimensional infinite chain structure through hydrogen bonds. Anhydrous proton conductivity was investigated by alternating current (AC impedance spectroscopy in the range of 313–393 K, exhibiting a maximum value of 1.7 × 10−5 S cm−1 at 373 K.

  11. 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

  12. Detoxification of azo dyes in the context of environmental processes. (United States)

    Rawat, Deepak; Mishra, Vandana; Sharma, Radhey Shyam


    Azo dyes account for >70% of the global industrial demand (∼9 million tons). Owing to their genotoxic/carcinogenic potential, the annual disposal of ∼4,500,000 tons of dyes and/or degraded products is an environmental and socio-economic concern. In comparison to physico-chemical methods, microbe-mediated dye degradation is considered to be low-input, cost-effective and environmentally-safe. However, under different environmental conditions, interactions of chemically diverse dyes with metabolically diverse microbes produce metabolites of varying toxicity. In addition, majority of studies on microbial dye-degradation focus on decolorization with least attention towards detoxification. Therefore, the environmental significance of microbial dye detoxification research of past >3 decades is critically evaluated with reference to dye structure and the possible influence of microbial interactions in different environments. In the absence of ecosystem-based studies, the results of laboratory-based studies on dye degradation, metabolite production and their genotoxic impact on model organisms are used to predict the possible fate and consequences of azo dyes/metabolites in the environment. In such studies, the predominance of fewer numbers of toxicological assays that too at lower levels of biological organization (molecular/cellular/organismic) suggests its limited ecological significance. Based on critical evaluation of these studies the recommendations on inclusion of multilevel approach (assessment at multiple levels of biological organization), multispecies microcosm approach and native species approach in conjunction with identification of dye metabolites have been made for future studies. Such studies will bridge the gap between the fundamental knowledge on dye-microbe-environment interactions and its application to combat dye-induced environmental toxicity. Thus an environmental perspective on dye toxicity in the background of dye structure and effects of

  13. The Study of Microwave and Electric Hybrid Sintering Process of AZO Target

    Directory of Open Access Journals (Sweden)

    Ling-yun Han


    Full Text Available We simulated the microwave sintering of ZnO by 3D modelling. A large-size Al-doped ZnO (AZO green ceramic compact was prepared by slurry casting. Through studying the microwave and electric hybrid sintering of the green compact, a relative density of up to 98.1% could be obtained by starting microwave heating at 1200°C and increasing the power 20 min later to 4 kW for an AZO ceramic target measuring 120 × 240 × 12 mm. The resistivity of AZO targets sintered with microwave assistance was investigated. The energy consumption of sintering could be greatly reduced by this heating method. Until now, few studies have been reported on the microwave and electric hybrid sintering of large-size AZO ceramic targets. This research can aid in developing sintering technology for large-size high-quality oxide ceramic targets.

  14. Light sensitive polymer obtained by dispersion of azo-functionalized POSS nanoparticles (United States)

    Miniewicz, A.; Tomkowicz, M.; Karpinski, P.; Sznitko, L.; Mossety-Leszczak, B.; Dutkiewicz, M.


    Hybrid inorganic-organic nanoparticles based on cubic siloxane cage (RSiO3/2)8, known as polyhedral oligosilsesquioxane (POSS), have been functionalized by eight groups of azo-benzene mesogens and dispersed in poly(methyl methacrylate) PMMA matrix. Presence of azo-benzene units adds an important light-driven functionality to the system due to their photoisomerization resulting in refractive index and/or absorption changes of the whole system. The polymer films containing various concentrations of azo-POSS nanoparticles show remarkable changes of surface morphology being either transparent (at low POSS concentration) or highly scattering (at high POSS concentration) for visible light. Surface structures were examined by optical microscopy as well as by atomic force microscopy (AFM). Results of photoinduced alignment are discussed in the framework of light-induced modification of the aliphatic chains containing azo-benzene photoisomerizing moieties and self-organization process.

  15. Synthesis of heterocyclic chalcone derivatives and their radical scavenging ability toward 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Kijun; Kim, Hoseok; Kim, Beomtae [Research Center of Bioactive Materials, Hwaseong (Korea, Republic of); Han, Incheol [Chonbuk National Univ., Jeonju (Korea, Republic of)


    A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalcones was distinctly demonstrated in our work.

  16. Acid- and Au(i)-mediated synthesis of hexathymidine-DNA-heterocycle chimeras, an efficient entry to DNA-encoded libraries inspired by drug structures† †Electronic supplementary information (ESI) available: Experimental procedures, compound characterization data, analysis of ligation reactions, and analysis of the tiDEL. See DOI: 10.1039/c7sc00455a Click here for additional data file. (United States)

    Škopić, Mateja Klika; Salamon, Hazem; Bugain, Olivia; Jung, Kathrin; Gohla, Anne; Doetsch, Lara J.; dos Santos, Denise; Bhat, Avinash; Wagner, Bernd


    Libraries of DNA-tagged compounds are a validated screening technology for drug discovery. They are synthesized through combinatorial iterations of alternated coding and preparative synthesis steps. Thus, large chemical space can be accessed for target-based screening. However, the need to preserve the functionality of the DNA tag severely restricts the choice of chemical methods for library synthesis. Acidic organocatalysts, transition metals, and oxidants furnish diverse drug-like structures from simple starting materials, but cause loss of genetic information by depurination. A hexathymidine oligonucleotide, called “hexT” allows the chemist utilizing these classes of catalysts to access a potentially broad variety of structures in the initial step of library synthesis. We exploited its catalyst tolerance to efficiently synthesize diverse substituted β-carbolines, pyrazolines, and pyrazoles from readily available starting materials as hexT conjugates by acid- and Au(i)-catalysis, respectively. The hexT conjugates were ligated to coding DNA sequences yielding encoded screening libraries inspired by drug structures. PMID:28507705

  17. Photoluminescence analysis of self induced planer alignment in azo dye dispersed nematic liquid crystal complex

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Rishi, E-mail:; Sood, Srishti, E-mail:; Raina, K. K., E-mail: [School of Physics and Materials Science, Thapar University, Patiala-147004 (India)


    We have developed azo dye doped nematic liquid crystal complex for advanced photonic liquid crystal display technology aspects. Disperse orange azo dye self introduced planer alignment in the nematic liquid crystal without any surface anchoring treatment. Planer alignment was characterized by optical polarizing microscopy. The electro-optical switching response of dye disperse planer aligned nematic cell was investigated as a function of applied voltage with the help of photoluminescence spectrophotometer for the tuning of photoluminescence contrast.

  18. Azo-sulforhodamine dyes: a novel class of broad spectrum dark quenchers. (United States)

    Chevalier, Arnaud; Renard, Pierre-Yves; Romieu, Anthony


    A rapid access to a novel class of water-soluble dark quencher dyes was achieved using an azo-coupling reaction between a fluorescent primary arylamine derived from a sulforhodamine 101 scaffold and a tertiary aniline equipped with different bioconjugatable groups. The thus obtained nonfluorescent azo-sulforhodamine hybrids display a broad quenching range spanning the visible to NIR regions. This was demonstrated through the preparation and enzymatic activation of FRET-based fluorogenic substrates of urokinase.

  19. Photoresponse and photocapacitor properties of Au/AZO/p-Si/Al diode with AZO film prepared by pulsed laser deposition (PLD) method (United States)

    Alyamani, A.; Tataroğlu, A.; El Mir, L.; Al-Ghamdi, Ahmed A.; Dahman, H.; Farooq, W. A.; Yakuphanoğlu, F.


    The electrical and photoresponse properties of Au/nanostructure AZO/p-Si/Al diode were investigated. Al-doped ZnO (AZO) thin films were deposited via pulsed laser deposition method on silicon substrate. Structural properties of the films were performed by using transmission electron microscopy and X-ray powder diffraction (XRD). The XRD patterns showed that the AZO films are polycrystalline with hexagonal wurtzite structure preferentially oriented in (002) direction. Electrical and photoresponse properties of the diode were analyzed under in a wide range of frequencies and illumination intensities. It is observed that the reverse current of the diode increases with increasing illumination intensity. This result confirms that the diode exhibits both photoconducting and photovoltaic behavior. Also, the transient photocurrent, photocapacitance and photoconductance measured as a function of time highly depend on transient illumination. In addition, the frequency dependence of capacitance and conductance is attributed to the presence of interface states.

  20. Impact of terminal dimethylation on the resistance profile of α-N-heterocyclic thiosemicarbazones. (United States)

    Heffeter, Petra; Pirker, Christine; Kowol, Christian R; Herrman, Gerrit; Dornetshuber, Rita; Miklos, Walter; Jungwirth, Ute; Koellensperger, Gunda; Keppler, Bernhard K; Berger, Walter


    Triapine is an α-N-heterocyclic thiosemicarbazone with promising anticancer activity against hematologic malignancies but widely ineffective against solid tumor types in clinical trials. The anticancer activity of thiosemicarbazones can be dramatically increased by terminal dimethylation. KP1089 is a gallium compound containing two terminal dimethylated thiosemicarbazone ligands. To gain insights on the vulnerability of this highly active terminal dimethylated thiosemicarbazone to drug resistance mechanisms, a new cell model with acquired resistance against the lead compound KP1089 was established. Subsequent genomic analyses (arrayCGH and FISH) revealed amplification of the ABCC1 gene on double minute chromosomal DNA in KP1089-resistant cells as well as overexpression of ABCC1 and ABCG2 on the protein level. KP1089 was further confirmed as a substrate of ABCC1 and ABCG2 but not of ABCB1 using a panel of ABC transporter-overexpressing cell models as well as ABC transporter inhibitors. Moreover, glutathione depletion strongly enhanced KP1089 activity, although no glutathione conjugate formation by glutathione-S-transferase was observed. Thus, a co-transport of KP1089 together with glutathione is suggested. Finally, a panel of thiosemicarbazone derivatives was tested on the new KP1089-resistant cell line. Notably, KP1089-resistant cells were not cross-resistant against thiosemicarbazones lacking terminal dimethylation (e.g. Triapine) which are less active than KP1089. This suggests that terminal dimethylation of thiosemicarbazones - linked with distinctly enhanced anticancer activity - leads to altered resistance profiles compared to classical thiosemicarbazones making this compound class of interest for further (pre)clinical evaluation. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Equilibrium and thermodynamics of azo dyes biosorption onto Spirulina platensis

    Directory of Open Access Journals (Sweden)

    G. L. Dotto


    Full Text Available The equilibrium and thermodynamics of azo dye (tartrazine and allura red biosorption onto Spirulina platensis biomass were investigated. The equilibrium curves were obtained at 298, 308, 318 and 328 K, and four isotherm models were fitted the experimental data. Biosorption thermodynamic parameters (ΔG, ΔH and ΔS were estimated. The results showed that the biosorption was favored by a temperature decrease. For both dyes, the Sips model was the best to represent the equilibrium experimental data (R²>0.99 and ARE<5.0% and the maximum biosorption capacities were 363.2 and 468.7 mg g-1 for tartrazine and allura red, respectively, obtained at 298 K. The negative values of ΔG and ΔH showed that the biosorption of both dyes was spontaneous, favorable and exothermic. The positive values of ΔS suggested that the system disorder increases during the biosorption process.

  2. Enhancement of oxyanion and diatrizoate reduction kinetics using selected azo dyes on Pd-based catalysts. (United States)

    Shuai, Danmeng; Chaplin, Brian P; Shapley, John R; Menendez, Nathaniel P; McCalman, Dorrell C; Schneider, William F; Werth, Charles J


    Azo dyes are widespread pollutants and potential cocontaminants for nitrate; we evaluated their effect on catalytic reduction of a suite of oxyanions, diatrizoate, and N-nitrosodimethylamine (NDMA). The azo dye methyl orange significantly enhanced (less than or equal to a factor of 5.24) the catalytic reduction kinetics of nitrate, nitrite, bromate, perchlorate, chlorate, and diatrizoate with several different Pd-based catalysts; NDMA reduction was not enhanced. Nitrate was selected as a probe contaminant, and a variety of azo dyes (methyl orange, methyl red, fast yellow AB, metanil yellow, acid orange 7, congo red, eriochrome black T, acid red 27, acid yellow 11, and acid yellow 17) were evaluated for their ability to enhance reduction. Hydrogenation energies of azo dyes were calculated using density functional theory and a volcano relationship between hydrogenation energies and reduction rate enhancement was observed. A kinetic model based on Brønsted-Evans-Polanyi (BEP) theory matched the volcano relationship and suggests sorbed azo dyes enhance reduction kinetics through hydrogen atom shuttling between reduced azo dyes (i.e., hydrazo dyes) and oxyanions or diatrizoate. This is the first research that has identified this synergetic effect, and it has implications for designing more efficient catalysts and reducing Pd costs in water treatment systems.

  3. Light sensitive polymer obtained by dispersion of azo-functionalized POSS nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Miniewicz, A., E-mail: [Advanced Materials Engineering and Modelling, Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw (Poland); Tomkowicz, M.; Karpinski, P.; Sznitko, L. [Advanced Materials Engineering and Modelling, Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw (Poland); Mossety-Leszczak, B. [Faculty of Chemistry, Rzeszow University of Technology, Al. Powstancow Warszawy 12, 35-959 Rzeszow (Poland); Dutkiewicz, M. [Faculty of Chemistry, Adam Mickiewicz University of Poznan, Umultowska 89 B, 61-614 Poznan (Poland)


    Highlights: • Nanocomposite material PMMA containing azo-functionalized POSS has been prepared. • Surface topographies of prepared films are porous and dependent on azo-POSS content. • Photo-induced optical anisotropies both static and dynamic have been characterized. - Abstract: Hybrid inorganic–organic nanoparticles based on cubic siloxane cage (RSiO{sub 3/2}){sub 8}, known as polyhedral oligosilsesquioxane (POSS), have been functionalized by eight groups of azo-benzene mesogens and dispersed in poly(methyl methacrylate) PMMA matrix. Presence of azo-benzene units adds an important light-driven functionality to the system due to their photoisomerization resulting in refractive index and/or absorption changes of the whole system. The polymer films containing various concentrations of azo-POSS nanoparticles show remarkable changes of surface morphology being either transparent (at low POSS concentration) or highly scattering (at high POSS concentration) for visible light. Surface structures were examined by optical microscopy as well as by atomic force microscopy (AFM). Results of photoinduced alignment are discussed in the framework of light-induced modification of the aliphatic chains containing azo-benzene photoisomerizing moieties and self-organization process.

  4. Azo biphenyl polyurethane: Preparation, characterization and application for optical waveguide switch (United States)

    Jiang, Yan; Da, Zulin; Qiu, Fengxian; Yang, Dongya; Guan, Yijun; Cao, Guorong


    Azo waveguide polymers are of particular interest in the design of materials for applications in optical switch. The aim of this contribution was the synthesis and thermo-optic waveguide switch properties of azo biphenyl polyurethanes. A series of monomers and azo biphenyl polyurethanes (Azo BPU1 and Azo BPU2) were synthesized and characterized by FT-IR, UV-Vis spectroscopy and 1H NMR. The physical and mechanical properties of thin polymer films were measured. The refractive index and thermo-optic coefficient (dn/dT) of polymer films were investigated for TE (transversal electric) polarizations by ATR technique. The transmission loss of film was measured using the Charge Coupled Device digital imaging devices. The results showed the Azo BPU2 containing chiral azobenzene chromophore had higher dn/dT and lower transmission loss. Subsequently, a 1 × 2 Y-branch and 2 × 2 Mach-Zehnder optical switches based on the prepared polymers were designed and simulated. The results showed that the power consumption of all switches was less than 1.0 mW. Compared with 1 × 2 Y-branch optical switch, the 2 × 2 Mach-Zehnder optical switches based on the same polymer have the faster response time, which were about only 1.2 and 2.0 ms, respectively.

  5. Occurrence of azo food dyes and their effects on cellular inflammatory responses. (United States)

    Leo, Latasha; Loong, Claudine; Ho, Xing Lin; Raman, Muhammed Faiz B; Suan, Melissa Yue Tian; Loke, Wai Mun


    The aim of this study was to examine the occurrence of five azo food dyes-tartrazine, sunset yellow, carmoisine, allura red, and ponceau 4 R-in the food supply chain of Singapore and their effects on the in vitro synthesis of leukotriene B4 (LTB4) and F2-isoprostanes. Trained personnel recorded the names of foods and beverages sold in a local supermarket that contained at least one of the five azo dyes. The occurrence of the azo dyes in the local food supply was computed. The synthesis of LTB4 and F2-isoprostanes from freshly isolated blood neutrophils were measured using gas chromatography-mass spectrometry. Of the 1681 processed food items, 194 (11.54%) contained at least one of the five azo dyes. Tartrazine was most prevalent in food and beverage products sold in Singapore, followed by allura red, sunset yellow, ponceau 4 R, and carmoisine. The five azo dyes augmented the in vitro synthesis of LTB4 and F2-isoprostanes from blood neutrophils. Tartrazine was significantly more potent in increasing LTB4 synthesis than the other dyes, which exhibited similar potencies. The five food dyes increased the formation of F2-isoprostanes from blood neutrophils at all tested concentrations. The high prevalence of azo dyes in the food supply of Singapore and their ability to elicit proinflammatory responses in vitro suggest a potential health risk to the local population. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Design, synthesis and structure-activity relationships of (indo-3-yl) heterocyclic derivatives as agonists of the CB1 receptor. Discovery of a clinical candidate. (United States)

    Ratcliffe, Paul; Adam, Julia M; Baker, James; Bursi, Roberta; Campbell, Robert; Clark, John K; Cottney, Jean E; Deehan, Maureen; Easson, Anna-Marie; Ecker, Daniel; Edwards, Darren; Epemolu, Ola; Evans, Louise; Fields, Ruth; Francis, Stuart; Harradine, Paul; Jeremiah, Fiona; Kiyoi, Takao; McArthur, Duncan; Morrison, Angus; Passier, Paul; Pick, Jack; Schnabel, Peter G; Schulz, Jurgen; Steinbrede, Heinz; Walker, Glenn; Westwood, Paul; Wishart, Grant; Udo de Haes, Joanna


    We report an expansion of the structure-activity relationship (SAR) of a novel series of indole-3-heterocyclic CB1 receptor agonists. Starting from the potent but poorly soluble lead, 1, a rational approach was taken in order to balance solubility, hERG activity and potency while retaining the desired long duration of action within the mouse tail flick test. This led to the discovery of compound 38 which successfully progressed into clinical development. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Carbohydrates as a reagent in multicomponent reactions: one-pot access to a new library of hydrophilic substituted pyrimidine-fused heterocycles. (United States)

    Nourisefat, Maryam; Panahi, Farhad; Khalafi-Nezhad, Ali


    In this study a multicomponent reaction involving carbohydrate derivatives as the main component in order to prepare a new library of polyhydroxy compounds incorporating pyrimidine-fused heterocycles (PFHs) is introduced. A set of polyhydroxy functionalized PFHs were synthesized using multicomponent reactions of sugar (glucose, galactose, arabinose and lactose), barbituric acid and amines. Also, the three-component condensation reaction between D-glucosamine, aldehyde, and barbituric acid efficiently provided polyhydroxy substituted PFH derivatives in a one-pot reaction under mild and green conditions. These new one-pot reactions gave a range of polyhydroxy substituted PFHs in good to excellent yield.

  8. Synthesis of palladium(0) and -(II) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation. (United States)

    Sluijter, Soraya N; Warsink, Stefan; Lutz, Martin; Elsevier, Cornelis 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)(η(2)-ma)] (3a), was confirmed by X-ray crystal structure determination. In contrast to the transfer semihydrogenation, in which only low activity was observed, complex 3a showed activity (TOF = 49 mol(sub) mol(cat)(-1) h(-1)) and selectivity comparable to its monodentate counterparts in the semihydrogenation of 1-phenyl-1-propyne with molecular hydrogen.

  9. Click Chemistry Route to the Synthesis of Unusual Amino Acids, Peptides, Triazole-Fused Heterocycles and Pseudodisaccharides. (United States)

    Chandrasekaran, Srinivasan; Ramapanicker, Ramesh


    Conjugation of different molecular species using copper(I)-catalyzed click reaction between azides and terminal alkynes is among the best available methods to prepare multifunctional compounds. The effectiveness of this method has provided wider acceptance to the concept of click chemistry, which is now widely employed to synthesize densely functionalized organic molecules. This article summarizes the contributions from our group in the development of new methods for the synthesis of functional molecules using copper(I)-catalyzed click reactions. We have developed very efficient methods for the synthesis of peptides and amino acids conjugated with carbohydrates, thymidine and ferrocene. We have also developed an efficient strategy to synthesize triazole-fused heterocycles from primary amines, amino alochols and diols. Finally, an interesting method for the synthesis of pseudodisaccharides linked through triazoles, starting from carbohydrate-derived donor-acceptor cyclopropanes is discussed. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

  11. Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

    Directory of Open Access Journals (Sweden)

    Mohsine Driowya


    Full Text Available This review describes the recent advances in the microwave-assisted synthesis of 7-membered and larger heterocyclic compounds. Several types of reaction for the cyclization step are discussed: Ring Closing Metathesis (RCM, Heck and Sonogashira reactions, Suzuki-Miyaura cross-coupling, dipolar cycloadditions, multi-component reactions (Ugi, Passerini, etc. Green syntheses and solvent-free procedures have been introduced whenever possible. The syntheses discussed herein have been selected to illustrate the huge potential of microwave in the synthesis of highly functionalized molecules with potential therapeutic applications, in high yields, enhanced reaction rates and increased chemoselectivity, compared to conventional methods. More than 100 references from the recent literature are listed in this review.

  12. Azo coupling of 4-nitrophenyldiazonium chloride with aliphatic nucleophiles: an integrated organic synthesis and X-ray crystallography experiment; Acoplamento de cloreto de 4-nitrofenildiazonio com nucleofilos alifaticos: experimento integrado de sintese organica e cristalografia de raios X

    Energy Technology Data Exchange (ETDEWEB)

    Cunha, Silvio; Marques, Monique F.; Rocha, Valeria, E-mail: [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Instituto de Quimica; Lariucci, Carlito; Vencato, Ivo [Universidade Federal de Goiania (UFG), GO (Brazil). Instituto de Fisica


    This article describes an undergraduate experiment for the synthesis of p-nitrophenyldiazonium chloride and its coupling with acetylacetone and two enaminones, 4-phenylamino-pent-3-en-2-one and 4-amino-pent-3-en-2-one, in an adaptation of a previously reported synthetic protocol. The azo dyes 4-(E)-phenylamino-3-[(E)-2-(4-nitrophenylazo)]-3-penten-2-one and 4-(E)-amino-3-[(E)-2-(4-nitrophenylazo)]-3-penten-2-one were obtained, and the solid state structure of this latter azo compound was characterized by single crystal X-ray diffraction studies. This two-week integrated laboratory approach involves simple synthetic experiments and microwave chemistry in the organic laboratory plus crystallography analysis, suitable for novice students on undergraduate experimental chemistry courses. (author)

  13. Sulforaphane Analogues with Heterocyclic Moieties: Syntheses and Inhibitory Activities against Cancer Cell Lines

    Directory of Open Access Journals (Sweden)

    Ye-Hui Shi


    Full Text Available Recent studies have shown that sulforaphane (SFN selectively inhibits the growth of ALDH+ breast cancer stem-like cells.Herein, a series of SFN analogues were synthesized and evaluated against breast cancer cell lines MCF-7 and SUM-159, and the leukemia stem cell-like cell line KG-1a. These SFN analogues were characterized by the replacement of the methyl group with heterocyclic moieties, and the replacement of the sulfoxide group with sulfide or sulfone. A growth inhibitory assay indicated that the tetrazole analogs 3d, 8d and 9d were significantly more potent than SFN against the three cancer cell lines. Compound 14c, the water soluble derivative of tetrazole sulfide 3d, demonstrated higher potency against KG-1a cell line than 3d. SFN, 3d and 14c significantly induced the activation of caspase-3, and reduced the ALDH+ subpopulation in the SUM159 cell line, while the marketed drug doxrubicin(DOX increased the ALDH+ subpopulation.

  14. Microwave-Mediated Hetero Diels-Alder reaction: Synthesis of biologically active compounds


    D’Aurizio, Antonio


    Heterocyclic compounds represent almost two-thirds of all the known organic compounds: they are widely distributed in nature and play a key role in a huge number of biologically important molecules including some of the most significant for human beings. A powerful tool for the synthesis of such compounds is the hetero Diels-Alder reaction (HDA), that involve a [4+2] cycloaddition reaction between heterodienes and suitable dienophiles. Among heterodienes to be used in such six-membered ...

  15. Ring-strain-enabled reaction discovery: new heterocycles from bicyclo[1.1.0]butanes. (United States)

    Walczak, Maciej A A; Krainz, Tanja; Wipf, Peter


    Mechanistically as well as synthetically, bicyclo[1.1.0]butanes represent one of the most fascinating classes of organic compounds. They offer a unique blend of compact size (four carbon atoms), high reactivity (strain energy of 66 kcal/mol), and mechanistic pathway diversity that can be harvested for the rapid assembly of complex scaffolds. The C(1)-C(3) bond combines the electronic features of both σ and π bonds with facile homolytic and heterolytic bond dissociation properties and thereby readily engages pericyclic, transition-metal-mediated, nucleophilic, and electrophilic pathways as well as radical acceptor and donor substrates. Despite this multifaceted reaction profile and recent advances in the preparation of bicylo[1.1.0]butanes, the current portfolio of synthetic applications is still limited compared with those of cyclopropanes and cyclobutanes. In this Account, we describe our work over the past decade on the exploration of substituent effects on the ring strain and the reactivity of bicyclo[1.1.0]butanes, particularly in the context of metal-mediated processes. We first describe Rh(I)-catalyzed cycloisomerization reactions of N-allyl amines to give pyrrolidine and azepine heterocycles. The regioselectivity of the C,C-bond insertion/ring-opening step in these reactions is controlled by the phosphine ligand. After metal carbene formation, an intramolecular cyclopropanation adds a second fused ring system. A proposed mechanism rationalizes why rhodium(I) complexes with monodentate ligands favor five-membered heterocycles, as opposed to Rh(I)-bidentate ligand catalysts, which rearrange N-allyl amines to seven-membered heterocycles. The scope of Rh(I)-catalyzed cycloisomerization reactions was extended to allyl ethers, which provide a mixture of five- and seven-membered cyclic ethers regardless of the nature of the phosphine additive and Rh(I) precatalyst. The chemical diversity of these cycloisomerization products was further expanded by a consecutive

  16. 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.

  17. Highly sulfurated heterocycles via dithiiranes and trithietanes as key intermediates

    DEFF Research Database (Denmark)

    Mloston, Gregorz; Majchrazak, Agnieszka; Senning, Alexander Erich Eugen


    2,2,4,4-Tetramethyl-3-thioxocyclobutanone (8b) easily reacts with gaseous chlorine to yield the stable alpha-chloro sulfenyl chloride 10. The same product was obtained when 8b was treated either with phosphorus pentachloride (PCl5) or sulfuryl chloride (SO2Cl2) in CCl4 solution. Sulfur dichloride...... thiosulfenyl chloride 12 added to adamantanethione (8e) yielded the unsymmetrical trisulfide 13c. When 12 was treated with thioacetic acid, the acetylated trisulfide 17 was formed in high yield. "Unzipping" reactions with the acetylated disulfide 16 and trisulfide 17 with morpholine in THF at -40 degreesC led...... to the formation of mixtures of two sulfur-rich heterocycles identified as the pentathiepane 6b and the hexathiepane 7b. A mixture of analogous products was obtained when alpha-chloro sulfenyl chloride 10 was treated with sodium sulfide in anhydrous THF at -40 degreesC. The formation of 6b and 7b is believed...

  18. Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor (United States)

    Kumar, Vinay; Kashyap, D. M. Nikhila; Hebbar, Suraj; Swetha, R.; Prasad, Sujay; Kamala, T.; Srikanta, S. S.; Krishnaswamy, P. R.; Bhat, Navakanta


    Direct Electron Transfer biosensors, facilitating direct communication between the biomolecule of interest and electrode surface, are preferable compared to enzymatic and mediator based sensors. Although hemoglobin (Hb) contains four redox active iron centres, direct detection is not possible due to inaccessibility of iron centres and formation of dimers, blocking electron transfer. Through the coordination of iron with aza-heterocyclic receptors - pyridine and imidazole - we report a cost effective, highly sensitive and simple electrochemical Hb sensor using cyclic voltammetry and chronoamperometry. The receptor can be either in the form of liquid micro-droplet mixed with blood or dry chemistry embedded in paper membrane on top of screen printed carbon electrodes. We demonstrate excellent linearity and robustness against interference using clinical samples. A truly point of care technology is demonstrated by integrating disposable test strips with handheld reader, enabling finger prick to result in less than a minute.

  19. Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

    Directory of Open Access Journals (Sweden)

    Cristina Tubaro


    Full Text Available Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3. Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

  20. Heterocyclic inhibitors of AChE acylation and peripheral sites. (United States)

    Bolognesi, Maria Laura; Andrisano, Vincenza; Bartolini, Manuela; Cavalli, Andrea; Minarini, Anna; Recanatini, Maurizio; Rosini, Michela; Tumiatti, Vincenzo; Melchiorre, Carlo


    Notwithstanding the criticism to the so called " cholinergic hypothesis", the therapeutic strategies for the treatment of Alzheimer's disease (AD) have been mainly centered on the restoration of cholinergic functionality and, until the last year, the only drugs licensed for the management of AD were the acetycholinesterase (AChE) inhibitors. Target enzyme AChE consists of a narrow gorge with two separate ligand binding sites: an acylation site at the bottom of the gorge containing the catalytic triad and a peripheral site located at the gorge rim, which encompasses binding sites for allosteric ligands. The aim of this short review is to update the knowledge on heterocyclic AChE inhibitors able to interact with the two sites of enzymes, structurally related to the well known inhibitors physostigmine, rivastigmine and propidium. The therapeutic potential of the dual site inhibithors in inhibiting amyloid-beta aggregatrion and deposition is also briefly summarised.

  1. Absorption tuning of the green fluorescent protein chromophore: synthesis and studies of model compounds

    DEFF Research Database (Denmark)

    Brøndsted Nielsen, Mogens; Andersen, Lars Henrik; Rinza, Tomás Rocha


    The green fluorescent protein (GFP) chromophore is a heterocyclic compound containing a p-hydroxybenzylidine attached to an imidazol-5(4H)-one ring. This review covers the synthesis of a variety of model systems for elucidating the intrinsic optical properties of the chromophore in the gas phase...

  2. N-heterocyclic carbene catalyzed synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol

    Directory of Open Access Journals (Sweden)

    Guang-Fen Du


    Full Text Available An organocatalytic protocol for the synthesis of dimethyl carbonate has been developed. Under the catalysis of 5 mol% N-heterocyclic carbenes, ethylene carbonate undergoes transesterification reaction with methanol under very mild reaction conditions, producing dimethyl carbonate with high efficiency. Furthermore, this N-heterocyclic carbene promoted transesterification can be scaled-up easily without lose of the conversion of dimethyl carbonate.

  3. Comparative study of toxicity of azo dye Procion Red MX-5B following biosorption and biodegradation treatments with the fungi Aspergillus niger and Aspergillus terreus. (United States)

    Almeida, E J R; Corso, C R


    Azo dyes are an important class of environmental contaminants and are characterized by the presence of one or more azo bonds (-N=N-) in their molecular structure. Effluents containing these compounds resist many types of treatments due to their molecular complexity. Therefore, alternative treatments, such as biosorption and biodegradation, have been widely studied to solve the problems caused by these substances, such as their harmful effects on the environment and organisms. The aim of the present study was to evaluate biosorption and biodegradation of the azo dye Procion Red MX-5B in solutions with the filamentous fungi Aspergillus niger and Aspergillus terreus. Decolorization tests were performed, followed by acute toxicity tests using Lactuca sativa seeds and Artemia salina larvae. Thirty percent dye removal of the solutions was achieved after 3 h of biosorption. UV-Vis spectroscopy revealed that removal of the dye molecules occurred without major molecular changes. The acute toxicity tests confirmed lack of molecular degradation following biosorption with A. niger, as toxicity to L. sativa seed reduced from 5% to 0%. For A. salina larvae, the solutions were nontoxic before and after treatment. In the biodegradation study with the fungus A. terreus, UV-Vis and FTIR spectroscopy revealed molecular degradation and the formation of secondary metabolites, such as primary and secondary amines. The biodegradation of the dye molecules was evaluated after 24, 240 and 336 h of treatment. The fungal biomass demonstrated considerable affinity for Procion Red MX-5B, achieving approximately 100% decolorization of the solutions by the end of treatment. However, the solutions resulting from this treatment exhibited a significant increase in toxicity, inhibiting the growth of L. sativa seeds by 43% and leading to a 100% mortality rate among the A. salina larvae. Based on the present findings, biodegradation was effective in the decolorization of the samples, but generated

  4. Evaluation of in vitro efficacy for decolorization and degradation of commercial azo dye RB-B by Morganella sp. HK-1 isolated from dye contaminated industrial landfill. (United States)

    Pathak, Hilor; Soni, Dhaval; Chauhan, Kishor


    Reactive Black-B (RB-B) - one of the multi-sulphonated reactive azo dye - is being used extensively in textile as well as paper industries. Reactive azo dyes comprise of a significant group of synthetic compounds categorized as xenobiotics and its abatement from the environment still remains a challenge. In the present study, a newly isolated indigenous bacterial strain Morganella sp. HK-1 was exploited for its ability to decolorize and degrade RB-B dye. The isolate completely degraded RB-B (20 g L(-1)) within 24h under static conditions. Furthermore, the visible and FTIR spectral analysis established the bio-degradation of RB-B. The degraded metabolites of RB-B by Morganella sp. HK-1 were identified by GC-MS analysis as disodium 3,4,6-triamino-5-hydroxynaphthalene-2,7-disulfonate, 4-aminophenylsulfonylethyl hydrogen sulfate, naphthalene-1-ol, aniline and benzene. Based on this information, a putative pathway of degradation of RB-B by Morganella sp. HK-1 has been proposed. This study is the first report on elucidation of mechanism of bacterial degradation of RB-B dye. Furthermore, phytotoxicity, genotoxicity and aquatic acute toxicity studies of the parent dye and the bio-degraded dye products revealed drastic reduction in the toxicity of metabolites as compared to the parent dye. This implies that the biotreatment of the dye is of non-toxic nature. This study thus indicates the effectiveness of Morganella sp. HK-1 for the treatment of textile effluents containing sulphonated azo dyes. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. 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.

  6. New heterocycles having double characters; as antimicrobial and surface active agents.

    Directory of Open Access Journals (Sweden)

    El-Sayed, R.


    Full Text Available Fatty acids isothiocyanate (1 was used as a starting material to synthesize some important heterocycles such as triazoles, oxazoles, thiazoles, benzoxazoles and quinazolines by treating with different types of nucleophiles such as nitrogen nucleophiles, oxygen nucleophiles, and sulfur nucleophiles. The produced compounds were subjected to propylene oxide in different moles (n = 3, 5 and 7 to produce novel groups of nonionic compounds having the double function as antimicrobial and surface active agents which can be used in the manufacturing of drugs, cosmetics, pesticides or can be used as antibacterial and/or antifungal. The physical properties as surface and interfacial tension, cloud point, foaming height, wetting time, emulsification power and the critical micelle concentration (CMC were determined, antimicrobial and biodegradability were also determined.Isocianatos de acidos grasos se utilizaron como material de partida para la síntesis de importantes heterociclos tales como triazoles, oxazoles, thoazoles, benzoxazoles y quinazolinas mediante el tratamiento de los mismos con diferentes tipos de nucleofilos tales como nucleofilos nitrogenados, oxigenados, o azufrados. Los compuestos producidos se trataron con oxido de propileno a diferentes concentraciones molares (n = 3, 5 y 7 para producir nuevos grupos de compuestos no iónicos que tuvieran la doble función de ser compuestos antimicrobianos y agentes de superficie, que se pudieran usar en la fabricación de medicinas, cosméticos, pesticidas o como antibacterianos o antifúngicos. Se determinaron sus propiedades tales como tensión superficial e interfacial, punto de turbidez, altura de espuma, tiempo de mojado, poder de emulsificación y concentración micelar crítica (CMC, asi como sus propiedades antimicrobianas y de degradabilidad.

  7. O-heterocyclic derivatives with antibacterial properties from marine bacterium Bacillus subtilis associated with seaweed, Sargassum myriocystum. (United States)

    Chakraborty, Kajal; Thilakan, Bini; Chakraborty, Rekha Devi; Raola, Vamshi Krishna; Joy, Minju


    The brown seaweed, Sargassum myriocystum associated with heterotrophic bacterium, Bacillus subtilis MTCC 10407 (JF834075) exhibited broad-spectra of potent antibacterial activities against pathogenic bacteria Aeromonas hydrophila, Vibrio vulnificus, and Vibrio parahaemolyticus. B. subtilis MTCC 10407 was found to be positive for polyketide synthetase (pks) gene, and therefore, was considered to characterize secondary metabolites bearing polyketide backbone. Using bioassay-guided fractionation, two new antibacterial O-heterocyclic compounds belonging to pyranyl benzoate analogs of polyketide origin, with activity against pathogenic bacteria, have been isolated from the ethyl acetate extract of B. subtilis MTCC 10407. In the present study, the secondary metabolites of B. subtilis MTCC 10407 with potent antibacterial action against bacterial pathogens was recognized to represent the platform of pks-1 gene-encoded products. Two homologous compounds 3 (3-(methoxycarbonyl)-4-(5-(2-ethylbutyl)-5,6-dihydro-3-methyl-2H-pyran-2-yl)-butyl benzoate) and 4 [2-(8-butyl-3-ethyl-3,4,4a,5,6,8a-hexahydro-2H-chromen-6-yl)-ethyl benzoate] also have been isolated from the ethyl acetate extract of host seaweed S. myriocystum. The two compounds isolated from ethyl acetate extract of S. myriocystum with lesser antibacterial properties shared similar structures with the compounds purified from B. subtilis that suggested the ecological and metabolic relationship between these compounds in seaweed-bacterial relationship. Tetrahydropyran-2-one moiety of the tetrahydropyrano-[3,2b]-pyran-2(3H)-one system of 1 might be cleaved by the metabolic pool of seaweeds to afford methyl 3-(dihydro-3-methyl-2H-pyranyl)-propanoate moiety of 3, which was found to have no significant antibacterial activity. It is therefore imperative that the presence of dihydro-methyl-2H-pyran-2-yl propanoate system is essentially required to impart the greater activity. The direct involvement of polarisability (Pl) with

  8. Characterization of Sulfur Compounds in MTBE

    Directory of Open Access Journals (Sweden)

    Mingqing Wu


    Full Text Available A study is carried out on chemical constitution of sulfur compounds in MTBE and their formation mechanisms. These sulfur compounds are classified into three types: common sulfur compounds, newly formed sulfur compounds, and high boiling sulfur compounds. Common sulfur compounds which include mercaptans, low molecule sulfides and disulfides, are directly from C4, one of the stocks for production of MTBE. The newly formed sulfur compounds, with one sulfur atom and five or more total carbon atoms in one molecule, are mainly tert-butyl methyl sulfide and tert-butyl ethyl sulfide, thioetherification products of thiols with butenes. Many high boiling sulfur compounds, including polysulfides such as dimethyl trisulfide, multisulfur heterocyclic compounds such as 3,5-dimethyl-1,2,4-trithiolane, and oxygen-containing sulfur compounds such as 2-methoxy-3-methylthio-butane, are also found newly formed in the processes of LPG refining and succedent etherification reaction for producing MTBE. Polysulfides are additional products of elemental sulfur to disulfides, and other high boiling sulfur compounds may be formed by thiols reacting with dienes.

  9. Sonochemical Synthesis of a Cobalt(II Coordination Polymer Nano-structure with azo ligand: A New Precursor for Preparation Pure Phase of Co3O4 Nanostructure

    Directory of Open Access Journals (Sweden)

    M. Hosseyni Sadr


    Full Text Available A new nano-sized cobalt(II coordination polymer, (CoL1.0.5DMF.1.5CH3OH(1; [H2L1 = 5-(4-Carboxy phenyl azo salicyilic acid] has been synthesized by a sonochemical method. The thermal stability of compound 1 was studied by thermo- gravimetric and differential thermal analyses. Nano-structure of this coordination polymer was characterized by elemental analyses, IR spectroscopy,  powder X-ray diffraction and scanning electron microscopy. Nano-particles of Co3O4 were obtained by calcination of compound 1 at 550°C. The Co3O4  nano-particles were characterized by powder X-ray diffraction and scanning electron microscopy.

  10. 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.

  11. Direct, catalytic, and regioselective synthesis of 2-alkyl-, aryl-, and alkenyl-substituted N-heterocycles from N-oxides. (United States)

    Larionov, Oleg V; Stephens, David; Mfuh, Adelphe; Chavez, Gabriel


    A one-step transformation of heterocyclic N-oxides to 2-alkyl-, aryl-, and alkenyl-substituted N-heterocycles is described. The success of this broad-scope methodology hinges on the combination of copper catalysis and activation by lithium fluoride or magnesium chloride. The utility of this method for the late-stage modification of complex N-heterocycles is exemplified by facile syntheses of new structural analogues of several antimalarial, antimicrobial, and fungicidal agents.

  12. Direct, Catalytic and Regioselective Synthesis of 2-Alkyl, Aryl, and Alkenyl-Substituted N-Heterocycles from N-Oxides (United States)

    Larionov, Oleg V.; Stephens, David; Mfuh, Adelphe; Chavez, Gabriel


    A one-step transformation of heterocyclic N-oxides to 2-alkyl, aryl, and alkenyl-substituted N-heterocycles is described. The success of this broad-scope methodology hinges on the combination of copper catalysis and activation by lithium fluoride or magnesium chloride. The utility of this method for the late-stage modification of complex N-heterocycles is exemplified by facile syntheses of new structural analogs of several antimalarial, antimicrobial and fungicidal agents. PMID:24410049

  13. Synthetic and mechanistic aspects of the regioselective base-mediated reaction of perfluoroalkyl- and perfluoroarylsilanes with heterocyclic N-oxides. (United States)

    Stephens, David E; Chavez, Gabriel; Valdes, Martin; Dovalina, Monica; Arman, Hadi D; Larionov, Oleg V


    The scope and mechanistic implications of the direct transformation of heterocyclic N-oxides to 2-trifluoromethyl-, and related perfluoroalkyl- and perfluoroaryl-substituted N-heterocycles has been studied. The reaction is effected by perfluoroalkyl- and perfluorophenyltrimethylsilane in the presence of strong base. In situ displacement of the para-fluoro substituent in the pentafluorophenyl ring and the methoxy group in 8-methoxyquinolines with additional nucleophiles allows for further site-selective refunctionalization of the N-heterocyclic products.

  14. Molecular dynamics study of biodegradation of azo dyes via their interactions with AzrC azoreductase. (United States)

    Haghshenas, Hamed; Kay, Maryam; Dehghanian, Fariba; Tavakol, Hossein


    Azo dyes are one of the most important class of dyes, which have been widely used in industries. Because of the environmental pollution of azo dyes, many studies have been performed to study their biodegradation using bacterial systems. In present work, the AzrC of mesophilic gram-positive Bacillus sp. B29 has been considered to study its interaction with five common azo dyes (orange G, acid red 88, Sudan I, orange I, and methyl red). The molecular dynamics simulations have been employed to study the interaction between AzrC and azo dyes. The trajectory was confirmed using root mean square deviation and the root mean square fluctuation analyses. Then, the hydrogen bond and alanine scanning analyses were performed to reveal active site residues. Phe105 (A), Phe125 (B), Phe172 (B), and Pro132 (B) have been found as the most important hydrophobic residues whereas Asn104 (A), Tyr127 (B), and Asn187 (A) have key role in making hydrogen bond. The results of molecular mechanics Poisson-Boltzmann surface area and molecular mechanics generalized Born surface area calculations proved that the hydrophobic azo dyes like Acid red 88 binds more tightly to the AzrC protein. The calculated data suggested MR A 121 (B) I as a potential candidate for improving the AzrC-MR interactions.

  15. Reduction and partial degradation mechanisms of naphthylaminesulfonic azo dye amaranth by Shewanella decolorationis S12. (United States)

    Hong, Yiguo; Guo, Jun; Xu, Zhicheng; Mo, Cuiyun; Xu, Meiying; Sun, Guoping


    Reduction and biodegradation mechanisms of naphthylaminesulfonic azo dye amaranth using a newly isolated Shewanella decolorationis strain S12 were investigated. Under anaerobic conditions, amaranth was reduced by strain S12, and a stoichiometric amount of two reduction products RP-1 and RP-2 were generated. UV/visible spectrophotometric and high performance liquid chromatography (HPLC) analysis indicated that RP-1 and RP-2 were 1-aminenaphthylene -4-sulfonic acid and 1-aminenaphthylene-2-hydroxy-3, 6-disulfonic acid. The result strongly supports a mechanism of azo dye reduction by the process via the reductive cleavage of the azo bond to form corresponding aromatic amines. The result of HPLC analyses revealed that these aromatic amines were not able to be mineralized by strain S12 under anaerobic conditions. But after re-aeration of the decolorized culture, RP-2 was mineralized completely by this microorganism, but the consumption of RP-1 was not observed. Ames test showed that amaranth had mutagenic but no cytotoxic potential. The mutagenic potential was relieved after the anaerobic treatment with strain S12 as the mutagenic effect of the two reduction products from amaranth was not detected by Ames test. Thus, the ability of strain S12 to reduce and partially mineralize the naphthylaminesulfonic azo dye efficiently was demonstrated, which can potentially be used to biodegrade and detoxify wastewater containing azo dyes using an alternating anaerobic/aerobic treatment procedure.

  16. Use of titanium dioxide photocatalysis on the remediation of model textile wastewaters containing azo dyes. (United States)

    Saggioro, Enrico Mendes; Oliveira, Anabela Sousa; Pavesi, Thelma; Maia, Cátia Gil; Ferreira, Luis Filipe Vieira; Moreira, Josino Costa


    The photocatalytic degradation of two commercial textile azo dyes, namely C.I Reactive Black 5 and C.I Reactive Red 239, has been studied. TiO(2) P25 Degussa was used as catalyst and photodegradation was carried out in aqueous solution under artificial irradiation with a 125 W mercury vapor lamp. The effects of the amount of TiO(2) used, UV-light irradiation time, pH of the solution under treatment, initial concentration of the azo dye and addition of different concentrations of hydrogen peroxide were investigated. The effect of the simultaneous photodegradation of the two azo dyes was also investigated and we observed that the degradation rates achieved in mono and bi-component systems were identical. The repeatability of photocatalytic activity of the photocatalyst was also tested. After five cycles of TiO(2) reuse the rate of colour lost was still 77% of the initial rate. The degradation was followed monitoring the change of azo dye concentration by UV-Vis spectroscopy. Results show that the use of an efficient photocatalyst and the adequate selection of optimal operational parameters may easily lead to a complete decolorization of the aqueous solutions of both azo dyes.

  17. Decolorization of azo dyes by Shewanella oneidensis MR-1 in the presence of humic acids. (United States)

    Liu, Guangfei; Zhou, Jiti; Wang, Jing; Wang, Xiujuan; Jin, Ruofei; Lv, Hong


    The effects of humic acid (HA) on azo dye decolorization by Shewanella oneidensis MR-1 were studied. It was found that HA species isolated from different sources could all accelerate the decolorization of Acid Red 27 (AR27). Anoxic and anaerobic conditions were required for the enhancement of azo dye decolorization by HA. In the presence of 50 mg DOC L⁻¹ Aldrich HA, 15-29% increases in decolorization efficiencies of azo dyes with different structures were achieved in 11 h. The enhancing effects increased with the increase of HA concentrations ranging from 25 to 150 mg DOC L⁻¹, and the decolorization rates were directly proportional to the HA concentrations when they were below 100 mg DOC L⁻¹. Lactate and formate were good electron donors for AR27 decolorization in the presence of HA. Both nitrate (0.1-3.0 mM) and nitrite (0.3-1.2 mM) inhibited AR27 decolorization in the presence of HA, and negligible decolorization was observed before their removal. Soluble FeCl₃ could accelerate the decolorization process in the presence of HA, whereas insoluble hematite could not. These findings may affect the understanding of bioremediation of azo dye-polluted environments and help improve the treatment of azo dye wastewaters.

  18. The non-enzymatic reduction of azo dyes by flavin and nicotinamide cofactors under varying conditions. (United States)

    Morrison, Jessica M; John, Gilbert H


    Azo dyes are ubiquitous in products and often become environmental pollutants due to their anthropogenic nature. Azoreductases are enzymes which are present within many bacteria and are capable of breaking down the azo dyes via reduction of the azo bond. Often, though, carcinogenic aromatic amines are formed as metabolites and are of concern to humans. Azoreductases function via an oxidation-reduction reaction and require cofactors (a nicotinamide cofactor and sometimes a flavin cofactor) to perform their function. Non-enzymatic reduction of azo dyes in the absence of an azoreductase enzyme has been suggested in previous studies, but has never been studied in detail in terms of varying cofactor combinations, different oxygen states or pHs, nor has the enzymatic reduction been compared to azoreduction in terms of dye reduction or metabolites produced, which was the aim of this study. Reduction of azo dyes by different cofactor combinations was found to occur under both aerobic and anaerobic conditions and under physiologically-relevant pHs to produce the same metabolites as an azoreductase. Our results show that, in some cases, the non-enzymatic reduction by the cofactors was found to be equal to that seen with the azoreductase, suggesting that all dye reduction in these cases is due to the cofactors themselves. This study details the importance of the use of a cofactor-only control when studying azoreductase enzymes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Preparation of ZnO Photocatalyst for the Efficient and Rapid Photocatalytic Degradation of Azo Dyes (United States)

    Chen, Xiaoqing; Wu, Zhansheng; Liu, Dandan; Gao, Zhenzhen


    Zinc oxide (ZnO) photocatalysts were synthesized by sol-gel method using zinc acetate as precursor for degradation of azo dyes under UV irradiation. The resultant samples were characterized by different techniques, such as XRD, SEM, and EDX. The influence of preparation conditions such as calcination temperature and composite ratio on the degradation of methyl orange (MO) was investigated. ZnO prepared with a composite ratio of 4:1 and calcination temperature of 400 °C exhibited 99.70% removal rate for MO. The effect of operation parameters on the degradation was also studied. Results showed that the removal rate of azo dyes increased with the increased dosage of catalyst and decreased initial concentration of azo dyes and the acidic condition is favorable for degradation. Furthermore, the kinetics and scavengers of the reactive species during the degradation were also investigated. It was found that the degradation of azo dyes fitted the first-order kinetics and superoxide ions were the main species. The proposed photocatalyst can efficiently and rapidly degrade azo dyes; thus, this economical and environment-friendly photocatalyst can be applied to the treatment of wastewater contaminated with synthetic dyes.

  20. Electrolysis within anaerobic bioreactors stimulates breakdown of toxic products from azo dye treatment. (United States)

    Gavazza, Sávia; Guzman, Juan J L; Angenent, Largus T


    Azo dyes are the most widely used coloring agents in the textile industry, but are difficult to treat. When textile effluents are discharged into waterways, azo dyes and their degradation products are known to be environmentally toxic. An electrochemical system consisting of a graphite-plate anode and a stainless-steel mesh cathode was placed into a lab-scale anaerobic bioreactor to evaluate the removal of an azo dye (Direct Black 22) from synthetic textile wastewater. At applied potentials of 2.5 and 3.0 V when water electrolysis occurs, no improvement in azo dye removal efficiency was observed compared to the control reactor (an integrated system with electrodes but without an applied potential). However, applying such electric potentials produces oxygen via electrolysis and promoted the aerobic degradation of aromatic amines, which are toxic, intermediate products of anaerobic azo dye degradation. The removal of these amines indicates a decrease in overall toxicity of the effluent from a single-stage anaerobic bioreactor, which warrants further optimization in anaerobic digestion.

  1. Microstructure and Electrical Properties of AZO/Graphene Nanosheets Fabricated by Spark Plasma Sintering. (United States)

    Yang, Shuang; Chen, Fei; Shen, Qiang; Lavernia, Enrique J; Zhang, Lianmeng


    In this study we report on the sintering behavior, microstructure and electrical properties of Al-doped ZnO ceramics containing 0-0.2 wt. % graphene sheets (AZO-GNSs) and processed using spark plasma sintering (SPS). Our results show that the addition of <0.25 wt. % GNSs enhances both the relative density and the electrical resistivity of AZO ceramics. In terms of the microstructure, the GNSs are distributed at grain boundaries. In addition, the GNSs are also present between ZnO and secondary phases (e.g., ZnAl₂O₄) and likely contribute to the measured enhancement of Hall mobility (up to 105.1 cm²·V(-1)·s(-1)) in these AZO ceramics. The minimum resistivity of the AZO-GNS composite ceramics is 3.1 × 10(-4) Ω·cm which compares favorably to the value of AZO ceramics which typically have a resistivity of 1.7 × 10(-3) Ω·cm.

  2. 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.

  3. Biodegradation of azo dyes in cocultures of anaerobic granular sludge with aerobic aromatic amine degrading enrichment cultures

    NARCIS (Netherlands)

    Tan, N.C.G.; Prenefeta-Boldú, F.X.; Opsteeg, J.L.; Lettinga, G.; Field, J.A.


    A prerequisite for the mineralization (complete biodegradation) of many azo dyes is a combination of reductive and oxidative steps. In this study, the biodegradation of two azo dyes, 4-phenylazophenol (4-PAP) and Mordant Yellow 10 (4-sulfophenylazo-salicylic acid; MY10), was evaluated in batch

  4. Csbnd N bond formation in alicyclic and heterocyclic compounds by amine-modified nanoclay (United States)

    Zarnegar, Zohre; Alizadeh, Roghayeh; Ahmadzadeh, Majid; Safari, Javad


    In the current protocol, amine functionalized montmorillonite K10 nanoclay (NH2-MMT) was applied to catalyze the formation of Csbnd N bonds in the synthesis of azines and 2-aminothiazoles at room temperature. In comparison with the current methods of Csbnd N bond formation, this approach displays specific advantages include atom economy, clean conversion, design for energy efficiency, the use of nontoxic and heterogeneous catalyst, higher purity and yields, safer solvent and reagents for this organic transformation.

  5. 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.

  6. Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu₂(CNC(t-Bu))₂](PF₆)₂. (United States)

    Riener, Korbinian; Pöthig, Alexander; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E


    In recent years, the use of copper N-heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ-1,3-bis(3-tert-butylimidazolin-2-yliden-1-yl)pyridine]-1κ(4)C(2),N:N,C(2');2κ(4)C(2),N:N,C(2')-dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N-heterocyclic carbene)pyridine, ligands. Each Cu(I) atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV-Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.

  7. Synthesis and Pharmacological Evaluation of New 3,4-Dihydroisoquinolin Derivatives Containing Heterocycle as Potential Anticonvulsant Agents

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    Hong-Jian Zhang


    Full Text Available Two novel series of 3,4-dihydroisoquinolin with heterocycle derivatives (4a–t and 9a–e were synthesized and evaluated for their anticonvulsant activity using maximal electroshock (MES test and pentylenetetrazole (PTZ-induced seizure test. All compounds were characterized by IR, 1H-NMR, 13C-NMR, and mass spectral data. Among them, 9-(exyloxy-5,6-dihydro-[1,2,4]triazolo[3,4-a]isoquinolin-3(2H-one (9a showed significant anticonvulsant activity in MES tests with an ED50 value of 63.31 mg/kg and it showed wide margins of safety with protective index (PI > 7.9. It showed much higher anticonvulsant activity than that of valproate. It also demonstrated potent activity against PTZ-induced seizures. A docking study of compound 9a in the benzodiazepine (BZD-binding site of γ-aminobutyric acidA (GABAA receptor confirmed possible binding of compound 9a with the BZD receptors.

  8. 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.


    Directory of Open Access Journals (Sweden)

    Jagadeesan Vijayaraghavan


    Full Text Available This paper deals with the intensive review of reactive azo dye, Reactive Black 5. Various physicochemical methods namely photo catalysis, electrochemical, adsorption, hydrolysis and biological methods like microbial degradation, biosorption and bioaccumulation have been analyzed thoroughly along with the merits and demerits of each method. Among these various methods, biological treatment methods are found to be the best for decolorization of Reactive Black 5. With respect to dye biosorption, microbial biomass (bacteria, fungi, microalgae, etc, and outperformed macroscopic materials (seaweeds, crab shell, etc. are used for decolorization process. The use of living organisms may not be an option for the continuous treatment of highly toxic organic/inorganic contaminants. Once the toxicant concentration becomes too high or the process operated for a long time, the amount of toxicant accumulated will reach saturation. Beyond this point, an organism's metabolism may be interrupted, resulting in death of the organism. This scenario is not existed in the case of dead biomass, which is flexible to environmental conditions and toxicant concentrations. Thus, owing to its favorable characteristics, biosorption has received much attention in recent years.

  10. Examination of the Impact of Copper(II) α-(N)-Heterocyclic Thiosemicarbazone Complexes on DNA Topoisomerase IIα. (United States)

    Wilson, James T; Jiang, Xiaohua; McGill, Bradley C; Lisic, Edward C; Deweese, Joseph E


    Type II DNA topoisomerases resolve topological knots and tangles in DNA that result from routine cellular processes and are effective targets for anticancer therapeutics. To this end, thiosemicarbazones have been identified as having the ability to kill cancer cells from several cell lines. Literature evidence suggests that at least some thiosemicarbazones have an impact on topoisomerase II activity. However, the mechanism is not as clearly defined. Therefore, we set out to analyze the activity of four α-(N)-heterocyclic thiosemicarbazone compounds against topoisomerase IIα. The ligands, acetylpyridine-ethylthiosemicarbazone (APY-ETSC) and acetylpyrazine-methylthiosemicarbazone (APZ-MTSC), and their copper(II) [Cu(II)] complexes [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] were examined for the ability to impact the catalytic cycle of human topoisomerase IIα. Both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] were more effective at inhibiting DNA relaxation compared with the ligands alone. Further, both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl] increased double-stranded DNA cleavage levels without inhibiting topoisomerase IIα-mediated DNA ligation. The Cu(II) complexes inactivate enzyme activity over time suggesting a critical interaction with the enzyme. Additionally, we found that the Cu(II)-thiosemicarbazone complexes do not significantly impact DNA cleavage by the catalytic core of the enzyme. This evidence is supported by the fact that both [Cu(APY-ETSC)Cl] and [Cu(APZ-MTSC)Cl], and to a lesser extent the ligands, inhibit topoisomerase IIα-mediated ATP hydrolysis. Based upon kinetic analysis, the Cu(II) complexes appear to be noncompetitive inhibitors of the ATPase domain of topoisomerase IIα. Taken together, our results provide evidence that Cu(II) complexes of α-(N)-heterocyclic thiosemicarbazones catalytically inhibit the enzyme through the ATPase domain but also promote double-stranded DNA cleavage by the enzyme.

  11. 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

  12. 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.

  13. Microextraction by packed sorbent and salting-out-assisted liquid-liquid extraction for the determination of aromatic amines formed from azo dyes in textiles. (United States)

    Sánchez, Miguel del Nogal; Santos, Patricia Martín; Sappó, Cristina Pérez; Pavón, José Luis Pérez; Cordero, Bernardo Moreno


    EU legislation prohibits the use of certain azo dyes which, on reduction, form any of 22 aromatic amines listed in Regulation (EC) 1907/2006 at concentrations above the threshold limit of 30 mg Kg(-1). Two different extraction techniques for the determination of aromatic amines formed from azo dyes in textiles in combination with gas chromatography-mass spectrometry (GC-MS) are described. The first one is based on microextraction by packed sorbent (MEPS) and the other approach involves salting-out-assisted liquid-liquid extraction (SALLE). The influence of several parameters on the efficiency of the extraction using MEPS (sorbent material, sample volume, elution solvent, elution volume and washing steps, among others) and SALLE (extraction volume and amount of salt) were investigated. In addition, chromatographic separation was optimized and quadrupole mass spectrometry was evaluated using the synchronous SIM/scan data acquisition mode. The repeatability (n=8, S/N=3) of the methods, calculated as the relative standard deviation (RSD) was below 15 and 11% for all compounds when MEPS and SALLE were used, respectively. Standard additions procedure was used to quantify the aromatic amines in the textil samples. The detection limits in the samples for both methods were lower than the maximum value allowed by legislation. The results obtained in the analysis of textiles revealed the presence of o-anisidine, p-chloroaniline, 4-chloro-o-toluidine, 2-naphthylamine and 3,3'-dimethoxybenzidine in some of them. © 2013 Elsevier B.V. All rights reserved.

  14. 454-Pyrosequencing analysis of highly adapted azo dye-degrading microbial communities in a two-stage anaerobic-aerobic bioreactor treating textile effluent. (United States)

    Köchling, Thorsten; Ferraz, Antônio Djalma Nunes; Florencio, Lourdinha; Kato, Mario Takayuki; Gavazza, Sávia


    Azo dyes, which are widely used in the textile industry, exhibit significant toxic characteristics for the environment and the human population. Sequential anaerobic-aerobic reactor systems are efficient for the degradation of dyes and the mineralization of intermediate compounds; however, little is known about the composition of the microbial communities responsible for dye degradation in these systems. 454-Pyrosequencing of the 16S rRNA gene was employed to assess the bacterial biodiversity and composition of a two-stage (anaerobic-aerobic) pilot-scale reactor that treats effluent from a denim factory. The anaerobic reactor was inoculated with anaerobic sludge from a domestic sewage treatment plant. Due to the selective composition of the textile wastewater, after 210 days of operation, the anaerobic reactor was dominated by the single genus Clostridium, affiliated with the Firmicutes phylum. The aerobic biofilter harbored a diverse bacterial community. The most abundant phylum in the aerobic biofilter was Proteobacteria, which was primarily represented by the Gamma, Delta and Epsilon classes followed by Firmicutes and other phyla. Several bacterial genera were identified that most likely played an essential role in azo dye degradation in the investigated system.

  15. Excellent capability in degrading azo dyes by MgZn-based metallic glass powders. (United States)

    Wang, Jun-Qiang; Liu, Yan-Hui; Chen, Ming-Wei; Louzguine-Luzgin, Dmitri V; Inoue, Akihisa; Perepezko, John H


    The lack of new functional applications for metallic glasses hampers further development of these fascinating materials. In this letter, we report for the first time that the MgZn-based metallic glass powders have excellent functional ability in degrading azo dyes which are typical organic water pollutants. Their azo dye degradation efficiency is about 1000 times higher than that of commercial crystalline Fe powders, and 20 times higher than the Mg-Zn alloy crystalline counterparts. The high Zn content in the amorphous Mg-based alloy enables a greater corrosion resistance in water and higher reaction efficiency with azo dye compared to crystalline Mg. Even under complex environmental conditions, the MgZn-based metallic glass powders retain high reaction efficiency. Our work opens up a new opportunity for functional applications of metallic glasses.

  16. Thermally stable water insoluble azo-azomethine dyes: synthesis, characterization and solvatochromic properties. (United States)

    Khanmohammadi, Hamid; Rezaeian, Khatereh


    Six new water insoluble azo-azomethine dyes have been synthesized via condensation reaction of α,α'-bis(o-aminophenylthio)-1,2-xylene with substituted azo-coupled salicylaldehyde. The condensation reaction provides the expected bis-iminated azo-azomethine dyes in good yields, ranging from 59% to 90%. The dyes have been characterized by IR, UV-Vis and (1)H NMR spectroscopic methods as well as elemental analysis. The thermal behavior of the prepared dyes has been determined using thermogravimetry technique. Furthermore, the effect of various organic solvents with different polarities on the UV-Vis spectra of the dyes has been also studied. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Phosphoric acid loaded azo (-N═N-) based covalent organic framework for proton conduction. (United States)

    Chandra, Suman; Kundu, Tanay; Kandambeth, Sharath; Babarao, Ravichandar; Marathe, Yogesh; Kunjir, Shrikant M; Banerjee, Rahul


    Two new chemically stable functional crystalline covalent organic frameworkds (COFs) (Tp-Azo and Tp-Stb) were synthesized using the Schiff base reaction between triformylphloroglucinol (Tp) and 4,4'-azodianiline (Azo) or 4,4'-diaminostilbene (Stb), respectively. Both COFs show the expected keto-enamine form, and high stability toward boiling water, strong acidic, and basic media. H3PO4 doping in Tp-Azo leads to immobilization of the acid within the porous framework, which facilitates proton conduction in both the hydrous (σ = 9.9 × 10(-4) S cm(-1)) and anhydrous state (σ = 6.7 × 10(-5) S cm(-1)). This report constitutes the first emergence of COFs as proton conducting materials.

  18. Methods for the analysis of azo dyes employed in food industry--A review. (United States)

    Yamjala, Karthik; Nainar, Meyyanathan Subramania; Ramisetti, Nageswara Rao


    A wide variety of azo dyes are generally added for coloring food products not only to make them visually aesthetic but also to reinstate the original appearance lost during the production process. However, many countries in the world have banned the use of most of the azo dyes in food and their usage is highly regulated by domestic and export food supplies. The regulatory authorities and food analysts adopt highly sensitive and selective analytical methods for monitoring as well as assuring the quality and safety of food products. The present manuscript presents a comprehensive review of various analytical techniques used in the analysis of azo dyes employed in food industries of different parts of the world. A brief description on the use of different extraction methods such as liquid-liquid, solid phase and membrane extraction has also been presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Research on Synthesis of New Azo Calix[4]arene and its Dyeing Properties


    Tang Jun; Sun Yu; Li Lingling; Xu Zhen; Lv Zaosheng


    With the raw materials of calix[4]arene, benzocaine, tricaine and procaine hydrochloride, three new azo calix[4]arene derivatives—6a, 6b and 6c are synthesized by diazotization–coupling reaction of an aromatic amine, with its yield of 83%, 81% and 83% respectively. The structural characterization is in a way of IR, 1H NMR and elemental analysis. This paper investigates the spectral properties of azo calix[4]arene derivatives under different solution pH conditions through the UV–visible spectr...

  20. Nano-Sized Zero Valent Iron and Covalent Organic Polymer Composites for Azo Dye Remediation

    DEFF Research Database (Denmark)

    Mines, Paul D.; Byun, Jeehye; Hwang, Yuhoon


    Having superior reductive properties and large surface areas, nanosized zero valent iron (nZVI) is ideal for the degradation of chemicals such as azo dyes and trichloroethylene (TCE). However, immobilization of nZVI is a key parameter in its effectiveness as a chemical degradation agent...... contaminant removal. Composites of nZVI impregnated within COPs of high surface areas exhibit effective ability to degrade azo dyes, up to 95%, over a 30-minute reaction period. Dye decolorization results were designated a precursor for effectiveness of pollutant decontamination; pollutants ranging...

  1. Effect of Azo Dyes on the Thermal Degradation of Post-consumer Polyester Fabrics

    Directory of Open Access Journals (Sweden)

    Qin Dan


    Full Text Available Thermogravimetric analysis(TGA and pyrolysis gas chromatography mass spectrometry (Py-GC-MS investigations were carried out on the thermal degradation of white and red post-consumer polyester fabrics. The results show that red PET fabrics which was dyed with C.I. Disperse red 167 for its typical azo structure exhibits larger activation energy compared with white PET. The addition of azo dyes displays an inhibiting effect on the deep pyrolysis and the formation of biphenyl and bis(2-hydroxybutyl terephthalate produced by the free radical mechanism.

  2. Synthesis and characterization of high wash fastness novel azo reactive dyes incorporating aromatic bridged diamines


    Aamer Saeed; Ghulam Shabir


    A new series of azo reactive dyes containing free chlorine atoms have been synthesized. The synthetic methodology involves the diazotization of 4′4-diamino diphenylamine-2-sulfonic acid (2) followed by azo coupling with 1-amino-8-naphthol-3,6-disulfonic acid (3) in alkaline medium to yield intermediate dye (4). Condensation of the latter with 1,3,5-trichlorotriazine afforded the cyanurated dye (5). A number of novel bis aromatic diamines (1a–j) were separately synthesized as bridging groups a...

  3. Conjugated iminopyridine based Azo dye derivatives with efficient charge transfer for third order nonlinearities (United States)

    Kerasidou, A. P.; Khammar, F.; Iliopoulos, K.; Ayadi, A.; El-Ghayoury, A.; Zouari, N.; Mhiri, T.; Sahraoui, B.


    The third order nonlinearities of two azobenzene-iminopyridine molecular systems have been investigated employing the Z-scan technique at 532 nm, 30 ps. The objective of the work has been to study and to compare the nonlinearity of two iminopyridine based ligands substituted with one (NO2AzoIminoPy, A) and two azobenzene units ((NO2Azo)2IminoPy, B). The ligand B exhibits an extended conjugated structure and higher charge transfer within the molecule. Our results show high dependence of the nonlinearity on both the conjugation length within the molecule and on the number of the electron accepting units.

  4. Third-order nonlinear optical properties of organic azo dyes by using strength of nonlinearity parameter and Z-scan technique (United States)

    Motiei, H.; Jafari, A.; Naderali, R.


    In this paper, two chemically synthesized organic azo dyes, 2-(2,5-Dichloro-phenyazo)-5,5-dimethyl-cyclohexane-1,3-dione (azo dye (i)) and 5,5-Dimethyl-2-tolylazo-cyclohexane-1,3-dione (azo dye (ii)), have been studied from optical Kerr nonlinearity point of view. These materials were characterized by Ultraviolet-visible spectroscopy. Experiments were performed using a continous wave diode-pumped laser at 532 nm wavelength in three intensities of the laser beam. Nonlinear absorption (β), refractive index (n2) and third-order susceptibility (χ (3)) of dyes, were calculated. Nonlinear absorption coefficient of dyes have been calculated from two methods; 1) using theoretical fits and experimental data in the Z-scan technique, 2) using the strength of nonlinearity curves. The values of β obtained from both of the methods were approximately the same. The results demonstrated that azo dye (ii) displays better nonlinearity and has a lower two-photon absorption threshold than azo dye (i). Calculated parameter related to strength of nonlinearity for azo dye (ii) was higher than azo dye (i), It may be due to presence of methyl in azo dye (ii) instead of chlorine in azo dye (i). Furthermore, The measured values of third order susceptibility of azo dyes were from the order of 10-9 esu . These azo dyes can be suitable candidate for optical switching devices.

  5. Synthesis and cytotoxic potential of heterocyclic cyclohexanone analogues of curcumin. (United States)

    Yadav, Babasaheb; Taurin, Sebastien; Rosengren, Rhonda J; Schumacher, Marc; Diederich, Marc; Somers-Edgar, Tiffany J; Larsen, Lesley


    A series of 18 heterocyclic cyclohexanone analogues of curcumin have been synthesised and screened for their activity in both adherent and non-adherent cancer cell models. Cytotoxicity towards MBA-MB-231 breast cancer cells, as well as ability to inhibit NF-kappaB transactivation in non-adherent K562 leukemia cells were investigated. Three of these analogues 3,5-bis(pyridine-4-yl)-1-methylpiperidin-4-one B1, 3,5-bis(3,4,5-trimethoxybenzylidene)-1-methylpiperidin-4-one B10, and 8-methyl-2,4-bis((pyridine-4-yl)methylene)-8-aza-bicyclo[3.2.1]octan-3-one C1 showed potent cytotoxicity towards MBA-MB-231, MDA-MB-468, and SkBr3 cell lines with EC50 values below 1 microM and inhibition of NF-kappaB activation below 7.5 microM. The lead drug candidate, B10, was also able to cause 43% of MDA-MB-231 cells to undergo apoptosis after 18 h. This level of activity warrants further investigation for the treatment of ER-negative breast cancer and/or chronic myelogenous leukemia as prototypical cellular models for solid and liquid tumors. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  6. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes. (United States)

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia


    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone.

  7. Fusing N-heterocyclic carbenes with carborane anions. (United States)

    El-Hellani, Ahmad; Lavallo, Vincent


    Here we describe the fusion of two families of unusual carbon-containing molecules that readily disregard the tendency of carbon to form four chemical bonds, namely N-heterocyclic carbenes (NHCs) and carborane anions. Deprotonation of an anionic imidazolium salt with lithium diisopropylamide at room temperature leads to a mixture of lithium complexes of C-2 and C-5 dianionic NHC constitutional isomers as well as a trianionic (C-2, C-5) adduct. Judicious choice of the base and reaction conditions allows the selective formation of all three stable polyanionic carbenes. In solution, the so-called abnormal C-5 NHC lithium complex slowly isomerizes to the normal C-2 NHC, and the process can be proton-catalyzed by the addition of the anionic imidazolium salt. These results indicate that the combination of two unusual forms of carbon atoms can lead to unexpected chemical behavior, and that this strategy paves the way for the development of a broad new generation of NHC ligands for catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. [Metabolism and gene regulation of important volatile sulfur compounds in wine--a review]. (United States)

    Ma, Jie; Liu, Yanlin


    Wine microbes can produce volatile sulfur compounds during wine fermentation. The main volatile sulfur compounds found in wine are hydrogen sulfide, sulfides, thiol, thiolesters, sulful-containing fusel alcohols, sulful-containing heterocycles and "fruity volatile thiols". They can affect the wine flavor dramatically. Metabolism pathways and related gene regulations of these compounds are discussed in this review. This review also proposes that research on wine microbes is an effective way to increase concentrations of flavor compounds in wine and inhibit undesirable off-flavor compounds at the same time.

  9. Heterociclos 1,2,3-triazólicos: histórico, métodos de preparação, aplicações e atividades farmacológicas 1,2,3-triazolic heterocycles: history, preparations, applications and pharmacological activities

    Directory of Open Access Journals (Sweden)

    Júlio O. F. Melo


    Full Text Available The 1,2,3-triazole, known since the end of 19th century, is a very widely used heterocyclic system present in many synthetic substances and commercial pharmaceutical compounds. In fact, 1,2,3-triazoles show several applications in many areas especially as medicines against many diseases like cancer, AIDS, Parkinson and Alzheimer. Nowadays there is a large variety of known methods to obtain these heterocyclic compounds comprising mainly three synthetic routes. Nevertheless, there is no article that gives an objective overview of the synthetic methods for obtaining these kinds of azoheterocycles. This paper presents a brief history of this class of compounds, and a synthetic discussion concerning the main synthetic methods for its preparation, such as cyclization through hydrazones, concerted cycloadditon [2+3] and pseudopericyclic cyclization - and some others of restricted application, but also important. Finally, this paper also provides a brief overview on pharmacological applications of some 1,2,3-triazoles.

  10. Coordination chemistry and catalytic activity of N-heterocyclic carbene iridium(I) complexes. (United States)

    Fu, Ching-Feng; Chang, Yung-Hung; Liu, Yi-Hong; Peng, Shei-Ming; Elsevier, Cornelis J; Chen, Jwu-Ting; Liu, Shiuh-Tzung


    Iridium complexes [(CO)2Ir(NHC-R)Cl] (R = Et-, 3a; PhCH2-, 3b; CH3OCH2CH2-, 3c; o-CH3OC6H4CH2-, 3d; NHC: N-heterocyclic carbene) are prepared via the carbene transfer from [(NHC-R)W(CO)5] to [Ir(COD)Cl]2. By using substitution with 13CO, we are able to estimate the activation energy (G) of the CO-exchange in 3a-d, which are in the range of 12-13 kcal mol-1, significantly higher than those for the phosphine analog [(CO)2Ir(PCy3)Cl]. Reactions of 3b and 3d with an equimolar amount of PPh3 result in the formation of the corresponding [(NHC-R)Ir(CO)(PPh3)Cl] with the phosphine and NHC in trans arrangement. In contrast, the analogous reaction of 3a or 3c with phosphine undergoes substitution followed by the anion metathesis to yield the corresponding di-substituted [(NHC-R)Ir(CO)(PPh3)2]BF4 (5) directly. Treatment of 3b or 3d with excess of PPh3 leads to the similar product of disubstitution 5b and 5d. The analysis for the IR data of carbonyliridium complexes provides the estimation of electron-donating power of NHCs versus phosphines. The NHC moiety on the iridium center cannot be replaced by phosphines, even 1,2-bis(diphenylphohino)ethane (dppe). All the carbene moieties on the iridium complexes are inert toward sulfur treatment, indicating a strong interaction between NHC and the iridium centers. Complexes 3a-c are active on the catalysis of the oxidative cyclization of 2-(o-aminophenyl)ethanol to yield the indole compound. The phosphine substituted complexes or analogs are less active.

  11. 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.

  12. 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.

  13. 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.

  14. Asymmetric allylic alkylation in combination with ring-closing metathesis for the preparation of chiral N-heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Zhang, Suyan; Zijl, Anthoni W. van; Slaa, Jan Willem; Minnaard, Adriaan J.; Feringa, Bernard


    Asymmetric copper-catalyzed allylic substitution with methylmagnesium bromide is employed in combination with ring-closing olefin metathesis or ene-yne metathesis to achieve the synthesis of chiral, unsaturated nitrogen heterocycles. The resulting six- to eight-membered chiral heterocycles are

  15. Interaction of Two Water Soluble Heterocyclic Hydrazones on Copper in Nitric Acid: Electrochemical, Surface Morphological, and Quantum Chemical Investigations

    Directory of Open Access Journals (Sweden)

    Vinod P. Raphael


    Full Text Available Two novel heterocyclic compounds (E-2-(1-(pyridin-3-ylethylidenehydrazinecarbothioamide (3APTSC and (E-3-(1-(2-phenylhydrazonoethylpyridine (3APPH derived from 1-(pyridin-3-ylethanone were synthesized and characterized by various spectroscopic techniques. The corrosion inhibition efficacies of these compounds on copper in 0.1 M HNO3 were screened by electrochemical corrosion monitoring techniques such as potentiodynamic polarization studies and impedance spectroscopy. Investigations clearly established that 3APPH displayed higher corrosion inhibition efficiency on Cu than 3APTSC at all concentrations. The mechanism of inhibition was verified with the help of adsorption isotherms. 3APTSC and 3APPH obeyed Langmuir adsorption isotherm on Cu surface. Thermodynamic parameters such as adsorption equilibrium constant (Kads and free energy of adsorption (ΔGads were also evaluated. Potentiodynamic polarization investigations confirmed that the 3APTSC and 3APPH act as mixed type inhibitors. Surface analysis of the metal specimens was performed by scanning electron microscopy. Energy of HOMO and LUMO, their difference, number of electrons transferred, electronegativity, chemical hardness, and so forth were evaluated by quantum chemical studies. Agreeable correlation was observed between the results of quantum chemical calculations and other corrosion monitoring techniques.

  16. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    KAUST Repository

    Li, Shenyu


    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol- 2-ylidene, X = Br, 4a, and X = Cl, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO 2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h-1) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br- destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations. © 2010 American Chemical Society.


    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...

  18. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.


    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  19. 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.

  20. Can creatine supplementation form carcinogenic heterocyclic amines in humans? (United States)

    Pereira, Renato Tavares dos Santos; Dörr, Felipe Augusto; Pinto, Ernani; Solis, Marina Yazigi; Artioli, Guilherme Giannini; Fernandes, Alan Lins; Murai, Igor Hisashi; Dantas, Wagner Silva; Seguro, Antônio Carlos; Santinho, Mirela Aparecida Rodrigues; Roschel, Hamilton; Carpentier, Alain; Poortmans, Jacques Remi; Gualano, Bruno


    There is a long-standing concern that creatine supplementation could be associated with cancer, possibly by facilitating the formation of carcinogenic heterocyclic amines (HCAs). This study provides compelling evidence that both low and high doses of creatine supplementation, given either acutely or chronically, does not cause a significant increase in HCA formation. HCAs detection was unrelated to creatine supplementation. Diet was likely to be the main factor responsible for HCAs formation after either placebo (n = 6) or creatine supplementation (n = 3). These results directly challenge the recently suggested biological plausibility for the association between creatine use and risk of testicular germ cell cancer. Creatine supplementation has been associated with increased cancer risk. In fact, there is evidence indicating that creatine and/or creatinine are important precursors of carcinogenic heterocyclic amines (HCAs). The present study aimed to investigate the acute and chronic effects of low- and high-dose creatine supplementation on the production of HCAs in healthy humans (i.e. 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (8-MeIQx), 2-amino-(1,6-dimethylfuro[3,2-e]imidazo[4,5-b])pyridine (IFP) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx)). This was a non-counterbalanced single-blind crossover study divided into two phases, in which low- and high-dose creatine protocols were tested. After acute (1 day) and chronic supplementation (30 days), the HCAs PhIP, 8-MeIQx, IFP and 4,8-DiMeIQx were assessed through a newly developed HPLC-MS/MS method. Dietary HCA intake and blood and urinary creatinine were also evaluated. Out of 576 assessments performed (from 149 urine samples), only nine (3 from creatine and 6 from placebo) showed quantifiable levels of HCAs (8-MeIQx: n = 3; 4,8-DiMeIQx: n = 2; PhIP: n = 4). Individual analyses revealed that diet rather than creatine supplementation was

  1. A spectral approach to determine location and orientation of azo dyes within surfactant aggregates. (United States)

    Karukstis, Kerry K; Litz, Jonathan P; Garber, Matthew B; Angell, Laura M; Korir, George K


    The UV-vis absorption properties of azo dyes are known to exhibit a variation with the polarity and acidity of the dye environment. The spectral properties of a series of anionic azo dyes were characterized to further probe the interaction of these dyes with two types of surfactant aggregates: (1) the spherical micelles formed in aqueous solution by alkyltrimethylammonium bromide (C(n)TAB) surfactants with n=10-16 and (2) the unilamellar vesicles spontaneously formed in water from binary mixtures of the oppositely-charged double-tailed surfactants cationic didodecyldimethylammonium bromide (DDAB) and anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT). The observed dye spectra reflect the solvatochromic behavior of the dyes and suggest the location and orientation of the dye within the surfactant aggregates. Deconvolution of the overall spectra into sums of Gaussian curves more readily displays any contributions of tautomeric forms of the azo dyes resulting from intramolecular hydrogen bonding. The rich variation in UV/vis absorption properties of these anionic azo dyes supports their use as sensitive tools to explore the nanostructures of surfactant aggregates. Copyright 2010 Elsevier B.V. All rights reserved.


    Bobb, Dolores; Liebes, Dorothy; Salzberg, David A.


    Bobb, Dolores (Palo Alto Medical Research Foundation, Palo Alto, Calif.), Dorothy Liebes, and David A. Salzberg. Effect of azo dyes on growth and metabolism of Neurospora crassa. I. Relative resistance of Neurospora strains to azo dye inhibition. J. Bacteriol. 84:242–249. 1962.—Under conditions where growth factors were not limiting, 3′-methyl-4-monoaminoazobenzene, a rat hepatocarcinogen, inhibited growth of six Neurospora strains studied. The strains could be divided into three groups with regard to sensitivity. A wild-type and a leucine-requiring mutant were the most resistant, and the riboflavine-deficient strain, 51602, showed greatest susceptibility. Results suggested a possible correlation between the inhibition of strain 51602 and the ability of the mutant to synthesize riboflavine from its precursors. Inhibition was not dependent on the utilization of externally supplied riboflavine. The azo dye inhibition of all strains resulted primarily in a prolonged lag phase, although growth rates were affected to some degree. Spore germination did not appear to be retarded. A dose-response curve was developed to measure quantitatively the growth inhibition by azo dyes; it was based on the time required for inhibited and control cultures to reach identical growth weights. PMID:13870285

  3. Reductive decolourisation of azo dyes by mesophilic and thermophilic methanogenic consortia

    NARCIS (Netherlands)

    Cervantes, F.J.; Santos, dos A.B.; Madrid, de M.P.; Stams, A.J.M.; Lier, van J.B.


    The contribution of acidogenic bacteria and methanogenic archaea on the reductive decolourisation of azo dyes was assessed in anaerobic granular sludge. Acidogenic bacteria appeared to play an important role in the decolourising processes when glucose was provided as an electron donor; whereas


    AbstractIn previous papers, the synthesis and chemical properties of iron-complexed azo and formazan dyes were reported. In this regard, it was shown that in certain cases iron could be substituted for the traditionally used metals, chromium and cobalt, without having an adve...

  5. Decolorization of azo dyes by marine Shewanella strains under saline conditions. (United States)

    Liu, Guangfei; Zhou, Jiti; Meng, Xianming; Fu, Shiang Q; Wang, Jing; Jin, Ruofei; Lv, Hong


    Azo dye decolorization was studied with Shewanella strains under saline conditions. Growing cells of Shewanella algae and Shewanella marisflavi isolated from marine environments demonstrated better azo dye decolorization capacities than the other three strains from non-saline sources. Cell suspensions of S. algae and S. marisflavi could decolorize single or mixed azo dyes with different structures. Decolorization kinetics were described with Michaelis-Menton equation, which indicated better decolorization performance of S. algae over S. marisflavi. Lactate and formate were identified as efficient electron donors for amaranth decolorization by the two strains. S. algae and S. marisflavi could decolorize amaranth at up to 100 g L(-1) NaCl or Na2SO4. However, extremely low concentration of NaNO3 exerted strong inhibition on decolorization. Both strains could remove the color and COD of textile effluent during sequential anaerobic-aerobic incubation. Lower concentrations of NaCl (20-30 g L(-1)) stimulated the activities of azoreductase, laccase, and NADH-DCIP reductase. The decolorization intermediates were identified by high-performance liquid chromatography and Fourier transform infrared spectroscopy. Decolorization metabolites of amaranth were less toxic than original dye. These findings improved our knowledge of azo-dye-decolorizing Shewanella species and provided efficient candidates for the treatment of dye-polluted saline wastewaters.

  6. Toxic Effect Of Azo Dyes On Nitrite-N Utilization By Nitrobacter ...

    African Journals Online (AJOL)

    The toxicity of five azo dyes (toxicants) on Nitrobacter was investigated. The index for toxicity was inhibition of rate of nitrite-N utilization. The rate of nitrite-N utilization decreased with increase in concentration of each toxicant at specific exposure time. However, stimulation of utilization was obtained at low concentrations ...

  7. Cancer risk assessment of azo dyes and aromatic amines from garment and footwear

    NARCIS (Netherlands)

    Zeilmaker MJ; Kroese ED; Haperen P van; Veen MP van; Bremmer HJ; Kranen HJ van; Wouters MFA; Janus J; LBM


    A quantitative assessment was performed to estimate the cancer risk to individuals wearing garment and footwear coloured with azo dyes. Basically, the risk assessment consists of both a comparison of the (estimated) level of aromatic amines which, during the wearing of garment and footwear, enters

  8. Thermal Behaviour of Some Azo Dyes Containing Sterically Hindered and Water-Soluble Groups


    KOCAOKUTGEN, Hasan; HEREN, Zerrin


    Thermal behaviour of six azo dyes containing steric hindered groups such as tert-butyl, sec-butyl and isopropyl, were investigated by means of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG). The thermal decomposition points and amount of volatile pyrolysis products, were determined in nitrogen atmosphere using TG, DTA and DTG curves.

  9. Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations (United States)

    Karabacak Atay, Çiğdem; Gökalp, Merve; Kart, Sevgi Özdemir; Tilki, Tahir


    Four new azo dyes: 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A), 2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B), 2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (C) and 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D) which have the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups are synthesized in this work. The structures and spectroscopic properties of these new azo dyes are characterized by using spectroscopic methods such as FT-IR, 1H NMR, 13C NMR and UV-vis. Their solvatochromic properties in chloroform, acetic acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO) are studied. Moreover, molecular structures and some spectroscopic properties of azo dyes are investigated by utilizing the quantum computational chemistry method based on Density Functional Theory (DFT) employing B3LYP hybrid functional level with 6-31G(d) basis set. It is seen that experimental and theoretical results are compatible with each other.

  10. Structure and Second Harmonic Generation of Langmuir-Blodgett Films of Two Chiral Amphiphilic Azo Dyes

    NARCIS (Netherlands)

    Schoondorp, Monique A.; Schouten, Arend Jan; Hulshof, Johannes; Feringa, Ben L.


    The properties and structure of Langmuir-Blodgett films of two new amphiphilic nonlinear optical dyes containing stereogenic (chiral) centers were studied. The dye molecule 4-[[4’-[(3R)-palmitoylpyrrolidin-1-yl]phenyl]azo]-3-nitrobenzoic acid (KZ16) forms homogeneous structures in the plane of the

  11. The effect of cyclic anaerobic-aerobic conditions on biodegradation of azo dyes. (United States)

    Yaşar, Semra; Cirik, Kevser; Cinar, Ozer


    The effect of cyclic anaerobic-aerobic conditions on the biodegradative capability of the mixed microbial culture for the azo dye Remazol Brilliant Violet 5R (RBV-5R) was investigated in the sequencing batch reactor (SBR) fed with a synthetic textile wastewater. The SBR had a 12-h cycle time with anaerobic-aerobic periods of 3/9, 6/6 and 9/3 h. General SBR performance was assessed by measurement of catabolic enzymes (catechol 2,3-dioxygenase, azo reductase), chemical oxygen demand (COD), color and amount of aromatic amines. In this study, under steady-state conditions, the anaerobic period of the cyclic SBR was found to allow the reductive decolorization of azo dye. Longer anaerobic periods resulted in higher color removal efficiencies, approximately 71% for the 3-h, 87% for 6-h and 92% for the 9-h duration. Total COD removal efficiencies were over 84% under each of the cyclic conditions and increased as the length of the anaerobic period was increased; however, the highest color removal rate was attained for the cycle with the shortest anaerobic period of 3 h. During the decolorization of RBV-5R, two sulfonated aromatic amines (benzene based and naphthalene based) were formed. Additionally, anaerobic azo reductase enzyme was found to be positively affected with the increasing duration of the anaerobic period; however; it was vice versa for the aerobic catechol 2,3-dioxygenase (C23DO) enzyme.

  12. Preparation and characterization of high-transmittance AZO films using RF magnetron sputtering at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jian [College of Materials and Chemical Engineering, Collaborative Innovation Center for Energy Equipment of Three Gorges Region, China Three Gorges University, Yichang 443002 (China); Sun, Yihua, E-mail: [College of Materials and Chemical Engineering, Collaborative Innovation Center for Energy Equipment of Three Gorges Region, China Three Gorges University, Yichang 443002 (China); Lv, Xin; Li, Derong [Glass Industry Engineering Research Center of Hubei Province, Hubei Sanxia New Building Materials Co., Ltd., Dangyang 444105 (China); Fang, Liang; Wang, Hailin; Sun, Xiaohua; Huang, Caihua; Yu, Haizhou; Feng, Ping [College of Materials and Chemical Engineering, Collaborative Innovation Center for Energy Equipment of Three Gorges Region, China Three Gorges University, Yichang 443002 (China)


    Highlights: • We prepared the AZO thin films on soda-lime glass without the substrate heated. • High-transmittance AZO films had been obtained by RF magnetron sputtering using a ceramic target. • The minimum resistivity of 2.55 × 10{sup −3} Ω cm combined with highest transmittance of 91% was obtained at a sputtering power of 400 W. • The resistivity decreased and transmittance improved with the sputtering power increase. - Abstract: Aluminum-doped zinc oxide (AZO) thin films with 250 nm thickness had been prepared on soda-lime glass substrate without heated by RF magnetron sputtering using a ceramic target. The microstructure, surface morphology, electrical and optical properties of AZO thin films had been investigated by X-ray diffraction, scanning electron microscope, four-point probe method and optical transmission spectroscopy. The results indicated that all of the films obtained were polycrystalline with a hexagonal structure and oriented with the c-axis perpendicular to the substrate. The resistivity decreased and transmittance improved with the sputtering power increase. The minimum resistivity of 2.55 × 10{sup −3} Ω cm combined with highest transmittance of 91% was obtained at a sputtering power of 400 W. The optical bandgap at different sputtering power varied among 3.81–4.04 eV.

  13. Inhibition of corrosion of mild steel in hydrochloric acid by some azo ...

    African Journals Online (AJOL)

    Inhibition of corrosion of mild steel in hydrochloric acid by some azo dyes. EE Ebenso. Abstract. No Abstract. Nigerian Journal of Chemical Research Vol. 6 2001: 8-12. Full Text: EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. Article Metrics. Metrics Loading ... Metrics ...

  14. Adsorption of direct black-38 azo dye on p-tert-butylcalix[6]arene immobilized material

    Directory of Open Access Journals (Sweden)

    Muhammad Afzal Kamboh


    Full Text Available The present study demonstrates the adsorption of the direct black-38 (DB-38 azo dye on potential and newly synthesized p-tert-butylcalix[6]arene based silica resin (4. Resin 4 was synthesized via the modification of pure silica 1 as 2 followed by the immobilization of p-tert-butylcalix[6]arene (3 onto modified silica (2. It was characterized by using different analytical techniques such as FT-IR, scanning electron microscopy (SEM and thermo gravimetric analysis (TGA. The effect of adsorbent dosage, pH and the electrolyte effect on the removal of the DB-38 azo dye were evaluated through batch wise adsorption experiments. Maximum adsorption of 91% was achieved at pH 9.0. The textile wastewater samples were used to ensure the field applicability of the newly synthesized adsorbent 4 for the treatment of dye contaminated effluents. All results regarding the removal of the DB-38 azo dye from the aqueous environment prop up resin 4 as an effective adsorbent and it was found that resin 4 has high adsorption efficiency toward the DB-38 azo dye at a wide range of pH as compared to 1 and 2.

  15. 40 CFR 721.1555 - Substituted phenyl azo substituted benzenediazonium salt. (United States)


    ... benzenediazonium salt. 721.1555 Section 721.1555 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... generically as a substituted phenyl azo substituted benzenediazonium salt (PMN P-92-652) is subject to... this part apply to this section except as modified by this paragraph. (1) Recordkeeping. Recordkeeping...

  16. Facile synthesis of 1-naphthol azo dyes with nano SiO 2 /HIO 4 ...

    African Journals Online (AJOL)

    Nano-silica supported periodic acid (nano-SPIA) has been utilized as a heterogeneous reagent for a highly efficient and one pot synthesis of azo dyes based on 1-naphthol under solvent-free conditions at room temperature. This method has some advantages, the reaction workup is very easy and the catalyst can be easily ...

  17. Photoelectric and passivation properties of atomic layer deposited gradient AZO thin film (United States)

    Zhao, Bin; Tang, Li-dan; Wang, Bing; Jia, Yi; Feng, Jia-heng


    Gradient Al-doped ZnO (AZO) thin films were deposited at 150 °C by atomic layer deposition (ALD) with different Al concentration gradient, and their photoelectric and passivation properties were investigated. With increasing Al concentration gradient from 0.09 to 1.21%/nm, Hall-effect showed that the resistivity of gradient AZO thin films deteriorates. The minimal resistivity (2.81 × 10-3 Ω cm), the maximum mobility (9.03 cm2/Vs) and the maximum carrier concentration (2.46 × 1020 cm-3) were obtained at 0.09%/nm Al concentration gradient. The average transmittance of all the gradient AZO films can be more than 85% in the visible region. In addition, gradient AZO thin films demonstrated excellent passivation properties. The maximum minority carrier lifetime (120.6 μs) and the minimal surface recombination velocity (≤208.3 cm/s) were obtained at 0.71%/nm Al concentration gradient.


    Directory of Open Access Journals (Sweden)

    Is Fatimah


    Full Text Available Dalam penelitian ini dilakukan preparasi material Fe3+/TiO2-Montmorillonit dan uji aktivitasnya sebagai katalis pada degradasi senyawa azo. Keberhasilan preparasi material dipelajari melalui karakterisasi menggunakan X-ray Diffraction, BET surface area analyzer dan Diffuse Reflectance UV-Visible. Peranan katalitik material hasil preparasi pada degradasi senyawa azo: metil jingga(MO dan metilena biru(MB dipelajari melalui studi kinetika reaksi dengan mekanisme mirip foto-Fenton (Photo-Fenton like mechanism. Hasil penelitian menunjukkan keberhasilan preparasi material Fe3+/TiO2-Montmorillonit serta tercapainya tujuan penggunaannya sebagai katalis untuk degradasi zat warna azo melalui mekanisme Photo-Fenton like. Simulasi terhadap data kinetika menunjukkan bahwa degradasi kedua zat warna azo dengan katalis hasil preparasi mengikuti  model kinetika Langmuir-Hinshelwood dengan nilai k dan K untuk MO berturut-turut adalah sebesar 8,83x10-7 M/detik dan 328,29 dan untuk MB sebesar 4,56x10-5 M dan 555,60. Nilai konstanta laju reaksi dan konstanta adsorpsi-desorpsi reaksi degradasi kedua zat warna menjelaskan peranan mekanisme interaksi permukaan dalam proses katalisis.

  19. Reduction of azo dyes by flavin reductase from Citrobacter freundii A1

    Directory of Open Access Journals (Sweden)

    Mohd Firdaus Abdul-Wahab


    Full Text Available Citrobacter freundii A1 isolated from a sewage treatment facility was demonstrated to be able to effectively decolorize azo dyes as pure and mixed culture. This study reports on the investigation on the enzymatic systems involved. An assay performed suggested the possible involvement of flavin reductase (Fre as an azo reductase. A heterologouslyexpressed recombinant Fre from C. freundii A1 was used to investigate its involvement in the azo reduction process. Three model dyes were used, namely Acid Red 27 (AR27, Direct Blue 15 (DB15 and Reactive Black 5 (RB5. AR27 was found to be reduced the fastest by Fre, followed by RB5, and lastly DB15. Redox mediators nicotinamide adenine dinucleotide (NADH and riboflavin enhance the reduction, suggesting the redox activity of the enzyme. The rate and extent of reduction of the model dyes correlate well with the reduction potentials (Ep. The data presented here strongly suggest that Fre is one of the enzymes responsible for azo reduction in C. freundii A1, acting via an oxidation-reduction reaction.

  20. Microstructure and Electrical Properties of AZO/Graphene Nanosheets Fabricated by Spark Plasma Sintering


    Yang, Shuang; Chen, Fei; Shen, Qiang; Enrique J. Lavernia; Zhang, Lianmeng


    In this study we report on the sintering behavior, microstructure and electrical properties of Al-doped ZnO ceramics containing 0?0.2 wt. % graphene sheets (AZO-GNSs) and processed using spark plasma sintering (SPS). Our results show that the addition of

  1. Photocatalytic oxidation of a reactive azo dye and evaluation of the ...

    African Journals Online (AJOL)

    The purpose of this study was to investigate the photocatalytic oxidation of a reactive azo dye and determine the improvement in the biodegradability when photocatalytic oxidation was used as a pretreatment step prior to biological treatment. The results obtained from the experiments adding H2O2/TiO2 show that the ...

  2. An experimental study on relationship between hammett substituent constant and electronic absorption wavelength of some azo dyes


    Sidir, Yadigar Gülseven; Sidir, Isa; Berber, Halil; Tasal, Erol


    In this study, absorption spectra of sixteen azo dyes have been recorded in various solvents. These azo dyes have substituents such as OH, SO3H, Cl, I, NO2, C2H5 and OCH3 in different positions of phenyl ring. There is a shift in ?max whose amount is dependent upon the type and position of substituent on the ring. The effects of substituent on the absorption spectra of azo dyes are interpreted by correlation of absorption maximum wavelengths (nm) with the hammett substituent parameters. Charg...

  3. All-optical switchable holographic Fresnel lens based on azo-dye-doped polymer-dispersed liquid crystals. (United States)

    Jashnsaz, Hossein; Nataj, Nahid Hosain; Mohajerani, Ezeddin; Khabbazi, Amir


    Fabrication of an all-optical switchable holographic liquid crystal (LC) Fresnel lens based on azo-dye-doped polymer-dispersed LCs is reported using a Michelson interferometer. It is found that, upon circularly polarized photoirradiation, the diffraction efficiency of the fabricated Fresnel lens was increased significantly in a reversible manner. We believe this is due to the anisotropy induced by reorientation of the LC molecules coupled with azo-dye molecule orientation due to trans-cis-trans photoisomerization, which modulates the refractive index of the LC-rich regions. We also studied the effect of azo dye on the polarization dependency of the fabricated lens.

  4. Synthesis, characterization and antimicrobial activities of mixed ligand transition metal complexes with isatin monohydrazone Schiff base ligands and heterocyclic nitrogen base (United States)

    Devi, Jai; Batra, Nisha


    Mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with various uninegative tridentate ligands derived from isatin monohydrazone with 2-hydroxynapthaldehyde/substituted salicylaldehyde and heterocyclic nitrogen base 8-hydroxyquinoline have been synthesized and characterized by elemental analysis, conductometric studies, magnetic susceptibility and spectroscopic techniques (IR, UV-VIS, NMR, mass and ESR). On the basis of these characterizations, it was revealed that Schiff base ligands existed as monobasic tridentate ONO bonded to metal ion through oxygen of carbonyl group, azomethine nitrogen and deprotonated hydroxyl oxygen and heterocyclic nitrogen base 8-hydroxyquinoline existed as monobasic bidentate ON bonded through oxygen of hydroxyl group and nitrogen of quinoline ring with octahedral or distorted octahedral geometry around metal ion. All the compounds have been tested in vitro against various pathogenic Gram positive bacteria, Gram negative bacteria and fungi using different concentrations (25, 50, 100, 200 μg/mL) of ligands and their complexes. Comparative study of antimicrobial activity of ligands, and their mixed complexes indicated that complexes exhibit enhanced activity as compared to free ligands and copper(II) Cu(LIV)(Q)ṡH2O complex was found to be most potent antimicrobial agent.

  5. Discovery of the aryl heterocyclic amine insecticides: synthesis, insecticidal activity, field results, mode of action and bioavailability of a leading field candidate. (United States)

    Dent, William H; Pobanz, Mark A; Geng, Chaoxian; Sparks, Thomas C; Watson, Gerald B; Letherer, Theodore J; Beavers, Kenneth W; Young, Cathy D; Adelfinskaya, Yelena A; Ross, Ronald R; Whiteker, Greg; Renga, James


    γ-Amino butyric acid (GABA) antagonists are proven targets for control of lepidopteran and other pests. New heterocyclic compounds with high insecticidal activity were discovered using a competitive-intelligence-inspired scaffold-hopping approach to generate analogs of fipronil, a known GABA antagonist. These novel aryl heterocyclic amines (AHAs) displayed broad-spectrum activity on a number of chewing insect pests. Through >370 modifications of the core AHA structure, a 7-pyrazolopyridine lead molecule was found to exhibit much improved activity on a number of insect pests. In field trial studies, its performance was 2-4 times lower than commercial standards and also appeared to be species dependent, with good activity seen for larvae of Spodoptera exigua, but inactivity on larvae of Trichoplusia ni. An extensive investigational biology effort demonstrated that these AHA analogs appear to have multiple modes of action, including GABA receptor antagonism and mitopotential or uncoupler activity. The limited capability in larvae of T. ni to convert the lead molecule to its associated open form correlates with the low toxicity of the lead molecule in this species. This work has provided information that could aid investigations of novel GABA antagonists. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  6. Kinetics of azoreductase and assessment of toxicity of metabolic products from azo dyes by Pseudomonas luteola. (United States)

    Hu, T L


    This is a continuous study on a decolorization strain, Pseudomonas luteola, which involves treating seven azo dyes with different structures. This study focuses mainly on determining both the mechanism of decolorization by P. luteola and the activity of azoreductase from P. luteola as well as identifying and assessing the toxicity of metabolic products of azo dyes. The growth of P. luteola reached the stationary phase after shaking incubation for 24 hours. Then, while being kept static, the color of seven tested azo dyes (100 mg/l) could be removed. The proportion of color removal was between 59-99%, which figure is related to the structure of the dye. Monoazo dyes (RP2B, V2RP and Red 22) showed the fastest rate of decolorization, i.e. from 0.23-0.44 mg dye-mg cell-1 hr-1. P. luteola could remove the color of V2RP and a leather dye at a concentration of 200 mg/l, and as to the rest of the azo dyes, it could remove at a concentration of up to 100 mg/l. Decolorization of RP2B and Red 22 required activation energy of 7.00 J/mol and 6.63 J/mole, respectively, indicating that it was easier for azoreductase to decolorize structurally simple dyes. The kinetics of azoreductase towards seven azo dyes suggested a competitive inhibition model be applied. Microtox was used to analyze the toxicity of the metabolic products of azo dyes. EC50 showed differences in toxicity before and after the azo dyes had been metabolized. Analysis revealed significant differences between the results obtained by EC50 with Blue 15 and those obtained with the leather dye, indicating that the toxicities of the metabolic products were increased. The differences obtained by EC50 with Red 22, RP2P and V2RP were small, and Black 22 showed no such difference. Sulfanic acid and orthanilic acid may be the intermediate products of Violet 9 and RP2B, respectively. However, according to FT-IR analysis, aromatic amines were present in the metabolic product.

  7. Z-scan measurements of the third-order optical nonlinearities and vibrational spectral studies by DFT computations on azo dye 1-(2-Methylphenylazo)-2-napthol (United States)

    Sreenath, M. C.; Mathew, S.; Hubert Joe, I.; Rastogi, V. K.


    The nonlinear optical properties of azo dye 1-(2-Methylphenylazo)-2-napthol have been studied. The complete vibrational features and electronic absorption spectra of the title compound were analyzed by FT-IR, FT-Raman and UV-visible spectra combined with density functional theory and time-dependent density functional computations respectively. Nonlinear optical behavior was investigated by calculating the second-order hyperpolarizablity at DFT level. Third-order nonlinear optical parameters of 1-(2-Methylphenylazo)-2-napthol were measured using closed and open aperture Z-scan technique. The Z-scan result confirms, the dye exhibit self-focusing effect and the sign of the refractive nonlinearity is positive. The nonlinear refractive index (n2), nonlinear absorption coefficient (β), real and imaginary parts of third-order susceptibility (χ (3)) and second-order hyperpolarizability (γ) are calculated. The calculated results indicated that 1-(2-Methylphenylazo)-2-napthol have potential applications in optoelectronics and photonics.

  8. Synthesis and characterization of near-IR absorbing metal-free and zinc(II phthalocyanines modified with aromatic azo groups

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    Mukaddes Özçeşmeci


    Full Text Available Metal-free and zinc(II phthalocyanine complexes bearing peripheral (E-4-((2-hydroxynaphthalen-1-yldiazenyl units have been synthesized. Novel phthalonitrile derivative required for the preparation of phthalocyanine complexes was prepared by coupling 4-aminophthalonitrile and 2-naphthol. The structures of these new compounds were characterized by using elemental analyses, proton nuclear magnetic resonance, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, fluorescence spectroscopy and mass spectrometry. In the UV-Vis spectra a broad absorption band appears for phthalocyanine complexes at around 450–500 nm resulting from azo-group introduced onto the phthalocyanine ring. The photophysical properties of metal-free and zinc(II phthalocyanines were studied in tetrahydrofuran.

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

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    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.

  10. 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.

  11. Olefin Metathesis With Ruthenium-Arene Catalysts Bearing N-Heterocyclic Carbene Ligands (United States)

    Delaude, Lionel; Demonceau, Albert

    In this chapter, we summarize the main results of our investigations on the ring-opening metathesis polymerization (ROMP) of cyclooctene catalyzed by various ruthenium (Ru)-arene complexes bearing imidazolin-2-ylidene, imidazolidin- 2-ylidene, or triazolin-5-ylidene ligands. Three major findings emerged from this study. First, we underscored the intervention of a photochemical activation step due to visible light illumination. Second, we established that the presence of an endocyclic double bond in the carbene ligand central heterocycle was not crucial to achieve high catalytic efficiencies. Third, we demonstrated that ortho-metallation of the N-heterocyclic carbene (NHC) ligand by the Ru center led to inactive catalysts.

  12. Genetically modified CHO cells for studying the genotoxicity of heterocyclic amines from cooked foods

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.H.; Wu, R.W.; Felton, J.S.


    We have developed metabolically competent CHO cells to evaluate the genotoxicity associated with heterocyclic amines, such as those that are present in cooked foods. Into repair-deficient UV5 cells we introduced cDNAs for expressing cytochrome P450IA2 and acetyltransferases. We then genetically reverted these transformed lines to obtain matched metabolically competent repair-deficient/proficient lines. For a high mutagenic response, we find a requirement for acetyltransferase with IQ but not with PhIP. This system allows for both quantifying mutagenesis and analyzing the mutational spectra produced by heterocyclic amines.

  13. Hyperpolarizabilities of hetero-cycle based chromophores: A semi-quantitative SOS scheme (United States)

    Nandi, P. K.; Panja, N.; Kar, T.


    The static first- and second-hyperpolarizabilities of isomeric hetero-cycle based chromophores have been calculated by using the CPHF and MP2 methods. A semi-quantitative scheme in the framework of sum-over-state (SOS) has been proposed to explain the variation of hyperpolarizabilities in terms of ground state electric properties. The hyperpolarizabilities calculated using this scheme correlate fairly with the corresponding MP2 values. Electron correlation effect, in general, appreciably enhances the hyperpolarizabilities. The rather larger enhancement of NLO responses of twisted intramolecular charge transfer (TICT) molecule arises from its sudden polarized ground state. Among the chosen hetero-cycles borrole leads to exceptionally large non-linearity.

  14. 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.

  15. Surface active properties and biological activity of novel nonionic surfactants containing pyrimidines and related nitrogen heterocyclic ring systems

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    El-Sayed, R.


    Full Text Available A series of annelated pyrimidine derivatives has been synthesized via different heterocyclization reactions of suitably functionalized 6-(4-octadecyloxyphenyl-4-oxo-2- thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile (4 with different electrophiles and nucleophiles. These heterocycles bear an active hydrogen atom (NH, OH or COOH which could be propoxylated using propylene oxide with different moles, 5, 10 and 15, to produce nonionic surfactant having a long alkyl chain with molecular weight suitable for becoming an amphiphilic molecule with correct hydrophilic-lypophilic balance which enhances solubility, biodegradability and hence lowers the toxicity to human beings and becomes environmentally friendly. In addition, the antimicrobial activities of these compounds were screened and it was found that some of these compounds have similar or higher activity compared with commercial antibiotic drugs (sulphadiazine, which make them suitable for diverse applications like the manufacturing of drugs, pesticides, emulsifiers, cosmetics, etc.Una serie de derivados pirimidínicos y relacionados han sido preparados vía diferentes reacciones de formación de heterociclos entre 6-(4-octadeciloxifenil-4-oxo-2-tioxo- 1,2,3,4-tetrahidropirimidina-5-carbonitrilo (4 y diferentes electrófilos y nucleófilos. Estos heterociclos tienen un átomo de hidrógeno activo (NH, OH, o COOH que fue propoxilado con diferentes moles de óxido de propileno (5, 10, o 15 para producir surfactantes no iónicos con una cadena alquílica larga y peso molecular apropiado para convertirse en una molécula anfifílica con un balance hidrofílico-lipofílico correcto que aumenta la solubilidad y la biodedradabilidad, decrece la toxicidad a los seres humanos, y se convierte en respetuoso con el medio ambiente. Además, las actividades antimicrobianas de estos compuestos fueron determinadas y se encontró que algunos de estos compuestos tuvieron una actividad similar o más alta que

  16. Biosurfactant production from Pseudomonas taiwanensis L1011 and its application in accelerating the chemical and biological decolorization of azo dyes. (United States)

    Liu, Cong; You, Yanting; Zhao, Ruofei; Sun, Di; Zhang, Peng; Jiang, Jihong; Zhu, Aihua; Liu, Weijie


    Dye dispersion and the interaction efficiency between azoreductases and dye molecules are rate-limiting steps for the decolorization of azo dyes. In this study, a biosurfactant-producing strain, Pseudomonas taiwanensis L1011, was isolated from crude oil. To increase the yield of the biosurfactant BS-L1011 from P. taiwanensis L1011, culture conditions were optimized including temperature, initial pH, carbon source, nitrogen source and C/N ratio. A maximum yield of 1.12g/L of BS-L1011 was obtained using D-mannitol as carbon source and yeast extract/urea as compound nitrogen source with C/N ratio of 10/4, pH 7.0 and 28°C. BS-L1011 exhibited a low critical micelle concentration (CMC) of 10.5mg/L and was able to reduce the surface tension of water to 25.8±0.1 mN/m. BS-L1011 was stable over a wide range of temperatures, pH values and salt concentrations. The biosurfactant is reported for the first time to accelerate chemical decolorization of Congo red by sodium hypochlorite, and biological decolorization of Amaranth by Bacillus circulans BWL1061, thus showing a potential in the treatment of dyeing wastewater. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Binding patterns and structure-affinity relationships of food azo dyes with lysozyme: a multitechnique approach. (United States)

    Peng, Wei; Ding, Fei; Peng, Yu-Kui; Jiang, Yu-Ting; Zhang, Li


    Food dyes serve to beguile consumers: they are often used to imitate the presence of healthful, colorful food produce such as fruits and vegetables. But considering the hurtful impact of these chemicals on the human body, it is time to thoroughly uncover the toxicity of these food dyes at the molecular level. In the present contribution, we have examined the molecular reactions of protein lysozyme with model food azo compound Color Index (C.I.) Acid Red 2 and its analogues C.I. Acid Orange 52, Solvent Yellow 2, and the core structure of azobenzene using a combination of biophysical methods at physiological conditions. Fluorescence, circular dichroism (CD), time-resolved fluorescence, UV-vis absorption as well as computer-aided molecular modeling were used to analyze food dye affinity, binding mode, energy transfer, and the effects of food dye complexation on lysozyme stability and conformation. Fluorescence emission spectra indicate complex formation at 10(-5) M dye concentration, and this corroborates time-resolved fluorescence results showing the diminution in the tryptophan (Trp) fluorescence mainly via a static type (KSV = 1.505 × 10(4) M(-1)) and Förster energy transfer. Structural analysis displayed the participation of several amino acid residues in food dye protein adducts, with hydrogen bonds, π-π and cation-π interactions, but the conformation of lysozyme was unchanged in the process, as derived from fluorescence emission, far-UV CD, and synchronous fluorescence spectra. The overall affinity of food dye is 10(4) M(-1) and there exists only one kind of binding domain in protein for food dye. These data are consistent with hydrophobic probe 8-anilino-1-naphthalenesulfonic acid (ANS) displacement, and molecular modeling manifesting the food dye binding patch was near to Trp-62 and Trp-63 residues of lysozyme. On the basis of the computational analyses, we determine that the type of substituent on the azobenzene structure has a powerful influence on the

  18. Bi-layer Channel AZO/ZnO Thin Film Transistors Fabricated by Atomic Layer Deposition Technique. (United States)

    Li, Huijin; Han, Dedong; Liu, Liqiao; Dong, Junchen; Cui, Guodong; Zhang, Shengdong; Zhang, Xing; Wang, Yi


    This letter demonstrates bi-layer channel Al-doped ZnO/ZnO thin film transistors (AZO/ZnO TFTs) via atomic layer deposition process at a relatively low temperature. The effects of annealing in oxygen atmosphere at different temperatures have also been investigated. The ALD bi-layer channel AZO/ZnO TFTs annealed in dry O2 at 300 °C exhibit a low leakage current of 2.5 × 10-13A, I on/I off ratio of 1.4 × 107, subthreshold swing (SS) of 0.23 V/decade, and high transmittance. The enhanced performance obtained from the bi-layer channel AZO/ZnO TFT devices is explained by the inserted AZO front channel layer playing the role of the mobility booster.

  19. Synthesis and antimicrobial activity of some novel fused heterocyclic 1,2,4-triazolo [3,4-b][1,3,4] thiadiazine derivatives

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    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.

  20. 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.