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Sample records for active methyl tert-butyl

  1. Estimation of the fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

    2008-01-01

    The fraction of biologically active methyl tert-butyl ether degraders in reactors is just as important for prediction of removal rates as knowledge of the kinetic parameters. The fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample, taken from a packed...... bed reactor, was determined using a batch kinetic based approach. The procedure involved modeling of methyl tert-butyl ether removal rates from batch experiments followed by parameter estimations. It was estimated to be 5-14% (w/w) of the measured volatile suspended solids concentration in the reactor....

  2. Methyl tert-butyl ether (MTBE) degradation by ferrous ion-activated persulfate oxidation: feasibility and kinetics studies.

    Science.gov (United States)

    Chen, K F; Kao, C M; Wu, L C; Surampalli, R Y; Liang, S H

    2009-07-01

    The objective of this study was to evaluate the feasibility of using ferrous ion-activated persulfate oxidation to remediate groundwater contaminated with methyl tert-butyl ether (MTBE). In this study, batch experiments were conducted to evaluate the effects of various factors on the efficiency of MTBE degradation including persulfate concentrations, ferrous ion concentrations, and persulfate coupled with hydrogen peroxide. Results show that ferrous ion-activated persulfate oxidation was capable of degrading MTBE efficiently. Persulfate and ferrous ion concentrations correlated with MTBE degradation rates. However, excess addition of ferrous ion resulted in decreased MTBE degrading rates most likely because of competition for sulfate free radicals between ferrous ion and MTBE. Two main byproducts of MTBE degradation, tert-butyl formate and tert-butyl alcohol, were detected in the experiments; both were, however, subsequently degraded. Results of sulfate analysis show that proper addition of ferrous ion could prevent unnecessary persulfate decomposition.

  3. Impact of activation methods on persulfate oxidation of methyl tert-butyl ether.

    Science.gov (United States)

    Deng, Dayi; Peng, Libin; Guan, Mengyun; Kang, Yuan

    2014-01-15

    To provide guidance on the selection of proper persulfate processes for the remediation of MTBE contaminated groundwater, MTBE aqueous solutions were treated with three common field persulfate processes including heat activated persulfate, Fe(III)-EDTA activated persulfate and alkaline persulfate, respectively. The results were compared with MTBE oxidation by Fenton's reagent and persulfate alone at 25°C. The impact of the activating conditions on the fate of MTBE and its daughter products was investigated. Heat activation at 40°C offered the most rapid removal of MTBE and its daughter products, while Fe(III)-EDTA activation showed higher efficiency of MTBE removal but low removal efficiency of its daughter products. On the other hand, alkaline persulfate showed slower kinetics for the removal of MTBE and less accumulation of the daughter products. Furthermore, tert-butyl alcohol and acetone were observed as the main purgeable daughter products along with a small amount of tert-butyl formate in persulfate oxidation of MTBE, while tert-butyl formate, tert-butyl alcohol and acetone were the main products in Fenton oxidation. Mechanistic analysis suggests that degradation of MTBE by persulfate most likely happens via non-oxygen demand pathways, different from the dominant oxygen demand degradation pathways observed in Fenton oxidation. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Adsorption of methyl tert-butyl ether using granular activated carbon : equilibrium and kinetic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Chen, D.Z.; Chen, J.M. [Zhejiang Univ. of Technology, Hangzhou (China). College of Biological and Environmental Engineering; Zhang, J.X. [Yuhuan County Environmental Protection Bureau, Yuhuan (China)

    2010-04-01

    Methyl tert-butyl ether (MTBE) is used in gasoline as a replacement for lead in order to promote combustion efficiency. However, MTBE is one of the most frequently detected underground water pollutants caused by leaks in underground fuel storage tanks, and has been classified as a potential human carcinogen. This study investigated that adsorption of MTBE through a granular activated carbon filter. Pseudo-first order, pseudo-second order equation and intraparticle diffusion equation kinetic models were used to predict the constant rate of adsorption. The study showed that the pseudo-second order model accurately described the adsorption kinetics for the removal of MTBE from an aqueous solution onto granular activated carbon. The Lagergren first-order rate constant k{sub 1} and the pseudo-second order rate constant k{sub 2} decreased with initial increases of MTBE. A Boyd plot was used to demonstrate that external mass transfer is the principal rate-limiting step during the initial stages of adsorption. Results of the study indicated that granular activated carbon is an effective adsorbent for MTBE. 34 refs., 2 tabs., 7 figs.

  5. An efficient and highly selective ortho-tert-butylation of p-cresol with methyl tert-butyl ether catalyzed by sulfonated ionic liquids

    Directory of Open Access Journals (Sweden)

    Alamdari Reza Fareghi

    2014-01-01

    Full Text Available A novel series of sulfonic acid-functionalized ionic liquids (SFILs was found to act as efficient catalysts for ortho-tert-butylation of p-cresol with methyl tert-butyl ether (MTBE as the tert-butylating agent without an added solvent. The mono o-tert-butylated product was obtained in up to 80.4% isolated yield and 95.2% selectivity under such green conditions. No O-tert-butylated byproducts were formed.

  6. Antichaperone activity and heme degradation effect of methyl tert-butyl ether (MTBE) on normal and diabetic hemoglobins.

    Science.gov (United States)

    Najdegerami, Ismaeil Hossein; Maghami, Parvaneh; Sheikh-Hasani, Vahid; Hosseinzadeh, Ghader; Sheibani, Nader; Moosavi-Movahedi, Ali A

    2017-05-01

    Because of the extensive use of methyl tert-butyl ether (MTBE) as an additive to increase the octane quality of gasoline, the environmental pollution by this compound has increased in recent decades. Environmental release of MTBE may lead to its entry to the blood stream through inhalation or drinking of contaminated water, and its interactions with biological molecules such as proteins. The present study was proposed to comparatively investigate the interactions of MTBE with hemoglobin (Hb) from diabetic and nondiabetic individuals using various spectroscopic methods including UV-visible, fluorescence, chemiluminescence, and circular dichroism. These results demonstrated the effects of MTBE on heme degradation of Hb and the reaction of these degradation products with water generating reactive oxygen species. Interaction of Hb with MTBE enhanced its aggregation rate and decreased lag time, indicating the antichaperone activity of MTBE upon interaction with Hb. Furthermore, the diabetic Hb showed more severe effects of MTBE, including heme degradation, reactive oxygen species production, unfolding, and antichaperone behavior than the nondiabetic Hb. The results from molecular docking suggested that the special interaction site of MTBE in the vicinity of Hb heme group is responsible for heme degradation. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Anaerobic biodegradation of methyl tert-butyl ether and tert-butyl alcohol in petrochemical wastewater.

    Science.gov (United States)

    Ghasemian, Mohammad; Amin, Mohammad Mehdi; Morgenroth, Eberhard; Jaafarzadeh, Neemat

    2012-09-01

    A laboratory-scale anaerobic sequencing batch reactor was used to evaluate treatment of a synthetic substrate mixture representing petrochemical wastewater containing methyl tert-butyl ether (MTBE), ethanol and acetic acid. Influent MTBE concentrations were 5, 10 and 50 mg/l (corresponding to MTBE loading rates of 0.2, 0.4 and 2 mg/l.d) with overall organic loading rates (OLRs) of 1.51, 3.23 and 3.25 g COD/1.d, respectively. These OLRs resulted in removal efficiencies for MTBE of 78%, 98% and 88%. Removal efficiencies for chemical oxygen demand were 85% and 90% with influent MTBE concentrations of 5 and 10mg/l, but were significantly reduced to 72% with influent MTBE concentrations of 50mg/l. During all reactor runs, effluent concentrations oftert-butyl alcohol (TBA) were below the detection limit. Batch degradation of the organic substrate mixture demonstrated initial inhibitory effects when exposed to MTBE concentrations of 50 mg/l and complete inhibition with MTBE concentrations above 2000 mg/l. It is interesting to note that in batch tests using MTBE as the sole organic substrate (initial MTBE concentrations of 50, 100 and 200 mg/l), the specific methanogenic activity decreased to below detection within the first 96 hours, but following a 72-hour lag phase the methane production increased again. Based on low volatile fatty acid (VFA) concentration, disappearance of TBA peaks and no findings of any other intermediate via gas chromatography/mass spectrometry, while the MTBE concentration is still high, it can be suggested that during the batch tests the breakdown of gas production and the following lag phase were the direct effect of higher MTBE concentrations (more than 50 mg/l) and not because of the TBA or VFA accumulations.

  8. EFFECTS OF STIMULATOR SUBSTANCES ON AEROBIC METHYL TERT-BUTYL ETHER BIODEGRADATION BY MICROBIAL CONSORTIUM

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    M. Farrokhi ، S. Ahmadizad

    2009-04-01

    Full Text Available In this study dissolved humic substances and yeast extract were tested in different concentrations for enhancing methyl tert-butyl ether mineralization by isolated microorganisms from a variety of sources. All experiments were conducted at a constant temperature of 25ºC. Vials of 50 mL and 125 mL volume sealed with Teflon-lined Mini-Nert caps was used for microcosm experiments. In all experiments 1% sodium azide were used as control. Samples of bacterial cultures that metabolize methyl tert-butyl ether have been analysed by direct GC analysis using flame ionization detector. Cultures able to metabolize have been found in activated sludge and soils. These microorganisms weregram-positive bacterium. An aerobic microbial consortium was enriched in laboratory for four months. Methyl tert-butyl ether has been shown to biodegrade under aerobic and co-metabolic conditions. A microbial consortium isolated from activated sludges was identified as Cocobacillus. The concentration of the initial attached biomass was about 0.11 g/L of dry weight. The maximum mineralization rate and beneficial effects of stimulator substances on aerobic biodegradation of methyl tert-butyl ether occurred with the culture by combined concentrations of 500 mg/L of yeast extract and 20 mg/L of peat humic growth support of microbial consortium within 216 h and in presence of high oxygen levels and well mixing conditions. It was shown that adding, peat humic and yeast extract together, had better stimulatory effect on methyl tert-butyl ether biodegradation. Results clearly showed a stimulatory effect on methyl tert-butyl ether consumption higher than 20%. Consortium was capable of degrading concentrations of ≤1000 mg/L, whereas concentrations of >1000 mg/L, were not degraded.

  9. Removal of methyl tert-butyl ether (MTBE) with Nafion.

    Science.gov (United States)

    Lien, Hsing-Lung; Zhang, Wei-Xian

    2007-06-01

    A solid organic polymer, Nafion, is tested for the removal of methyl tert-butyl ether (MTBE) in water. Nafion with perfluorosulfonic acid backbone and terminal sulfonic acid groups has a surface acidity similar to 100% sulfuric acid, and has been commonly used as a strong-acid catalyst in many organic reactions. Sorption and subsequent transformation of MTBE were observed in batch experiments. The transformation of MTBE by porous nanocomposite Nafion SAC-13 to tert-butyl alcohol (TBA), acetone, isobutene and probably methanol was found. Subsequent transformation of TBA to acetone was also observed. Results suggest that transformational pathways may include hydrolysis, dehydrogenation and oxidation. Dissolved oxygen is needed for the oxidation of isobutene to acetone. As Nafion is insoluble in water, chemically stable, and regenerable, its use in packed-bed reactors for MTBE removal looks promising.

  10. Hydrolysis of tert-butyl formate: Kinetics, products, and implications for the environmental impact of methyl tert-butyl ether

    Science.gov (United States)

    Church, Clinton D.; Pankow, James F.; Tratnyek, Paul G.

    1999-01-01

    Asessing the environmental fate of methyl tert-butyl ether (MTBE) has become a subject of renewed interest because of the large quantities of this compound that are being used as an oxygenated additive in gasoline. Various studies on the fate of MTBE have shown that it can be degraded to tert-butyl formate (TBF), particularly in the atmosphere. Although it is generally recognized that TBF is subject to hydrolysis, the kinetics and products of this reaction under environmentally relevant conditions have not been described previously. In this study, we determined the kinetics of TBF hydrolysis as a function of pH and temperature. Over the pH range of 5 to 7, the neutral hydrolysis pathway predominates, with kN = (1.0 ± 0.2) × 10−6/s. Outside this range, strong pH effects were observed because of acidic and basic hydrolyses, from which we determined that kA = (2.7 ± 0.5) × 10−3/(M·s) and kB = 1.7 ± 0.3/(M·s). Buffered and unbuffered systems gave the same hydrolysis rates for a given pH, indicating that buffer catalysis was not significant under the conditions tested. The activation energies corresponding to kN, kA, and kBwere determined to be 78 ± 5, 59 ± 4, and 88 ±11 kJ/mol, respectively. In all experiments, tert-butyl alcohol was found at concentrations corresponding to stoichiometric formation from TBF. Based on our kinetics data, the expected half-life for hydrolysis of TBF at pH = 2 and 4°C (as per some standard preservation protocols for water sampling) is 6 h. At neutral pH and 22°C, the estimated half-life is 5 d, and at pH = 11 and 22°C, the value is only 8 min.

  11. Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Francois, A.

    2002-11-01

    Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

  12. Biodegradation of methyl tert-butyl ether by Kocuria sp.

    Directory of Open Access Journals (Sweden)

    Kiković Dragan D.

    2012-01-01

    Full Text Available Methyl tert-butyl ether (MTBE has been used to replace the toxic compounds from gasoline and to reduce emission of air pollutants. Due to its intensive use, MTBE has become one of the most important environment pollutants. The aim of this paper is isolation and identification of the bacteria from wastewater sample of “HIP Petrohemija” Pančevo (Serbia, capable of MTBE biodegradation. The results of the investigation showed that only the bacterial isolate 27/1 was capable of growth on MTBE. The result of sequence analyzes of 16S rDNA showed that this bacterial isolate belongs to the Kocuria sp. After the incubation period of 86 days, the degradation rates of initial MTBE concentration of 25 and 125 μg/ml were 55 and 36%, respectively. These results indicated that bacteria Kocuria sp. is successfully adapted on MTBE and can be potentially used in bioremediation of soils and waters contaminated with MTBE.

  13. Community characterization of anaerobic methyl tert-butyl ether (MTBE)-degrading enrichment cultures.

    Science.gov (United States)

    Youngster, Laura K G; Kerkhof, Lee J; Häggblom, Max M

    2010-05-01

    Use of the fuel oxygenate methyl tert-butyl ether (MTBE) has led to widespread environmental contamination. Anaerobic biodegradation of MTBE observed under different redox conditions is a potential means for remediation of contaminated aquifers; however, no responsible microorganisms have been identified as yet. We analyzed the bacterial communities in anaerobic-enriched cultures originating from three different contaminated sediments that have retained MTBE-degrading activity for over a decade. MTBE was transformed to tert-butyl alcohol and the methyl group used as a carbon and energy source. Terminal restriction fragment length polymorphism (T-RFLP) analysis of bacterial 16S rRNA genes showed that the MTBE-utilizing microcosms established from different sediment sources had substantially different community profiles, suggesting that multiple species are capable of MTBE biodegradation. The 16S rRNA genes from one enrichment culture were cloned and sequenced. Phylogenetic analysis showed a diverse community, with phylotypes belonging to the Proteobacteria, Bacteroidetes, Firmicutes, Chloroflexi and Thermotogae. Continued enrichment on MTBE further reduced the community to three predominant phylotypes, as evidenced by T-RFLP analysis, which were most closely related to the Deltaproteobacteria, Firmicutes and Chloroflexi. These three common operational taxonomic units were detectable in the enrichments from Atlantic and Pacific coastal samples. Identification of the microorganisms important in mediating anaerobic MTBE transformation will provide the foundation for developing tools for site assessment and bioremediation monitoring.

  14. The screening of microorganisms capable of methyl tert-butyl ether (MTBE) biodegradation.

    Science.gov (United States)

    Wieczorek, Andrzej; Przybulewska, Krystyna; Karpowicz, Katarzyna; Nowak, Maciej J

    2013-01-01

    As a result of examinations carried out, 16 strains of microorganisms able to grow on mineral media with methyl tert-butyl ether as the sole source of carbon and energy were isolated. Bacteria prevailed among the isolated microorganisms. The growth of microorganisms under laboratory conditions was long and accompanied by low biomass increase. Under the conditions of the experiment, the isolated microorganisms did not show any quantitatively measurable biodegradability of methyl tert-butyl ether (MTBE) under aerobic conditions. This requires far-reaching caution with respect to trading in MTBE-modified petrols in order to protect the natural environment in Poland against contamination with that hard-to-biodegrade substance.

  15. TREATMENT OF METHYL TERT-BUTYL ETHER CONTAMINATED WATER USING PHOTOCATALYSIS

    Science.gov (United States)

    The feasibility of photo-oxidation treatment of methyl tert-butyl ether (MTBE) in water was investigated in three ways, 1) using a slurry falling film photo-reactor, 2) a batch solar reactor system, and 3) a combination of air-stripping and gas phase photooxidation system. MTBE-c...

  16. and triorganotin(IV) complexes of 2-tert-butyl-4-methyl phenol

    Indian Academy of Sciences (India)

    TECS

    of organotin(IV) complexes of phenols are found in literature. 13–17 .... method suggested them to exist as monomers. 3.1 IR spectra. In the IR .... Tert-butyl. Phenolic butyl substituent. Phenolic ring carbon. Phenolic ring substituent Methyl. 119. Sn. Compound group protons protons protons R–Sn –CH3. –C o, m and p Cipso.

  17. Degradation of methyl tert-butyl ether (MTBE) in water by glow discharge plasma.

    Science.gov (United States)

    Tong, Shaoping; Ni, Yanyan; Shen, Chensi; Wen, Yuezhong; Jiang, Xuanzhen

    2011-01-01

    This study evaluated the ability of the glow discharge plasma (GDP) technique to degrade methyl tert-butyl ether (MTBE) in an aqueous solution. The results showed that a large amount of hydrogen peroxide and highly active *OH free radicals were produced during the treatment. Various experimental parameters including discharge current, initial MTBE concentration and initial pH played significant roles on MTBE degradation. In addition, Fe2+ had a catalytic effect on the degradation of MTBE, which is potentially attributable to the reaction between Fe3+ and the hydrated electron. It was also confirmed that GDP was comparable to electrocatalytic oxidation and high-density plasma and more efficient than photocatalytic degradation techniques. These results suggest that GDP may become a competitive MTBE wastewater treatment technology.

  18. Artificial Neural Network Approach to Predict Biodiesel Production in Supercritical tert-Butyl Methyl Ether

    OpenAIRE

    Obie Farobie; Nur Hasanah

    2016-01-01

    In this study, for the first time artificial neural network was used to predict biodiesel yield in supercritical tert-butyl methyl ether (MTBE). The experimental data of biodiesel yield conducted by varying four input factors (i.e. temperature, pressure, oil-to-MTBE molar ratio, and reaction time) were used to elucidate artificial neural network model in order to predict biodiesel yield. The main goal of this study was to assess how accurately this artificial neural network model to predict b...

  19. [Degradation of methyl tert-butyl ether (MTBE) by O3/H2O2].

    Science.gov (United States)

    Hu, Qin-Hai; Mao, Ke-Hui; Zhu, Miao-Jun; Zhang, Xing-Qing; Xiong, Yun-Long; Wang, Juan

    2008-05-01

    The degradation of methyl tert-butyl ether (MTBE) in water solution has been studied using the combination of ozone/hydrogen peroxide in a bubble column. Effects of air (containing O3) currents, quantities of H2O2, initial concentrations of MTBE, pH values and temperatures on the oxidation of MTBE have been tested, and it is implicated that under the conditions of initial MTBE concentration of 10 mg x L(-1), air current of 0.5 L x min(-1), pH 6.5, 293 K and 2.4 mg x L(-1) H2O2 addition, MTBE can be reduced by 75.5% and the removal rate of COD reaches 68.0% within 30 min. The main of degradation products identified are tert-butyl formate (TBF), tert-butyl alcohol (TBA), acetone (AC) and methyl acetate (MA). On the basis of that, the probable mechanism and pathway of the oxidation of MTBE by ozone/hydrogen peroxide have been proposed.

  20. Photo catalytic degradation of methyl tert-Butyl Ether (MTBE) from contaminated water: complete mineralization

    Energy Technology Data Exchange (ETDEWEB)

    Eslami, A.; Nasseri, S.; Maleki, A.; Aghvami, T.

    2009-07-01

    Methyl tert-butyl ether (MTBE) has been commercially used as an octane enhancer to replace tetraethyl lead in gasoline since 1979. The high mobility, water solubility, and resistance to natural attenuation associated with MTBE may result in contamination of ground and surface waters. In this investigation the degradation of aqueous MTBE at relatively high concentrations was studied by UV-vis/TiO{sub 2}/O{sub 2} photo catalytic process. The effect of important operational parameters such as ph, oxygen flow, catalyst loading, and irradiation time were also studied. (Author)

  1. Enzymes and genes involved in the aerobic biodegradation of methyl tert-butyl ether (MTBE).

    Science.gov (United States)

    Lopes Ferreira, Nicolas; Malandain, Cédric; Fayolle-Guichard, Françoise

    2006-09-01

    Fuel oxygenates, mainly methyl tert-butyl ether (MTBE) but also ethyl tert-butyl ether (ETBE), are added to gasoline in replacement of lead tetraethyl to enhance its octane index. Their addition also improves the combustion efficiency and therefore decreases the emission of pollutants (CO and hydrocarbons). On the other hand, MTBE, being highly soluble in water and recalcitrant to biodegradation, is a major pollutant of water in aquifers contaminated by MTBE-supplemented gasoline during accidental release. MTBE was shown to be degraded through cometabolic oxidation or to be used as a carbon and energy source by a few microorganisms. We have summarized the present state of knowledge about the microorganisms involved in MTBE degradation and the MTBE catabolic pathways. The role of the different enzymes is discussed as well as the rare and recent data concerning the genes encoding the enzymes involved in the MTBE pathway. The phylogeny of the microorganisms isolated for their capacity to grow on MTBE is also described.

  2. Biodegradation of methyl tert-butyl ether (MTBE) by Enterobacter sp. NKNU02.

    Science.gov (United States)

    Chen, Ssu Ching; Chen, Colin S; Zhan, Kai-Van; Yang, Kai-Hsing; Chien, Chih-Ching; Shieh, Bao-Sen; Chen, Wen-Ming

    2011-02-28

    We previously isolated and identified Enterobacter sp. NKNU02 as a methyl tert-butyl ether (MTBE)-degrading bacterial strain from gasoline-contaminated water. In this study, tert-butyl alcohol, acetic acid, 2-propanol, and propenoic acid were detected using gas chromatography/mass spectrometry when MTBE was degraded by rest cells of Enterobacter sp. NKNU02 cells. We also found that biodegradation of MTBE was decreased, but not totally inhibited in mixtures of benzene, toluene, ethylbenzene and xylene. The effects of MTBE on the biology of Enterobacter sp. NKNU02 were elucidated using 2D proteomic analysis. The cytoplasmic proteins isolated from these MTBE-treated and -untreated cells were carried out for proteomic analysis. Results showed that there were 6 differential protein spots and 8 differential protein spots, respectively, as compared to their corresponding control (without MTBE addition), at the indicated incubation times when 40% and 60% of 100 mg/L of MTBE had been removed, Among these proteins, nine were successfully identified with matrix-assisted laser desorption ionization-time of flight-mass spectrometry. Proteins identified included extracellular solute-binding protein, periplasmic-binding protein ytfQ, cationic amino acid ABC transporter, isocitrate dehydrogenase, cysteine synthase A, alkyl hydroperoxide reductase (AhpC), transaldolase, and alcohol dehydrogenase. Based on these differential proteins, we discuss the bacterial responses to MTBE at the molecular level. Copyright © 2010 Elsevier B.V. All rights reserved.

  3. Biodegradation of Methyl tert-Butyl Ether by Co-Metabolism with a Pseudomonas sp. Strain

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    Shanshan Li

    2016-09-01

    Full Text Available Co-metabolic bioremediation is supposed to be an impressive and promising approach in the elimination technology of methyl tert-butyl ether (MTBE, which was found to be a common pollutant worldwide in the ground or underground water in recent years. In this paper, bacterial strain DZ13 (which can co-metabolically degrade MTBE was isolated and named as Pseudomonas sp. DZ13 based on the result of 16S rRNA gene sequencing analysis. Strain DZ13 could grow on n-alkanes (C5-C8, accompanied with the co-metabolic degradation of MTBE. Diverse n-alkanes with different carbon number showed a significant influence on the degradation rate of MTBE and accumulation of tert-butyl alcohol (TBA. When Pseudomonas sp. DZ13 co-metabolically degraded MTBE with n-pentane as the growth substrate, a higher MTBE-degrading rate (Vmax = 38.1 nmol/min/mgprotein, Ks = 6.8 mmol/L and lower TBA-accumulation was observed. In the continuous degradation experiment, the removal efficiency of MTBE by Pseudomonas sp. Strain DZ13 did not show an obvious decrease after five times of continuous addition.

  4. Pyrolysis of methyl tert-butyl ether (MTBE). 2. Theoretical study of decomposition pathways.

    Science.gov (United States)

    Zhang, Taichang; Zhang, Lidong; Wang, Jing; Yuan, Tao; Hong, Xin; Qi, Fei

    2008-10-23

    The thermal decomposition pathways of MTBE have been investigated using the G3B3 method. On the basis of the experimental observation and theoretical calculation, the pyrolysis channels are provided, especially for primary pyrolysis reactions. The primary decomposition pathways include formation of methanol and isobutene, CH4 elimination, H2 elimination and C-H, C-C, C-O bond cleavage reactions. Among them, the formation channel of methanol and isobutene is the lowest energy pathway, which is in accordance with experimental observation. Furthermore, the secondary pyrolysis pathways have been calculated as well, including decomposition of tert-butyl radical, isobutene, methanol and acetone. The radicals play an important role in the formation of pyrolysis products, for example, tert-butyl radical and allyl radical are major precursors for the formation of allene and propyne. Although some isomers (isobutene and 1-butene, allene and propyne, acetone and propanal) are identified in our experiment, these isomerization reaction pathways occur merely at the high temperature due to their high activation energies. The theoretical calculation can explain the experimental results reported in part 1 and shed further light on the thermal decomposition pathways.

  5. Epidemiology, toxicokinetics, and health effects of methyl tert-butyl ether (MTBE).

    Science.gov (United States)

    Phillips, Scott; Palmer, Robert B; Brody, Aaron

    2008-06-01

    This paper reviews the published information assessing the kinetics and potential for adverse health effects related to exposure to the fuel oxygenate, methyl tert-butyl ether (MTBE). Data were obtained from previously published reports, using human data where possible. If human data were not available, animal studies were cited. The kinetic profile of MTBE in humans is similar for ingestion and inhalation. The concentrations of MTBE to which the general public is expected to be exposed are orders of magnitude below concentrations that have caused adverse health effects in animals. Controlled human studies have not replicated early epidemiology studies that suggested, but did not confirm, a possible association between MTBE exposure and nonspecific health complaints.

  6. Degradation of aqueous methyl tert-butyl ether by photochemical, biological, and their combined processes

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    Azadeh Asadi

    2006-01-01

    Full Text Available The degradation of aqueous methyl tert-butyl ether (MTBE at relatively high concentrations was investigated by various photo-induced oxidation processes such as UV/H2O2 and UV/TiO2 as well as biological processes and their combination. It was shown that the degradation of MTBE by UV/H2O2 and TiO2 photocatalytic followed a first-order model with apparent rate constant of 1.31×10−1 and 1.21×10−2 min-1, respectively. It was observed that UV/H2O2/TiO2 process did not have any advantages over each of the other processes alone. The biodegradation of methyl tert-butyl ether (MTBE was evaluated using aerobic mixed culture with three different approaches, including ultimate biological oxygen demand (BODU assessment, nonacclimated, and acclimated mixed cultures. The apparent rate constant for the biodegradation of MTBE by nonacclimated mixed culture was 4.36×10−2 day-1. It was shown that the acclimatization of the mixed cultures enhanced the rate of biodegradation of MTBE to 3.24×10−1mg L-1h-1. Finally, the effects of the photocatalytic pretreatment of aqueous MTBE on its subsequent biological treatment were studied. It was observed that the rate of bioreaction was not enhanced and the photocatalytic pretreatment had adverse effects on its biological treatment so that the apparent rate constant decreased to 2.83×10−1 mg L-1h-1.

  7. Thermally Activated Paramagnets from Diamagnetic Polymers of Biphenyl-3,5-diyl Bis(tert-butyl Nitroxides Carrying Methyl and Fluoro Groups at the 2’- and 5’-Positions

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    Toru Yoshitake

    2016-03-01

    Full Text Available Three new biradicals—2’,5’-dimethyl-, 2’-fluoro-5’-methyl-, and 5’-fluoro-2’-methyl- biphenyl-3,5-diyl bis(tert-butyl nitroxides—were synthesized. The magnetic susceptibility measurements revealed their diamagnetism below and around room temperature. The nitroxide groups are located close to each other in an intermolecular fashion to form a weakly covalent head-to-tail (NO2 ring. Biradical molecules are connected on both radical sites, constructing a diamagnetic chain. The dimethyl derivative underwent a structural phase transition at 83 °C, clarified via differential scanning calorimetry and powder X-ray diffraction, and a paramagnetic solid phase with S = 1 irreversibly appeared. The other analogues exhibited a similar irreversible upsurge of the magnetic susceptibility on heating, but the transition was characterized as the melting.

  8. Exposure to methyl tert-butyl ether (MTBE) is associated with mitochondrial dysfunction in rat.

    Science.gov (United States)

    Saeedi, Arastoo; Omidi, Mahmoud; Khoshnoud, Mohammad Javad; Mohammadi-Bardbori, Afshin

    2017-05-01

    1. Methyl tert-butyl ether (MTBE) is commonly used as an octane booster and oxygenate additive to gasoline. The assumed toxic effects of MTBE on human health are a matter of great debate. Exposure to MTBE has been shown to induce oxidative damage and no mechanistic explanation is available so far. Our goals were to determine whether MTBE is a mitochondrial toxicant, if so, what mechanism(s) is involved. 2. Male Sprague-Dawley rats were received MTBE in drinking water for 3 months. At the end of treatments, animals were killed, liver and blood samples were collected for biochemical and histopathological studies, and oxidative stress biomarkers. The rat liver mitochondria were isolated and several mitochondrial indices were measured. 3. We found that zinc plasma levels were remarkably declined with MTBE and N, N, N', N'-Tetrakis (2-pyridylmethyl) ethylenediamine (TPEN; a zinc chelator) exposure. MTBE induced oxidative damage and caused mitochondrial dysfunctions in rats. Supplementation with zinc was able to protect against MTBE-induced cellular and sub-cellular toxicity. 4. Our results demonstrated that long-term exposure to MTBE is associated with zinc deficiency, oxidative stress, and mitochondrial energy failure in rat.

  9. Toxicity and biofilm-based selection for methyl tert-butyl ether bioremediation technology.

    Science.gov (United States)

    Guisado, I M; Purswani, J; Catón-Alcubierre, L; González-López, J; Pozo, C

    2016-12-01

    Extractive membrane biofilm reactor (EMBFR) technology offers productive solutions for volatile and semi-volatile compound removal from water bodies. In this study, the bacterial strains Paenibacillus etheri SH7(T) (CECT 8558), Agrobacterium sp. MS2 (CECT 8557) and Rhodococcus ruber strains A5 (CECT 8556), EE6 (CECT 8612) and EE1 (CECT 8555), previously isolated from fuel-contaminated sites, were tested for adherence on tubular semipermeable membranes in laboratory-scale systems designed for methyl tert-butyl ether (MTBE) bioremediation. Biofilm formation on the membrane surface was evaluated through observation by field-emission scanning electron microscope (FESEM) as well as the acute toxicity (as EC50) of the bacterial growth media. Moreover, extracellular polymeric substance (EPS) production for each strain under different MTBE concentrations was measured. Strains A5 and MS2 were biofilm producers and their adherence increased when the MTBE flowed through the inner tubular semipermeable membrane. No biofilm was formed by Paenibacillus etheri SH7(T), nevertheless, the latter and strain MS2 exhibited the lowest toxicity after growth on the EMBFR. The results obtained from FESEM and toxicity analysis demonstrate that bacterial strains R. ruber EE6, A5, P. etheri SH7(T) and Agrobacterium sp. MS2 could be excellent candidates to be used as selective inocula in EMBFR technology for MTBE bioremediation.

  10. Artificial Neural Network Approach to Predict Biodiesel Production in Supercritical tert-Butyl Methyl Ether

    Directory of Open Access Journals (Sweden)

    Obie Farobie

    2016-05-01

    Full Text Available In this study, for the first time artificial neural network was used to predict biodiesel yield in supercritical tert-butyl methyl ether (MTBE. The experimental data of biodiesel yield conducted by varying four input factors (i.e. temperature, pressure, oil-to-MTBE molar ratio, and reaction time were used to elucidate artificial neural network model in order to predict biodiesel yield. The main goal of this study was to assess how accurately this artificial neural network model to predict biodiesel yield conducted under supercritical MTBE condition. The result shows that artificial neural network is a powerful tool for modeling and predicting biodiesel yield conducted under supercritical MTBE condition that was proven by a high value of coefficient of determination (R of 0.9969, 0.9899, and 0.9658 for training, validation, and testing, respectively. Using this approach, the highest biodiesel yield was determined of 0.93 mol/mol (corresponding to the actual biodiesel yield of 0.94 mol/mol that was achieved at 400 °C, under the reactor pressure of 10 MPa, oil-to-MTBE molar ratio of 1:40 within 15 min of reaction time.

  11. Cometabolism of methyl tert-butyl ether by a new microbial consortium ERS.

    Science.gov (United States)

    Li, Shanshan; Li, Danni; Yan, Wei

    2015-07-01

    The release of methyl tert-butyl-ether (MTBE) into the environment has increased the worldwide concern about the pollution of MTBE. In this paper, a microbial consortium was isolated from the soil sample near an oil station, which can degrade MTBE directly with a low biomass yield and MTBE degrading efficiency. Further research has indicated that this consortium can degrade MTBE efficiently when grown on n-octane as the cometabolic substrate. The results of 16S rDNA based on phylogenetic analysis of the selected operating taxonomic units (OTUs) involved in the consortium revealed that one OTU was related to Pseudomonas putida GPo1, which could cometabolically degrade MTBE on the growth of n-octane. This may help explain why n-octane could be the optimal cometabolic substrate of the consortium for MTBE degradation. Furthermore, the degradation of MTBE was observed along with the consumption of n-octane. Different K s values for MTBE were observed for cells grown with or without n-octane, suggesting that different enzymes are responsible for the oxidation of MTBE in cells grown on n-octane or MTBE. The results are discussed in terms of their impacts on our understanding of MTBE biodegradation and cometabolism.

  12. Adsorption of methyl tert-butyl ether (MTBE) from aqueous solution by porous polymeric adsorbents.

    Science.gov (United States)

    Ji, Biyan; Shao, Fei; Hu, Guanjiu; Zheng, Shourong; Zhang, Qingmei; Xu, Zhaoyi

    2009-01-15

    MTBE has emerged as an important water pollutant because of its high mobility, persistence, and toxicity. In this study, a postcrosslinked polymeric adsorbent was prepared by postcrosslinking of a commercial chloromethylated polymer, and a nonpolar porous polymer with comparable surface area and micropore volume to the postcrosslinked polymer was prepared by suspended polymerization. The postcrosslinked polymer, nonpolar porous polymer and chloromethylated polymer were characterized by N2 adsorption, FTIR and XPS analysis. Results showed that postcrosslinking reaction led to the generation of a microporous postcrosslinked polymer with BET surface area 782m2g(-1), average pore width 3.0nm and micropore volume 0.33cm3g(-1). FTIR and XPS analysis indicated the formation of surface oxygen-containing groups on the postcrosslinked polymer. The three polymers were used as adsorbents to remove aqueous methyl tert-butyl ether (MTBE). Adsorption of MTBE over the postcrosslinked polymeric adsorbent was found to follow the linear adsorption isotherm, whereas MTBE adsorption onto the nonpolar porous polymer and chloromethylated polymer followed Langmuir adsorption model. Comparison of adsorption capacities of the postcrosslinked polymer, chloromethylated polymer and nonpolar porous polymer revealed that the adsorption of MTBE from aqueous solution is dependent on both pore structure and surface chemistry of polymeric adsorbents, and the high adsorption efficiency of the postcrosslinked polymer towards MTBE is attributed to its high surface area, large micropore volume and moderate hydrophility. The process of MTBE adsorption onto the adsorbents can be well described by pseudo-second-order kinetics, and the rate of adsorption decreased at higher MTBE initial concentration.

  13. The effects of methyl tert-butyl ether (MTBE) on the male rat reproductive system.

    Science.gov (United States)

    Li, Dongmei; Yuan, Chuntao; Gong, Yi; Huang, Yufeng; Han, Xiaodong

    2008-07-01

    Methyl tert-butyl ether (MTBE) is an oxygenated compound, which has been widely used in Asia, Europe and North America. Although numerous in vitro and in vivo studies have demonstrated the carcinogenicity and the toxicity of MTBE, there is still a lack of data on reproductive system exposure of MTBE in male rodent animals. We studied subacute exposure of MTBE on the reproductive systems of male Sprague-Dawley rats. MTBE was administered to rats at dose levels of 0, 400, 800 and 1600 mg/kg/day. After 2 or 4 weeks of treatments, the rats were euthanized, and their serum, epididymis and testes were collected. Significant adverse effects in their reproductive system were observed including: a significant increase in the percentage of abnormal sperm; an irregular and disordered arrangement of the seminiferous epithelium indicated by a histopathological examination; changed serum levels of testosterone (T), luteinizing hormone (LH) and follicle stimulating hormone (FSH); and decreased levels of mRNA and of androgen binding protein (ABP). In the oxidative stress study, results indicated an increased maleic dialdehyde (MDA) content, implying a raised peroxide level, and that the total antioxidant ability in serum was significantly increased. This finding was especially strong at 1600 mg/kg/day MTBE. In the 2-week treatment, at 1600 mg/kg/day, the mRNA level of 8-oxoguanine DNA glycosidase (OGG1) was significantly decreased, and the mRNA level of the extra-cellular form of superoxide dismutase (SOD(EX)) was significantly increased. Our experiments suggest that relatively high doses of MTBE can exert reproductive system toxicity of male rats and disturb the secretions of T, LH and FSH, possibly due to oxidative stress induced by MTBE.

  14. Oxidation of methyl tert-butyl ether by alkane hydroxylase in dicyclopropylketone-induced and n-octane-grown Pseudomonas putida GPo1.

    Science.gov (United States)

    Smith, Christy A; Hyman, Michael R

    2004-08-01

    The alkane hydroxylase enzyme system in Pseudomonas putida GPo1 has previously been reported to be unreactive toward the gasoline oxygenate methyl tert-butyl ether (MTBE). We have reexamined this finding by using cells of strain GPo1 grown in rich medium containing dicyclopropylketone (DCPK), a potent gratuitous inducer of alkane hydroxylase activity. Cells grown with DCPK oxidized MTBE and generated stoichiometric quantities of tert-butyl alcohol (TBA). Cells grown in the presence of DCPK also oxidized tert-amyl methyl ether but did not appear to oxidize either TBA, ethyl tert-butyl ether, or tert-amyl alcohol. Evidence linking MTBE oxidation to alkane hydroxylase activity was obtained through several approaches. First, no TBA production from MTBE was observed with cells of strain GPo1 grown on rich medium without DCPK. Second, no TBA production from MTBE was observed in DCPK-treated cells of P. putida GPo12, a strain that lacks the alkane-hydroxylase-encoding OCT plasmid. Third, all n-alkanes that support the growth of strain GPo1 inhibited MTBE oxidation by DCPK-treated cells. Fourth, two non-growth-supporting n-alkanes (propane and n-butane) inhibited MTBE oxidation in a saturable, concentration-dependent process. Fifth, 1,7-octadiyne, a putative mechanism-based inactivator of alkane hydroxylase, fully inhibited TBA production from MTBE. Sixth, MTBE-oxidizing activity was also observed in n-octane-grown cells. Kinetic studies with strain GPo1 grown on n-octane or rich medium with DCPK suggest that MTBE-oxidizing activity may have previously gone undetected in n-octane-grown cells because of the unusually high K(s) value (20 to 40 mM) for MTBE.

  15. Cytotoxicity and oxidative stress study in cultured rat Sertoli cells with methyl tert-butyl ether (MTBE) exposure.

    Science.gov (United States)

    Li, Dongmei; Liu, Qin; Gong, Yi; Huang, Yufeng; Han, Xiaodong

    2009-04-01

    Cultured Sertoli cells were tested for their cytotoxicity and oxidative stress induced by methyl tert-butyl ether (MTBE) which has been extensively used as a gasoline additive. In cytotoxic experiments, Sertoli cells were cultured with medium alone (control), 5, 500, or 50,000 microM MTBE. Lactate dehydrogcnase (LDH) leakage assay, staining with fluorescein diacetate (FDA) and propidium iodide (PI), and flow cytometric analyses were used. In oxidative stress experiments, Sertoli cells were cultured with medium alone (control), 0.5, 50, or 5000 microM MTBE. The production of reactive oxygen species (ROS), maleic dialdehyde (MDA) content and the level of superoxide dismutase (SOD) activity in cell supernatants were measured. Meanwhile, the expression level of 8-oxoguanine DNA glycosidase (OGG1) and extracellular form of superoxide dismutase (SOD(EX)) in Sertoli cells were determined by RT-PCR. We also compared the current findings with the previous findings in rat spermatogenic cells exposed to MTBE. The present data indicate that high dose MTBE may exert a direct toxic effect on Sertoli cells. Oxidative stress induced by MTBE is a possible mechanism of cytotoxicity.

  16. Methyl tert-butyl ether (MTBE) induced Ca(2+)-dependent cytotoxicity in isolated rabbit tracheal epithelial cells.

    Science.gov (United States)

    Wang, Yajing; Chen, Chang; Wu, Tao; Xu, Jing; Han, Xiaodong

    2008-10-01

    As a volatile synthetic organic chemical, methyl tert-butyl ether (MTBE) was the most common gasoline additive. The increasing use of MTBE raised concern over its health safety. Inhalation was the principle route of exposure for the general population. This study used a model of rabbit tracheal epithelial cells (RTEs) in primary culture to investigate the cytotoxic effects induced by MTBE and the potential mechanism. RTEs were incubated with medium alone (control), 0.5, 50, 5000ppm MTBE respectively. MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazo liumbromide) assay, staining with fluorescein diacetate, propidium iodide and lactate dehydrogenase leakage ratio were used to assess MTBE cytotoxicity on cells. We also observed a significant elevation in cytosolic Ca2+ by fluorescence probe Fluo-3AM at 3, 6 and 12h following exposure to MTBE. Loss of mitochondrial membrane potential (MMP) was detected following 12 and 24h treatment of NP and assessment by rhodamine 123 (Rh123) staining. Activity changes of the Ca(2+)-ATPase, Ca(2+)-Mg(2+)-ATPase following MTBE treatment displayed a similar trend, suggesting an initial elevation before 6h and subsequent dramatic decrease at 12h. Our results demonstrated that induction of cell injury, associated with mitochondrial dysfunction, and alterations in cytosolic Ca2+ in RTEs represent key mechanisms by which MTBE exerts its cytotoxic effects.

  17. [Biodegradation of methyl tert-butyl ether by stabilized immobilized Methylibium petroleiphilum PM1 cells and its biodegradation kinetics analysis].

    Science.gov (United States)

    Cheng, Zhuo-wei; Fu, Ling-xiao; Jiang, Yi-feng; Chen, Jian-meng; Zhang, Rong

    2011-05-01

    Methylibium petroleiphilum PM1, which is capable of degrading methyl tert-butyl ether (MTBE) , was immobilized in calcium alginate gel beads. Several methods were explored to increase the strength of these gel beads. The central composite design analysis indicated that the introduction of 0.2 mol x L(-1) Ca2+ into the crosslinking solution, 1.38 mmol x L(-1) Ca2+ into the growth medium and 0.1% polyethyleneimine (PEI) as the chemical crosslinking agent could increase the stability of the Ca-alginate gel beads with no loss of biodegradation activity. The stabilized immobilized cells could be used 400 h continuously with no breakage and no bioactivity loss. Examination of scanning electron microscope demonstrated that a membrane surrounding the gel beads was formed and the cells could grow and breed well in the stabilized calcium alginate gel beads. Kinetic analysis of the gel bead-degradation indicated that the rate-limiting step was biochemical process instead of intraparticle diffusion process. The diameter of 3 mm affected the biodegradability less while high concentration of PEI induced much more serious mass transfer restraint.

  18. Vacuum ultraviolet photoionization and ab initio Investigations of methyl tert-butyl ether (MTBE) clusters and MTBE-water clusters

    Science.gov (United States)

    Di Palma, Tonia M.; Bende, Attila

    2013-03-01

    The structures and energetics of neutral, ionized and protonated methyl tert-butyl ether (MTBE) clusters and (MTBE)m(H2O)n clusters are investigated by tunable vacuum-UV photoionization mass spectrometry and DFT calculations. While the mass spectra of bare MTBE clusters show unprotonated and protonated clusters ions, the mass spectra of mixed clusters show protonated ions that exhibit magic numbers that correspond to n = m - 2 combinations. Ab initio calculations show that in the larger clusters a multiple proton transfer leads to a protonated water core where all available hydrogen bonds interact with MTBE molecules. The resulting bond structure explains the cluster stability.

  19. Methyl tert-Butyl Ether (MTBE) in Ground Water, Air, and Precipitation at North Windham, Maine

    Science.gov (United States)

    Nielsen, Martha G.; Peckenham, John M.

    2000-01-01

    Thirty-one monitoring wells in the Windham aquifer in North Windham, Maine, were sampled for methyl tert-butyl ether (MTBE) from July 1998 to May 1999. MTBE was detected in 35 percent of the wells sampled in the Windham aquifer. MTBE was detected in 64 percent of wells in the high-yielding part of the aquifer; these wells account for 82 percent of all wells with detectable MTBE. Land cover also was found to be associated with MTBE in the wells in the study area, with the urban and low-density residential areas having more MTBE than undeveloped areas. The median concentration in wells with detectable MTBE was 1.13 micrograms per liter. Air and precipitation samples were collected in North Windham along with ground-water samples. Air samples were collected every 10 days from December 1998 to July 1999 (20 samples). MTBE was present in all 20 air samples collected, at concentrations ranging from 0.03 ppbv (parts per billion by volume) to 1.0 ppbv. Before Maine opted out of the reformulated gasoline (RFG) program in the spring of 1999, median concentrations in air at the North Windham site were 0.25 ppbv. After Maine stopped using RFG, the median concentration in air dropped to 0.09 ppbv. No MTBE was detected in four samples of precipitation at North Windham. The lack of rainfall during the study period prevented the collection of an adequate number of samples, and technical difficulties negated the results of some of the analyses of the samples that were collected. Based on the equilibrium partitioning of MTBE from the air into rain, the hypothetical average concentration of MTBE in rainfall during months when recharge typically occurs (March-April and October-December) would be approximately 0.3 to 0.4 micrograms per liter during the time that RFG was being used in Maine. After the phaseout of RFG, the maximum average concentration of MTBE in rainfall during these months would be approximately 0.1 micrograms per liter. The distribution and concentrations of MTBE that

  20. [Methyl tert-butyl ether (MTBE) in atmosphere of the Pearl River Delta, China].

    Science.gov (United States)

    Wang, Bo-guang; Shao, Min; Zhang, Yuan-hang; Lü, Wan-Ming; Zhou, Yan

    2007-07-01

    The concentration of methyl tert-butyl ether (MTBE) and its spatio-temporal distribution were researched in atmosphere of the Pearl River Delta (PRD) by sampling with air sampling canisters and analyzing with pre-concentrator and gas chromatograph-mass spectrum instrument. The results showed that 1) MTBE could be prevalently checked in atmosphere of traffic area, industrial area, residential area and commercial area of the PRD, and its range of hourly average concentration in the long-term observation was from 0 - 1.250 microg m(-3), the summer had more serious pollution than the spring, and urban was the central area of high MTBE concentration, and suburban in the downwind was obviously polluted by the urban air. 2) During the enhanced observation in summertime, the diurnal average concentration of Guangzhou urban site was (1.520 +/- 0.370) microg m(-3), which was about 7 times of Huadou site in the downwind of Guangzhou and over 100 times of Conghua site in the background of Guangzhou. In urban, 2 peak values appeared in the period of 10:00 - 12:00 and 16:00 - 18:00 respectively, and the nighttime had the lowest average concentration, but the suburban in the downwind had the peak value in the nighttime. 3) During the enhanced observation in wintertime, the diurnal average concentration of Guangzhou urban site was (0.950 +/- 0.240) microg m(-3), which was 3.6 times of Xinken site in the downwind of Guangzhou. Several peak values appeared on the diurnal variation, the high concentration period of urban was in 18:00 - 22:00, and that of suburban was in 04:00 - 10:00 of the next day. 4) When it was weak sunshine, the concentration of MTBE beside the urban traffic roadside was decreasing with the height increasing, but when it was strong sunshine, it was increasing with the height increasing. So, except the original emission from the automobiles, MTBE still had the secondary pollution sources formed by air photochemical reaction.

  1. Methyl tert-butyl ether (MTBE) in river and wastewater in Germany.

    Science.gov (United States)

    Achten, Christine; Kolb, Axel; Püttmann, Wilhelm; Seel, Peter; Gihr, Regine

    2002-09-01

    An overview of methyl tert-butyl ether (MTBE) concentrations in German river water (315 samples) and wastewater (82 samples) is given. In the agglomerated area of Frankfurt/M, several samples of surface water, wastewater, and industrial effluents were analyzed for its MTBE content from 1999 to 2001. MTBE was analyzed by a combination of headspace-solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME/GC-MS). Rhine and Main water concentrations of MTBE in the lower parts of the rivers were approximately 250 ng/L and 200 ng/L, respectively. The concentrations increased from the upper parts of the rivers to its mouths. Water from the Elbe, Neckar, and Weser rivers showed lower MTBE concentrations, and the ether was not detected in the Danube river. Generally, higher MTBE concentrations were detected at urban agglomerations compared to rural areas. Small urban creeks without significant industrial input showed MTBE concentrations of approximately 50 ng/L, and it was hardly detectable in small rural creeks. Higher MTBE concentrations in river water were correlated with increased concentrations of the oxygenate measured in precipitation. Most MTBE concentrations in river water fell in the range of 50-200 ng/L (32%), 10-50 ng/L (28%), and 200-1000 ng/L (26%). MTBE concentrations in German surface water and air are 3-17 times lower compared to Californian data. Wastewater samples from influents of two sewage plants showed MTBE concentrations of approximately 100-300 ng/L, and a loading of 2-37 kg/a was calculated. An eliminated MTBE percentage of roughly 30-35% of MTBE in the plants was estimated. Industrially influenced samples of river water or public wastewater and industrial effluents showed MTBE concentrations of up to 2267 ng/L and 28 microg/L, respectively. This input has not been considered before because only 1.5% of the produced amount of MTBE in Germany is used for industrial processes, but it should not be neglected because MTBE is very

  2. Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

    Science.gov (United States)

    Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

    2017-06-15

    Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Methyl tert-butyl ether (MTBE)-induced cytotoxicity and oxidative stress in isolated rat spermatogenic cells.

    Science.gov (United States)

    Li, Dongmei; Yin, Daqiang; Han, Xiaodong

    2007-01-01

    Methyl tert-butyl ether (MTBE) is a class of synthetic organic chemical. In the USA, MTBE pollution is regarded as a serious environmental problem. The objective of the present study was to investigate the cytotoxic effects and oxidative stress induced by MTBE in isolated rat spermatogenic cells. In cytotoxic experiments, spermatogenic cells isolated from the testes of adult Sprague-Dawley rats by a mechanical procedure without the use of trypsin were incubated with medium alone (control), 0.5, 5, 50 mm MTBE, respectively, for 6, 12 and 18 h. MTT assay, staining with fluorescein diacetate (FDA) and propidium iodide (PI) and flow cytometric analyses were used. In oxidative stress experiments, the spermatogenic cells were incubated with medium alone (control) and with 0.5, 50 microm, 5 mm MTBE. For 1, 2, 6, 12, 18 h incubation, ROS production was tested using a 2',7'-dichlorofluorescein diacetate (DCHF-DA) probe; for 1, 3, 6, 12, 18 h incubation, cytosolic superoxide dismutase (SOD) and extracellular SOD (SOD(EX)) activity was assessed; and for 18 h incubation, lipid peroxidation was assessed. The results showed that MTBE at high doses significantly decreased the spermatogenic cell viability and increased plasma membrane damage and the ratio of necrotic cells compared with the control. Assessment of the MTBE-induced oxidative stress revealed that MTBE increased the production of reactive oxygen species (ROS) and enhanced lipid peroxidation. In addition, although SOD(EX) activity increased at a high dose level, cytosolic SOD activity decreased. These results suggest that an increase of MTBE-induced ROS production and an enhancement of membrane lipid peroxidation may play an important role in its cytotoxicity in isolated rat spermatogenic cells. Copyright 2006 John Wiley & Sons, Ltd.

  4. An extractive membrane biofilm reactor as alternative technology for the treatment of methyl tert-butyl ether contaminated water.

    Science.gov (United States)

    Guisado, I M; Purswani, J; González-López, J; Pozo, C

    2016-09-01

    Among the strategies developed for contaminated groundwater bioremediation, those based on the use of bacteria adhering to inert supports and establishing biofilms have gained great importance in this field. Extractive membrane biofilm reactor (EMBFR) technology offers productive solutions for the removal of volatile and semi-volatile compounds. EMBFR technology is based on the use of extractive semipermeable membranes through which contaminants migrate to the biological compartment in which microorganisms with pollutant biotransformation and/or mineralization capacities can grow, forming an active biofilm on the membrane surface. The objective of this study was to assess the use of three bacterial strains (Paenibacillus sp. SH7 CECT 8558, Agrobacterium sp. MS2 CECT 8557, and Rhodococcus ruber EE6 CECT 8612), as inoculum in a lab-scale EMBFR running for 28 days under aerobic conditions to eliminate methyl tert-butyl ether (MTBE) from water samples. Three different hydraulic retention times (1, 6, and 12 h) were employed. MTBE degradation values were determined daily by a gas GC-MS technique, as well as suspended bacterial growth. The biofilm established by the bacterial strains on the semipermeable membrane was detected by Field-Emission Scanning Electron Microscopy (FESEM) at the end of each experiment. The acute toxicity of the treated effluents and biomedium was determined by Microtox(©) assay (EC50 ).The results achieved from the MTBE degradation, biofilm formation, and toxicity analysis indicated that bacterial strains MS2 and EE6 were the best options as selective inoculum, although further research is needed, particularly with regard to their possible use as a mixed culture. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1238-1245, 2016. © 2016 American Institute of Chemical Engineers.

  5. A comparative study of biodiesel production using methanol, ethanol, and tert-butyl methyl ether (MTBE) under supercritical conditions.

    Science.gov (United States)

    Farobie, Obie; Matsumura, Yukihiko

    2015-09-01

    In this study, biodiesel production under supercritical conditions among methanol, ethanol, and tert-butyl methyl ether (MTBE) was compared in order to elucidate the differences in their reaction behavior. A continuous reactor was employed, and experiments were conducted at various reaction temperatures (270-400 °C) and reaction times (3-30 min) and at a fixed pressure of 20 MPa and an oil-to-reactant molar ratio of 1:40. The results showed that under the same reaction conditions, the supercritical methanol method provided the highest yield of biodiesel. At 350 °C and 20 MPa, canola oil was completely converted to biodiesel after 10, 30, and 30 min in the case of - supercritical methanol, ethanol, and MTBE, respectively. The reaction kinetics of biodiesel production was also compared for supercritical methanol, ethanol, and MTBE. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Energy analysis for the production of biodiesel in a spiral reactor using supercritical tert-butyl methyl ether (MTBE).

    Science.gov (United States)

    Farobie, Obie; Matsumura, Yukihiko

    2015-11-01

    In this study, energy analysis was conducted for the production of biodiesel in a spiral reactor using supercritical tert-butyl methyl ether (MTBE). This study aims to determine the net energy ratio (NER) and energy efficiency for the production of biodiesel using supercritical MTBE and to verify the effectiveness of the spiral reactor in terms of heat recovery efficiency. The analysis results revealed that the NER for this process was 0.92. Meanwhile, the energy efficiency was 0.98, indicating that the production of biodiesel in a spiral reactor using supercritical MTBE is an energy-efficient process. By comparing the energy supply required for biodiesel production between spiral and conventional reactors, the spiral reactor was more efficient than the conventional reactor. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Distribution of methyl tert-butyl ether (MTBE) and selected water-quality constituents in the surficial aquifer at the Dover National Test Site, Dover Air Force Base, Delaware, 2001

    Science.gov (United States)

    Stewart, Marie; Guertal, William R.; Barbaro, Jeffrey R.; McHale, Timothy J.

    2004-01-01

    A joint study by the Dover National Test Site, Dover Air Force Base, Delaware, and the U.S. Geological Survey was conducted from June 27 through July 18, 2001, to determine the spatial distribution of the gasoline oxygenate additive methyl tert-butyl ether and selected water-quality constituents in the surficial aquifer underlying the Dover National Test Site. This report provides a summary assessment of the distribution of methyl tert-butyl ether and a preliminary screening of selected constituents that may affect natural attenuation and remediation demonstrations at the Dover National Test Site. The information gathered during this study is designed to assist potential remedial investigators who are considering conducting a methyl tert-butyl ether remedial demonstration at the test site. In addition, the study supported a planned enhanced bioremediation demonstration and assisted the Dover National Test Site in identifying possible locations for future methyl tert-butyl ether remediation demonstrations. A direct-push drill rig was used to collect a total of 147 ground-water samples (115 VOC samples and 32 quality-assurance samples) at varying depths. Volatile organic compounds were above the method reporting limits in 59 of the 115 ground-water samples. The concentrations ranged from below detection limits to maximum values of 12.4 micrograms per liter of cis-1,2-dichloro-ethene, 1.14 micrograms per liter of trichloro-ethene, 2.65 micrograms per liter of tetrachloro-ethene, 1,070 micrograms per liter of methyl tert-butyl ether, 4.36 micrograms per liter of benzene, and 1.8 micrograms per liter of toluene. Vinyl chloride, ethylbenzene, p,m-xylene, and o-xylene were not detected in any of the samples collected during this investigation. Methyl tert-butyl ether was detected in 47 of the 115 ground-water samples. The highest concentrations of methyl tert-butyl ether were detected in the surficial aquifer from ?4.6 to 6.4 feet mean sea level; however, methyl tert-butyl

  8. Effects of co-substrates and inhibitors on the anaerobic O-demethylation of methyl tert-butyl ether (MTBE).

    Science.gov (United States)

    Youngster, Laura K G; Somsamak, Piyapawn; Häggblom, Max M

    2008-10-01

    Methyl tert-butyl ether (MTBE) contamination is widespread in aquifers near urban areas around the world. Since this synthetic fuel oxygenate is resistant to most physical methods of treating fuel-contaminated water, biodegradation may be a useful means of remediation. Currently, information on anaerobic MTBE degradation is scarce. Depletion has been observed in soil and sediment microcosms from a variety of locations and under several redox conditions, but the responsible organisms are unknown. We are studying anaerobic consortia, enriched from contaminated sediments for MTBE-utilizing microorganisms for over a decade. MTBE degradation occurred in the presence of other fuel components and was not affected by toluene, benzene, ethanol, methanol, or gasoline. Many aryl O-methyl ethers, such as syringic acid, that are O-demethylated by acetogenic bacteria, were also O-demethylated by the MTBE-utilizing enrichment cultures. The addition of these compounds as co-substrates increased the rate of MTBE degradation, offering a potentially useful method of stimulating the MTBE degradation rate in situ. Propyl iodide caused light-reversible inhibition of MTBE degradation, suggesting that the MTBE degradation process is corrinoid dependent. The anaerobic MTBE degradation process was not directly coupled to methanogenesis or sulfidogenesis and was inhibited by the bactericidal antibiotic, rifampicin. These results suggest that MTBE degradation is mediated by acetogenic bacteria.

  9. Disturbance of zinc and glucose homeostasis by methyl tert-butyl ether (MTBE); evidence for type 2 diabetes.

    Science.gov (United States)

    Saeedi, Arastoo; Fardid, Reza; Khoshnoud, Mohammad Javad; Kazemi, Elaheh; Omidi, Mahmoud; Mohammadi-Bardbori, Afshin

    2017-06-01

    1. The prevalence of diabetes and the other metabolic disorders has noticeably increased worldwide. A causal link between increasing risk of type 2 diabetes and exposure to environmental pollutants has been reported. 2. We hypothesized that exposure to methyl tert-butyl ether (MTBE), an oxygenate additive to gasoline would hinder zinc and glucose homeostasis in rats. 3. Male Sprague-Dawley rats received MTBE in drinking water for 90 days. At the end of the treatment, pancreas and blood samples were collected for biochemical and molecular examinations. Expression of four candidate genes, including Insulin1, Insulin2, MT1A, SLC30A8 by Real-Time Quantitative PCR (Q-PCR) as well as biochemical parameters, including fasting blood glucose (FBS), triglycerides (TG), cholesterol (CHO), low-density lipoprotein (LDL), high-density lipoprotein (HDL), copper (Cu(2+)) and calcium (Ca(2+)) levels as well as High-sensitive C-reactive protein were assessed as endpoints. 4. This study suggested that MTBE exposure can be associated with disruption in zinc homeostasis and glucose tolerance.

  10. Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water.

    Science.gov (United States)

    O'Neill, Dennis T; Rochette, Elizabeth A; Ramsey, Philip J

    2002-11-15

    Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.

  11. Synthesis of tert-butyl (substituted benzamido)phenylcarbamate derivatives: anti-inflammatory activity and docking studies.

    Science.gov (United States)

    Bhookya, Shankar; Pochampally, Jalapathi; Valeru, Anil; Sunitha, Vianala; Balabadra, Saikrishna; Manga, Vijjulatha; Kudle, Karunakar Rao

    2017-07-01

    A series of new tert-butyl 2-(substituted benzamido) phenylcarbamate (4a-4j) were synthesized by the condensation of tert-butyl 2-amino phenylcarbamate (3) with various substituted carboxylic acid in the presence of EDCI and HOBt as coupling reagent, obtain in excellent yields. The structures of all newly synthesized compounds were characterized spectroscopically and evaluated for in vivo anti-inflammatory activity compared to the standard drug, indomethacin, by using the carrageenan-induced rat paw edema protocol. Most of the compounds exhibited a promising anti-inflammatory activity within 9 to 12 h, the percentage of inhibition values ranging from 54.239 to 39.021%. The results revealed that the compounds 4i and 4a exhibited better or equivalent anti-inflammatory activity with the percentage of inhibition of 54.239 and 54.130%, respectively, which was comparable to standard drug. In addition to experimental results, in silico docking studies was used as a tool to verify and expand the experimental outcomes.

  12. Manipulation of the HIF-Vegf pathway rescues methyl tert-butyl ether (MTBE)-induced vascular lesions.

    Science.gov (United States)

    Bonventre, Josephine A; Kung, Tiffany S; White, Lori A; Cooper, Keith R

    2013-12-15

    Methyl tert-butyl ether (MTBE) has been shown to be specifically anti-angiogenic in piscine and mammalian model systems at concentrations that appear non-toxic in other organ systems. The mechanism by which MTBE targets developing vascular structures is unknown. A global transcriptome analysis of zebrafish embryos developmentally exposed to 0.00625-5mM MTBE suggested that hypoxia inducible factor (HIF)-regulated pathways were affected. HIF-driven angiogenesis via vascular endothelial growth factor (vegf) is essential to the developing vasculature of an embryo. Three rescue studies were designed to rescue MTBE-induced vascular lesions: pooled blood in the common cardinal vein (CCV), cranial hemorrhages (CH), and abnormal intersegmental vessels (ISV), and test the hypothesis that MTBE toxicity was HIF-Vegf dependent. First, zebrafish vegf-a over-expression via plasmid injection, resulted in significantly fewer CH and ISV lesions, 46 and 35% respectively, in embryos exposed to 10mM MTBE. Then HIF degradation was inhibited in two ways. Chemical rescue by N-oxaloylglycine significantly reduced CCV and CH lesions by 30 and 32% in 10mM exposed embryos, and ISV lesions were reduced 24% in 5mM exposed zebrafish. Finally, a morpholino designed to knock-down ubiquitin associated von Hippel-Lindau protein, significantly reduced CCV lesions by 35% in 10mM exposed embryos. In addition, expression of some angiogenesis related genes altered by MTBE exposure were rescued. These studies demonstrated that MTBE vascular toxicity is mediated by a down regulation of HIF-Vegf driven angiogenesis. The selective toxicity of MTBE toward developing vasculature makes it a potentially useful chemical in the designing of new drugs or in elucidating roles for specific angiogenic proteins in future studies of vascular development. © 2013.

  13. Trends in Methyl tert-Butyl Ether Concentrations in Private Wells in Southeast New Hampshire: 2005 to 2015.

    Science.gov (United States)

    Flanagan, Sarah M; Levitt, Joseph P; Ayotte, Joseph D

    2017-02-07

    In southeast New Hampshire, where reformulated gasoline was used from the 1990s to 2007, methyl tert-butyl ether (MtBE) concentrations ≥0.2 μg/L were found in water from 26.7% of 195 domestic wells sampled in 2005. Ten years later in 2015, and eight years after MtBE was banned, 10.3% continue to have MtBE. Most wells (140 of 195) had no MtBE detections (concentrations MtBE concentrations increased in 4 wells, decreased in 47 wells, and did not change in 4 wells. On average, MtBE concentrations decreased 65% among 47 wells whereas MtBE concentrations increased 17% among 4 wells between 2005 and 2015. The percent change in detection frequency from 2005 to 2015 (the decontamination rate) was lowest (45.5%) in high-population-density areas and in wells completed in the Berwick Formation geologic units. The decontamination rate was the highest (78.6%) where population densities were low and wells were completed in bedrock composed of granite, metamorphic, and mafic rocks. Wells in the Berwick Formation are characteristically deeper and have lower yields than wells in other rock types and have shallower overburden cover, which may allow for more rapid transport of MtBE from land-surface releases. Low-yielding, deep bedrock wells may require large contributing areas to achieve adequate well yield, and thus have a greater chance of intercepting MtBE, in addition to diluting contaminants at a slower rate and thus requiring more time to decontaminate.

  14. Exposure to methyl tert-butyl ether, benzene, and total hydrocarbons at the Singapore-Malaysia causeway immigration checkpoint

    Energy Technology Data Exchange (ETDEWEB)

    Tan, C.; Ong, H.Y.; Kok, P.W. [and others

    1996-12-31

    The primary aim of this study was to determine the extent and levels of exposure to volatile organic compounds (VOCs) from automobile emissions in a group of immigration officers at a busy cross-border checkpoint. A majority (80%) of the workers monitored were exposed to benzene at levels between 0.01 and 0.5 ppm, with only 1.2% exceeding the current Occupational Safety and Health Administration occupational exposure limit of 1 ppm. The geometric mean (GM) concentrations of 8-hr time-weighted average exposure were 0.03 ppm, 0.9 ppm, and 2.46 ppm for methyl-tert-butyl ether (MTBE), benzene, and total hydrocarbons (THC), respectively. The highest time-weighted average concentrations measured were 1.05 ppm for MTBE, 2.01 ppm for benzene, and 34 ppm for THC. It was found that motorbikes emitted a more significant amount of pollutants compared with motor cars. On average, officers at the motorcycle booths were exposed to four to five times higher levels of VOCs (GMs of 0.07 ppm, 0.23 ppm, and 4.7 ppm for MTBE, benzene, and THC) than their counterparts at the motor car booths (GMs of 0.01 ppm, 0.05 ppm, and 1.5 ppm). The airborne concentrations of all three pollutants correlated with the flow of vehicle traffic. Close correlations were also noted for the concentrations in ambient air for the three pollutants measured. Benzene and MTBE had a correlation coefficient of 0.97. The overall findings showed that the concentrations of various VOCs were closely related to the traffic density, suggesting that they were from a common source, such as exhaust emissions from the vehicles. The results also indicated that although benzene, MTBE, and THC are known to be volatile, a significant amount could still be detected in the ambient environment, thus contributing to our exposure to these compounds. 4 refs., 6 figs.

  15. The interactions of methyl tert-butyl ether on high silica zeolites: a combined experimental and computational study.

    Science.gov (United States)

    Sacchetto, V; Gatti, G; Paul, G; Braschi, I; Berlier, G; Cossi, M; Marchese, L; Bagatin, R; Bisio, C

    2013-08-28

    In this work, the interactions of methyl tert-butyl ether (MTBE) on different dealuminated high silica zeolites were studied by means of both experimental and computational approaches. Zeolites with different textural and surface features were selected as adsorbents and the effect of their physico-chemical properties (i.e. pore size architecture and type and amount of surface OH sites) on sorption capacity were studied. High silica mordenite (MOR) and Y zeolites (both with a SiO2/Al2O3 ratio of 200) and ZSM-5 solid (SiO2/Al2O3 ratio of 500) were selected as model sorbents. By combining FTIR and SS-NMR (both (1)H and (13)C CPMAS NMR) spectroscopy it was possible to follow accurately the MTBE adsorption process on highly defective MOR characterized by a high concentration of surface SiOH groups. The adsorption process is found to occur in different steps and to involve isolated silanol sites, weakly interacting silanols, and the siloxane network of the zeolite, respectively. H-bonding and van der Waals interactions occurring between the mordenite surface and MTBE molecules were modeled by DFT calculations using a large cluster of the MOR structure where two adjacent side-pockets were fused in a large micropore to simulate a dealumination process leading to silanol groups. This is the locus where MTBE molecules are more strongly bound and stabilized. FTIR spectroscopy and gravimetric measurements allowed determination of the interaction strength and sorption capacities of all three zeolites. In the case of both Y and MOR zeolites, medium-weak H-bonding with isolated silanols (both on internal and external zeolite surfaces) and van der Waals interactions are responsible for MTBE adsorption, whereas ZSM-5, in which a negligible amount of surface silanol species is present, displays a much lower amount of adsorbed MTBE retained mainly through van der Waals interactions with zeolite siloxane network.

  16. Polypyrrole-Grafted Coconut Shell Biological Carbon as a Potential Adsorbent for Methyl Tert-Butyl Ether Removal: Characterization and Adsorption Capability

    Directory of Open Access Journals (Sweden)

    Shanshan Li

    2017-01-01

    Full Text Available Methyl tert-butyl ether (MTBE has been used as a common gasoline additive worldwide since the late twentieth century, and it has become the most frequently detected groundwater pollutant in many countries. This study aimed to synthesize a novel microbial carrier to improve its adsorptive capacity for MTBE and biofilm formation, compared to the traditional granular activated carbon (GAC. A polypyrrole (PPy-modified GAC composite (PPy/GAC was synthesized, and characterized by Fourier transform infrared spectroscopy (FT-IR and Brunauer-Emmett-Teller (BET surface area analysis. The adsorption behaviors of MTBE were well described by the pseudo-second-order and Langmuir isotherm models. Furthermore, three biofilm reactors were established with PPy/GAC, PPy, and GAC as the carriers, respectively, and the degradation of MTBE under continuous flow was investigated. Compared to the biofilm reactors with PPy or GAC (which both broke after a period of operation, the PPy/GAC biofilm column produced stable effluents under variable treatment conditions with a long-term effluent MTBE concentration <20 μg/L. Pseudomonas aeruginosa and Acinetobacter pittii may be the predominant bacteria responsible for MTBE degradation in these biofilm reactors.

  17. Polypyrrole-Grafted Coconut Shell Biological Carbon as a Potential Adsorbent for Methyl Tert-Butyl Ether Removal: Characterization and Adsorption Capability.

    Science.gov (United States)

    Li, Shanshan; Qian, Keke; Wang, Shan; Liang, Kaiqiang; Yan, Wei

    2017-01-24

    Methyl tert-butyl ether (MTBE) has been used as a common gasoline additive worldwide since the late twentieth century, and it has become the most frequently detected groundwater pollutant in many countries. This study aimed to synthesize a novel microbial carrier to improve its adsorptive capacity for MTBE and biofilm formation, compared to the traditional granular activated carbon (GAC). A polypyrrole (PPy)-modified GAC composite (PPy/GAC) was synthesized, and characterized by Fourier transform infrared spectroscopy (FT-IR) and Brunauer-Emmett-Teller (BET) surface area analysis. The adsorption behaviors of MTBE were well described by the pseudo-second-order and Langmuir isotherm models. Furthermore, three biofilm reactors were established with PPy/GAC, PPy, and GAC as the carriers, respectively, and the degradation of MTBE under continuous flow was investigated. Compared to the biofilm reactors with PPy or GAC (which both broke after a period of operation), the PPy/GAC biofilm column produced stable effluents under variable treatment conditions with a long-term effluent MTBE concentration MTBE degradation in these biofilm reactors.

  18. Excess enthalpy, density, and speed of sound determination for the ternary mixture (methyl tert-butyl ether + 1-butanol + n-hexane)

    Energy Technology Data Exchange (ETDEWEB)

    Mascato, Eva [Departamento de Fisica Aplicada, Facultade de Ciencias, Universidade de Vigo, E-36310 Vigo (Spain); Mariano, Alejandra [Laboratorio de Fisicoquimica, Departamento de Quimica, Facultad de Ingenieria, Universidad Nacional del Comahue, 8300 Neuquen (Argentina); Pineiro, Manuel M. [Departamento de Fisica Aplicada, Facultade de Ciencias, Universidade de Vigo, E-36310 Vigo (Spain)], E-mail: mmpineiro@uvigo.es; Legido, Jose Luis [Departamento de Fisica Aplicada, Facultade de Ciencias, Universidade de Vigo, E-36310 Vigo (Spain); Paz Andrade, M.I. [Departamento de Fisica Aplicada, Facultade de Fisica, Universidade de Santiago de Compostela, E-15706 Santiago de Compostela (Spain)

    2007-09-15

    Density, ({rho}), and speed of sound, (u), from T = 288.15 to T = 308.15 K, and excess molar enthalpies, (h{sup E}) at T = 298.15 K, have been measured over the entire composition range for (methyl tert-butyl ether + 1-butanol + n-hexane). In addition, excess molar volumes, V{sup E}, and excess isentropic compressibility, {kappa}{sub s}{sup E}, were calculated from experimental data. Finally, experimental excess enthalpies results are compared with the estimations obtained by applying the group-contribution models of UNIFAC (in the versions of Dang and Tassios, Larsen et al., Gmehling et al.), and DISQUAC.

  19. Manipulation of the HIF–Vegf pathway rescues methyl tert-butyl ether (MTBE)-induced vascular lesions

    Energy Technology Data Exchange (ETDEWEB)

    Bonventre, Josephine A., E-mail: josephine.bonventre@oregonstate.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); Oregon State University, Department of Environmental and Molecular Toxicology, 1011 Agricultural and Life Sciences Bldg, Corvallis, OR 97331 (United States); Kung, Tiffany S., E-mail: tiffany.kung@rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); White, Lori A., E-mail: lawhite@aesop.rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); Cooper, Keith R., E-mail: cooper@aesop.rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States)

    2013-12-15

    Methyl tert-butyl ether (MTBE) has been shown to be specifically anti-angiogenic in piscine and mammalian model systems at concentrations that appear non-toxic in other organ systems. The mechanism by which MTBE targets developing vascular structures is unknown. A global transcriptome analysis of zebrafish embryos developmentally exposed to 0.00625–5 mM MTBE suggested that hypoxia inducible factor (HIF)-regulated pathways were affected. HIF-driven angiogenesis via vascular endothelial growth factor (vegf) is essential to the developing vasculature of an embryo. Three rescue studies were designed to rescue MTBE-induced vascular lesions: pooled blood in the common cardinal vein (CCV), cranial hemorrhages (CH), and abnormal intersegmental vessels (ISV), and test the hypothesis that MTBE toxicity was HIF–Vegf dependent. First, zebrafish vegf-a over-expression via plasmid injection, resulted in significantly fewer CH and ISV lesions, 46 and 35% respectively, in embryos exposed to 10 mM MTBE. Then HIF degradation was inhibited in two ways. Chemical rescue by N-oxaloylglycine significantly reduced CCV and CH lesions by 30 and 32% in 10 mM exposed embryos, and ISV lesions were reduced 24% in 5 mM exposed zebrafish. Finally, a morpholino designed to knock-down ubiquitin associated von Hippel–Lindau protein, significantly reduced CCV lesions by 35% in 10 mM exposed embryos. In addition, expression of some angiogenesis related genes altered by MTBE exposure were rescued. These studies demonstrated that MTBE vascular toxicity is mediated by a down regulation of HIF–Vegf driven angiogenesis. The selective toxicity of MTBE toward developing vasculature makes it a potentially useful chemical in the designing of new drugs or in elucidating roles for specific angiogenic proteins in future studies of vascular development. - Highlights: • Global gene expression of MTBE exposed zebrafish suggested altered HIF1 signaling. • Over expression of zebrafish vegf-a rescues MTBE

  20. Effect of Ethanol and Methyl-tert-Butyl Ether on Monoaromatic Hydrocarbon Biodegradation: Response Variability for Different Aquifer Materials Under Various Electron-Accepting Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Aguilar, G L; Fernandez-Sanchez, J M; Kane, S R; Kim, D; Alvarez, P J

    2003-10-06

    Aquifer microcosms were used to determine how ethanol and methyl-tert-butyl ether (MtBE) affect monoaromatic hydrocarbon degradation under different electron-accepting conditions commonly found in contaminated sites experiencing natural attenuation. Response variability was investigated by using aquifer material from four sites with different exposure history. The lag phase prior to BTEX (benzene, toluene, ethylbenzene, and xylenes) and ethanol degradation was typically shorter in microcosms with previously contaminated aquifer material, although previous exposure did not always result in high degradation activity. Toluene was degraded in all aquifer materials and generally under a broader range of electron-accepting conditions compared to benzene, which was degraded only under aerobic conditions. MtBE was not degraded within 100 days under any condition, and it did not affect BTEX or ethanol degradation patterns. Ethanol was often degraded before BTEX compounds, and had a variable effect on BTEX degradation as a function of electron-accepting conditions and aquifer material source. An occasional enhancement of toluene degradation by ethanol occurred in denitrifying microcosms with unlimited nitrate; this may be attributable to the fortuitous growth of toluene-degrading bacteria during ethanol degradation. Nevertheless, experiments with flow-through aquifer columns showed that this beneficial effect could be eclipsed by an ethanol-driven depletion of electron acceptors, which significantly inhibited BTEX degradation and is probably the most important mechanism by which ethanol could hinder BTEX natural attenuation. A decrease in natural attenuation could increase the likelihood that BTEX compounds reach a receptor as well as the potential duration of exposure.

  1. Occurrence of methyl tert-butyl ether (MTBE) in riverbank fiftered water and drnking water produced by riverbank filtration. 2.

    Science.gov (United States)

    Achten, Christine; Kolb, Axel; Püttmann, Wilhelm

    2002-09-01

    Bank filtration of river or lake water represents an efficient and natural purification process used for the drinking water production in many countries and at an amount of about 15-16% in Germany. From experiences over decades particularly at the river Rhine and Elbe, it is known that the occurrence of persistent pollutants in river water can represent a problem for the quality of drinking water produced by bank filtration. The common detection of the gasoline additive methyl tert-butyl ether (MTBE) in drinking water and the announced phase-out of the oxygenate in the U.S. show that MTBE can contaminate large water amounts due to its physicochemical properties. The MTBE situation in the U.S differs from Europe, and significantly lower concentrations in the German environment can be expected. Average MTBE concentrations of 200-250 ng/L in the Lower Main and Lower Rhine river in 2000/2001 were reported. At two sites at the Lower Rhine and Lower Main rivers MTBE concentrations in bank filtered water (n = 22), recovering well water, raw water, and drinking water produced by the water utility at the Lower Rhine site (n = 30) and tap water at Frankfurt/M City (n = 13) were analyzed from 1999 to 2001. Sample analysis is performed by a combination of headspace-solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC/MS) with a detection limit of 10 ng/L and a relative standard deviation of 11%. At the Lower Rhine site up to 80 m from the river an average MTBE concentration of 88 ng/L in riverbank filtered water, recovering well water, and raw water (n = 7) and of 43-110 ng/L in drinking water (n = 3) result. At the Lower Main site up to 400 m from the river MTBE concentrations from 52 to 250 ng/L (n = 7) were measured. Tap water samples at Frankfurt/M (mean of 35 ng/L, maximum of 71 ng/L) were in the same range as MTBE amounts in drinking water at the Lower Rhine site. Measured MTBE amounts eliminated by bank filtration at the Lower Rhine site

  2. Anti-inflammatory activity of the artificial antioxidants 2-tert-butyl-4-methoxyphenol (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,4,6-tri-tert-butylphenol (TBP), and their various combinations.

    Science.gov (United States)

    Murakami, Yukio; Kawata, Akifumi; Katayama, Tadashi; Fujisawa, Seiichiro

    2015-01-01

    The artificial complex phenols, 2-tert-butyl-4-methoxyphenol (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,4,6-tri-tert-butylphenol (TBP) exert efficient antioxidant activity; however, they are considerable toxic and potentially tumor-promoting. These phenols, particularly in combinations, have enhanced antioxidant activity due to synergistic interactions and produce bioactive intermediates such as quinone methide. We investigated the anti-inflammatory activity of BHA, BHT and TBP, and combinations of BHT/BHA (in molar ratios of 1:1, 1:2, 1:3 and 2:1), BHT/TBP (1:1), and BHA/TBP (1:1), using gene-expression systems for cyclooxygenase-2 (Cox2) and tumor necrosis facto-alpha (Tnfa) in RAW264.7 cells. The inhibitory effects of BHA, BHT and TBP on expression of Cox2 and Tnfa genes upon stimulation with Escherichia coli lipopolysaccharide (LPS) or Porphyomonas gingivalis (Pg) fimbriae were determined using real-time polymerase chain reaction. The inhibitory effect on expression of Cox2 and Tnfa genes upon stimulation with LPS and fimbriae was greatly enhanced by the combination of two antioxidants (molar ratio 1:1), BHT/BHA. In addition, that of the Cox2 gene, but not of Tnfa gene was slightly enhanced by a combination of equimolar BHT/TBP and BHA/TBP. None of the antioxidants alone exerted any anti-inflammatory activity upon stimulation with LPS, but a slight anti-inflammatory activity was observed upon stimulation with Pg fimbriae. The inhibitory effect of the BHT/BHA combination on expression of Cox2 mRNA upon stimulation with LPS was investigated at afferent molar ratios, and a molar ratio of 1:1 was found to have considerably less effect than a molar ratio of 1:2 or 2:1. The 1:3 combination had no effect. The combination of BHT and BHA at a molar ratio of 0.5-2 exerts potent anti-inflammatory activity. This anti-inflammatory activity on the generation of inflammatory mediators in LPS-activated RAW264.7 cells may be attributable to complex synergistic

  3. 7-[(3,5-Di-tert-butyl-2-hydroxybenzylideneamino]-4-methyl-2H-chromen-2-one

    Directory of Open Access Journals (Sweden)

    Orhan Büyükgüngör

    2010-10-01

    Full Text Available The title compound, C25H29NO3, is a Schiff base derivative of coumarin 120. There are two structurally similar but crystallographically independent molecules in the asymmetric unit. Both molecules exist in E configurations with respect to the C=N double bonds. The dihedral angles between the coumarin and 3,5-di-tert-butyl-2-hydroxybenzylidene ring planes are 4.62 (7 and 14.62 (7° for the two molecules. Intramolecular O—H...N hydrogen bonding involving the O—H groups and the azomethine N atoms generate S(6 rings. In the crystal structure, independent molecules are linked by C—H...π interactions, with groups of four molecules stacked along the c axis.

  4. The effect of loading palladium on zinc oxide on the photocatalytic degradation of methyl tert-butyl ether (MTBE) in water.

    Science.gov (United States)

    Seddigi, Zaki S; Ahmed, Saleh A; Ansari, Shahid P; Yarkandi, Naeema H; Danish, Ekram; Alkibash, Abdullah Abu; Oteef, Mohammed D Y; Ahmed, Shakeel

    2014-01-01

    A series of heterogeneous catalysts was prepared by doping zinc oxide with different palladium loadings in the range of 0.5%-1.5%. The prepared catalysts were characterized by SEM, TEM and XRD. These catalysts were applied to study the degradation of Methyl tert-Butyl Ether (MTBE). An amount of 100 mg of each of these catalysts was added to an aqueous solution of 100 ppm of MTBE. The resulting mixtures were irradiated with UV light for a period of 5 h. A 99.7% removal of MTBE was achieved in the case of the zinc oxide photocatalyst particles doped with 1% Pd. The photoreaction was found to be a first-order one. © 2014 The American Society of Photobiology.

  5. The application of silicalite-1/fly ash cenosphere (S/FAC) zeolite composite for the adsorption of methyl tert-butyl ether (MTBE).

    Science.gov (United States)

    Lu, Jia; Xu, Fang; Wang, Deju; Huang, Jue; Cai, Weimin

    2009-06-15

    Silicalite-1/fly ash cenosphere (S/FAC) zeolite composite has been applied for batch adsorption of methyl tert-butyl ether (MTBE) from water systems. Here the key experimental conditions, including the ratio of initial MTBE concentration to the amount weight of S/FAC, adsorption time and temperature, have been discussed in detail. The results show that approximately 93-95% MTBE could be adsorbed with initial concentration of MTBE solution 1000 microg l(-1). The column flow-through experiments also prove the high capacity of S/FAC composite for MTBE removal. The distinct advantages of S/FAC zeolite composite as adsorbent lie in (1) enhanced adsorption rate and capacity based on hierarchical micro and meso/macroporosity of S/FAC; (2) more easily operation and recycling process by assembly of nano-sized silicalite-1 zeolite on FAC support.

  6. Kinetic Analysis of the Gas-Phase Reactions of Methyl Tert-Butyl Ether with the OH Radical in the Presence of NOx

    Directory of Open Access Journals (Sweden)

    Pimentel André Silva

    1998-01-01

    Full Text Available An explicit chemical mechanism for the reaction of methyl tert-butyl ether (MTBE with OH radicals in NOx-air systems, was simulated by solving the corresponding ordinary differential equations using Runge-Kutta-4-semi-implicit method. The simulated results are consistent with the published experimental data and the model accounts for all the major pathways by which MTBE reacts in NOx-air systems. An eigenvalue-eigenvector analysis is used to extract meaningful kinetic information from linear sensitivity coefficients computed for all species of the chemical mechanism at several time points. This method is used to get an objective condition for constructing a minimal reaction set. Also, a classic method called rate of production analysis (ROPA was used for the study of the reactions relevance. Using the principal component information as well as the rate of production analysis the main paths of reaction are identified and discussed.

  7. Crystal structure of (1,3-di-tert-butyl-η(5)-cyclo-penta-dien-yl)tri-methyl-hafnium(IV).

    Science.gov (United States)

    Pérez-Redondo, Adrián; Varela-Izquierdo, Víctor; Yélamos, Carlos

    2015-05-01

    The mol-ecule of the title organometallic hafnium(IV) com-pound, [Hf(CH3)3(C13H21)] or [HfMe3(η(5)-C5H3-1,3- (t) Bu2)], adopts the classical three-legged piano-stool geometry for mono-cyclo-penta-dienylhafnium(IV) derivatives with the three methyl groups bonded to the Hf(IV) atom at the legs. The C atoms of the two tert-butyl group bonded to the cyclo-penta-dienyl (Cp) ring are 0.132 (5) and 0.154 (6) Å above the Cp least-squares plane. There are no significant inter-molecular inter-actions present between the mol-ecules in the crystal structure.

  8. Crystal structure of (1,3-di-tert-butyl-η5-cyclo­penta­dien­yl)tri­methyl­hafnium(IV)

    Science.gov (United States)

    Pérez-Redondo, Adrián; Varela-Izquierdo, Víctor; Yélamos, Carlos

    2015-01-01

    The mol­ecule of the title organometallic hafnium(IV) com­pound, [Hf(CH3)3(C13H21)] or [HfMe3(η5-C5H3-1,3-tBu2)], adopts the classical three-legged piano-stool geometry for mono­cyclo­penta­dienylhafnium(IV) derivatives with the three methyl groups bonded to the Hf(IV) atom at the legs. The C atoms of the two tert-butyl group bonded to the cyclo­penta­dienyl (Cp) ring are 0.132 (5) and 0.154 (6) Å above the Cp least-squares plane. There are no significant inter­molecular inter­actions present between the mol­ecules in the crystal structure. PMID:25995884

  9. Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Ellermann, T.

    1995-01-01

    UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... 10(-18) cm(2) molecule(-1) and sigma(RO2) = (4.1 +/- 0.6) X 10(-18) cm(2) molecule(-1) (base e). The rate constant for the self-reaction of the alkyl radicals is (2.5 +/- 1.1) X 10(-11) cm(3) molecule(-1) s(-1). The rate constants for reaction of the alkyl radicals with molecular oxygen...

  10. Temperature-Induced Desorption of Methyl tert-Butyl Ether Confined on ZSM-5: An In Situ Synchrotron XRD Powder Diffraction Study

    Directory of Open Access Journals (Sweden)

    Elisa Rodeghero

    2017-02-01

    Full Text Available The temperature-induced desorption of methyl tert-butyl ether (MTBE from aqueous solutions onto hydrophobic ZSM-5 was studied by in situ synchrotron powder diffraction and chromatographic techniques. This kind of information is crucial for designing and optimizing the regeneration treatment of such zeolite. The evolution of the structural features monitored by full profile Rietveld refinements revealed that a monoclinic (P21/n to orthorhombic (Pnma phase transition occurred at about 100 °C. The MTBE desorption process caused a remarkable change in the unit-cell parameters. Complete MTBE desorption was achieved upon heating at about 250 °C. Rietveld analysis demonstrated that the desorption process occurred without any significant zeolite crystallinity loss, but with slight deformations in the channel apertures.

  11. Light-emitting thin films of glassy forming organic compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene

    Science.gov (United States)

    Vembris, Aivars; Pudzs, Kaspars; Muzikante, Inta

    2012-06-01

    Low molecular mass organic compounds which make thin films from volatile organic solutions would be great benefit in future organic light emitting systems. Two most important advantages could be mentioned. First - the repetition of synthesis of small molecules is better than for polymers. Second - wet casting methods could be used. In this work we are presenting optical, electroluminescence and amplified spontaneous emission properties of four original glassy forming compounds containing 2-tert-butyl-6-methyl-4H-pyran-4-ylidene fragment as backbone of the molecule. They has the same N,N-dialkylamino electron donating group with incorporated bulky trityloxy ethyl groups. The difference of these compounds is in electron acceptor group. One has 1H-indene-1,3(2H)-dione group, second has pyrimidine-2,4,6(1H,3H,5H)-trione group, third has malononitrile group and fourth has 2-ethyl-2-cyanoacetate. Absorption maximum of the compounds is between 420 and 500 nm and is red shifted from weaker acceptor group to stronger one. The electroluminescence efficiency for simple device ITO/PEDOT:PSS/Organic compound/BaF/Al is low. For the best one with malononitrile group it was 0.13 cd/A and 0.036 lm/W. It could be increased by optimising the sample geometry or adding addition layers for charge carrier transport and exciton blocking. But nevertheless the use of these compounds in organic light emitting devices in neat films is unlikely. Attached bulky trityloxy ethyl groups and tert-butyl group decrease interaction between the molecules thus allowing to obtain amplified spontaneous emission in neat thin films for all investigated compounds.

  12. Pyrolysis of methyl tert-butyl ether (MTBE). 1. Experimental study with molecular-beam mass spectrometry and tunable synchrotron VUV photoionization.

    Science.gov (United States)

    Zhang, Taichang; Wang, Jing; Yuan, Tao; Hong, Xin; Zhang, Lidong; Qi, Fei

    2008-10-23

    An experimental study of methyl tert-butyl ether (MTBE) pyrolysis (3.72% MTBE in argon) has been performed at low pressure (267 Pa) within the temperature range from 700 to 1420 K. The pyrolysis process was detected with the tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry (MBMS). About thirty intermediates are identified from near-threshold measurements of photoionization mass spectrum and photoionization efficiency spectrum. Among them, H2, CO, CH4, CH3OH and C4H8 are the major pyrolysis products. The radicals such as methyl, methoxy, propargyl, allyl, C4H5 and C4H7 are detected. The isomers of pyrolysis products are identified as well, i.e., propyne and allene, 1,2,3-butatriene and vinylacetylene, isobutene and 1-butene, propanal and acetone. Furthermore, the mole fractions of the pyrolysis products have been evaluated under various temperatures. Meanwhile, the initial formation temperatures of different pyrolysis products can be obtained. This work is anticipated to present a new experimental method for pyrolysis study and help understand the pyrolysis and combustion chemistry of MTBE and other oxygenated fuels.

  13. Synthesis of [[sup 123]I]tert-Butyl 8-iodo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a][1,4]benzodiaze pine 3-carboxylate, a potential SPECT imaging agent for diazepam-intensive (DI) benzodiazepine receptors

    Energy Technology Data Exchange (ETDEWEB)

    Xiaoshu He; Matecka, Dorota; Ziqiang Gu; Rice, K.C.; Costa, B.R. de (National Inst. of Diabetes and Digestive and Kidney Diseases, Bethesda, MD (United States)); Lee, K.S. (National Inst. of Mental Health, Washington, DC (United States)); Wong, Garry; Skolnick, Phil (National Inst. of Diabetes and Digestive and Kidney Diseases, Bethesda, MD (United States). Lab. of Neuroscience)

    1994-01-01

    [[sup 123]I]tert-Butyl 8-iodo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo [1,5-a] [1,4]benzodiazepine 3-carboxylate ([[sup 123]I]3), a high affinity and selective radioligand for the diazepam insensitive (DI) benzodiazepine receptor was synthesized in 2 steps from tert-butyl 8-bromo-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a][1,4]benzodiaz epine 3-carboxylate. (Author).

  14. Toxicokinetics of methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME) in humans, and implications to their biological monitoring.

    Science.gov (United States)

    Vainiotalo, Sinikka; Riihimäki, Vesa; Pekari, Kaija; Teräväinen, Eija; Aitio, Antero

    2007-10-01

    Healthy male volunteers were exposed via inhalation to gasoline oxygenates methyl tert-butyl ether (MTBE) or tert-amyl methyl ether (TAME). The 4-hr exposures were carried out in a dynamic chamber at 25 and 75 ppm for MTBE and at 15 and 50 ppm for TAME. The overall mean pulmonary retention of MTBE was 43 +/- 2.6%; the corresponding mean for TAME was 51 +/- 3.9%. Approximately 52% of the absorbed dose of MTBE was exhaled within 44 hr following the exposure; for TAME, the corresponding figure was 30%. MTBE and TAME in blood and exhaled air reached their highest concentrations at the end of exposure, whereas the concentrations of the metabolites tert-butanol (TBA) and tert-amyl alcohol (TAA) concentrations were highest 0.5-1 hr after the exposure and then declined slowly. Two consecutive half-times were observed for the disappearance of MTBE and TAME from blood and exhaled air. The half-times for MTBE in blood were about 1.7 and 3.8 hr and those for TAME 1.2 and 4.9 hr. For TAA, a single half-time of about 6 hr best described the disappearance from blood and exhaled air; for TBA, the disappearance was slow and seemed to follow zero-order kinetics for 24 hr. In urine, maximal concentrations of MTBE and TAME were observed toward the end of exposure or slightly (MTBE and 0.1% of the dose of TAME was excreted unchanged in urine, whereas the urinary excretion of free TBA and TAA was 1.2% and 0.3% within 48 hr. The blood/air and oil/blood partition coefficients, determined in vitro, were 20 and 14 for MTBE and 20 and 37 for TAME. By intrapolation from the two experimental exposure concentrations, biomonitoring action limits corresponding to an 8-hr time-weighted average (TWA) exposure of 50 ppm was estimated to be 20 micro mol/L for post-shift urinary MTBE, 1 mu mol/L for exhaled air MTBE in a post-shift sample, and 30 micro mol/L for urinary TBA in a next-morning specimen. For TAME and TAA, concentrations corresponding to an 8-hr TWA exposure at 20 ppm were estimated to be

  15. Paenibacillus etheri sp. nov., able to growth on media supplemented with methyl tert-butyl ether (MTBE) isolated from hydrocarbon contaminated soil.

    Science.gov (United States)

    Guisado, Isabel M; Purswani, Jessica; González-López, Jesús; Pozo, Clementina

    2015-11-26

    A bacterial strain designated as strain SH7T was isolated from the hydrocarbon contaminated soil of a pilot plant (Granada, Spain). The strain was selected for its capacity to growth in media supplemented with methyl tert-butyl ether (MTBE) as sole energy and carbon source. Strain SH7T was a Gram-stain-positive, facultatively anaerobic, spore-forming, rod-shaped bacterium. Phylogenetic analysis using 16S rRNA gene sequences showed that strain SH7T belongs to a cluster comprising species of the genus Paenibacillus and was closely related to Paenibacillus borealis DSM 13188T (97%) and Paenibacillus odorifer DSM 15391T (98%). DNA-DNA hybridization tests showed low relatedness of the strain SH7T with Paenibacillus borealis (16.9±1.5%) and Paenibacillus odorifer (16.6±2.1%) respectively. The cell wall contained meso-diaminopimelic acid. The predominant respiratory quinone was MK-7, anteiso-C15:0 (32.9%) and C16:0 (29.0%) were the predominant cellular fatty acids. Phosphatidylglycerol, phosphatidylethanolamine, diphosphatidylglycerol and three unknown aminophospholipids were the major phospholipids. The DNA G+C content was 44.3 mol%. The data obtained in this study indicate that the SH7Tstrain represents a novel species of the genus Paenibacillus, for which the name Paenibacillus etheri sp. nov. is proposed. The type strain is SH7T (= CECT 8558T =DSM 29760T).

  16. Mechanistic considerations for the degradation of methyl tert-butyl ether (MTBE) by sonolysis: effect of argon vs. oxygen saturated solutions.

    Science.gov (United States)

    Kim, Duk Kyung; O'Shea, Kevin E; Cooper, William J

    2012-07-01

    The ultrasonic degradation mechanism of methyl tert-butyl ether (MTBE) in aqueous solution is complex because of the competition between hydroxyl radical attack, pyrolysis, and hydrolysis reactions. A detailed investigation of degradation pathways using sonolysis has been performed using reaction byproducts identification. The observed bi-product distributions are rationalized in terms of hydroxyl radical (()OH) mediated processes and pyrolysis. The role of oxygen mediated and pyrolytic pathways were assessed using O(2) and Ar saturated solutions. Chemical destruction by sonolysis is often rationalized using hydroxyl radical chemistry. Pyrolysis is unique to this advanced oxidation process, and is important in the case of MTBE because it transfers into the cavitating bubbles. While α-hydrogen abstraction by ()OH and low temperature pyrolysis was important, it was also shown that β-hydrogen abstraction leads, in some cases, to the same reaction byproducts, which emphasized the importance of α-hydrogen abstraction. High temperature pyrolysis resulted in minor degradation reactions based on the formation of reaction by-products. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Naturally occurring bacteria similar to the methyl tert-butyl ether (MTBE)-degrading strain PM1 are present in MTBE-contaminated groundwater.

    Science.gov (United States)

    Hristova, Krassimira; Gebreyesus, Binyam; Mackay, Douglas; Scow, Kate M

    2003-05-01

    Methyl tert-butyl ether (MTBE) is a widespread groundwater contaminant that does not respond well to conventional treatment technologies. Growing evidence indicates that microbial communities indigenous to groundwater can degrade MTBE under aerobic and anaerobic conditions. Although pure cultures of microorganisms able to degrade or cometabolize MTBE have been reported, to date the specific organisms responsible for MTBE degradation in various field studies have not be identified. We report that DNA sequences almost identical (99% homology) to those of strain PM1, originally isolated from a biofilter in southern California, are naturally occurring in an MTBE-polluted aquifer in Vandenberg Air Force Base (VAFB), Lompoc, California. Cell densities of native PM1 (measured by TaqMan quantitative PCR) in VAFB groundwater samples ranged from below the detection limit (in anaerobic sites) to 10(3) to 10(4) cells/ml (in oxygen-amended sites). In groundwater from anaerobic or aerobic sites incubated in microcosms spiked with 10 microg of MTBE/liter, densities of native PM1 increased to approximately 10(5) cells/ml. Native PM1 densities also increased during incubation of VAFB sediments during MTBE degradation. In controlled field plots amended with oxygen, artificially increasing the MTBE concentration was followed by an increase in the in situ native PM1 cell density. This is the first reported relationship between in situ MTBE biodegradation and densities of MTBE-degrading bacteria by quantitative molecular methods.

  18. Use of Methyl Tert-Butyl Ether for the Treatment of Refractory Intrahepatic Biliary Strictures and Bile Casts: A Modern Perspective

    Directory of Open Access Journals (Sweden)

    Gregory Kim

    2015-01-01

    Full Text Available Cholelithiasis is a prevalent problem in the United States with 14% or more adults affected. Definitive treatment of cholelithiasis is cholecystectomy. When cholecystectomy yields minimal resolution treatment options include expectant management of asymptomatic gallstones or endoscopic retrograde cholangiopancreatogram. We present a case of intrahepatic biliary casts where surgical option was not possible, interventional radiology was unsuccessful, and methyl tert-butyl ether was used to dissolve the biliary obstruction. Dissolution therapy of gallstones was first reported in 1722 when Vollisnieri used turpentine in vitro. While diethyl ether has excellent solubilizing capacity, its low boiling point limited its use surgically as it vaporizes immediately. Diethyl ether can expand 120-fold during warming to body temperature after injection into the biliary system making it impractical for routine use. The use of dissolution is out of favor due to the success of laparoscopic cholecystectomy. Epidemiological studies have shown the general population should have minimal concerns from passive exposure. Dissolution using MTBE remains a viable option if surgical or endoscopic options are not available. However, because of risks involved to both the patient and the staff, careful multidisciplinary team approach must be undertaken to minimize the risks and provide the best possible care to the patient.

  19. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Tang, G.H. [Xian Medical Univ. (China); Shen, Y.; Shen, H.M. [National Univ. of Singapore (Singapore)] [and others

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  20. Response surface analysis of photocatalytic degradation of methyl tert-butyl ether by core/shell Fe3O4/ZnO nanoparticles.

    Science.gov (United States)

    Safari, Mojtaba; Rostami, Mohammad Hossein; Alizadeh, Mehriana; Alizadehbirjandi, Atefeh; Nakhli, Seyyed Ali Akbar; Aminzadeh, Reza

    2014-01-06

    The degradation of methyl tert-butyl ether (MTBE) was investigated in the aqueous solution of coated ZnO onto magnetite nanoparticale based on an advanced photocatalytic oxidation process. The photocatalysts were synthesized by coating of ZnO onto magnetite using precipitation method. The sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and vibration sample magnetometer (VSM). Besides, specific surface area was also determined by BET method. The four effective factors including pH of the reaction mixture, Fe3O4/ZnO magnetic nanoparticles concentration, initial MTBE concentration and molar ratio of [H2O2]/ [MTBE] were optimized using response surface modeling (RSM). Using the four-factor-three-level Box-Behnken design, 29 runs were designed considering the effective ranges of the influential factors. The optimized values for the operational parameters under the respective constraints were obtained at PH of 7.2, Fe3O4/ZnO concentration of 1.78 g/L, initial MTBE concentration of 89.14 mg/L and [H2O2]/ [MTBE] molar ratio of 2.33. Moreover, kinetics of MTBE degradation was determined under optimum condition. The study about core/shell magnetic nanoparticles (MNPs) recycling were also carried out and after about four times, the percentage of the photocatalytic degradation was about 70%.

  1. The study of binding of methyl tert-butyl ether to human telomeric G-quadruplex and calf thymus DNA by gas chromatography, a thermodynamic discussion.

    Science.gov (United States)

    Ghasemi, Sahar; Ahmadi, Farhad

    2014-11-15

    Methyl-tert-butyl ether (MTBE) is widely used as an antiknock additive for increasing octane number of gasoline. Recently, the in vivo studies demonstrated that MTBE has genotoxic potential and able to form adducts with DNA. In the work, the interactions of MTBE with calf thymus DNA (ct-DNA) and the Na(+) form of G-quadruplex DNA (wtTel22) were studied by using of head space-solid phase microextraction technique coupled to gas chromatography. The binding equilibrium constants were measured through the equilibriums of a four phase system. In addition, the MTBE Henry's law constants for two different buffers in the temperature range of 283-303K were measured. Thermodynamic studies revealed that the complexation of MTBE to both DNAs is enthalpy favored and entropy disfavored. The thermodynamic results revealed that MTBE may have interaction with ct-DNA via the minor groove of DNA. Also, MTBE may be complexed into the basket of G-quadruplex structure. In addition, the low difference in the binding constants of MTBE for both different DNA targets may confirm that MTBE is poorly selective for different conformations of DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. National survey of Methyl tert-Butyl Ether and other Volatile Organic Compounds in drinking-water sources: Results of the random source-water survey

    Science.gov (United States)

    Grady, Stephen J.

    2002-01-01

    Methyl tert-butyl ether (MTBE) was detected in source water used by 8.7 percent of randomly selected community water systems (CWSs) in the United States at concentrations that ranged from 0.2 to 20 micrograms per liter (?g/L). The Random Survey conducted by the U.S. Geological Survey, in cooperation with the Metropolitan Water District of Southern California and the Oregon Health & Science University, was designed to provide an assessment of the frequency of detection, concentration, and distribution of MTBE, three other ether gasoline oxygenates, and 62 other volatile organic compounds (VOCs) in ground- and surface-water sources used for drinking-water supplies. The Random Survey was the first of two components of a national assessment of the quality of source water supplying CWSs sponsored by the American Water Works Association Research Foundation. A total of 954 CWSs were selected for VOC sampling from the population of nearly 47,000 active, self-supplied CWSs in all 50 States, Native American Lands, and Puerto Rico based on a statistical design that stratified on CWS size (population served), type of source water (ground and surface water), and geographic distribution (State).At a reporting level of 0.2 ?g/L, VOCs were detected in 27 percent of source-water samples collected from May 3, 1999 through October 23, 2000. Chloroform (in 13 percent of samples) was the most frequently detected of 42 VOCs present in the source-water samples, followed by MTBE. VOC concentrations were generally less than 10 ?g/L?95 percent of the 530 detections?and 63 percent were less than 1.0 ?g/L. Concentrations of 1,1-dichloroethene, tetrachloroethene, trichloroethene, vinyl chloride, and total trihalomethanes (TTHMs), however, exceeded drinking-water regulations in eight samples.Detections of most VOCs were more frequent in surface-water sources than in ground-water sources, with gasoline compounds collectively and MTBE individually detected significantly more often in surface

  3. Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2.

    Science.gov (United States)

    Hu, Qinhai; Zhang, Chunlong; Wang, Zhirong; Chen, Yan; Mao, Kehui; Zhang, Xingqing; Xiong, Yunlong; Zhu, Miaojun

    2008-06-15

    Two UV-based advanced oxidation processes (AOPs), UV/H2O2 and UV/TiO2, were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of methyl tert-butyl ether (MTBE). The optimal conditions at an initial MTBE concentration of 1 mM ([MTBE]0=1 mM) were acidic and 15 mM H2O2 in UV/H2O2 system, and pH 3.0 and 2.0 g/l TiO2 in UV/TiO2 suspended slurries system under 254-nm UV irradiation. Under the optimal conditions, MTBE photodegradation during the initial period of 60 min in UV/H2O2 and UV/TiO2 systems reached 98 and 80%, respectively. In both systems, MTBE photodegradation decreased with increasing [MTBE]0. While MTBE photodegradation rates increased with increasing dosage of H2O2 (5-15 mM) and TiO2 (0.5-3 g/l), further increase in the dosage of H2O2 (20 mM) or TiO2 (4 g/l) adversely reduced the MTBE photodegradation. Pseudo first-order kinetics with regard to [MTBE] can be used to describe the MTBE photodegradation in both systems. The pseudo first-order rate constants linearly increased with the increase in the molar ratio of [H2O2]0 to [MTBE]0 in UV/H2O2 system and linearly increased with the decrease in [MTBE]0 in UV/TiO2 system.

  4. Application of artificial neural networks for modeling of the treatment of wastewater contaminated with methyl tert-butyl ether (MTBE) by UV/H2O2 process.

    Science.gov (United States)

    Salari, D; Daneshvar, N; Aghazadeh, F; Khataee, A R

    2005-10-17

    During the last two decades, methyl tert-butyl ether (MTBE) has been widely used as an additive to gasoline (up to 15%) both to increase the octane number and as a fuel oxygenate to improve air quality by reducing the level of carbon monoxide in vehicle exhausts. The present work mainly deals with photooxidative degradation of MTBE in the presence of H2O2 under UV light illumination (30W). We studied the influence of the basic operational parameters such as initial concentration of H2O2 and irradiation time on the photodegradation of MTBE. The oxidation rate of MTBE was low when the photolysis was carried out in the absence of H2O2 and it was negligible in the absence of UV light. The addition of proper amount of hydrogen peroxide improved the degradation, while the excess hydrogen peroxide could quench the formation of hydroxyl radicals (OH). The semi-log plot of MTBE concentration versus time was linear, suggesting a first order reaction. Therefore, the treatment efficiency was evaluated by figure-of-merit electrical energy per order (E(Eo)). Our results showed that MTBE could be treated easily and effectively with the UV/H2O2 process with E(Eo) value 80 kWh/m3/order. The proposed model based on artificial neural network (ANN) could predict the MTBE concentration during irradiation time in optimized conditions. A comparison between the predicted results of the designed ANN model and experimental data was also conducted.

  5. Using groundwater age distributions to understand changes in methyl tert-butyl ether (MtBE) concentrations in ambient groundwater, northeastern United States

    Science.gov (United States)

    Lindsey, Bruce; Ayotte, Joseph; Jurgens, Bryant; DeSimone, Leslie

    2017-01-01

    Temporal changes in methyl tert-butyl ether (MtBE) concentrations in groundwater were evaluated in the northeastern United States, an area of the nation with widespread low-level detections of MtBE based on a national survey of wells selected to represent ambient conditions. MtBE use in the U.S. peaked in 1999 and was largely discontinued by 2007. Six well networks, each representing specific areas and well types (monitoring or supply wells), were each sampled at 10 year intervals between 1996 and 2012. Concentrations were decreasing or unchanged in most wells as of 2012, with the exception of a small number of wells where concentrations continue to increase. Statistically significant increasing concentrations were found in one network sampled for the second time shortly after the peak of MtBE use, and decreasing concentrations were found in two networks sampled for the second time about 10 years after the peak of MtBE use. Simulated concentrations from convolutions of estimates for concentrations of MtBE in recharge water with age distributions from environmental tracer data correctly predicted the direction of MtBE concentration changes in about 65 percent of individual wells. The best matches between simulated and observed concentrations were found when simulating recharge concentrations that followed the pattern of national MtBE use. Some observations were matched better when recharge was modeled as a plume moving past the well from a spill at one point in time. Modeling and sample results showed that wells with young median ages and narrow age distributions responded more quickly to changes in the contaminant source than wells with older median ages and broad age distributions. Well depth and aquifer type affect these responses. Regardless of the timing of decontamination, all of these aquifers show high susceptibility for contamination by a highly soluble, persistent constituent.

  6. Methyl tert-butyl ether (MTBE) and other volatile organic compounds in lakes in Byram Township, Sussex County, New Jersey, summer 1998

    Science.gov (United States)

    Baehr, Arthur L.; Zapecza, Otto S.

    1998-01-01

     Water samples were collected from four lakes in Byram Township, Sussex County, N.J., in the summer of 1998 as part of an investigation of the occurrence of volatile organic compounds (VOCs) in domestic wells of lakeside communities. Cranberry Lake and Lake Lackawanna are surrounded by densely populated communities where the use of gasoline-powered watercraft is prevalent, and water is supplied by lakeside wells. Forest Lake is surrounded by a densely populated community where the use of gasoline-powered watercraft is prohibited. Stag Pond is privately owned, is situated in a sparsely populated area, and is not navigated by gasoline-powered watercraft. Samples were collected from Cranberry Lake in early summer and again in late summer 1998. Concentrations of the gasoline oxygenate methyl tert-butyl ether (MTBE) ranged from 1.6 to 15.0 µg/L (micrograms per liter) on June 24 and decreased with depth. The depth-related concentration gradient is attributed to density stratification caused by the temperature gradient that is present in the lake during the early summer. MTBE concentrations ranged from 7.4 to 29.0 µg/L on September 8 and were uniform with depth, as was water temperature, indicating that the lake was vertically mixed. On the basis of these concentration profiles, the mass of MTBE in Cranberry Lake was estimated to be 15 kilograms on June 24 and 27 kilograms on September 8. These mass estimates are equal to the amount of MTBE in 52 and 95 gallons, respectively, of gasoline that contains 10 percent MTBE by volume. Concentrations of another gasoline oxygenate, tert-amyl-methyl ether (TAME), ranged from 0.07 to 0.43 µg/L on June 24 and from 0.2 to 0.69 µg/L on September 8. The highest concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX) were 0.18, 1.2, 0.18, and 0.97 µg/L, respectively, on June 24. All BTEX concentrations in Cranberry Lake on September 8 were less than 0.2 µg/L.

  7. Methyl tert butyl ether (MTBE) is anti- angiogenic in both in vitro and in vivo mammalian model systems

    Science.gov (United States)

    Kozlosky, John; Bonventre, Josephine; Cooper, Keith

    2015-01-01

    Methyl-tertiary butyl ether (MTBE), a well known gasoline oxygenate, and FDA approved gallstone treatment, has been previously shown to specifically target teleost embryonic angiogenesis. The studies reported here were to determine if similar vascular disrupting effects occurred in higher vertebrate models. Rat brain endothelial cells were isolated and allowed to form microcapillary-like tubes on Matrigel. MTBE (0.34–34.0 mM) exposure resulted in a dose-dependent reduction of tube formation, with the LOAEL at 0.34 mM, while MTBE’s primary metabolite, tertiary butyl alcohol had no effect on tube formation. HUVECs, a primary cell line representing macrovascular cells, were able to form tubes on Matrigel in the presence of MTBE (1.25 – 80 mM), but the tubes were narrower than those formed in the absence of MTBE. In a mouse Matrigel plug implantation assay, 34.0 mM MTBE completely inhibited vessel invasion into plugs containing Endothelial Cell Growth Supplement (ECGS) compared to control plugs with ECGS alone. When timed-pregnant Fisher 344 rats were gavaged with MTBE (500–1500 mg/kg) from day 6 of organogenesis through 10 days post parturition, no organ toxicity or histological changes in pup vasculature were observed. Therefore, MTBE is anti-angiogenic at mM concentrations and therefore a potential use as an anti-angiogenic treatment for solid tumors with minimal toxicity. PMID:22407988

  8. tert-Butyl 3-[2,2-bis-(ethoxy-carbon-yl)vin-yl]-2-bromo-methyl-1H-indole-1-carboxyl-ate.

    Science.gov (United States)

    Thenmozhi, M; Kavitha, T; Dhayalan, V; Mohanakrishnan, A K; Ponnuswamy, M N

    2009-10-17

    In the title compound, C(22)H(26)BrNO(6), the indole ring system is planar [maximum deviation 0.029 (2) Å]. The tert-butyl bound carboxyl-ate group forms a dihedral angle of 17.54 (8)° with the indole ring system. In the crystal, mol-ecules are linked into centrosymmetric R(2) (2)(10) dimers by paired C-H⋯O hydrogen bonds.

  9. Preparation and characterization of Pd doped ceria–ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation

    Energy Technology Data Exchange (ETDEWEB)

    Seddigi, Zaki S. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Bumajdad, Ali [Chemistry Department, Faculty of Science, Kuwait University (Kuwait); Ansari, Shahid P. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Saleh A., E-mail: saleh_63@hotmail.com [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Danish, Ekram Y. [Chemistry Department, King Abdulaziz University, Jeddah (Saudi Arabia); Yarkandi, Naeema H. [Chemistry Department, Umm Al-Qura University, Makkah (Saudi Arabia); Ahmed, Shakeel [Center for Refining and Petrochemicals, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

    2014-01-15

    Highlights: • Novel Pd supported ceria–ZnO photocatalysts were prepared with different amounts of palladium. • The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. • Near complete removal of MTBE was achieved using 1% Pd doped ceria–ZnO catalyst and UV irradiation. • Highest rate constant was obtained in case of 1% Pd doped ceria–ZnO catalyst. • Shape and size of pores are important factors for high photoactivity of catalyst. -- Abstract: A series of binary oxide catalysts (ceria–ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%–1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N{sub 2} sorptiometry study. The XPS results confirmed the structure of the Pd CeO{sub 2−x}-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100 ppm aqueous solution of MTBE upon UV irradiation for 5 h in the presence of 100 mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria–ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N{sub 2} sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction.

  10. Preparation and characterization of Pd doped ceria-ZnO nanocomposite catalyst for methyl tert-butyl ether (MTBE) photodegradation.

    Science.gov (United States)

    Seddigi, Zaki S; Bumajdad, Ali; Ansari, Shahid P; Ahmed, Saleh A; Danish, Ekram Y; Yarkandi, Naeema H; Ahmed, Shakeel

    2014-01-15

    A series of binary oxide catalysts (ceria-ZnO) were prepared and doped with different amounts of palladium in the range of 0.5%-1.5%. The prepared catalysts were characterized by SEM, TEM, XRD and XPS, as well as by N2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO2-x-ZnO. The photocatalytic activity of these catalysts was evaluated for degradation of MTBE in water. These photocatalyst efficiently degrade a 100ppm aqueous solution of MTBE upon UV irradiation for 5h in the presence of 100mg of each of these photocatalysts. The removal of 99.6% of the MTBE was achieved with the ceria-ZnO catalyst doped with 1% Pd. In addition to the Pd loading, the N2 sorptiometry study introduced other factors that might affect the catalytic efficiency is the catalyst average pore sizes. The photoreaction was determined to be a first order reaction. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Temperature effect on tert-butyl alcohol (TBA biodegradation kinetics in hyporheic zone soils

    Directory of Open Access Journals (Sweden)

    Sims Ronald C

    2007-09-01

    Full Text Available Abstract Background Remediation of tert-butyl alcohol (TBA in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE, ethyl tert-butyl ether (ETBE, and tert-butyl formate (TBF. The effect of temperature on TBA biodegradation has not been not been published in the literature. Methods Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. Results First order mineralization rate constants of TBA at 5°C, 15°C and 25°C were 7.84 ± 0.14 × 10-3, 9.07 ± 0.09 × 10-3, and 15.3 ± 0.3 × 10-3 days-1, respectively (or 2.86 ± 0.05, 3.31 ± 0.03, 5.60 ± 0.14 years-1, respectively. Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A and activation energy (Ea of 154 day-1 and 23,006 mol/J, respectively. Conclusion Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

  12. Linking low-level stable isotope fractionation to expression of the cytochrome P450 monooxygenase-encoding ethB gene for elucidation of methyl tert-butyl ether biodegradation in aerated treatment pond systems.

    Science.gov (United States)

    Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H

    2011-02-01

    Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ε(C)] of -0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ε(H)]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ε(C) of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ε(H) of -5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem.

  13. Linking Low-Level Stable Isotope Fractionation to Expression of the Cytochrome P450 Monooxygenase-Encoding ethB Gene for Elucidation of Methyl tert-Butyl Ether Biodegradation in Aerated Treatment Pond Systems▿ †

    Science.gov (United States)

    Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M.; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H.

    2011-01-01

    Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ɛC] of −0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ɛH]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ɛC of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ɛH of −5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem. PMID:21148686

  14. Tailored Interfaces for Biosensors and Cell-Surface Interaction Studies via Activation and Derivatization of Polystyrene-block-poly(tert-butyl acrylate) Thin Films

    NARCIS (Netherlands)

    Feng, C.L.; Embrechts, A.; Bredebusch, Ilona; Bouma, Anita; Schnekenburger, Jürgen; Garcia Parajo, M.F.; Domschke, Wolfram; Vancso, Gyula J.; Schönherr, Holger

    2007-01-01

    Thin spin-coated films of polystyrene-block-poly(tert-butyl acrylate) (PS690-b-PtBA1210) on various substrates are introduced as versatile, robust reactive platform for the immobilization of (bio)molecules for the fabrication of tailored biointerfaces. The films are characterized by high stability

  15. Crystal structure of (tert-butyl-carbamo-yl)(4-chloro-2-oxo-2H-chromen-3-yl)methyl acetate.

    Science.gov (United States)

    Moriguchi, Tetsuji; Jalli, Venkataprasad; Krishnamurthy, Suvratha; Tsuge, Akihiko; Yoja, Kenji

    2015-12-01

    In the title compound, C17H18ClNO5, which was synthesized by reacting 4-chloro-3-formyl-coumarin, acetic acid and tert-butyl isocyanide, the acetamido side chain is convoluted with ring-to-side chain C-C-C-C, C-C-C-N and C-C-N-C torsion angles of -123.30 (14), -135.73 (12) and 176.10 (12)°, respectively. In the crystal, N-H⋯O and weak C-H⋯O hydrogen bonds are present, which together with π-π coumarin-ring inter-actions [ring centroid separations = 3.4582 (8) and 3.6421 (9) Å], give rise to a layered structure lying parallel to (001).

  16. Methyl tert-butyl ether in ground and surface water of the United States: National-scale relations between MTBE occurrence in surface and ground water and MTBE use in gasoline

    Science.gov (United States)

    Moran, M.J.; Clawges, R.M.; Zogorski, J.S.

    2002-01-01

    The detection frequency of methyl tert-butyl ether (MTBE) in ground and surface water of the United States is positively related to the content of MTBE in gasoline in various metropolitan areas of the U.S. The frequency of detection of MTBE is generally higher in areas that use larger amounts of MTBE in gasoline. Sampling of surface and ground water by the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program between 1993 and 1998 revealed a frequent detection of low concentrations of MTBE. In this analysis, data from several national-scale gasoline surveys are examined and data from one survey that is most extensive in geographic and temporal coverage is used to relate the detection of MTBE in ground and surface water to the volumetric content of MTBE in gasoline.

  17. Ionic-liquid-mediated poly(dimethylsiloxane)- grafted carbon nanotube fiber prepared by the sol-gel technique for the head space solid-phase microextraction of methyl tert-butyl ether using GC.

    Science.gov (United States)

    Vatani, Hossein; Yazdi, Ali Sarafraz

    2014-01-01

    A headspace solid-phase microextraction method was developed for the preconcentration and extraction of methyl tert-butyl ether. An ionic-liquid-mediated multiwalled carbon nanotube-poly(dimethylsiloxane) hybrid coating, which was prepared by covalent functionalization of multiwalled carbon nanotubes with hydroxyl-terminated poly(dimethylsiloxane) using the sol-gel technique, was used as solid-phase microextraction adsorbent. This innovative fiber exhibited a highly porous surface structure, high thermal stability (at least 320°C) and long lifespan (over 210 uses). Potential factors affecting the extraction efficiency were optimized. Under the optimum conditions, the method LOD (S/N = 3) was 0.007 ng/mL and the LOQ (S/N = 10) was 0.03 ng/mL. The calibration curve was linear in the range of 0.03-200 ng/mL. The RSDs for one fiber (repeatability, n = 5) at three different concentrations (0.05, 1, and 150 ng/mL) were 5.1, 4.2, and 4.6% and for the fibers obtained from different batches (reproducibility, n = 3) were 6.5, 5.9, and 6.3%, respectively. The developed method was successfully applied to the determination of methyl tert-butyl ether in different real water samples on three consecutive days. The relative recoveries for the spiked samples with 0.05, 1, and 150 ng/mL were between 94-104%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Gastroprotective activity of ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylidene amino]benzoate against ethanol-induced gastric mucosal ulcer in rats.

    Directory of Open Access Journals (Sweden)

    Mohammed Farouq Halabi

    Full Text Available BACKGROUND: The study was carried out to determine the cytotoxic, antioxidant and gastro-protective effect of ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylid eneamino] benzoate (ETHAB in rats. METHODOLOGY/PRINCIPAL FINDINGS: The cytotoxic effect of ETHAB was assessed using a MTT cleavage assay on a WRL68 cell line, while its antioxidant activity was evaluated in vitro. In the anti-ulcer study, rats were divided into six groups. Group 1 and group 2 received 10% Tween 20 (vehicle. Group 3 received 20 mg/kg Omeprazole. Groups 4, 5 and 6 received ETHAB at doses of 5, 10, and 20 mg/kg, respectively. After an hour, group 1 received the vehicle. Groups 2-6 received absolute ethanol to induce gastric mucosal lesions. In the WRL68 cell line, an IC50 of more than 100 µg/mL was observed. ETHAB results showed antioxidant activity in the DPPH, FRAP, nitric oxide and metal chelating assays. There was no acute toxicity even at the highest dosage (1000 mg/kg. Microscopy showed that rats pretreated with ETHAB revealed protection of gastric mucosa as ascertained by significant increases in superoxide dismutase (SOD, pH level, mucus secretion, reduced gastric lesions, malondialdehyde (MDA level and remarkable flattened gastric mucosa. Histologically, pretreatment with ETHAB resulted in comparatively better gastric protection, due to reduction of submucosal edema with leucocyte infiltration. PAS staining showed increased intensity in uptake of Alcian blue. In terms of immunohistochemistry, ETHAB showed down-expression of Bax proteins and over-expression of Hsp70 proteins. CONCLUSION/SIGNIFICANCE: The gastroprotective effect of ETHAB may be attributed to antioxidant activity, increased gastric wall mucus, pH level of gastric contents, SOD activity, decrease in MDA level, ulcer area, flattening of gastric mucosa, reduction of edema and leucocyte infiltration of the submucosal layer, increased PAS staining, up-regulation of Hsp70 protein and suppressed expression of

  19. Gastroprotective Activity of Ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylidene) Amino]benzoate against Ethanol-Induced Gastric Mucosal Ulcer in Rats

    Science.gov (United States)

    Halabi, Mohammed Farouq; Shakir, Raied Mustafa; Bardi, Daleya Abdulaziz; Al-Wajeeh, Nahla Saeed; Ablat, Abdulwali; Hassandarvish, Pouya; Hajrezaie, Maryam; Norazit, Anwar; Abdulla, Mahmood Ameen

    2014-01-01

    Background The study was carried out to determine the cytotoxic, antioxidant and gastro-protective effect of ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylid ene)amino] benzoate (ETHAB) in rats. Methodology/Principal Findings The cytotoxic effect of ETHAB was assessed using a MTT cleavage assay on a WRL68 cell line, while its antioxidant activity was evaluated in vitro. In the anti-ulcer study, rats were divided into six groups. Group 1 and group 2 received 10% Tween 20 (vehicle). Group 3 received 20 mg/kg Omeprazole. Groups 4, 5 and 6 received ETHAB at doses of 5, 10, and 20 mg/kg, respectively. After an hour, group 1 received the vehicle. Groups 2–6 received absolute ethanol to induce gastric mucosal lesions. In the WRL68 cell line, an IC50 of more than 100 µg/mL was observed. ETHAB results showed antioxidant activity in the DPPH, FRAP, nitric oxide and metal chelating assays. There was no acute toxicity even at the highest dosage (1000 mg/kg). Microscopy showed that rats pretreated with ETHAB revealed protection of gastric mucosa as ascertained by significant increases in superoxide dismutase (SOD), pH level, mucus secretion, reduced gastric lesions, malondialdehyde (MDA) level and remarkable flattened gastric mucosa. Histologically, pretreatment with ETHAB resulted in comparatively better gastric protection, due to reduction of submucosal edema with leucocyte infiltration. PAS staining showed increased intensity in uptake of Alcian blue. In terms of immunohistochemistry, ETHAB showed down-expression of Bax proteins and over-expression of Hsp70 proteins. Conclusion/Significance The gastroprotective effect of ETHAB may be attributed to antioxidant activity, increased gastric wall mucus, pH level of gastric contents, SOD activity, decrease in MDA level, ulcer area, flattening of gastric mucosa, reduction of edema and leucocyte infiltration of the submucosal layer, increased PAS staining, up-regulation of Hsp70 protein and suppressed expression of Bax. Key words

  20. gamma-Aminobutyric acid(A) (GABA(A)) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of methyl tert-butyl ether (MTBE)-induced impairment of spatial memory.

    Science.gov (United States)

    Zheng, Gang; Zhang, Wenbin; Zhang, Yun; Chen, Yaoming; Liu, Mingchao; Yao, Ting; Yang, Yanxia; Zhao, Fang; Li, Jingxia; Huang, Chuanshu; Luo, Wenjing; Chen, Jingyuan

    2009-04-15

    Experimental and occupational exposure to methyl tert-butyl ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA(A) receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA(A) receptor alpha1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA(A) receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

  1. Aerobic mineralization of MTBE and tert-butyl alcohol by stream-bed sediment microorganisms

    Science.gov (United States)

    Bradley, P.M.; Landmeyer, J.E.; Chapelle, F.H.

    1999-01-01

    Microorganisms indigenous to the stream-bed sediments at two gasoline- contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.Microorganisms indigenous to the stream-bed sediments at two gasoline-contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.

  2. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate)-poly(poly(ethylene glycol) methyl ether methacrylate) Copolymers

    OpenAIRE

    Patcharin Kanhakeaw; Boonjira Rutnakornpituk; Uthai Wichai; Metha Rutnakornpituk

    2015-01-01

    This work presented the surface modification of magnetite nanoparticle (MNP) with poly[(t-butyl acrylate)-stat-(poly(ethylene glycol) methyl ether methacrylate)] copolymers (P[(t-BA)-stat-PEGMA]) via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP). Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp.) such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water,...

  3. Surface-Initiated Atom Transfer Radical Polymerization of Magnetite Nanoparticles with Statistical Poly(tert-butyl acrylate-poly(poly(ethylene glycol methyl ether methacrylate Copolymers

    Directory of Open Access Journals (Sweden)

    Patcharin Kanhakeaw

    2015-01-01

    Full Text Available This work presented the surface modification of magnetite nanoparticle (MNP with poly[(t-butyl acrylate-stat-(poly(ethylene glycol methyl ether methacrylate] copolymers (P[(t-BA-stat-PEGMA] via a surface-initiated “grafting from” atom transfer radical polymerization (ATRP. Loading molar ratio of t-BA to PEGMA was systematically varied (100 : 0, 75 : 25, 50 : 50, and 25 : 75, resp. such that the degree of hydrophilicity of the copolymers, affecting the particle dispersibility in water, can be fine-tuned. The reaction progress in each step of the synthesis was monitored via Fourier transform infrared spectroscopy (FTIR. The studies in the reaction kinetics indicated that PEGMA had higher reactivity than that of t-BA in the copolymerizations. Gel permeation chromatography (GPC indicated that the molecular weights of the copolymers increased with the increase of the monomer conversion. Transmission electron microscopy (TEM revealed that the particles were spherical with averaged size of 8.1 nm in diameter. Dispersibility of the particles in water was apparently improved when the copolymers were coated as compared to P(t-BA homopolymer coating. The percentages of MNP and the copolymer in the composites were determined via thermogravimetric analysis (TGA and their magnetic properties were investigated via vibrating sample magnetometry (VSM.

  4. Synthesis of [[sup 3]H]tert-butyl 8-chloro-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a][1,4]benzodia zepine 3-carboxylate, a selective, high affinity ligand for the diazepam insensitive (DI) subtype of the benzodiazepine receptor

    Energy Technology Data Exchange (ETDEWEB)

    Ziqiang Gu; Costa, B.R. de; Wong, Garry; Rice, K.C.; Skolnick, Phil (National Inst. of Diabetes and Digestive and Kidney Diseases, Bethesda, MD (United States))

    1992-12-01

    The preparation of [[sup 3]H]-labelled tert-butyl 8-chloro-5,6-dihydro-5-methyl-6-oxo-4H-imidazo[1,5-a]benzodiazepine 3-carboxylate (TCIB, 6), a high affinity ligand for the diazepam insensitive (DI) subtype of the benzodiazepine receptor (BZR) is described. Synthesis of [[sup 3]H]TCIB was accomplished in 4 steps starting from 5-chloroisatoic anhydride. Tritium-label introduction was achieved in the final step by selective catalytic tritiolysis in 62% radiochemical yield with quantitative isotopic incorporation. (Author).

  5. (6R-2-tert-Butyl-6-[(4R,5S-3-isopropyl-4-methyl-5-phenyloxazolidin-2-yl]phenol

    Directory of Open Access Journals (Sweden)

    Takaoki Koyanagi

    2010-04-01

    Full Text Available In the title compound, C23H31NO2, the lone pair on the nitrogen atom is oriented to facilitate intramolecular hydrogen bonding with the hydroxy group residing on the phenyl substituent. The five-membered ring adopts an envelope confornmation with the O atom at the flap. The absolute stereochemistry was verified by measurement of optical activity using a digital polarimeter.

  6. 1-[(E-2-(5-tert-Butyl-2-hydroxyphenyldiazen-1-yl]naphthalen-2-ol

    Directory of Open Access Journals (Sweden)

    Hassiba Bougueria

    2014-02-01

    Full Text Available The non-H atoms of the title compound, C20H20N2O2, is located on a mirror plane except two methyl groups of the tert-butyl group. Intramolecular N—H...O hydrogen bonds exist between the hydroxy and diazenyl groups. In the crystal, molecules are linked by weak C—H...O hydrogen bonds into supramolecular chains running along the a-axis direction.

  7. Synthesis and Characterization of a Gasoline Oxygenate, Ethyl tert-Butyl Ether

    Science.gov (United States)

    Donahue, Craig J.; D'Amico, Teresa; Exline, Jennifer A.

    2002-06-01

    A laboratory procedure involving the synthesis and characterization of ethyl tert-butyl ether (ETBE) is described. This experiment has been used in a general chemistry sequence that includes a section on organic chemistry, but is also well suited for an introductory organic chemistry laboratory course. ETBE is prepared by the acid-catalyzed reaction of tert-butyl alcohol with ethyl alcohol. The product is recovered as a low-boiling azeotrope and purified by liquid liquid extraction with water. By using gas chromatography and IR spectroscopy to examine both the crude and the purified products, students can see how much the purity of their sample improves. They can also appreciate the value of these methods (especially GC) as tools to establish purity. Student results are presented. The use of ETBE and its more prominent cousin methyl tert-butyl ether (MTBE) as gasoline oxygenates has become very controversial because they have polluted underground water supplies. This lab permits students to prepare a compound that has a real use and regularly makes headlines in the news. This lab experiment is part of an effort to develop a general chemistry sequence for engineering students using the theme of "Chemistry and the Automobile".

  8. Reversal of age-related increase in brain protein oxidation, decrease in enzyme activity, and loss in temporal and spatial memory by chronic administration of the spin-trapping compound N-tert-butyl-alpha-phenylnitrone

    Energy Technology Data Exchange (ETDEWEB)

    Carney, J.M.; Starke-Reed, P.E.; Oliver, C.N.; Landum, R.W.; Cheng, M.S.; Wu, J.F.; Floyd, R.A. (Univ. of Kentucky, Lexington (USA))

    1991-05-01

    Oxygen free radicals and oxidative events have been implicated as playing a role in bringing about the changes in cellular function that occur during aging. Brain readily undergoes oxidative damage, so it is important to determine if aging-induced changes in brain may be associated with oxidative events. Previously we demonstrated that brain damage caused by an ischemia/reperfusion insult involved oxidative events. In addition, pretreatment with the spin-trapping compound N-tert-butyl-alpha-phenylnitrone (PBN) diminished the increase in oxidized protein and the loss of glutamine synthetase (GS) activity that accompanied ischemia/reperfusion injury in brain. We report here that aged gerbils had a significantly higher level of oxidized protein as assessed by carbonyl residues and decreased GS and neutral protease activities as compared to young adult gerbils. We also found that chronic treatment with the spin-trapping compound PBN caused a decrease in the level of oxidized protein and an increase in both GS and neutral protease activity in aged Mongolian gerbil brain. In contrast to aged gerbils, PBN treatment of young adult gerbils had no significant effect on brain oxidized protein content or GS activity. Male gerbils, young adults (3 months of age) and retired breeders (15-18 months of age), were treated with PBN for 14 days with twice daily dosages of 32 mg/kg. If PBN administration was ceased after 2 weeks, the significantly decreased level of oxidized protein and increased GS and neutral protease activities in old gerbils changed in a monotonic fashion back to the levels observed in aged gerbils prior to PBN administration. We also report that old gerbils make more errors than young animals and that older gerbils treated with PBN made fewer errors in a radial arm maze test for temporal and spatial memory than the untreated aged controls.

  9. Water Quality and Occurrence of Methyl Tert-Butyl Ether (MTBE) and Other Fuel-Related Compounds in Lakes and Ground Water at Lakeside Communities in Sussex and Morris Counties, New Jersey, 1998-1999

    Science.gov (United States)

    Baehr, Arthur L.; Reilly, Timothy J.

    2001-01-01

    Densely populated communities surround many of the larger lakes in northwestern New Jersey. These communities derive most of their water supply from wells. The lakes can be navigated by gasoline-powered watercraft, can be in various stages of eutrophication, may contain pathogens associated with bathing and waterfowl, and are periodically subjected to chemical applications to control aquatic plant growth. Another feature that contributes to water-quality concerns in lakeside communities is the widespread use of septic tanks. Concentrations of methyl tert-butyl ether (MTBE), a gasoline oxygenate, in samples from Cranberry Lake and Lake Lackawanna ranged from 20 to 30 ug/L (micrograms per liter) and 5 to 14 ug/L during the summers of 1998 and 1999, respectively. These levels were persistent throughout the depth of the lakes when mixing conditions were present. MTBE concentrations in samples from the top 20 feet of Lake Hopatcong during summer 1999 were about 10 ug/L and about 2 to 3 ug/L in samples below 20 feet. The source of the MTBE in the lakes was determined to be gasoline-powered watercraft. Other constituents of gasoline--tertiary amyl methyl ether (TAME) and benzene, toluene, ethylbenzene, and xylenes (BTEX)--were detected in the lakes but at much lower concentrations than MTBE. Ambient ground-water quality at Cranberry Lake and Lake Lackawanna appears to be affected by the use of gasoline-powered watercraft. MTBE was detected in water samples from 13 of the 14 wells sampled at Cranberry Lake in fall 1998 and summer 1999. The wells were selected to monitor ambient ground-water quality and had no history of contamination. In ground-water samples collected during fall 1998, MTBE concentrations ranged from 0.12 to 19.8 ug/L, and the median concentration was 0.43 ug/L. In samples from summer 1999, MTBE concentrations ranged from 0.14 to 13.2 ug/L, and the median concentration was 0.38 ug/L. MTBE was detected in samples from four of the five wells at Lake

  10. 4-tert-Butyl-pyridinium triiodide-4-tert-butyl-pyridine (1/1).

    Science.gov (United States)

    He, Hongshan; Sykes, Andrew G

    2011-01-22

    The title compound, C(9)H(14)N(+)·I(3) (-)·C(9)H(13)N, consists of monoprotonated 4-tert-butyl-pyridinium cations and triiodide anions. The triiodide ion has near-symmetric linear geometry, with bond lengths of 2.9105 (4) Å (I-I) and a bond angle of 177.55 (3)° (I-I-I). For this room-temperature structure, the butyl group on the pyridine ring is disordered and has been treated as a rigid rotator, modeled in three separate positions with 1/3, 1/3, 1/3 occupancies. The cations assemble into dimeric forms by way of N-H⋯N hydrogen bonds.

  11. 4-tert-Butyl­pyridinium triiodide–4-tert-butyl­pyridine (1/1)

    Science.gov (United States)

    He, Hongshan; Sykes, Andrew G.

    2011-01-01

    The title compound, C9H14N+·I3 −·C9H13N, consists of monoprotonated 4-tert-butyl­pyridinium cations and triiodide anions. The triiodide ion has near-symmetric linear geometry, with bond lengths of 2.9105 (4) Å (I—I) and a bond angle of 177.55 (3)° (I—I—I). For this room-temperature structure, the butyl group on the pyridine ring is disordered and has been treated as a rigid rotator, modeled in three separate positions with 1/3, 1/3, 1/3 occupancies. The cations assemble into dimeric forms by way of N—H⋯N hydrogen bonds. PMID:21523100

  12. 27 CFR 21.101 - tert-Butyl alcohol.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false tert-Butyl alcohol. 21.101 Section 21.101 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS FORMULAS FOR DENATURED ALCOHOL AND RUM Specifications for Denaturants § 21...

  13. 2,6-Di-tert-butyl-4-(methoxy-meth-yl)phenol.

    Science.gov (United States)

    Zeng, Tao; Sun, Ju-Feng

    2008-02-13

    The title compound, C(16)H(26)O(2), was easily obtained in high yield when 4-bromo-methyl-2,6-di-tert-butyl-phenol was reacted with methanol. There are two independent mol-ecules in the asymmetric unit. The meth-oxy group in each of the independent mol-ecules was found to be disordered, with site-occupation factors of 0.8728 (18)/0.1272 (18) and 0.8781 (17)/0.1219 (17).

  14. A novel organogelator incorporating tert-butyl esters of asparagines.

    Science.gov (United States)

    Lozano, Virginia; Hernández, Rebeca; Mijangos, Carmen; Pérez-Pérez, María-Jesús

    2009-01-21

    A novel organogelator based on tert-butyl esters of asparagines has been synthesized and its organogelation abilities have been investigated. The rheological characterization has confirmed the gelation behavior, and its thixotropic properties. Furthermore, the morphological studies performed reveal a spherical structure. Thus, this organogelator can be considered as a new example of the emerging, but still reduced, list of gels with a non-fibrillar assembly.

  15. 2-Benzhydryl-6-tert-butyl-4-methylphenol

    Directory of Open Access Journals (Sweden)

    Sungwoo Yoon

    2013-02-01

    Full Text Available The title compound, C24H26O, was prepared by the reaction between 2-tert-butyl-4-methylphenol and diphenylmethanol in the presence of sulfuric acid. Three benzene rings are attached directly to the central C—H group in a twisted propeller conformation with the local pseudo-C3 rotational axis coinciding with the C—H bond. There are three short C—H...O contacts in the molecule.

  16. tert-Butyl N-(thiophen-2-ylcarbamate

    Directory of Open Access Journals (Sweden)

    Gene C. Hsu

    2013-09-01

    Full Text Available In the title compound, C9H13NO2S, the dihedral angle between the thiophene ring and the carbamate group is 15.79 (14°. In the crystal structure, intramolecular C—H...O interactions in tandem with the tert-butyl groups render the packing of adjacent molecules in the [001] direction nearly perpendicular [the angle between adjacent thiophene rings is 74.83 (7°]. An intermolecular N—H...O hydrogen bond gives rise to a chain extending along [001]. The crystal studied was found to be a racemic twin.

  17. Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Ferreira, N.

    2005-11-15

    Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

  18. Crystal structure of (1,3-di-tert-butyl-η5-cyclopentadienyltrimethylhafnium(IV

    Directory of Open Access Journals (Sweden)

    Adrián Pérez-Redondo

    2015-05-01

    Full Text Available The molecule of the title organometallic hafnium(IV compound, [Hf(CH33(C13H21] or [HfMe3(η5-C5H3-1,3-tBu2], adopts the classical three-legged piano-stool geometry for monocyclopentadienylhafnium(IV derivatives with the three methyl groups bonded to the Hf(IV atom at the legs. The C atoms of the two tert-butyl group bonded to the cyclopentadienyl (Cp ring are 0.132 (5 and 0.154 (6 Å above the Cp least-squares plane. There are no significant intermolecular interactions present between the molecules in the crystal structure.

  19. Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

    KAUST Repository

    Xie, Yihui

    2016-03-24

    For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

  20. Electrochemical degradation of methyl tert-butyl ether

    Directory of Open Access Journals (Sweden)

    Aleksandr B. Velichenko

    2014-12-01

    Full Text Available In this paper, we have examined the performance of PbO2 anodes in the EC degradation of MTBE. It was shown that electrochemical oxidation of MTBE at lead dioxide anodes is effective method of anodic conversion of the organic pollutant to acetic acid as untoxic product. Proposed method is formally reagent treatment of water at the same time it does not need addition of any reagent in reaction media. All needed reagents formed directly from the solvent (water thanks to electrochemical reactions. According to obtained data the main electrochemical stages of the process of anodic conversion of MTBE are formation of hydroxyl-radicals and molecular oxygen. Then formed compounds take part in stages of chemical MTBE oxidation and intermediate species that led to deeper oxidation to form acetic acid as the result. Proposed mechanism of MTBE electrochemical oxidation is in satisfactory agreement with experimental data. Dependence of MTBE conversion rate from the nature of micro-doped and composite lead dioxide anodes is explained by difference in hydroxyl-radical bond strength with an electrode surface that determined it reaction ability in secondary chemical reactions of organic compounds oxidation.

  1. N-tert-Butyl-2-methyl­propanamide

    Science.gov (United States)

    Kluge, Kelly A.; Fridyland, Diana; MacBeth, Cora E.; Hardcastle, Kenneth I.

    2011-01-01

    The title compound, C8H17NO, crystallizes with two independent mol­ecules in the asymmetric unit. In the crystal, inter­molecular N—H⋯O hydrogen bonding is observed between neighboring mol­ecules, forming continuous mol­ecular chains along the c-axis direction. PMID:22091159

  2. Scanning thermal lithography of tailored tert-butyl ester protected carboxylic acid functionalized (meth)acrylate polymer platforms.

    Science.gov (United States)

    Duvigneau, Joost; Schönherr, Holger; Vancso, G Julius

    2011-10-01

    In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively.

  3. Electrochemical nucleophilic synthesis of di-tert-butyl-(4-[18F]fluoro-1,2-phenylene)-dicarbonate.

    Science.gov (United States)

    He, Qinggang; Wang, Ying; Alfeazi, Ines; Sadeghi, Saman

    2014-09-01

    An electrochemical method with the ability to conduct (18)F-fluorination of aromatic molecules through direct nucleophilic fluorination of cationic intermediates is presented in this paper. The reaction was performed on a remote-controlled automatic platform. Nucleophilic electrochemical fluorination of tert-butyloxycarbonyl (Boc) protected catechol, an intermediate model molecule for the positron emission tomography (PET) probe (3,4-dihydroxy-6-[(18)F]fluoro-L-phenylalanine), was performed. Fluorination was achieved under potentiostatic anodic oxidation in acetonitrile containing Et3N·3HF and other supporting electrolytes. Radiofluorination efficiency was influenced by a number of variables, including the concentration of the precursor, concentration of Et3N·3HF, type of supporting electrolyte, temperature and time, as well as applied potentials. Radio-fluorination efficiency of 10.4±0.6% (n=4) and specific activity of up to 43GBq/mmol was obtained after 1h electrolysis of 0.1M of 4-tert-butyl-diboc-catechol in the acetonitrile solution of Et3N·3HF (0.033M) and NBu4PF6 (0.05M). Density functional theory (DFT) was employed to explain the tert-butyl functional group facilitation of electrochemical oxidation and subsequent fluorination. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Selective enzymatic hydrolysis of C-terminal tert-butyl esters of peptides

    NARCIS (Netherlands)

    Eggen, I.F.; Boeriu, C.G.

    2007-01-01

    The present invention relates to a process for the selective enzymatic hydrolysis of C-terminal esters of peptide substrates in the synthesis of peptides, comprising hydrolysing C-terminal tert-butyl esters using the protease subtilisin. This process is useful in the production of protected or

  5. Selective enzymatic hydrolysis of C-terminal tert-butyl esters of peptides

    OpenAIRE

    Eggen, I.F.; Boeriu, C.G.

    2007-01-01

    The present invention relates to a process for the selective enzymatic hydrolysis of C-terminal esters of peptide substrates in the synthesis of peptides, comprising hydrolysing C-terminal tert-butyl esters using the protease subtilisin. This process is useful in the production of protected or unprotected peptides.

  6. (R-N-{2-tert-Butyl-2-[(R-tert-butylsulfonamido]ethylidene}-tert-butanesulfonamide

    Directory of Open Access Journals (Sweden)

    Cong-Bin Fan

    2008-10-01

    Full Text Available The title compound, C14H30N2O2S2, is the product of the monoaddition reaction of tert-butyl magnesium chloride with bis-[(R-N-tert-butanesulfinyl]ethanediimine. There are two almost identical molecules in the asymmetric unit, the molecular conformation of which is stabilized by an intramolecular N—H...N hydrogen bond.

  7. A new efficient synthesis of isothiocyanates from amines using di-tert-butyl dicarbonate

    DEFF Research Database (Denmark)

    Munch, Henrik; Hansen, Jon S.; Pittelkow, Michael

    2008-01-01

    Alkyl and aryl amines are converted smoothly to the corresponding isothiocyanates via the dithiocarbamates in good to excellent yields using di-tert-butyl dicarbonate (Boc(2)O) and 1-3 mol% of DMAP or DABCO as catalyst. As most of the byproducts are volatile, the work-up involves simple evaporation...

  8. (1S,3S,4S-tert-Butyl N-[1-benzyl-3-hydroxy-5-phenyl-4-(picolinamidopentyl]carbamate

    Directory of Open Access Journals (Sweden)

    Jian-Feng Zheng

    2008-07-01

    Full Text Available The title compound, C29H35N3O4, was obtained by the reaction of (2S,4S,5S-tert-butyl N-(4-amino-1-benzyl-3-hydroxy-5-phenylpentylcarbamate and picolinic acid using oxalyl chloride as a chlorinating reagent to activate the carboxyl group. In the crystal structure there are two molecules in the asymmetric unit, which are aligned edge-to-face. In one molecule, the pyridyl ring forms a dihedral angle of 22.0 (1° with the phenyl ring of the terminal benzyl group and 14.3 (1° with the other phenyl ring; in the other molecule, the corresponding angles are 12.1 (1 and 10.6 (1°, respectively. The packing is stabilized by intermolecular hydrogen bonds and C—H...π interactions.

  9. Impact of tert-butyl alcohol on crystallization kinetics of gemcitabine hydrochloride in frozen aqueous solutions.

    Science.gov (United States)

    Munjal, Bhushan; Bansal, Arvind K

    2015-01-01

    The effect of tert-butyl alcohol (TBA) on isothermal crystallization kinetics of gemcitabine hydrochloride (GHCl) in frozen aqueous solutions was assessed by cold-stage microscopy. Addition of TBA (0%-5%, w/w) increased the value of Johnson-Mehl-Avrami rate constant (1.3-33.3 h⁻¹) and reduced the Avrami exponent (2.5-1.0). Thermodynamic parameters [enthalpy (ΔH(‡)), entropy (ΔS(‡)), and free energy (ΔG(‡)) of activation], calculated using Arrhenius and Eyring-Polanyi equations, established that TBA (2%, w/w) accelerated GHCl crystallization by reducing its ΔH(‡) (53.9 cf. 96.5 kJ/mol⁻¹) and ΔG(‡) (68.5 cf. 74.9 kJ/mol⁻¹). Further, to explore insights into the effect of TBA on nucleation and crystal growth of GHCl, crystallization kinetics data were deconvolved using Finke-Watzky model. This revealed that addition of TBA decreased ΔH(‡) of nucleation and increased ΔS(‡) of crystal growth, thereby reducing ΔG(‡) of nucleation and crystal growth by 11.7% and 4.2%, respectively. Finkey-Watzky model also predicted a reduction in the crystal size upon TBA addition, which was confirmed by comparing particle size of GHCl lyophilized in the presence and absence of TBA. In conclusion, TBA reduces ΔG(‡) of nucleation and crystal growth in a differential manner, thereby enhancing the crystallization kinetics of GHCl and affecting its morphological features. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  10. Persulfate Oxidation of MTBE- and Chloroform-Spent Granular Activated Carbon

    Science.gov (United States)

    Activated persulfate (Na2S2O8) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H2O2–persulfate binary mixtur...

  11. Tert-butyl alcohol used to fabricate nano-cellulose aerogels via freeze-drying technology

    Science.gov (United States)

    Wang, Xiaoyu; Zhang, Yang; Jiang, Hua; Song, Yuxuan; Zhou, Zhaobing; Zhao, Hua

    2017-06-01

    Aerogel, a highly porous material, is attracting increasing attention owing to low thermal conductivity and high specific surface area. Freeze-drying technology has been employed to produce nano-cellulose aerogels; however, the resultant product has low specific surface areas. Here, a modified approach to prepare nano-cellulose aerogels was reported, which involves tert-butyl alcohol as a solvent. Nano-cellulose aerogels were prepared via a spontaneous gelation fashion using calcium chloride solution, followed by tert-butyl alcohol solvent displacement and freeze drying. Addition of calcium chloride (0.25%) accelerated the physical gelation process. The application of tert-butyl alcohol as a solvent contributed to preservation of gel network. The obtained spherical nano-cellulose aerogels had a shrinkage rate of 5.89%. The specific surface area and average pore size was 164. 9666 m2 g-1 and 10.01 nm, respectively. Additionally, nano-cellulose aerogels had a comparable thermal degradation property when compared to microcrystalline cellulose. These biophysical properties make nano-cellulose aerogels as a promising absorption material.

  12. Fenton-Driven Regeneration of MTBE-spent Granular Activated Carbon

    Science.gov (United States)

    Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves the combined, synergistic use of two treatment technologies: adsorption of organic chemicals onto activated carbon and Fenton-driven oxidation regeneration of the spent-GAC...

  13. Red fluorescent materials based on julolidine/chromene with the bulky tert-butyl and trimethylsilyl substituents for organic light-emitting diodes.

    Science.gov (United States)

    Na, Eun Jae; Kim, Hye Jeong; Lee, Kum Hee; Lee, Seok Jae; Kim, Young Kwan; Yoon, Seung Soo

    2014-08-01

    In this work, we designed and synthesized two red emitters 2-(6,8-di-tert-butyl-2-(2-(1,1-dimethyl-7-(trimethylsilyl)-7-((trimethylsilyl)methyl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-9-yl)vinyl)-4H-chromen-4-ylidene)malononitrile (Red 1) and 2-(6,8-di-tert-butyl-2-(2-(1,1,7-trimethyl-7-t-butyl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-9-yl)vinyl)-4H-chromen-4-ylidene)malononitrile (Red 2). To explore the electro-luminescence properties of these materials, multilayered OLEDs using these materials as dopants in a Alq3 host were fabricated. Particularly, by using Red 1 as a dopant in emitting layer, device 1 showed the luminous and power efficiencies of 0.81 cd/A and 0.43 lm/W at 20 mA/cm2, respectively. The CIE coordinates of this device was (0.65, 0.34) at 7.0 V, which is close to the NTSC standard CIE coordinates of (0.67,0.32) for red emission.

  14. Cultivation of Aquincola tertiaricarbonis L108 on the fuel oxygenate intermediate tert-butyl alcohol induces aerobic anoxygenic photosynthesis at extremely low feeding rates.

    Science.gov (United States)

    Rohwerder, Thore; Müller, Roland H; Weichler, M Teresa; Schuster, Judith; Hübschmann, Thomas; Müller, Susann; Harms, Hauke

    2013-10-01

    Aerobic anoxygenic photosynthesis (AAP) is found in an increasing number of proteobacterial strains thriving in ecosystems ranging from extremely oligotrophic to eutrophic. Here, we have investigated whether the fuel oxygenate-degrading betaproteobacterium Aquincola tertiaricarbonis L108 can use AAP to compensate kinetic limitations at low heterotrophic substrate fluxes. In a fermenter experiment with complete biomass retention and also during chemostat cultivation, strain L108 was challenged with extremely low substrate feeding rates of tert-butyl alcohol (TBA), an intermediate of methyl tert-butyl ether (MTBE). Interestingly, formation of photosynthetic pigments, identified as bacteriochlorophyll a and spirilloxanthin, was only induced in growing cells at TBA feeding rates less than or equal to maintenance requirements observed under energy excess conditions. Growth continued at rates between 0.001 and 0.002 h(-1) even when the TBA feed was decreased to values close to 30 % of this maintenance rate. Partial sequencing of genomic DNA of strain L108 revealed a bacteriochlorophyll synthesis gene cluster (bchFNBHL) and photosynthesis regulator genes (ppsR and ppaA) typically found in AAP and other photosynthetic proteobacteria. The usage of light as auxiliary energy source enabling evolution of efficient degradation pathways for kinetically limited heterotrophic substrates and for lowering the threshold substrate concentration Smin at which growth becomes zero is discussed.

  15. 5-tert-Butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl-2-thienyl]-1,3-benzoxazole

    Directory of Open Access Journals (Sweden)

    Fang-Fang Jian

    2008-12-01

    Full Text Available The title compound, C26H26N2O2S, was prepared by the reaction of thiophene-2,5-dicarboxylic acid and 2-amino-4-tert-butylphenol. One of the tert-butyl groups is disordered over two conformations, with occupancies of 0.539 (1 and 0.461 (2. The two 1,3-benzoxazole rings are almost planar, with dihedral angles of 0.83 (18 and 1.64 (17° between the five- and six-membered rings. The thiophene ring makes dihedral angles of 21.54 (19 and 4.49 (18° with the planes of the five-membered oxazole rings. The crystal packing is controlled by π–π stacking interactions involving the thiophene and benzene rings, with a centroid–centroid distance of 3.748 (2 Å.

  16. Iron Amendment and Fenton Oxidation of MTBE-Spent Granular Activated Carbon

    Science.gov (United States)

    Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves Fe amendment to the GAC to catalyze H2O2 reactions and to enhance the rate of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, fer...

  17. Effect of Water Clustering on the Activity of Candida antarctica Lipase B in Organic Medium

    DEFF Research Database (Denmark)

    Banik, Sindrila Dutta; Nordblad, Mathias; Woodley, John M.

    2017-01-01

    The effect of initial water activity of MTBE (methyl tert-butyl ether) medium on CALB (Candida antarctica lipase B) catalyzed esterification reaction is investigated using experimental methods and classical molecular dynamics (MD) simulations. The experimental kinetic studies show that the initial...

  18. Gabapentin-base synthesis and theoretical studies of biologically active compounds: N-cyclohexyl-3-oxo-2-(3-oxo-2-azaspiro[4.5] decan-2-yl)-3-arylpropanamides and N-(tert-butyl)-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)-2-arylacetamide derivatives

    Science.gov (United States)

    Amirani Poor, Mahboobe; Darehkordi, Ali; Anary-Abbasinejad, Mohammad; Mohammadi, Marziyeh

    2018-01-01

    An intermolecular Ugi reaction of 2-(1-(aminomethyl)cyclohexyl)acetic acid (gabapentin) with glyoxal and cyclohexyl isocyanide or aromatic aldehyde and tertbutyl isocyanide under mild conditions in ethanol have been developed to produce two novel class of N-cyclohexyl-3-(aryl)-3-oxo-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)propanamideins and N-(tert-butyl)-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)-2-arylacetamide derivatives in good to excellent yields. This presents the first report for the intermolecular Ugi three component reaction of gabapentin, glyoxal, and an isocyanide. Also according to the theoretical studies the electron-donating groups increase the strength of intramolecular hydrogen bond and electron-withdrawing groups decrease the strength of intramolecular hydrogen bond.

  19. Crystal structure of trans-N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyloxamide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Miguel-Ángel Velázquez-Carmona

    2016-07-01

    Full Text Available The here crystallized oxamide was previously characterized as an unsolvated species [Jímenez-Pérez et al. (2000. J. Organomet. Chem. 614–615, 283–293], and is now reported with methanol as a solvent of crystallization, C30H44N2O4·CH3OH, in a different space group. The introduction of the solvent influences neither the molecular symmetry of the oxamide, which remains centrosymmetric, nor the molecular conformation. However, the unsolvated molecule crystallized as an ordered system, while many parts of the solvated crystal are disordered. The hydroxy group in the oxamide is disordered over two chemically equivalent positions, with occupancies 0.696 (4:0.304 (4; one tert-butyl group is disordered by rotation about the C—C bond, and was modelled with three sites for each methyl group, each one with occupancy 1/3. Finally, the methanol solvent, which lies on a twofold axis, is disordered by symmetry. The disorder affecting hydroxy groups and the solvent of crystallization allows the formation of numerous supramolecular motifs using four hydrogen bonds, with N—H and O—H groups as donors and the oxamide and methanol molecule as acceptors.

  20. Directed Evolution of Carbonyl Reductase from Rhodosporidium toruloides and Its Application in Stereoselective Synthesis of tert-Butyl (3R,5S)-6-Chloro-3,5-dihydroxyhexanoate.

    Science.gov (United States)

    Liu, Zhi-Qiang; Wu, Lin; Zhang, Xiao-Jian; Xue, Ya-Ping; Zheng, Yu-Guo

    2017-05-10

    tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key intermediate of atorvastatin and rosuvastatin synthesis. Carbonyl reductase RtSCR9 from Rhodosporidium toruloides exhibited excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH). For the activity of RtSCR9 to be improved, random mutagenesis and site-saturation mutagenesis were performed. Three positive mutants were obtained (mut-Gln95Asp, mut-Ile144Lys, and mut-Phe156Gln). These mutants exhibited 1.94-, 3.03-, and 1.61-fold and 1.93-, 3.15-, and 1.97-fold improvement in the specific activity and kcat/Km, respectively. Asymmetric reduction of (S)-CHOH by mut-Ile144Lys coupled with glucose dehydrogenase was conducted. The yield and enantiomeric excess of (3R,5S)-CDHH reached 98 and 99%, respectively, after 8 h bioconversion in a single batch reaction with 1 M (S)-CHOH, and the space-time yield reached 542.83 mmol L-1 h-1 g-1 wet cell weight. This study presents a new carbonyl reductase for efficient synthesis of (3R,5S)-CDHH.

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

    NARCIS (Netherlands)

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

    1996-01-01

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

  2. tert-Butyl 2-(3-acetylamino-2-oxo-1,2-dihydro-1-pyridylacetate

    Directory of Open Access Journals (Sweden)

    Peter C. Healy

    2008-12-01

    Full Text Available The title compound, C13H18N2O4, crystallizes as discrete molecules associated as N—H...O hydrogen-bonded dimers disposed about a crystallographic inversion centre. The structure is the first solid-state structure for a 3-acetylpyridone without C-4 to C-6 substituents. The amide subsituent at C-3 is coplanar with the pyridone ring, while the tert-butyl ester group is orthogonal to the pyridine ring. The amide and ester carbonyl O atoms are not involved in strong hydrogen bonding with only a number of intramolecular and intermolecular C—H...O interactions apparent in the structure.

  3. One-electron redox reaction of di-tert-butyl nitroxide at platinum electrode in acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Kishioka, Shin-ya; Yamada, Akifumi [Nagaoka University of Technology, Nagaoka, Niigata (Japan). Department of Chemistry, Faculty of Engineering

    2005-10-20

    The electrochemical oxidation of di-tert-butyl nitroxide (DTBN) at a platinum electrode in acetonitrile was examined. The cyclic voltammogram indicated an irreversible response during a normal time scale measurement, whereas chemically reversible voltammograms were obtained during a shorter time using a micro disk electrode with relatively fast sweep rates. The apparent formal redox potential and heterogeneous electron transfer rate constant were estimated to be 0.218 V (versus Fc{sup +}Fc) and 0.035 {+-} 0.015 cms{sup -1} from the digital simulation analysis. (author)

  4. Protective Effects of Rooibos (Aspalathus linearis and/or Red Palm Oil (Elaeis guineensis Supplementation on tert-Butyl Hydroperoxide-Induced Oxidative Hepatotoxicity in Wistar Rats

    Directory of Open Access Journals (Sweden)

    Olawale R. Ajuwon

    2013-01-01

    Full Text Available The possible protective effects of an aqueous rooibos extract (Aspalathus linearis, red palm oil (RPO (Elaeis guineensis, or their combination on tert-butyl-hydroperoxide-(t-BHP-induced oxidative hepatotoxicity in Wistar rats were investigated. tert-butyl hydroperoxide caused a significant (P<0.05 elevation in conjugated dienes (CD and malondialdehyde (MDA levels, significantly (P<0.05 decreased reduced glutathione (GSH and GSH : GSSG ratio, and induced varying changes in activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione reductase in the blood and liver. This apparent oxidative injury was associated with histopathological changes in liver architecture and elevated levels of serum alanine aminotransferase (ALT, aspartate aminotransferase (AST, and lactate dehydrogenase (LDH. Supplementation with rooibos, RPO, or their combination significantly (P<0.05 decreased CD and MDA levels in the liver and reduced serum level of ALT, AST, and LDH. Likewise, changes observed in the activities of antioxidant enzymes and impairment in redox status in the erythrocytes and liver were reversed. The observed protective effects when rooibos and RPO were supplemented concomitantly were neither additive nor synergistic. Our results suggested that rooibos and RPO, either supplemented alone or combined, are capable of alleviating t-BHP-induced oxidative hepatotoxicity, and the mechanism of this protection may involve inhibition of lipid peroxidation and modulation of antioxidants enzymes and glutathione status.

  5. Protective Effects of Rooibos (Aspalathus linearis) and/or Red Palm Oil (Elaeis guineensis) Supplementation on tert-Butyl Hydroperoxide-Induced Oxidative Hepatotoxicity in Wistar Rats.

    Science.gov (United States)

    Ajuwon, Olawale R; Katengua-Thamahane, Emma; Van Rooyen, Jacques; Oguntibeju, Oluwafemi O; Marnewick, Jeanine L

    2013-01-01

    The possible protective effects of an aqueous rooibos extract (Aspalathus linearis), red palm oil (RPO) (Elaeis guineensis), or their combination on tert-butyl-hydroperoxide-(t-BHP-)induced oxidative hepatotoxicity in Wistar rats were investigated. tert-butyl hydroperoxide caused a significant (P < 0.05) elevation in conjugated dienes (CD) and malondialdehyde (MDA) levels, significantly (P < 0.05) decreased reduced glutathione (GSH) and GSH : GSSG ratio, and induced varying changes in activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione reductase in the blood and liver. This apparent oxidative injury was associated with histopathological changes in liver architecture and elevated levels of serum alanine aminotransferase (ALT), aspartate aminotransferase (AST), and lactate dehydrogenase (LDH). Supplementation with rooibos, RPO, or their combination significantly (P < 0.05) decreased CD and MDA levels in the liver and reduced serum level of ALT, AST, and LDH. Likewise, changes observed in the activities of antioxidant enzymes and impairment in redox status in the erythrocytes and liver were reversed. The observed protective effects when rooibos and RPO were supplemented concomitantly were neither additive nor synergistic. Our results suggested that rooibos and RPO, either supplemented alone or combined, are capable of alleviating t-BHP-induced oxidative hepatotoxicity, and the mechanism of this protection may involve inhibition of lipid peroxidation and modulation of antioxidants enzymes and glutathione status.

  6. Biosynthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by carbonyl reductase from Rhodosporidium toruloides in mono and biphasic media.

    Science.gov (United States)

    Liu, Zhi-Qiang; Wu, Lin; Zheng, Ling; Wang, Wen-Zhong; Zhang, Xiao-Jian; Jin, Li-Qun; Zheng, Yu-Guo

    2017-10-05

    tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is the key intermediate for synthesis of atorvastatin and rosuvastatin. Carbonyl reductase exhibits excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) to synthesize (3R,5S)-CDHH. In this study, a whole cell biosynthesis reaction system to produce (3R,5S)-CDHH was constructed in organic solvents. A solution of 10% (v/v) Tween-80 was introduced to the reaction system as a co-solvent, which greatly enhanced biotransformation process, giving 98.9% yield, >99% ee and 1.8-fold higher space time yield in 5 h bioconversion of 1 M (S)-CHOH, compared with 98.7% yield and >99% ee in 9 h bioconversion of a purely aqueous reaction system. Moreover, a water-octanol biphasic reaction system was built and 20% of octanol was added as reservoir of substrate resulting in 98% yield, >99% ee and 4.08 mmol L-1 h-1 g-1 (wet cell weight) space time yield. This study paved a way for the whole cell biosynthesis of (3R,5S)-CDHH in mono and biphasic media. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Mechanism-based inactivation of cytochromes P450 2E1 and 2E1 T303A by tert-butyl acetylenes: characterization of reactive intermediate adducts to the heme and apoprotein.

    Science.gov (United States)

    Blobaum, Anna L; Kent, Ute M; Alworth, William L; Hollenberg, Paul F

    2002-12-01

    The kinetics for the inactivation of cytochrome P450 2E1 and the mutant P450 2E1 T303A by tert-butyl acetylene (tBA) and tert-butyl 1-methyl-2-propynyl ether (tBMP) were investigated. The two acetylenes inactivated the 7-ethoxy-4-(trifluoromethyl)coumarin (7-EFC) O-deethylation activity of purified rabbit P450s 2E1 and 2E1 T303A in a reconstituted system in a time-, concentration-, and NADPH-dependent manner. The K(I) values for the inactivation of P450s 2E1 and 2E1 T303A by tBA were 1.0 and 2.0 mM, the k(inact) values were 0.20 and 0.38 min(-)(1), and the t(1/2) values were 3.5 and 1.8 min, respectively. The K(I) values for the tBMP-inactivated P450s were 0.1 and 1.0 mM, the k(inact) values were 0.12 and 0.07 min(-)(1), and the t(1/)(2) values were 5.9 and 10.2 min, respectively. Losses in enzyme activity occurred with concurrent losses in the P450 CO spectrum and P450 heme, which were accompanied by the appearance of two different tBA- or tBMP-modified heme products in each inactivated sample. LC-MS analysis of the adducts showed masses of 661 or 705 Da, consistent with the mass of an iron-depleted heme plus the masses of a tBA or tBMP reactive intermediate and one oxygen atom, respectively. Only the tBA-inactivated P450 2E1 revealed a tBA-adducted apoprotein with an increase in mass of 99 Da, corresponding to the mass of tBA plus one oxygen atom. Surprisingly, the inactivation, CO spectral and heme loss, and heme adduct formation of the tBA-inactivated T303A mutant were completely reversible after dialysis. In addition, metabolism of para-nitrophenol was not compromised by the tBA-inactivated T303A mutant. Therefore, our studies on the inactivation of P450s 2E1 and 2E1 T303A by tBA and tBMP suggest the existence of three distinct mechanisms for inactivation, among which includes a novel, reversible heme alkylation that has not been previously described with P450 enzymes.

  8. Enzymatic Kinetic Resolution of tert-Butyl 2-(1-Hydroxyethylphenylcarbamate, A Key Intermediate to Chiral Organoselenanes and Organotelluranes

    Directory of Open Access Journals (Sweden)

    Leandro Piovan

    2011-09-01

    Full Text Available The enzymatic kinetic resolution of tert-butyl 2-(1-hydroxyethyl phenylcarbamate via lipase-catalyzed transesterification reaction was studied. We investigated several reaction conditions and the carbamate was resolved by Candida antarctica lipase B (CAL-B, leading to the optically pure (R- and (S-enantiomers. The enzymatic process showed excellent enantioselectivity (E > 200. (R- and (S-tert-butyl 2-(1-hydroxyethylphenylcarbamate were easily transformed into the corresponding (R- and (S-1-(2-aminophenylethanols.

  9. 5-tert-Butyl-2-(4'-[{sup 18}F]fluoropropynylphenyl)-1,3-dithiane oxides: potential new GABA{sub A} receptor radioligands

    Energy Technology Data Exchange (ETDEWEB)

    Li Xuehe; Jung, Yong-Woon; Snyder, Scott E.; Blair, Joseph; Sherman, Philip S.; Desmond, Timothy; Frey, Kirk A. [Department of Radiology, University of Michigan Medical School, Ann Arbor, MI 48109 (United States); Kilbourn, Michael R. [Department of Radiology, University of Michigan Medical School, Ann Arbor, MI 48109 (United States)], E-mail: mkilbour@umich.edu

    2008-07-15

    As potential new ligands targeting the binding site of {gamma}-aminobutyric acid (GABA) receptor ionophore, trans-5-tert-butyl-2-(4'-fluoropropynylphenyl)-2-methyl-1,1-dioxo-1, 3-dithiane (1) and cis/trans-5-tert-butyl-2-(4'-fluoropropynylphenyl)-2-methyl-1,1,3, 3-tetroxo-1,3-dithiane (2) were selected for radiolabeling and initial evaluation as in vivo imaging agents for positron emission tomography (PET). Both compounds exhibited identical high in vitro binding affinities (K{sub i}=6.5 nM). Appropriate tosylate-substituted ethynyl precursors were prepared by multistep syntheses involving stepwise sulfur oxidation and chromatographic isolation of desired trans isomers. Radiolabeling was accomplished in one step using nucleophilic [{sup 18}F]fluorination. In vivo biodistribution studies with trans-[{sup 18}F]1 and trans-[{sup 18}F]2 showed significant initial uptake into mouse brain and gradual washout, with heterogeneous regional brain distributions and higher retention in the cerebral cortex and cerebellum and lower retention in the striatum and pons-medulla. These regional distributions of the new radioligands correlated with in vitro and ex vivo measures of standard radioligands binding to the ionophore- and benzodiazepine-binding sites of GABA{sub A} receptor in rodent brain. A comparison of these results with previously prepared radiotracers for other neurochemical targets, including successes and failures as in vivo radioligands, suggests that higher-affinity compounds with increased retention in target brain tissues will likely be needed before a successful radiopharmaceutical for human PET imaging can be identified.

  10. Protective Effects of Alkaloid Compounds from Nelumbinis Plumula on tert-Butyl Hydroperoxide-Induced Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Ze-Bin Guo

    2013-08-01

    Full Text Available This study was conducted to investigate the effect of Nelumbinis Plumula total alkaloid (NPA and its main alkaloid components on oxidative stress induced by tert-butyl hydroperoxide (t-BHP in the human hepatocellular HepG2 cell line. According to HPLC analysis, several major alkaloid compounds such as liensinine, isoliensinine and neferine were present in NPA. The cytotoxic effects in 0.55 mM t-BHP-induced HepG2 cells were significantly inhibited by NPA and the major compound in NPA, neferine, showed the strongest activities. The protective effect of neferine against oxidative stress induced by t-BHP may be associated with decreased ROS formation, TBARS generation, LDH release and increased GSH levels, suggesting their involvement of the cytoprotective on oxidative stress. The effects were comparable with quercetin, which was used as positive control. Overall, total alkaloid and alkaloid compounds from Nelumbinis Plumula displayed a significant cytoprotective effect against oxidative stress. Further study is needed to elucidate the relationship between the chemical structures of the components in NPA and their protective effect on oxidative stress.

  11. 2,4-Di-tert-butyl phenol as the antifungal, antioxidant bioactive purified from a newly isolated Lactococcus sp.

    Science.gov (United States)

    Varsha, Kontham Kulangara; Devendra, Leena; Shilpa, Ganesan; Priya, Sulochana; Pandey, Ashok; Nampoothiri, Kesavan Madhavan

    2015-10-15

    The volatile organic compound 2,4-di-tert-butyl phenol (2,4 DTBP) was purified from the cell free supernatant of a newly isolated Lactococcus sp. by solvent extraction and chromatographic techniques. Molecular characterization of the compound by ESI-MS, (1)H NMR and FTIR analysis revealed the structure, C14H22O. Fungicidal activity was demonstrated against Aspergillus niger, Fusarium oxysporum and Penicillium chrysogenum by disc diffusion assay. Among the cell lines tested for cytotoxicity of this compound (normal cell line H9c2 and cancer cell lines HeLa and MCF-7), a remarkable cytotoxicity against HeLa cells with an IC50 value of 10 μg/mL was shown. A biocontrol experiment with 2,4 DTBP supplemented fraction prevented growth of the abovementioned fungi on wheat grains. The study further strengthens the case for development of biopreservatives and dietary antioxidants from lactic acid bacteria for food applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Pápai, Mátyás Imre; Penfold, Thomas J.; Møller, Klaus Braagaard

    2016-01-01

    . This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck-Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet...

  13. Crystal structure of 2-tert-butyl-1,3-thiazolo[4,5-b]pyridine

    Directory of Open Access Journals (Sweden)

    Gamal A. El-Hiti

    2014-09-01

    Full Text Available The title compound, C10H12N2S, does not contain any strong hydrogen-bond donors but two long C—H...N contacts are observed in the crystal structure, with the most linear interaction linking molecules along [010]. The ellipsoids of the tert-butyl group indicate large librational motion.

  14. Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

    Science.gov (United States)

    Vlad, Elena; Bozga, Grigore

    2012-01-01

    Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA) etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics. PMID:23365512

  15. Volumetric properties of binary mixtures of alkoxyethanols with ethyl tert-butyl ether at various temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kinart, Cezary M. [Department of Chemistry, University of Lodz, 90-236 Lodz, Pomorska 163 (Poland)]. E-mail: ckinart@uni.lodz.pl; Nowak, Katarzyna [Department of Chemistry, University of Lodz, 90-236 Lodz, Pomorska 163 (Poland); Kinart, Wojciech J. [Department of Organic Chemistry, University of Lodz, 90-136 Lodz, Narutowicza 68 (Poland)

    2005-05-15

    Densities at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K in the binary liquid mixtures of ethyl tert-butyl ether with 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol or 2-{l_brace}2-(2-methoxyethoxy)ethoxy{r_brace}ethanol have been measured over the entire mixture compositions. These data have been used to compute the excess molar volumes. The excess molar volumes are negative over the entire range of composition for all mixtures. The changes of V{sup E} with variations of the composition and the chain-length of the alkyl groups in the alkoxyethanol molecules are discussed in terms of intermolecular interactions.

  16. Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

    Directory of Open Access Journals (Sweden)

    Elena Vlad

    2012-01-01

    Full Text Available Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics.

  17. Pressure effect on water dynamics in tert-butyl alcohol/water solutions

    Science.gov (United States)

    Calandrini, Vania; Deriu, Antonio; Onori, Giuseppe; Paciaroni, Alessandro; Telling, Mark T. F.

    2006-09-01

    We report here a quasi-elastic neutron scattering (QENS) investigation of the effect of pressure on the diffusivity properties of water in a dilute aqueous solution of hydrophobic molecules (tert-butyl alcohol, TBA). The experiment was performed at fixed TBA concentration (0.02 molar fraction) by varying pressure from 1 to 2000 bar at two different temperatures (268 and 278 K). The quasi-elastic line-shapes have been analysed in terms of a model based on the memory function formalism. Our data indicate that, on increasing pressure up to 2000 bar, the diffusion coefficient of water in the TBA/water mixture exhibits a relative increase larger than that of pure water under the same thermodynamic conditions. The extent of this effect increases with decreasing temperature. The observed behaviour is described in terms of pressure-induced distortions of the H-bonded random network of liquid water.

  18. (2S,4R)- and (2S,4S)-perfluoro-tert-butyl 4-hydroxyproline: two conformationally distinct proline amino acids for sensitive application in 19F NMR.

    Science.gov (United States)

    Tressler, Caitlin M; Zondlo, Neal J

    2014-06-20

    (2S,4R)- and (2S,4S)-perfluoro-tert-butyl 4-hydroxyproline were synthesized (as Fmoc-, Boc-, and free amino acids) in 2-5 steps. The key step of each synthesis was a Mitsunobu reaction with perfluoro-tert-butanol, which incorporated a perfluoro-tert-butyl group, with nine chemically equivalent fluorines. Both amino acids were incorporated in model α-helical and polyproline helix peptides. Each amino acid exhibited distinct conformational preferences, with (2S,4R)-perfluoro-tert-butyl 4-hydroxyproline promoting polyproline helix. Peptides containing these amino acids were sensitively detected by (19)F NMR, suggesting their use in probes and medicinal chemistry.

  19. Viscosities of binary mixtures of some n-ethoxyethanols with ethyl tert-butyl ether at T = (293.15, 298.15, and 303.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Cwiklinska, Aneta [Department of Chemistry, University of Lodz, 90-236 Lodz, Pomorska 163 (Poland); Dzikowski, Tomasz [Department of Physics, University of Lodz, 90-236 Lodz, Pomorska 148/153 (Poland); Szychowski, Dariusz [Warsaw University of Technology, Faculty of Civil Engineering, Mechanics and Petrochemistry, Institute of Chemistry in Plock, 09-400 Plock, Lukasiewicza 17 (Poland); Kinart, Wojciech J. [Department of Organic Chemistry, University of Lodz, 90-136 Lodz, Narutowicza 68 (Poland); Kinart, Cezary M. [Department of Chemistry, University of Lodz, 90-236 Lodz, Pomorska 163 (Poland)], E-mail: ckinart@uni.lodz.pl

    2007-09-15

    Viscosities at T = (293.15, 298.15, and 303.15) K in the binary mixtures of ethyl tert-butyl ether with 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol have been measured over the entire range of mixture compositions. From the experimental data, deviations in the viscosity ({delta}ln {eta}) and excess energies of activation for viscous flow ({delta}G{sup *E}) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Auslaender, and McAllister. The results for {delta}ln {eta} and {delta}G{sup *E} are discussed in terms of intermolecular interactions and structure of studied binary mixtures.

  20. Redox Regulation of the Tumor Suppressor PTEN by Hydrogen Peroxide and Tert-Butyl Hydroperoxide

    Directory of Open Access Journals (Sweden)

    Ying Zhang

    2017-05-01

    Full Text Available Organic peroxides and hydroperoxides are skin tumor promoters. Free radical derivatives from these compounds are presumed to be the prominent mediators of tumor promotion. However, the molecular targets of these species are unknown. Phosphatase and tensin homologs deleted on chromosome 10 (PTEN are tumor suppressors that play important roles in cell growth, proliferation, and cell survival by negative regulation of phosphoinositol-3-kinase/protein kinase B signaling. PTEN is reversibly oxidized in various cells by exogenous and endogenous hydrogen peroxide. Oxidized PTEN is converted back to the reduced form by cellular reducing agents, predominantly by the thioredoxin (Trx system. Here, the role of tert-butyl hydroperoxide (t-BHP in redox regulation of PTEN was analyzed by using cell-based and in vitro assays. Exposure to t-BHP led to oxidation of recombinant PTEN. In contrast to H2O2, PTEN oxidation by t-BHP was irreversible in HeLa cells. However, oxidized PTEN was reduced by exogenous Trx system. Taken together, these results indicate that t-BHP induces PTEN oxidation and inhibits Trx system, which results in irreversible PTEN oxidation in HeLa cells. Collectively, these results suggest a novel mechanism of t-BHP in the promotion of tumorigenesis.

  1. Acute toxicity and cancer risk assessment values for tert-butyl acetate.

    Science.gov (United States)

    Budroe, John D; Brown, Joseph P; Salmon, Andrew G; Salsmon, Andrew G; Marty, Melanie A

    2004-10-01

    tert-Butyl acetate (TBAc) is an industrial chemical with potential uses as a degreaser and in architectural coatings. Limited chronic toxicity data exist for TBAc. However, acute inhalation exposure data are available for TBAc. Additionally, TBAc has been demonstrated to be substantially metabolized to tert-butanol (TBA) in rats, and a positive TBA genotoxicity study suggests that TBA may cause oxidative DNA damage. TBA has been shown to induce tumors in both rats and mice, and the Office of Environmental Health Hazard Assessment has calculated an oral cancer potency factor (CSF) for TBA of 3 x 10(-3)(mg/kg-day)(-1). Therefore, TBAc should be considered to pose a potential cancer risk to humans because of the metabolic conversion to TBA. An acute 1-h reference exposure level of 1 mg/m3 can be calculated from the extrapolated no observed adverse effect level of 50 mg/m3. A CSF of 0.002(mg/kg-day)(-1) can be derived for TBAc, assuming 100% metabolism of TBAc to TBA. An inhalation unit risk value for TBAc of 4 x 10(-7)(microg/m(3))(-1) can then be derived from the CSF value for TBAc by assuming a human breathing rate of 20 m3/day, 70% fractional absorption, and an average human body weight of 70 kg.

  2. (RSS)-[N-Hydroxyethyloxy]-hexafluoroVal-MeLeu-Ala tert-butyl ester.

    Science.gov (United States)

    Eberle, Marcel K; Stoeckli-Evans, Helen; Keese, Reinhart

    2009-10-28

    THE TITLE COMPOUND [SYSTEMATIC NAME: (2S,5S,8R)-tert-butyl 8-(1,1,1,3,3,3-hexafluoropropan-2-yl)-12-hydroxy-5-isobutyl-2,6-dimethyl-4,7-dioxo-10-oxa-3,6,9-triazadodecanoate], C(21)H(36)F(6)N(3)O(6), is a tripeptide crystallizing in the chiral ortho-rhom-bic spacegroup P2(1)2(1)2(1). The absolute configuration (R) of the chiral center in the hexa-fluoro-valine unit is based on the known stereochemistry of MeLeu and Ala (SS). The N-hydroxy-ethyl-oxy substituent of hexa-fluoro-valine is positionally disordered [occupancy ratio 0.543 (9):0.457 (9)]. In the solid state structure there are N-H⋯F and N-H⋯O intra-molecular hydrogen bonds supporting the coiled structure of this tripeptide with the three hydro-phobic substituents on the outside.

  3. Molecular structures of tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium.

    Science.gov (United States)

    Rong, Yi; Sambade, David; Parkin, Gerard

    2016-11-01

    Cyclopentadienyl and tris(pyrazolyl)hydroborate have found much use as supporting ligands in the chemistry of titanium, zirconium and hafnium, especially with respect to applications involving olefin polymerization catalysis. In contrast, closely related tris(1-alkyl-2-mercaptoimidazolyl)hydroborate, [Tm(R)], ligands have so far found little application to the chemistry of these elements, despite the fact that such ligands are currently used extensively in coordination chemistry. In view of the fact that a substituent in the 2-position exerts a direct influence on the steric environment of the metal center, we report here the application of the sterically demanding tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate [Tm(t-Bu)] ligand to these metals. Dichlorido(η(5)-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ(3)S,S',H]zirconium(IV) benzene hemisolvate, [Zr(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (I), dichlorido(η(5)-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ(3)S,S',H]titanium(IV) benzene hemisolvate, [Ti(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (II), [bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ(3)S,S',H]dichlorido(η(5)-cyclopentadienyl)zirconium(IV), [Zr(C14H24BN4S2)(C5H5)Cl2], (III), (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ(2)N(3),S)dichlorido(η(5)-cyclopentadienyl)zirconium(IV) benzene monosolvate, [Zr(C7H11N2S)(C7H12N2S)(C5H5)Cl2]·C6H6, (IV), and tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ(3)S,S',S'']hafnium(IV) benzene tetrasolvate, [Hf(C7H7)3(C21H34BN6S3)]·4C6H6, (V), have been structurally characterized by X-ray diffraction. The [Tm(t-Bu)] ligand coordinates to Ti and Zr in Cp[κ(3)S2,H-Tm(t-Bu)]MCl2 [M = Zr, (I), and Ti, (II)] in a κ(3)S2,H mode, while the benzyl compounds [Tm(t-Bu)]M(CH2Ph)3 [M = Zr and Hf, (V)] exhibit κ(3)S3 coordination.

  4. Ethyl[tris(3-tert-butyl-5-methylpyrazol-1-yl)hydridoborato]zinc(II).

    Science.gov (United States)

    Kumar, Mukesh; Papish, Elizabeth T; Zeller, Matthias

    2010-08-01

    The X-ray crystal structure of the title compound, [Zn(C(2)H(5))(C(24)H(40)BN(6))], or Tp(tBu,Me)ZnEt [Tp(tBu,Me) is tris(3-tert-butyl-5-methylpyrazolyl)hydridoborate], reveals a distorted tetrahedral geometry around the Zn atom. The Zn center is coordinated by three N atoms of the borate ligand and by one C atom of the ethyl group. The present structure and other tetrahedral Tp zinc alkyl complexes are compared with similar Ttz ligands (Ttz is 1,2,4-triazolylborate), but no major differences in the structures are noted, and it can be assumed that variation of the substitution pattern of Tp or Ttz ligands has little or no influence on the geometry of alkylzinc complexes. Refinement of the structure is complicated by a combination of metric pseudosymmetry and twinning. The metrics of the structure could also be represented in a double-volume C-centered orthorhombic unit cell, and the structure is twinned by one of the orthorhombic symmetry operators not present in the actual structure. The twinning lies on the borderline between pseudomerohedral and nonmerohedral. The data were refined as being nonmerohedrally twinned, pseudomerohedrally twinned and untwinned. None of the approaches yielded results that were unambiguously better than any of the others: the best fit between structural model and data was observed using the nonmerohedral approach which also yielded the best structure quality indicators, but the data set is less than 80% complete due to rejected data. The pseudomerohedral and the untwinned structures are complete, but relatively large residual electron densities that are not close to the metal center are found with values up to three times higher than in the nonmerohedral approach.

  5. TRANSPORT OF METHYL TERT-BUTYL ETHER THROUGH ALFALFA PLANTS. (R825549C062)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  6. IRIS Toxicological Review and Summary Documents for Methyl Tert-Butyl Ether (MTBE)

    Science.gov (United States)

    MTBE is a volatile organic chemical used to oxygenate gasoline. Oxygenated gasoline improves the exhaust emissions from gasoline engines. Since 1992 it has been used to comply with the Federal Reformulated Gasoline (begun in 1995) and Wintertime Oxygenated Fuel (begun in 1992) p...

  7. Complexes of tetra-tert-butyl-tetraazaporphine with Al(III) and Zr(IV) cations as fluoride selective ionophores.

    Science.gov (United States)

    Górski, Lukasz; Mroczkiewicz, Monika; Pietrzak, Mariusz; Malinowska, Elzbieta

    2009-02-09

    In this work, complexes of Zr(IV) and Al(III) cations with 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraazaporphine (TAP) were tested as ionophores in plasticized PVC membranes of ion-selective electrodes. It was found that both tested ionophores show enhanced affinity towards fluoride anion. High fluoride selectivity was observed in the presence of anionic or cationic additives in the membrane, which indicates that proposed compounds work according to charged or neutral carrier mechanism, depending on membrane composition and pretreatment. tert-Butyl substituents, present in the structure of tested compounds, were supposed to prevent formation of ionophore dimers within the membrane phase. This process was found to be responsible for some unfavorable potentiometric properties of electrodes based on complexes of Zr(IV) and Al(III) cations with porphyrins (compounds closely related to tetra-tert-butyl-5,10,15,20-tetraazaporphine). As it was shown using spectrophotometrical measurements, Al(III)-TAP was not susceptible to dimerization, while dimer formation was observed for Zr(IV)-TAP. In full agreement with these observations, electrodes with membranes containing Al(III)-TAP responded in near-Nernstian and fast manner towards fluoride anion, while the employment of Zr(IV)-TAP as ionophore resulted in super-Nernstian and sluggish response. Plasticized PVC membranes doped with Al(III)-TAP and 20mol% of lipophilic anionic additives shown remarkable F(-) selectivity, with selectivity coefficients, logK(F-pot.).(Y-), as follows: -4.4 (Y(-)Br(-)), -4.3 (Cl(-)), -4.2 (NO(3)(-)), -3.6 (SCN(-)), -2.9 (ClO(4)(-)).

  8. Characterizing Effects of Nitric Oxide Sterilization on tert-Butyl Acrylate Shape Memory Polymers

    Science.gov (United States)

    Phillippi, Ben

    As research into the potential uses of shape memory polymers (SMPs) as implantable medical devices continues to grow and expand, so does the need for an accurate and reliable sterilization mechanism. The ability of an SMP to precisely undergo a programmed shape change will define its ability to accomplish a therapeutic task. To ensure proper execution of the in vivo shape change, the sterilization process must not negatively affect the shape memory behavior of the material. To address this need, this thesis investigates the effectiveness of a benchtop nitric oxide (NOx) sterilization process and the extent to which the process affects the shape memory behavior of a well-studied tert-Butyl Acrylate (tBA) SMP. Quantifying the effects on shape memory behavior was performed using a two-tiered analysis. A two-tiered study design was used to determine if the sterilization process induced any premature shape recovery and to identify any effects that NOx has on the overall shape memory behavior of the foams. Determining the effectiveness of the NOx system--specially, whether the treated samples are more sterile/less contaminated than untreated--was also performed with a two-tiered analysis. In this case, the two-tiered analysis was employed to have a secondary check for contamination. To elaborate, all of the samples that were deemed not contaminated from the initial test were put through a second sterility test to check for contamination a second time. The results of these tests indicated the NOx system is an effective sterilization mechanism and the current protocol does not negatively impact the shape memory behavior of the tBA SMP. The samples held their compressed shape throughout the entirety of the sterilization process. Additionally, there were no observable impacts on the shape memory behavior induced by NOx. Lastly, the treated samples demonstrated lower contamination than the untreated. This thesis demonstrates the effectiveness of NOx as a laboratory scale

  9. Formation of Germa-ketenimine on the Ge(100) Surface by Adsorption of tert-Butyl Isocyanide.

    Science.gov (United States)

    Shong, Bonggeun; Yoo, Jong Suk; Sandoval, Tania E; Bent, Stacey F

    2017-06-28

    Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

  10. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111).

    Science.gov (United States)

    Schuler, A; Greif, M; Seitsonen, A P; Mette, G; Castiglioni, L; Osterwalder, J; Hengsberger, M

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3',5,5'-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  11. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111

    Directory of Open Access Journals (Sweden)

    A. Schuler

    2017-01-01

    Full Text Available Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111 in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization.

  12. Effects of Consumption of Rooibos (Aspalathus linearis and a Rooibos-Derived Commercial Supplement on Hepatic Tissue Injury by tert-Butyl Hydroperoxide in Wistar Rats

    Directory of Open Access Journals (Sweden)

    B. D. Canda

    2014-01-01

    Full Text Available This study investigated the antioxidative effect of rooibos herbal tea and a rooibos-derived commercial supplement on tert-butyl hydroperoxide- (t-BHP- induced oxidative stress in the liver. Forty male Wistar rats consumed fermented rooibos, unfermented rooibos, a rooibos-derived commercial supplement, or water for 10 weeks, while oxidative stress was induced during the last 2 weeks via intraperitoneal injection of 30 µmole of t-BHP per 100 g body weight. None of the beverages impaired the body weight gain of the respective animals. Rats consuming the rooibos-derived commercial supplement had the highest (P<0.05 daily total polyphenol intake (169 mg/day followed by rats consuming the unfermented rooibos (93.4 mg/day and fermented rooibos (73.1 mg/day. Intake of both the derived supplement and unfermented rooibos restored the t-BHP-induced reduction and increased (P<0.05 the antioxidant capacity status of the liver, while not impacting on lipid peroxidation. The rooibos herbal tea did not affect the hepatic antioxidant enzymes, except fermented rooibos that caused a decrease (P<0.05 in superoxide dismutase activity. This study confirms rooibos herbal tea as good dietary antioxidant sources and, in conjunction with its many other components, offers a significantly enhanced antioxidant status of the liver in an induced oxidative stress situation.

  13. Effects of colored and noncolored phenolics of Echium plantagineum L. bee pollen in Caco-2 cells under oxidative stress induced by tert-butyl hydroperoxide.

    Science.gov (United States)

    Sousa, Carla; Moita, Eduarda; Valentão, Patrícia; Fernandes, Fátima; Monteiro, Pedro; Andrade, Paula B

    2015-02-25

    Bee pollen is used as a dietary supplement, being promoted as a health food. Echium plantagineum L. bee pollen fractions enriched in flavonols (fraction I) or anthocyanins (fraction II) and the whole extract were characterized by HPLC-DAD. Both in the whole extract and in fraction II seven flavonols and five anthocyanins were identified, while fraction I contained six flavonols (in higher levels than fraction II) and small amounts of petunidin-3-O-rutinoside. Antioxidant capacity was evaluated in Caco-2 cells under oxidative stress induced by tert-butyl hydroperoxide (t-BHP). Fraction I pre-exposure imparted a tendency to protect cells, while fraction II and the whole extract aggravated t-BHP toxicity at some concentrations. The protective effects seem to be correlated with the levels of total glutathione, while no correlation between cellular viability and reactive species was seen. The extracts displayed no significant effect on antioxidant enzymes activity. Overall, anthocyanins seem to abrogate the antioxidant potential of flavonoid-rich extracts.

  14. Smart polymeric cathode material with intrinsic overcharge protection based on a 2,5-di-tert-butyl- 1,4-dimethoxybenzene core structure

    Energy Technology Data Exchange (ETDEWEB)

    Weng, Wei; Zhang, Zhengcheng; Abouimrane, Ali; Redfern, Paul C.; Curtiss, Larry A.; Amine, Khalil [Chemical Sciences and Engineering, Division and Material Sciences Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, IL 60439 (United States)

    2012-11-07

    Polymer-based electroactive materials have been studied and applied in energy storage systems as a valid replacement for transition metal oxides. As early as 1999, Hass et al. proposed an interesting concept on the possible incorporation of both charge storage and overcharge protection functionality into a single material. However, there are virtually no examples of polymeric materials that can not only store the charge, but also consume the overcharge current. Herein, a new material based on a cross-linked polymer (I) with 2,5-di-tert-butyl-1,4-dimethoxybenzene as the core structure is reported. The cyclic voltammogram of the synthesized polymer shows a single oxidation/reduction peak at 3.9-4.0 V. At 1C rate (56 mA/g), polymer I shows stable cycling up to 200 cycles with <10% capacity loss. The redox shuttle mechanism remarkably can be activated when cell voltage is elevated to 4.3 V and the overcharge plateau at 4.2 V (2{sup nd} plateau) is persistent for more than 100 hours. The overcharge protection was due to the release of a chemical redox shuttle species in the electrolyte during the initial charging process. Both DFT calculations and NMR analysis of the aromatic signals in the {sup 1}H-NMR spectrum of electrolytes from ''overcharged'' cells provide evidence for this hypothesis. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysis of 3,5 di tert butyl 4 hydroxy benzoic acid

    Science.gov (United States)

    Mathammal, R.; Sangeetha, K.; Sangeetha, M.; Mekala, R.; Gadheeja, S.

    2016-09-01

    In this study, we report a combined experimental and theoretical study on molecular structure and vibrational spectra of 3,5 di tert butyl 4 hydroxy benzoic acid. The properties of title compound have been evaluated by quantum chemical calculation (DFT) using B3LYP functional and 6-31 + G (d, p) as basis set. IR Spectra has been recorded using Fourier transform infrared spectroscopy (FT-IR) in the region 4000-400 cm-1. The vibrational assignment of the calculated normal modes has been made on the basis set. The isotropic chemical shifts computed by 13C and 1H NMR (Nuclear Magnetic Resonance) analyses also show good agreement with experimental observations. The theoretical UV-Vis spectrum of the compound are used to study the visible absorption maxima (λ max). The structure activity relationship have been interpreted by mapping electrostatic potential surface (MEP), which is valuable information for the quality control of medicines and drug receptor interactions. The Mullikan charges, HOMO (Highest Occupied Molecular Orbital) - LUMO (Lowest Unoccupied Molecular Orbital) energy are analyzed. HOMO-LUMO energy gap and other related molecular properties are also calculated. The Natural Bond Orbital (NBO) analysis is carried out to investigate the various intra and inter molecular interactions of molecular system. The Non-linear optical properties such as dipole moment (μ), polarizability (αtot) and molecular first order hyperpolarizability (β) of the title compound are computed with B3LYP/6-31 + G (d,p) level of theory.

  16. Ferric chloride-catalyzed reaction of [60]fullerene with tert-butyl N-substituted carbamates: synthesis of oxazolidino[4,5:1,2][60]fullerenes.

    Science.gov (United States)

    You, Xun; Wang, Guan-Wu

    2014-01-03

    The rare oxazolidinofullerenes have been prepared by the ferric chloride-catalyzed reaction of [60]fullerene with various tert-butyl N-substituted carbamates via t-Bu-O bond cleavage and heteroannulation under mild conditions. A possible mechanism for the formation of oxazolidinofullerenes is proposed.

  17. Intra-arterial tert-Butyl-hydroperoxide infusion induces an exacerbated sensory response in the rat hind limb and is associated with an impaired tissue oxygen uptake.

    NARCIS (Netherlands)

    Tan, E.C.T.H.; Goor, H. van; Bahrami, S.; Kozlov, A.V.; Leixnering, M.; Redl, H.; Goris, R.J.A.

    2011-01-01

    The objective of this study was to investigate oxidative stress and oxygen extraction mechanisms in an animal model of continuous intra-arterial infusion of a free radical donor and in an in vitro model using isolated mitochondria. tert-Butyl-hydroperoxide (tert-BuOOH, 25 mM) was infused for 24 h in

  18. Interfacial Reactions in Confinement: Kinetics and Temperature Dependence of the Surface Hydrolysis of Polystyrene-block-poly(tert-butyl acrylate) Thin Films

    NARCIS (Netherlands)

    Feng, C.L.; Vancso, Gyula J.; Schönherr, Holger

    2005-01-01

    The effect of confinement on the kinetics of the surface hydrolysis of polystyrene-block-poly(tert-butyl acrylate) (PSn-b-PtBAm) thin films on oxidized silicon substrates in 3 M aqueous hydrochloric acid was systematically investigated. As shown by X-ray photoelectron spectroscopy (XPS) and contact

  19. (2E-4-tert-Butyl-2-(4-methoxybenzylidene-3,4-dihydronaphthalen-1(2H-one

    Directory of Open Access Journals (Sweden)

    Mohamed Akhazzane

    2011-07-01

    Full Text Available In the title compound C22H24O2, the exocyclic C=C double bond is in an E configuration and the tert-butyl group is in an axial position on the cyclohexanone ring. The cyclohexanone ring in the dihydronaphthalene fused-ring system adopts a half-chair conformation in both independent two molecules in the asymetric unit. The benzene ring system is oriented angles of 43.97 (12 and 39.24 (12° with respect to the naphthyl ring system in the two independent molecules. In the crystal, molecules are linked via C—H...O hydrogen bonds and C—H...π interactions.

  20. Structure-Dependent 4-Tert-Butyl Pyridine-Induced Band Bending at TiO2 Surfaces

    Directory of Open Access Journals (Sweden)

    Mats Göthelid

    2011-01-01

    Full Text Available The role of 4-tert butyl pyridine (4TBP adsorption on TiO2 surface band bending has been studied using photoelectron spectroscopy. Surface oxygen vacancies pin the Fermi level near the conduction band edge on rutile (110. 4TBP preferentially adsorbs in those vacancies and shift the Fermi level to lower binding energy in the band gap. This is done by transferring vacancy excess charge into the empty π∗ orbital in the pyridine ring. The anatase (100 surface contains much less oxygen vacancies although the surface is much rougher than the rutile (110. 4TBP adsorption does not have any significant effect on the surface band bending. Thus the positive role associated with 4TBP addition to solar cell electrolytes is suggested to protection against adsorption of other electrolyte components such as Li and I.

  1. Irreversible hyperoxidation of peroxiredoxin 2 is caused by tert-butyl hydroperoxide in human red blood cells

    Directory of Open Access Journals (Sweden)

    Y.I. Ishida

    2014-01-01

    Full Text Available Peroxiredoxin 2 (Prx2 is the third most abundant protein in red blood cells (RBCs. In this study, we have succeeded in implementing the rapid and simultaneous detection of the hyperoxidized (Prx2-SO2/3 and reduced (Prx2-SH forms of Prx2 in human RBCs using reverse phase high-performance liquid chromatography. The detection of a peak corresponding to Prx2-SO2/3 was clearly observed following treatment of tert-butyl hydroperoxide (t-BHP, but not H2O2, and was found to be dose-dependent. The identity of the peak was confirmed as Prx2 by immunoblotting and mass spectrometry analysis. Our results suggest that t-BHP hyperoxidizes cysteine residues in Prx2 more readily than H2O2, and that accumulation of hyperoxidized Prx2 might reflect disruption of redox homeostasis in RBCs.

  2. Incorporation of the hydrophobic probe N-t-BOC-L-tyrosine tert-butyl ester to red blood cell membranes to study peroxynitrite-dependent reactions.

    Science.gov (United States)

    Romero, Natalia; Peluffo, Gonzalo; Bartesaghi, Silvina; Zhang, Hao; Joseph, Joy; Kalyanaraman, Balaraman; Radi, Rafael

    2007-11-01

    We have previously demonstrated that red blood cells (RBC) are an important sink of intravascularly generated peroxynitrite even in the presence of physiological concentrations of CO2 or other plasmatic biotargets. Once inside erythrocytes, peroxynitrite reacts fast with oxyhemoglobin (oxyHb; k2=2 x 10(4) M(-1) s(-1) at 37 degrees C and pH 7.4) and isomerizes to nitrate. Herein, we investigated whether, in spite of the fast diffusion and consumption of extracellularly added peroxynitrite by intraerythrocytic oxyHb, peroxynitrite-dependent radical processes could occur at the RBC membrane, focusing on tyrosine nitration. For this purpose, the hydrophobic tyrosine analogue N-t-BOC-L-tyrosine tert-butyl ester (BTBE) was successfully incorporated for the first time to a biological membrane, that is, RBC membrane, with incorporation yields approximately 1-3 x 10(7) molecules per RBC. The membrane integrity of BTBE-containing RBC was not significantly altered after BTBE incorporation as demonstrated by permeability studies. The probe was then used to study peroxynitrite-dependent reactions. The addition of peroxynitrite to BTBE-containing RBC suspensions resulted in BTBE nitration and dimerization to 3-nitro-BTBE and 3,3'-di-BTBE, respectively, indicative of peroxynitrite-derived radicals reactions in the membrane. Peroxynitrite addition to RBC also caused tyrosine nitration of membrane-associated proteins. The free radical nature of the process was also shown by the detection of protein-derived radicals by DMPO-immunospin trapping. While the presence of extracellular CO2 was potently inhibitory of intracellular oxyHb oxidation, membrane protein and BTBE nitration by peroxynitrite at membrane, in spite of the significant peroxynitrite scavenging activity of oxyHb inside the RBC.

  3. Di-tert-butyl (2R,3R-2-{[(2E-3-(4-acetyloxy-3-methoxyphenylprop-2-enoyl]oxy}-3-hydroxybutanedioate

    Directory of Open Access Journals (Sweden)

    Edward R. T. Tiekink

    2012-03-01

    Full Text Available In the title molecule, C24H32O10, one tert-butyl ester group is folded towards the central benzene ring while the other is directed away. The acetyl group is almost perpendicular to the benzene ring to which it is connected [C—C—O—C torsion angle = 90.4 (12°]. The conformation about the ethene bond [1.313 (7 Å] is E. The atoms of the benzene ring and its attached ester group and part of the hydroxy tert-butyl ester side chain are disordered over two sets of sites in a 50:50 ratio. Linear supramolecular chains along the a axis mediated by hydroxy–carbonyl O—H...O hydrogen bonds feature in the crystal packing. The same H atom also partakes in an intramolecular O—H...O interaction.

  4. Vibrio fischeri and Escherichia coli adhesion tendencies towards photolithographically modified nanosmooth poly (tert-butyl methacrylate polymer surfaces

    Directory of Open Access Journals (Sweden)

    Elena P Ivanova

    2008-09-01

    Full Text Available Elena P Ivanova1, Natasa Mitik-Dineva1, Radu C Mocanasu1, Sarah Murphy1, James Wang2, Grant van Riessen3, Russell J Crawford11Faculty Life and Social Sciences; 2IRIS, Swinburne University of Technology, Hawthorn, Victoria, Australia; 3Centre for Materials and Surface Science, La Trobe University, Melbourne, Victoria, AustraliaAbstract: This study reports the adhesion behavior of two bacterial species, Vibrio fischeri and Escherichia coli, to the photoresistant poly(tert-butyl methacrylate (P(tBMA polymer surface. The data has demonstrated that ultraviolet irradiation of P(tBMA was able to provide control over bacterial adhesion tendencies. Following photolithography, several of the surface characteristics of P(tBMA were found to be altered. Atomic force microscopy analysis indicated that photolithographically modified P(tBMA (henceforth termed ‘modified polymer’ appeared as a ‘nanosmooth’ surface with an average surface roughness of 1.6 nm. Although confocal laser scanning microscopy and scanning electron microscopy analysis clearly demonstrated that V. fischeri and E. coli presented largely different patterns of attachment in order to adhere to the same surfaces, both species exhibited a greater adhesion propensity towards the ‘nanosmooth’ surface. The adhesion of both species to the modified polymer surface appeared to be facilitated by an elevated production of extracellular polymeric substances when in contact with the substrate.Keywords: poly(tert-butylmethacrylate polymeric surfaces, surface nanotopography, bacterial attachment, extracellular polymeric substances

  5. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...... the wavelength range 220-330 nm. At 240 nm, sigma((CH3)3COC(CH3)2CH2) = (3.6 +/- 0.4) X 10(-18) cm(2) molecule(-1) and at 260 nm, sigma((CH3)3COC(CH3)2CH2) = (3.8 +/- 0.3) X 10(-18) cm(2) molecule(-1) have been obtained. The observed rate constants for the self-reaction of (CH3)(3)COC(CH3)(2)CH2 and (CH3)(3)COC...

  6. Bis(formylphenolatocobalt(II-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

    Directory of Open Access Journals (Sweden)

    Sanjib Banerjee

    2017-12-01

    Full Text Available The organometallic-mediated radical polymerization (OMRP of vinyl acetate (VAc and its OMR copolymerization (OMRcoP with tert-butyl 2-trifluoromethylacrylate (MAF-TBE mediated by Co(SAL2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE copolymers at moderate temperature (<40 °C in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55 of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL2: a lower ability to trap radical chains as compared to Co(acac2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative.

  7. Diafenthiuron: 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenylthiourea

    Directory of Open Access Journals (Sweden)

    Youngeun Jeon

    2014-07-01

    Full Text Available The title compound, C23H32N2OS, is a thiourea-based insecticide. The dihedral angle between the phenyl ring and the diisopropyl benzene ring plane is 73.18 (6°, while that between the plane of the thiourea group and the diisopropyl benzene ring is 86.00 (5°. Disorder was modelled for the S atom and the two methyl C atoms of the isopropyl group over two sets of sites with an occupancy ratio of 0.742 (4:0.258 (4. In the crystal, N—H...S hydrogen bonds link adjacent molecules, forming R22(8 inversion dimers that pack into chains along the b-axis direction.

  8. Kinetic study of the 7-endo selective radical cyclization of N-tert-butyl-o-bromobenzylmethacryl amides: kinetic investigation of the cyclization and 1,7-hydrogen transfer of aromatic radicals.

    Science.gov (United States)

    Kamimura, Akio; Kotake, Tomoko; Ishihara, Yuriko; So, Masahiro; Hayashi, Takahiro

    2013-04-19

    A kinetic investigation of the radical cyclization of N-tert-butyl-o-bromobenzylmethacryl amides to give 2-benzazepines via 7-endo selective cyclization was undertaken. The aryl radical generated from the amide precursor by treatment with Bu3SnH gave the three compounds, which are a 7-endo cyclized adduct, a 6-exocyclized adduct, and a reduced product. The cyclization reactions under various Bu3SnH concentrations were traced by GC analysis. The 7-endo/6-exo selectivity was constant irrespective of variation in Bu3SnH concentration. These results revealed that regioselectivity is controlled in a kinetic manner and that there is no possibility of a neophyl rearrangement. The use of Bu3SnD revealed that 1,7-hydrogen transfer, in which an aryl radical abstracts a hydrogen atom from the methallylic methyl group, occurs during the reaction. Hydrogen abstraction from toluene, the reaction solvent, was also observed. The 1,7-transfer rate depended on the Bu3SnX (X = H or D), and the reaction kinetics was examined. The k(H)/k(D) value for the hydrogen abstraction of aryl radical from Bu3SnX (X = H or D) was estimated using 4-bromoanisol. The utilization of these values revealed the overall reaction kinetics and relative rates for the cyclization and reduction by Bu3SnX (X = H or D). Kinetic parameters for hydrogen abstraction from toluene by aryl radicals were also estimated.

  9. Synthesis and characterization of cationic selenium-nitrogen heterocycles from tert-butyl-DAB (DAB = 1,4-di-tert-butyl-1,3-diazabutadiene) and SeX4 via the reductive elimination of X2 (X = Cl, Br): a distinct contrast with tellurium.

    Science.gov (United States)

    Dutton, Jason L; Sutrisno, Andre; Schurko, Robert W; Ragogna, Paul J

    2008-07-14

    The synthesis and comprehensive characterisation of a series of 1,2,5-selenadiazolium salts, which were generated from the direct reaction between the neutral bidentate ligand tert-butyl-DAB and a variety of heavy chalcogen halides, are reported. The formation of the cationic heterocycle from the reaction of SeX4 (X = Cl, Br) and the ligand results in a two electron redox process where the chalcogen undergoes a two electron reduction concomitant with the elimination of X2, the oxidation by-product. A reaction pathway for this chemistry has been proposed necessitating several key intermediates. These species have been synthesized and used in a stepwise series of transformations that strongly supports this very unusual reactivity for the chalcogens. In contrast, the reaction between tert-butyl DAB and TeX4 (X = Cl, Br, I), does not result in redox, rather an octahedral Te(iv) x DAB complex is formed or no reaction was observed.

  10. Complexation study of a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand with uranium(VI) in non-aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Anne; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The actinide uranium, well known from nuclear power cycle, plays also a role in rare earth production as it is an undesired constituent of the respective ores. To facilitate the production of rare earth elements, uranium has to be removed. Due to their modifiable selectivity and solubility calix[n]arenes are interesting compounds for the extraction of actinides and lanthanides. The mechanism of uranium(VI) interaction with a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand (L1) was studied by TRLFS, UV-vis spectroscopy and isothermal calorimetry.

  11. INFLUENCE OF THE ISOBUTENE METHANOL RATIO AND OF THE METHYL TERT-BUTYL ETHER CONTENT ON THE REACTION-RATE OF THE SYNTHESIS OF METHYL TERT-BUTYL ETHER

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1995-01-01

    The forward reaction rate constant of the MtBE synthesis was determined for different reaction mixture compositions. The forward rate constant decreases continuously with increasing isobutene/methanol ratio, while an increase in reaction rate constant is observed with an increasing amount of MtBE in

  12. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al{sub 2}O{sub 3} supported copper and gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout, E-mail: rmeijboom@uj.ac.za

    2017-03-15

    Highlights: • Cu and Au on γ-Al{sub 2}O{sub 3} catalysts were prepared and characterized. • Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide in the absence of any solvent using the prepared catalysts. • The as prepared catalysts exhibited good performance in terms of conversion and selectivity towards benzaldehyde. • The kinetics of the reaction was investigated; k{sub app} was proportional to the amount of nano catalyst and oxidant present in the system. • The catalysts was recycled and reused with neither significant loss of activity nor selectivity. - Abstract: Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al{sub 2}O{sub 3} supported copper and gold nanoparticles. Li{sub 2}O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N{sub 2} absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol

  13. Polystyrene-b-poly(tert-butyl acrylate) and polystyrene-b-poly(acrylic acid) dendrimer-like copolymers: two-dimensional self-assembly at the air-water interface.

    Science.gov (United States)

    Joncheray, Thomas J; Bernard, Sophie A; Matmour, Rachid; Lepoittevin, Bénédicte; El-Khouri, Rita J; Taton, Daniel; Gnanou, Yves; Duran, Randolph S

    2007-02-27

    The two-dimensional self-assembly at the air/water (A/W) interface of two dendrimer-like copolymers based on polystyrene and poly(tert-butyl acrylate) (PS-b-PtBA) or poly(acrylic acid) (PS-b-PAA) was investigated through surface pressure measurements (isotherms, isochores, and compression-expansion hysteresis experiments) and atomic force microscopy (AFM) imaging. The two dendrimer-like block copolymers have an 8-arm PS core (Mn = 10 000 g/mol, approximately 12 styrene repeat units per arm) with a 16-arm PtBA (Mn = 230 000 g/mol, approximately 112 tert-butyl acrylate repeat units per arm) or PAA (Mn = 129 000 g/mol, approximately 112 acrylic acid repeat units per arm) corona. The PS-b-PtBA sample forms stable Langmuir monolayers and aggregates into circular surface micelles up to a plateau observed in the corresponding isotherm around 24 mN/m. Beyond this threshold, the monolayers collapse above the interface, resulting in the formation of large and irregular desorbed aggregates. The PS-b-PAA sample has ionizable carboxylic acid groups, and its A/W interfacial self-assembly was therefore investigated for various subphase pH values. Under basic conditions (pH = 11), the carboxylic acid groups are deprotonated, and the PS-b-PAA sample is therefore highly water-soluble and does not form stable monolayers, instead irreversibly dissolving in the aqueous subphase. Under acidic conditions (pH = 2.5), the PS-b-PAA sample is less water-soluble and becomes surface-active. The pseudoplateau observed in the isotherm around 5 mN/m corresponds to a pancake-to-brush transition with the PAA chains dissolving in the water subphase and stretching underneath the anchoring PS cores. AFM imaging revealed the presence of circular surface micelles for low surface pressures, whereas the biphasic nature of the pseudoplateau region was confirmed with the gradual aggregation of the micellar PS cores above the PAA chains. The aggregation numbers for both samples were estimated around 3

  14. Kinetics and Photodegradation Study of Aqueous Methyl tert-Butyl Ether Using Zinc Oxide: The Effect of Particle Size

    Directory of Open Access Journals (Sweden)

    Zaki S. Seddigi

    2013-01-01

    Full Text Available Zinc oxide of different average particle sizes 25 nm, 59 nm, and 421 nm as applied in the photodegradation of MTBE. This study was carried out in a batch photoreactor having a high pressure mercury lamp. Zinc oxide of particle size of 421 nm was found to be the most effective in degrading MTBE in an aqueous solution. On using this type of ZnO in a solution of 100 ppm MTBE, the concentration of MTBE has decreased to 5.1 ppm after a period of five hours. The kinetics of the photocatalytic degradation of MTBE was found to be a first order reaction.

  15. EXPERIMENTAL MEASUREMENT OF THE RATE OF METHYL TERT-BUTYL ETHER HYDROLYSIS IN SUB- AND SUPERCRITICAL WATER. (R826738)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. Preparation and characterization of a p-tert-butyl-calix[6]-1,4-benzocrown-4-bonded silica gel stationary phase for liquid chromatography.

    Science.gov (United States)

    Li, Lai-Sheng; Da, Shi-Lu; Feng, Yu-Qi; Liu, Min

    2004-06-18

    A p-tert-butyl-calix[6]-1,4-benzocrown-4-bonded silica gel stationary phase (CR6BS) was first prepared via 3-glycidoxypropyltrimethoxysilane as coupling reagent for high performance liquid chromatography. The structure of the new stationary phase was characterized by diffuse reflectance infrared fourier transform spectroscopy (DRIFT), elemental analysis and thermal analysis. The chromatographic performance of the bonded-stationary phase was evaluated by using neutral, acidic and basic solutes as probes. Meanwhile, comparative study of the new stationary phase with a p-tert-butyl-calix[6]arene-bonded silica gel stationary phase (C6BS, the parent) and ODS was done under the same chromatographic conditions. The results show that the new stationary phase has an excellent reversed-phase property, which is similar to C6BS and ODS. However, the selectivities for some aromatic compounds are different from the parent phase (C6BS) and ODS, especially the latter. In one hand, as hybrid of calixarene and crown ether, CR6BS with the oxygen atoms of ether-bridge can provide the complexation sites for the solutes, lacking of C6BS. On the other hand, the rigid conformation of CR6BS may be responsible to the different performance partially. CR6BS exhibits high selectivity in the separation of alkylated aromatics from their parents as compared with C6BS.

  17. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis[2-(2-chloroethoxyethoxy]-2,8,14,20-tetrasulfonylcalix[4]arene

    Directory of Open Access Journals (Sweden)

    Dian-Shun Guo

    2009-02-01

    Full Text Available Molecules of the title compound, C56H76Cl4O16S4, have crystallographic C2 symmetry and adopt a 1,3-alternate conformation where the four –OCH2CH2OCH2CH2Cl groups are located alternately above and below the virtual plane (R defined by the four bridging S atoms. The dihedral angles between the plane (R and the phenolic rings are 72.85 (7 and 74.57 (7°. An unusual 24-membered macrocyclic ring is formed in the crystal structure with an array of eight intramolecular C—H...O hydrogen bonds between the ether arm H atoms and the sulfonyl O atoms. In the supramolecular structure, the molecular components are linked into infinite zigzag one-dimensional chains by a combination of four intermolecular C—H...O hydrogen bonds, forming R22(13, R22(16, R22(21 and R22(26 ring motifs. These chains are augmented into a wave-like two-dimensional network by weak C...O interactions. One tert-butyl group shows rotational disorder, and one CH2CH2Cl group is disordered over two orientations; the site-occupation factors are 0.756 (6 and 0.244 (6 for the two tert-butyl groups, and 0.808 (3 and 0.192 (3 for the two CH2CH2Cl units.

  18. Sterically directed nitronate complexes of 2,6-di-tert-butyl-4-nitrophenoxide with Cu(ii) and Zn(ii) and their H-atom transfer reactivity.

    Science.gov (United States)

    Porter, Thomas R; Hayes, Ellen C; Kaminsky, Werner; Mayer, James M

    2017-02-21

    The bulky 2,6-di-tert-butyl-4-nitrophenolate ligand forms complexes with [TptBuCuII]+ and [TptBuZnII]+ binding via the nitro group in an unusual nitronato-quinone resonance form (TptBu = hydro-tris(3-tert-butyl-pyrazol-1-yl)borate). The Cu complex in the solid state has a five-coordinate κ2-nitronate structure, while the Zn analogue has a four-coordinate κ1-nitronate ligand. 4-Nitrophenol, without the 2,6-di-tert-butyl substituents, instead binds to [TptBuCuII]+ through the phenolate oxygen. This difference in binding is very likely due to the steric difficulty in binding a 2,6-di-tert-butyl-phenolate ligand to the [TptBuMII]+ unit. TptBuCuII(κ2-O2NtBu2C6H2O) reacts with the hydroxylamine TEMPO-H (2,2,6,6-tetramethylpiperidin-1-ol) by abstracting a hydrogen atom. This system thus shows an unusual sterically enforced transition metal-ligand binding motif and a copper-phenolate interaction that differs from what is typically observed in biological and chemical catalysis.

  19. Tetrachlorido[N2,N2′-(dimethylsilanediylbis(N-tert-butyl-3-methylbenzimidamidato-κ2N2,N2′]hafnium(IV

    Directory of Open Access Journals (Sweden)

    Sheng-Di Bai

    2013-12-01

    Full Text Available The symmetric title molecule, [Hf(C26H40N4SiCl4], lies about a twofold rotation axis. The HfIV and Si atoms lie on the rotation axis with all other atoms being in general positions. The HfIV atom is six-coordinated by two N atoms from the N2,N2′-(dimethylsilanediylbis(N-tert-butyl-3-methylbenzimidamidate ligand and four Cl− ions in a slightly distorted octahedral geometry. The two amidinate moieties are connected through the central Si atom with Si—N bond length of 1.762 (3 Å, generating the characteristic N—C—N—Si—N—C—N skeleton of a silyl-linked ansa-bis(amidine species.

  20. Poly[[[diisothiocyanatocobalt(II]-bis[μ-4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethylphenol

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available In the title compound, {[Co(NCS2(C16H20N6O2]·2C3H7NO·2H2O}n, each CoII ion located on an inversion center is six-coordinated by four equatorial N atoms from four different 4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethylphenol (L ligands, and by two N atoms from two axial thiocyanate anions [Co—N = 2.104 (3–2.144 (3 Å]. The metal centres are connected via the bidentate L ligands into two-dimensional polymeric layers parallel to bc plane. The dimethylformamide and solvent water molecules participate in intermolecular O—H...O and O—H...S hydrogen bonds, which consolidate the crystal packing.

  1. Crystal structure and DFT study of (E-2,6-di-tert-butyl-4-{[2-(pyridin-2-ylhydrazin-1-ylidenemethyl}phenol

    Directory of Open Access Journals (Sweden)

    Md. Serajul Haque Faizi

    2017-10-01

    Full Text Available The title compound, C20H27N3O, was synthesized by condensation reaction of 3,5-di-tert-butyl-4-hydroxybenzaldehyde and 2-hydrazinylpyridine, and crystallizes in the centrosymmetric monoclinic space group C2/c. The conformation about the C=N bond is E. The dihedral angle between the rings is 18.1 (3°. An intermolecular N—H...N hydrogen bond generates an R22(8 ring motif. In the crystal, N—H...N hydrogen bonds connect pairs of molecules, forming dimers. Density functional theory (DFT optimized structures at the B3LYP/6–311 G(d,p level are compared with the experimentally determined molecular structure in the solid state.

  2. 1,4-Di-tert-butyl (2R,3R-2-({(2E-3-[4-(acetyloxyphenyl]prop-2-enoyl}oxy-3-hydroxybutanedioate

    Directory of Open Access Journals (Sweden)

    Josh L. Hixson

    2012-02-01

    Full Text Available The title compound, C23H30O9, has an approximate T-shape with the tert-butyl ester groups lying either side of the benzene ring. The acetyl group is almost perpendicular to the benzene ring to which it is connected [C—C—O—C torsion angle = −106.7 (3°]. The conformation about the C=C double bond [1.331 (4 Å] is E. Linear supramolecular chains along the a axis mediated by hydroxy–carbonyl O—H...O hydrogen bonds feature in the crystal packing. The same H atom is also involved in an intramolecular O—H...O interaction.

  3. tert-Butyl (2S-2-{3-[(R-bis(tert-butoxycarbonylamino]-2-oxopiperidin-1-yl}-3-methylbutanoateCAS Registry Number 500222-63-9.

    Directory of Open Access Journals (Sweden)

    Michael J. Kangas

    2011-11-01

    Full Text Available The title compound, C24H42N2O7, is a chiral lactam-constrained amino acid with a six-membered ring backbone and isopropyl and tert-butyl ester side chains. The conformation of the six-membered ring can be described as a half chair, with two CH2 C atoms lying 0.443 (1 and −0.310 (1 Å out of the best plane of the other four atoms (mean deviation = 0.042 Å. Both N atoms are sp2 hybridized, lying 0.0413 (9 and 0.067 (1 Å out of the planes defined by the three C atoms bonded to them. The absolute configuration was determined, based on resonant scattering of light atoms in Cu Kα radiation.

  4. Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

    Science.gov (United States)

    Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

    2017-11-01

    A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R2>0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. On the competition between weak Osbnd H⋯F and Csbnd H⋯F hydrogen bonds, in cooperation with Csbnd H⋯O contacts, in the difluoromethane - tert-butyl alcohol cluster

    Science.gov (United States)

    Spada, Lorenzo; Tasinato, Nicola; Bosi, Giulio; Vazart, Fanny; Barone, Vincenzo; Puzzarini, Cristina

    2017-07-01

    The 1:1 complex of tert-butyl alcohol with difluoromethane has been characterized by means of a joint experimental-computational investigation. Its rotational spectrum has been recorded by using a pulsed-jet Fourier-Transform microwave spectrometer. The experimental work has been guided and supported by accurate quantum-chemical calculations. In particular, the computed potential energy landscape pointed out the formation of three stable isomers. However, the very low interconversion barriers explain why only one isomer, showing one Osbnd H⋯F and two Csbnd H⋯O weak hydrogen bonds, has been experimentally characterized. The effect of the H → tert-butyl-group substitution has been analyzed from the comparison to the difluoromethane-water adduct.

  6. De aanwezigheid van methyl tert-butylether (MTBE) in drinkwater en drinkwaterbronnen

    NARCIS (Netherlands)

    Morgenstern PP; Korte GAL de; Hogendoorn EA; Versteegh JFM; LWD; IEM

    2002-01-01

    In 2001 the National Institute for Public Health and the Environment (RIVM) in the Netherlands conducted a drinking water measurement programme in co-operation with the Netherlands Waterworks Association (VEWIN) for methyl tert-butyl ether (MTBE) in drinking water and the corresponding sources. This

  7. Contact allergy to 2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol, components of a phenolic resin used in marking pens

    DEFF Research Database (Denmark)

    Hagdrup, H; Egsgaard, H; Carlsen, L

    1994-01-01

    2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol were identified as contact allergens in a phenolic resin used as a tackifier in the ink of a marking pen, which, after being used directly on the skin, caused an acute contact dermatitis on the hand of a 13-year......-old boy. The patient also reacted to 4-tert-butylphenol-formaldehyde resin (BPF resin) 1% pet. included in the European standard series....

  8. Characterization of Individual Isopropylated and tert-Butylated Triarylphosphate (ITP and TBPP) Isomers in Several Commercial Flame Retardant Mixtures and House Dust Standard Reference Material SRM 2585.

    Science.gov (United States)

    Phillips, Allison L; Hammel, Stephanie C; Konstantinov, Alex; Stapleton, Heather M

    2017-11-21

    Since the phase-out of pentaBDE in the early 2000s, replacement flame-retardant mixtures including Firemaster 550 (FM 550), Firemaster 600 (FM 600), and organophosphate aryl ester technical mixtures have been increasingly used to treat polyurethane foam in residential upholstered furniture. These mixtures contain isomers of isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs), which have similar or greater neuro- and developmental toxicity compared to BDE 47 in high-throughput assays. Additionally, human exposure to ITPs and TBPPs has been demonstrated to be widespread in several recent studies; however, the relative composition of these mixtures has remained largely uncharacterized. Using available authentic standards, the present study quantified the contribution of individual ITP and TBPP isomers in four commercial flame retardant mixtures: FM 550, FM 600, an ITP mixture, and a TBPP mixture. Findings suggest similarities between FM 550 and the ITP mixture, with 2-isopropylphenyl diphenyl phosphate (2IPPDPP), 2,4-diisopropylphenyl diphenyl phosphate (24DIPPDPP), and bis(2-isopropylphenyl) phenyl phosphate (B2IPPPP) being the most prevalent ITP isomers in both mixtures. FM 600 differed from FM 550 in that it contained TBPP isomers instead of ITP isomers. These analytes were also detected and quantified in a house dust standard reference material, SRM 2585, demonstrating their environmental relevance.

  9. The Synergistic Effects of Heat Shock Protein 70 and Ginsenoside Rg1 against Tert-Butyl Hydroperoxide Damage Model In Vitro

    Directory of Open Access Journals (Sweden)

    Dan Lu

    2015-01-01

    Full Text Available Neural stem cells (NSCs transplanted is one of the hottest research to treat Alzheimer’s disease (AD, but cholinergic neurons from stem cells were also susceptible to cell death which Heat shock protein 70 (HSP70 was affirmed to reverse. Related to cognitive impairment, cholinergic nervous cells should be investigated and ginsenoside Rg1 (G-Rg1 was considered to increase them. We chose tert-butyl hydroperoxide (t-BHP damage model to study in vitro. Functional properties of our recombination plasmid pEGFP-C2-HSP70 were affirmed by SH-SY5Y cells. To opposite the transitory appearance of HSP70, NSCs used as the vectors of HSP70 gene overexpressed HSP70 for at least 7 days in vitro. After transfection for 3 days, G-Rg1 pretreatment for 4 hours, and coculture for 3 days, the expression of acetylcholinesterase (ChAT, synaptophysin, and the ratio of NeuN and GFAP were assessed by western blot; Morphological properties were detected by 3D reconstruction and immunofluorescence. ChAT was markedly improved in the groups contained G-Rg1. In coculture system, the ratio of neurons/astrocytes and the filaments of neurons were increased; apoptosis cells were decreased, compared to monotherapy (P<0.05. In conclusion, we demonstrated that, as a safe cotreatment affirmed in vitro, overexpression of HSP70 in NSCs plus G-Rg1 promoted nervous cells regeneration from chronic oxidative damage.

  10. Synthesis and molecular structure of indium complexes based on 3,6-di-tert-butyl-o-benzoquinone. Looking for indium(I) o-semiquinolate.

    Science.gov (United States)

    Piskunov, Alexandr V; Maleeva, Aryna V; Fukin, Georgii K; Baranov, Evgenii V; Bogomyakov, Artem S; Cherkasov, Vladimir K; Abakumov, Gleb A

    2011-01-21

    The interaction of 3,6-di-tert-butyl-o-benzoquinone (3,6-Q) with indium in toluene leads to the tris-o-semiquinolate derivative (3,6-SQ)(3)In (3,6-SQ - radical-anion of 3,6-Q). According to single-crystal X-ray diffraction analysis, this complex has a trigonal prismatic structure. Magnetic measurements revealed that the exchange interactions between odd electrons of the paramagnetic ligands in (3,6-SQ)(3)In are antiferromagnetic in character. The treatment of (3,6-SQ)(3)In with 2,2'-dipyridyl (Dipy) causes the displacement of one o-quinone ligand and the formation of the (3,6-SQ)In(Dipy)(3,6-Cat) (3,6-Cat - dianion of 3,6-Q) derivative containing mixed charged o-quinoid ligands. The reaction of InI with (3,6-SQ)K in THF solution is accompanied by a redox process and the potassium-indium(iii) catecholate derivative was obtained as a result. The oxidation of InI with 3,6-Q in THF produces the dimeric In(iii) iodo-catecholate complex [(3,6-Cat)(2)In·2THF]InI(2). The same derivative can be synthesized by the interaction of indium metal with a mixture of I(2) and 3,6-Q.

  11. Synthesis and Molecular Structure of Chiral (2S, 5S-tert-Butyl 3-Oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Tetsuji Moriguchi

    2014-01-01

    Full Text Available The title compound (2S, 5S-tert-butyl 3-oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate was synthesized as a chiral cyclic amino acid ester from the corresponding cis- and trans-5-hydroxypipecolic acid ethyl esters via an intramolecular lactonization reaction without using chiral catalyst or enzyme and without separation by chiral column chromatography. The chiral compound was characterized using 1H NMR spectroscopy and high-resolution mass spectrometry. Its exact structure was then determined via single crystal X-ray diffraction analysis of a single crystal obtained after recrystallization of the compound from ethyl acetate/diethyl ether. The crystal was found to be of the orthorhombic space group P212121 (No. 19, noncentrosymmetric, chiral with a=9.6402(10 Å, b=9.7026(10 Å, c=12.2155(12 Å, Dcalc=1.3194 g/cm3, and a Flack parameter of 0.0(5 at 90 K. The compound has a bicyclo[2.2.2]octane structure comprised of lactone and piperidine groups.

  12. Facile Synthesis of Novel Polyethylene-Based A-B-C Block Copolymers Containing Poly(methyl methacrylate) Using a Living Polymerization System.

    Science.gov (United States)

    Song, Xiangyang; Ma, Qiong; Cai, Zhengguo; Tanaka, Ryo; Shiono, Takeshi; Grubbs, Robert B

    2016-02-01

    Ethylene-propylene-methyl methacrylate (MMA) and ethylene-hexene-MMA A-B-C block copolymers with high molecular weight (>100,000) are synthesized using fluorenylamide-ligated titanium complex activated by modified methylaluminoxane and 2,6-di-tert-butyl-4-methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. TOXICITY OF METHYL-TERT BYTYL ETHER (MTBE) TO PLANTS (AVENA SATIVA, ZEA MAYS, TRITICUM AESTIVUM, AND LACTUCA SATIVA)

    Science.gov (United States)

    Effects of Methyl tert-butyl ether (MTBE) on the germination of seeds and growth of the plant were studied in some laboratory experiments. Test plants were wild oat (Avena sative), sweet corn (Zea mays), wheat (Triticum aestivum), and lettuce (Lactuca sativa). Seed germination,...

  14. Synthesis and biological activities of 4-chloroindole-3-acetic acid and its esters.

    Science.gov (United States)

    Katayama, M

    2000-04-01

    4-Chloroindole-3-acetic acid (4-Cl-IAA) and its esters were synthesized from 2-chloro-6-nitrotoluene as the starting material. The biological activities of 4-CI-IAA and its esters were determined by four bioassays. Except for the tert-butyl ester, 4-Cl-IAA and its esters had stronger elongation activity toward Avena coleoptiles than had indole-3-acetic acid. The biological activities of the methyl, ethyl and allyl esters were as strong as the activity of the free acid. All the esters, except for the tert-butyl, inhibited Chinese cabbage hypocotyl growth more than the free acid did, and all the esters induced severe swelling and formation of numerous lateral roots in black gram seedlings even at a low concentration. Furthermore, adventitious root formation was strongly promoted in Serissa japonica cuttings by all the esters. The root formation-promoting activities of the ethyl and allyl esters were about three times the value for indole-3-butyric acid which is used to promote and accelerate root formation in plant cuttings.

  15. Relationship between Sublethal Injury and Microbial Inactivation by the Combination of High Hydrostatic Pressure and Citral or tert-Butyl Hydroquinone ▿

    Science.gov (United States)

    Somolinos, Maria; García, Diego; Pagán, Rafael; Mackey, Bernard

    2008-01-01

    The aim was to investigate (i) the occurrence of sublethal injury in Listeria monocytogenes, Escherichia coli, and Saccharomyces cerevisiae after high hydrostatic pressure (HHP) treatment as a function of the treatment medium pH and composition and (ii) the relationship between the occurrence of sublethal injury and the inactivating effect of a combination of HHP and two antimicrobial compounds, tert-butyl hydroquinone (TBHQ) and citral. The three microorganisms showed a high proportion of sublethally injured cells (up to 99.99% of the surviving population) after HHP. In E. coli and L. monocytogenes, the extent of inactivation and sublethal injury depended on the pH and the composition of the treatment medium, whereas in S. cerevisiae, inactivation and sublethal injury were independent of medium pH or composition under the conditions tested. TBHQ alone was not lethal to E. coli or L. monocytogenes but acted synergistically with HHP and 24-h refrigeration, resulting in a viability decrease of >5 log10 cycles of both organisms. The antimicrobial effect of citral depended on the microorganism and the treatment medium pH. Acting alone for 24 h under refrigeration, 1,000 ppm of citral caused a reduction of 5 log10 cycles of E. coli at pH 7.0 and almost 3 log10 cycles of L. monocytogenes at pH 4.0. The combination of citral and HHP also showed a synergistic effect. Our results have confirmed that the detection of sublethal injury after HHP may contribute to the identification of those treatment conditions under which HHP may act synergistically with other preserving processes. PMID:18952869

  16. Simultaneous Analysis of Tertiary Butylhydroquinone and 2-tert-Butyl-1,4-benzoquinone in Edible Oils by Normal-Phase High-Performance Liquid Chromatography.

    Science.gov (United States)

    Li, Jun; Bi, Yanlan; Liu, Wei; Sun, Shangde

    2015-09-30

    During the process of antioxidation of tertiary butylhydroquinone (TBHQ) in oil and fat systems, 2-tert-butyl-1,4-benzoquinone (TQ) can be formed. The toxicity of TQ was much more than that of TBHQ. In the work, a normal-phase high-performance liquid chromatography (NP-HPLC) method for the accurate and simultaneous detection of TBHQ and TQ in edible oils was investigated. A C18 column was used to separate TBHQ and TQ, and the gradient elution solutions consisted of n-hexane containing 5% ethyl acetate and n-hexane containing 5% isopropanol. The ultraviolet (UV) detector was set at dual wavelength mode (280 nm for TBHQ and 310 nm for TQ). The column temperature was 30 °C. Before the NP-HPLC analysis, TBHQ and TQ were first extracted by methanol, subjected to vortex treatment, and then filtered through a 0.45 μm membrane filter. Results showed that linear ranges of TBHQ and TQ were both within 0.10-500.00 μg/mL (R(2) > 0.9999). The limit of detection (LOD) and limit of quantification (LOQ) of TBHQ and TQ were below 0.30 and 0.91 μg/mL and below 0.10 and 0.30 μg/mL, respectively. The recoveries of TBHQ and TQ were 98.92-102.34 and 96.28-100.58% for soybean oil and 96.11-99.42 and 98.83-99.24% for lard, respectively. These results showed that NP-HPLC can be successfully used to analyze simultaneously TBHQ and TQ in the oils and fats.

  17. The studies on complex formation of metal borides in the reaction system of epoxidation of 1-octene with tert-butyl hydroperoxide by IR spectroscopy

    OpenAIRE

    Makota, Oksana; Trach, Yuriy

    2007-01-01

    Вивчено комплексоутворення боридів молібдену і ванадію в реакційній системі епоксидування октену-1 гідропероксидом трет-бутилу методом інфрачервоної спектроскопії. Показано, що октен-1 утворює комплекс з металевою складовою у випадку бориду молібдену і з боридною складовою у випадку бориду ванадію.The complex formation of molybdenum and vanadium borides in the reaction system of 1-octene epoxidation with tert -butyl hydroperoxide by infrared spectroscopic analysis was studied. It was sh...

  18. Evaluation of ethyl tert-butyl ether biodegradation in a contaminated aquifer by compound-specific isotope analysis and in situ microcosms

    Energy Technology Data Exchange (ETDEWEB)

    Bombach, Petra, E-mail: petra.bombach@ufz.de [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany); Nägele, Norbert [Kuvier the Biotech Company S.L., Ctra. N-I, p.k. 234–P.E. INBISA 23" a, E-09001 Burgos (Spain); Rosell, Mònica [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB), C/Martí i Franquès s/n, 08028 Barcelona (Spain); Richnow, Hans H. [UFZ – Helmholtz Centre for Environmental Research, Department of Isotope Biogeochemistry, Permoserstrasse 15, D-04318 Leipzig (Germany); Fischer, Anko [Isodetect GmbH Leipzig, Deutscher Platz 5b, D-04103 Leipzig (Germany)

    2015-04-09

    Highlights: • In situ biodegradation of ETBE was investigated in a fuel contaminated aquifer. • Degradation was studied by CSIA and in situ microcosms in combination with TLFA-SIP. • ETBE was degraded when ETBE was the main groundwater contaminant. • ETBE was also degraded in the presence of BTEX and MTBE. • Hydrochemical analysis indicated aerobic and anaerobic ETBE biodegradation. - Abstract: Ethyl tert-butyl ether (ETBE) is an upcoming groundwater pollutant in Europe whose environmental fate has been less investigated, thus far. In the present study, we investigated the in situ biodegradation of ETBE in a fuel-contaminated aquifer using compound-specific stable isotope analysis (CSIA), and in situ microcosms in combination with total lipid fatty acid (TLFA)-stable isotope probing (SIP). In a first field investigation, CSIA revealed insignificant carbon isotope fractionation, but low hydrogen isotope fractionation of up to +14‰ along the prevailing anoxic ETBE plume suggesting biodegradation of ETBE. Ten months later, oxygen injection was conducted to enhance the biodegradation of petroleum hydrocarbons (PH) at the field site. Within the framework of this remediation measure, in situ microcosms loaded with [{sup 13}C{sub 6}]-ETBE (BACTRAP{sup ®}s) were exposed for 119 days in selected groundwater wells to assess the biodegradation of ETBE by TLFA-SIP under the following conditions: (i) ETBE as main contaminant; (ii) ETBE as main contaminant subjected to oxygen injection; (iii) ETBE plus other PH; (iv) ETBE plus other PH subjected to oxygen injection. Under all conditions investigated, significant {sup 13}C-incorporation into microbial total lipid fatty acids extracted from the in situ microcosms was found, providing clear evidence of ETBE biodegradation.

  19. Structural and functional changes in proteins induced by free radical-mediated oxidative stress and protective action of the antioxidants N-tert-butyl-alpha-phenylnitrone and vitamin E.

    Science.gov (United States)

    Butterfield, D A; Koppal, T; Howard, B; Subramaniam, R; Hall, N; Hensley, K; Yatin, S; Allen, K; Aksenov, M; Aksenova, M; Carney, J

    1998-11-20

    The free radical theory of aging proposes that reactive oxygen species (ROS) cause oxidative damage over the lifetime of the subject. It is the cumulative and potentially increasing amount of accumulated damage that accounts for the dysfunctions and pathologies seen in normal aging. We have previously demonstrated that both normal rodent brain aging and normal human brain aging are associated with an increase in oxidative modification of proteins and in changes in plasma membrane lipids. Several lines of investigation indicate that one of the likely sources of ROS is the mitochondria. There is an increase in oxidative damage to the mitochondrial genome in aging and a decreased expression of mitochondrial mRNA in aging. We have used a multidisciplinary approach to the characterization of the changes that occur in aging and in the modeling of brain aging, both in vitro and in vivo. Exposure of rodents to acute normobaric hyperoxia for up to 24 h results in oxidative modifications in cytosolic proteins and loss of activity for the oxidation-sensitive enzymes glutamine synthetase and creatine kinase. Cytoskeletal protein spin labeling also reveals synaptosomal membrane protein oxidation following hyperoxia. These changes are similar to the changes seen in senescent brains, compared to young adult controls. The antioxidant spin-trapping compound N-tert-butyl-alpha-phenylnitrone (PBN) was effective in preventing all of these changes. In a related study, we characterized the changes in brain protein spin labeling and cytosolic enzyme activity in a series of phenotypically selected senescence-accelerated mice (SAMP), compared to a resistant line (SAMR1) that was derived from the same original parents. In general, the SAM mice demonstrated greater oxidative changes in brain proteins. In a sequel study, a group of mice from the SAMP8-sensitive line were compared to the SAMR1-resistant mice following 14 days of daily PBN treatment at a dose of 30 mg/kg. PBN treatment resulted

  20. Kinetics of Methyl t-Butyl Ether Cometabolism at Low Concentrations by Pure Cultures of Butane-Degrading Bacteria

    Science.gov (United States)

    Liu, Catherine Y.; Speitel, Gerald E.; Georgiou, George

    2001-01-01

    Butane-oxidizing Arthrobacter (ATCC 27778) bacteria were shown to degrade low concentrations of methyl t-butyl ether (MTBE; range, 100 to 800 μg/liter) with an apparent half-saturation concentration (Ks) of 2.14 mg/liter and a maximum substrate utilization rate (kc) of 0.43 mg/mg of total suspended solids per day. Arthrobacter bacteria demonstrated MTBE degradation activity when grown on butane but not when grown on glucose, butanol, or tryptose phosphate broth. The presence of butane, tert-butyl alcohol, or acetylene had a negative impact on the MTBE degradation rate. Neither Methylosinus trichosporium OB3b nor Streptomyces griseus was able to cometabolize MTBE. PMID:11319100

  1. Structure of the mercury(II mixed-halide (Br/Cl complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzo[d]imidazole

    Directory of Open Access Journals (Sweden)

    Varsha Rani

    2017-03-01

    Full Text Available The mercury(II complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole, namely catena-poly[[dihalogenidomercury(II]-μ-2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole-κ2N3:N3′], [HgBr1.52Cl0.48(C34H42N4], 2, has a polymeric structure bridging via the N atoms from the benzimidazole moieties of the ligand. The compound crystallizes in the orthorhombic space group Pca21 and is a racemic twin [BASF = 0.402 (9]. The geometry around the HgII atom is distorted tetrahedral, with the HgII atom coordinated to two N atoms, one Br atom, and a fourth coordination site is occupied by a mixed halide (Br/Cl. For the two ligands in the asymmetric unit, there is disorder with one of the two tert-butyl groups and benzimidazole moieties showing twofold disorder, with occupancy factors of 0.57 (2:0.43 (2 for the tert-butyl group and 0.73 (3:0.27 (3 for the benzimidazole group. In addition, there is threefold disorder for two of the four n-pentyl groups, with occupancy factors of 0.669 (4:0.177 (4:0.154 (4 and 0.662 (4:0.224 (4:0.154 (4, respectively. The molecules form a one-dimensional helical polymer propagating in the b-axis direction. The helices are held together by intra-strand C—H...Br and C—H...Cl interactions. Each strand is further linked by inter-strand C—H...Br and C—H...Cl interactions. In addition, there are weak C—H...N inter-strand interactions which further stabilize the structural arrangement.

  2. Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

    Science.gov (United States)

    Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

    2016-09-02

    Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

  3. The mechanism of hyperoside protection of ECV-304 cells against tert-butyl hydroperoxide-induced injury.

    Science.gov (United States)

    Li, Hai Bo; Yi, Xin; Gao, Jian Mei; Ying, Xi Xiang; Guan, Hong Quan; Li, Jian Chun

    2008-01-01

    The aim of the present study was to investigate the mechanism of hyperoside protecting ECV-304 cells against tertbutyl hydroperoxide (TBHP)-induced injury. ECV-304 cell viability was measured by MTT assay. Cellular morphologic changes were observed using phase contrast microscopy. The genotoxic effects of TBHP and the protective ability of hyperoside were assessed by the Comet test. Lipid peroxidation was measured by HPLC method. The cellular redox status was determined from GSH/GSSG ratios. Apoptosis was detected by terminal deoxynucleotidyl transferase-mediated dUTP nick end-labeling (TUNEL) assay. Western blot analysis was used to evaluate the levels of cytochrome c, p53, SIRT1, Bax and Bcl-2 expression. The results showed that 128 mumol/l hyperoside could effectively protect TBHP-treated ECV-304 cells from death, increase superoxide dismutase activity and significantly decrease malondialdehyde production. Hyperoside was effective in protecting against the induction of oxidized DNA bases and redox state alterations induced by TBHP. Furthermore, the release of proapoptotic cytochrome c from mitochondria was reduced by hyperoside, which increased the expression of antiapoptotic SIRT1 and inhibited the translocation of Bax from cytoplasm to mitochondria. Taken together, these results indicate that hyperoside is effective in protecting against the oxidative damage induced by TBHP. The mechanism of hyperoside protecting against ECV-304 cell apoptosis by TBHP is related with resuming mitochondrial function and regulating the expression of SIRT1 and Bcl-2 family members. Copyright 2008 S. Karger AG, Basel.

  4. Mono- and Dinuclear Transition Metal Complexes of the Hexadentate Ligand Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (L).

    Science.gov (United States)

    Beissel, Thomas; Glaser, Thorsten; Kesting, Frank; Wieghardt, Karl; Nuber, Bernhard

    1996-06-19

    The hexadentate, pendant arm macrocycle 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane (H(3)L) has been synthesized and isolated as its trihydrochloride, H(3)L.3HCl, or sodium salt, Na(3)L, and its coordination chemistry with first-row transition metals has been studied. Mononuclear complexes of the type [LM(III)] (M = Ga (1), In (2), V (3), Cr (4), Mn (5), Fe,Co (6)) have been isolated as have the one-electron-oxidized forms [LM]PF(6) (M = V(IV) (3a), Mn(IV) (5a)). The crystal structure of 6 has been determined by single-crystal X-ray crystallography. Complex 6 crystallizes in the orthorhombic space group Iba2, with cell constants a = 14.206(8) Å, b = 22.53(1) Å, c = 26.07(1) Å, V = 8344.0(3) Å(3), and Z = 8. The cobalt(III) ion is in a distorted octahedral fac-N(3)S(3) donor set. The reaction of L with divalent metal chlorides in a 1:2 ratio in methanol affords the homodinuclear complexes [LM(II)(2)Cl] (M = Mn (7), Co (8), Ni (9), Zn (10), Cd (11)) where one metal is six- (N(3)MS(3)) and the other is four-coordinate (S(3)MCl); the two polyhedra are linked by three &mgr;(2)-thiolato bridges. Heterodinuclear complexes of the type [LM(1)M(2)Cl] have been obtained from [LM(2)Cl] species by abstraction of the four-coordinate metal ion and replacement by a different metal ion. The complexes [LZn(II)M(II)Cl] (M = Fe (12), Co (13), Ni (14)), [LNi(II)M(II)Cl] (M = Co (15), Zn (16)), and [LMn(II)M(II)Cl] (M = Fe (17), Co (18), Ni (19), Zn (20), Cd (21), Hg (22)) have been isolated as solid materials. The crystal structure of 14 has been determined by X-ray crystallography. Complex 14 crystallizes in the orthorhombic space group P2(1)2(1)2(1), with cell constants a = 15.45(1) Å, b = 17.77(1) Å, c = 17.58(1) Å, V = 4826.5(4) Å(3), and Z = 4. The linkage isomers 14 and 16 show characteristic electronic spectra for octahedrally and tetrahedrally coordinated Ni(II), respectively. The electronic structures of new complexes have been investigated by UV

  5. Discovery, Synthesis, And Structure-Based Optimization of a Series of N-(tert-Butyl)-2-(N-arylamido)-2-(pyridin-3-yl) Acetamides (ML188) as Potent Noncovalent Small Molecule Inhibitors of the Severe Acute Respiratory Syndrome Coronavirus (SARS-CoV) 3CL Protease

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Jon [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Grum-Tokars, Valerie [Northwestern Univ., Chicago, IL (United States); Zhou, Ya [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Turlington, Mark [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Saldanha, S. Adrian [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Chase, Peter [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Eggler, Aimee [Purdue Univ., West Lafayette, IN (United States); Dawson, Eric S. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Baez-Santos, Yahira M. [Purdue Univ., West Lafayette, IN (United States); Tomar, Sakshi [Purdue Univ., West Lafayette, IN (United States); Mielech, Anna M. [Loyola Univ. Medical Center, Maywood, IL (United States); Baker, Susan C. [Loyola Univ. Medical Center, Maywood, IL (United States); Lindsley, Craig W. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States); Hodder, Peter [Sripps Research Inst. Molecular Screening Center, Jupiter, FL (United States); Mesecar, Andrew [Purdue Univ., West Lafayette, IN (United States); Stauffer, Shaun R. [Vanderbilt Univ., Nashville, TN (United States); Vanderbilt Specialized Chemistry Center for Probe Development (MLPCN), Nashville, TN (United States)

    2012-12-11

    A high-throughput screen of the NIH molecular libraries sample collection and subsequent optimization of a lead dipeptide-like series of severe acute respiratory syndrome (SARS) main protease (3CLpro) inhibitors led to the identification of probe compound ML188 (16-(R), (R)-N-(4-(tert-butyl)phenyl)-N-(2-(tert-butylamino)-2-oxo-1-(pyridin-3-yl)ethyl)furan-2-carboxamide, Pubchem CID: 46897844). But, unlike the majority of reported coronavirus 3CLpro inhibitors that act via covalent modification of the enzyme, 16-(R) is a noncovalent SARS-CoV 3CLpro inhibitor with moderate MW and good enzyme and antiviral inhibitory activity. A multicomponent Ugi reaction was utilized to rapidly explore structure–activity relationships within S1', S1, and S2enzyme binding pockets. Moreover, the X-ray structure of SARS-CoV 3CLpro bound with 16-(R) was instrumental in guiding subsequent rounds of chemistry optimization. 16-(R) provides an excellent starting point for the further design and refinement of 3CLpro inhibitors that act by a noncovalent mechanism of action.

  6. Study of Methyl tert-butyl Ether (MTBE Photocatalytic Degradation with UV/TiO2-ZnO-CuO Nanoparticles

    Directory of Open Access Journals (Sweden)

    Mohsen Mansouri

    2017-01-01

    Full Text Available In this study, the TiO2-ZnO-CuO nanoparticles were primed by sol-gel method characterized by X-ray diffraction (XRD and Scanning Electron Microscopy (SEM, for degradation of MTBE solution in water. The effectiveness of the treatment method applied for the degradation of MTBE based on an advanced photocatalytic oxidation process was investigated. The three various key parameters were optimized using response surface modeling namely: pH, TiO2-ZnO-CuO concentration and the initial MTBE concentrations. The optimized values were obtained at the PH (7, TiO2-ZnO-CuO concentration (1.49 g/L, and the initial MTBE concentration (31.46 mg/L. Finally, kinetics reaction of degradtion MTBE was carried in the optimum conditions.

  7. Simulation of methyl tert-butyl ether (MTBE) transport to ground water from immobile sources of gasoline in the vadose zone

    Science.gov (United States)

    Lahvis, M.A.; Rehmann, L.C.

    1999-01-01

    The mathematical model, R-UNSAT, developed to simulate the transport of benzene and MTBE in representative sand and clay hydrogeologic systems was evaluated. The effects on groundwater were simulated for small, chronic-, and single-volume releases of gasoline trapped in unsaturated soil. Hydrocarbon biodegradation was simulated by using a dual Monod-type kinetics model that includes oxygen and the reactive constituents. MTBE was assumed to be non-reactive. For MTBE, infiltration had the greatest effect on transport to groundwater. Infiltration also affected mass losses of MTBE to the atmosphere, particularly, in fine-grained soils. Depth to groundwater and soil type primarily affected travel times of MTBE to groundwater, but could affect mass-loading rates to groundwater if infiltration is insignificant. For benzene, transport to groundwater was significant only if the depth to the water table was MTBE by more than two orders of magnitude. Thus, water that recharges an aquifer beneath a spill can be enriched in MTBE relative to benzene when compared to the composition of water in equilibrium with gasoline.

  8. Methyl tert-butyl ether (MTBE) detected in abnormally high concentrations in postmortem blood and urine from two persons found dead inside a car containing a gasoline spill.

    Science.gov (United States)

    Karinen, Ritva; Vindenes, Vigdis; Morild, Inge; Johnsen, Lene; Le Nygaard, Ilah; Christophersen, Asbjørg S

    2013-09-01

    Two deep frozen persons, a female and a male, were found dead in a car. There had been an explosive fire inside the car which had extinguished itself. On the floor inside the car were large pools of liquid which smelled of gasoline. The autopsy findings and routine toxicological analyses could not explain the cause of death. Carboxyhemoglobin levels in the blood samples were gasoline as a fuel oxygenate. Gasoline poisoning is likely to be the cause of the death in these two cases, and MTBE can be a suitable marker of gasoline exposure, when other volatile components have vaporized. © 2013 American Academy of Forensic Sciences.

  9. Inhibition of radical reactions for an improved potassium tert-butoxide-promoted (11) C-methylation strategy for the synthesis of α-(11) C-methyl amino acids.

    Science.gov (United States)

    Suzuki, Chie; Kato, Koichi; Tsuji, Atsushi B; Zhang, Ming-Rong; Arano, Yasushi; Saga, Tsuneo

    2015-03-01

    α-(11) C-Methyl amino acids are useful tools for biological imaging studies. However, a robust procedure for the labeling of amino acids has not yet been established. In this study, the (11) C-methylation of Schiff-base-activated α-amino acid derivatives has been optimized for the radiosynthesis of various α-(11) C-methyl amino acids. The benzophenone imine analog of methyl 2-amino butyrate was (11) C-methylated with [(11) C]methyl iodide following its initial deprotonation with potassium tert-butoxide (KOtBu). The use of an alternative base such as tetrabutylammonium fluoride, triethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene did not result in the (11) C-methylated product. Furthermore, the KOtBu-promoted (11) C-methylation of the Schiff-base-activated amino acid analog was enhanced by the addition of 1,2,4,5-tetramethoxybenzene or 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and inhibited by the addition of 1,10-phenanthroline. These results suggest that inhibition of radical generation induced by KOtBu improves the α-(11) C-methylation of the Schiff-base-activated amino acids. The addition of a mixture of KOtBu and TEMPO to a solution of Schiff-base-activated amino acid ester and [(11) C]methyl iodide provided optimal results, and the tert-butyl ester and benzophenone imine groups could be readily hydrolyzed to give the desired α-(11) C-methyl amino acids with a high radiochemical conversion. This strategy could be readily applied to the synthesis of other α-(11) C-methyl amino acids. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Synthesis and self-assembly of 2,9,16-tri(tert-butyl)-23-(10-mercaptodecyloxy)phthalocyanine and the application of its self-assembled monolayers in organic light-emitting diodes.

    Science.gov (United States)

    Huang, Xuebin; Liu, Yunqi; Wang, Shuai; Zhou, Shuqin; Zhu, Daoben

    2002-09-16

    2,9,16-Tri(tert-butyl)-23-(10-mercaptodecyloxy)phthalocyanine (8) and its disulfide (9) have been synthesized and characterized, and their self-assembling behaviors on gold substrates have been studied. Characteristic Q-bands were observed at about 630 nm in the UV/visible spectra of the self-assembling monolayers (SAMs). They were broadened and blue-shifted relative to those observed in solution. Binding energies for S2p have the same values (161.70 eV) and are in accord with those for gold thiolates. The application of the SAMs in organic light-emitting diode was investigated. It shows that the SAM promotes the hole injection process from the anode.

  11. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

    Energy Technology Data Exchange (ETDEWEB)

    Souane, R

    2005-03-15

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

  12. Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate.

    Science.gov (United States)

    Domańska, Urszula; Marciniak, Andrzej

    2008-09-04

    The activity coefficients at infinite dilution, gamma 13 (infinity) for 32 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, tetrahydrofurane, tert-butyl methyl ether, and water in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][CF3SO3] were determined by gas-liquid chromatography at the temperatures from 298.15 to 368.15 K. The partial molar excess enthalpies at infinite dilution values Delta H 1 (E,infinity) were calculated from the experimental gamma 13 (infinity) values obtained over the temperature range. The selectivities for the hexane/benzene, cyclohexane/benzene, n-hexane/thiophene, n-decane/thiophene, cyclohexane/thiophene, toluene/thiophene, and oct-1-ene/thiophene separation problems were calculated from the gamma 13 (infinity). Obtained values were compared to the literature values for the other ionic liquids, NMP, and sulfolane.

  13. A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate

    Directory of Open Access Journals (Sweden)

    Syang-Peng Rwei

    2017-02-01

    Full Text Available A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate, was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate and HEA (2-hydroxy ethyl acrylate. DAPP was blended with regular bisphenol A epoxy acrylate (BAEA in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI, reaching the saturated value of 26, and the heat release rate (HRR measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases.

  14. Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones

    Science.gov (United States)

    Kasumov, Veli T.; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

    2013-03-01

    New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X = H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X = H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, 1H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μB per CuII) and 6 (2.79 μB per CuII) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed.

  15. Renal histopathology in toxicity and carcinogenicity studies with tert-butyl alcohol administered in drinking water to F344 rats: a pathology working group review and re-evaluation.

    Science.gov (United States)

    Hard, Gordon C; Bruner, Richard H; Cohen, Samuel M; Pletcher, John M; Regan, Karen S

    2011-04-01

    An independent Pathology Working Group (PWG) re-evaluated the kidney changes in National Toxicology Program (NTP) toxicology/carcinogenicity studies of tert-butyl alcohol (TBA) in F344/N rats to determine possible mode(s) of action underlying renal tubule tumors in male rats at 2-years. In the 13-week study, the PWG confirmed that the normal pattern of round hyaline droplets in proximal convoluted tubules was replaced by angular droplet accumulation, and identified precursors of granular casts in the outer medulla, changes typical of alpha(2u)-globulin (α(2u)-g) nephropathy. In the 2-year study, the PWG confirmed the NTP observation of increased renal tubule tumors in treated male groups. Linear papillary mineralization, another hallmark of the α(2u)-g pathway was present only in treated male rats. Chronic progressive nephropathy (CPN) was exacerbated in high-dose males and females, with a relationship between advanced grades of CPN and renal tumor occurrence. Hyperplasia of the papilla lining was a component of CPN in both sexes, but there was no pelvic urothelial hyperplasia. High-dose females showed no TBA-related nephrotoxicity. The PWG concluded that both α(2u)-g nephropathy and exacerbated CPN modes of action were operative in TBA renal tumorigenicity in male rats, neither of which has relevance for human cancer risk. Copyright © 2011 Elsevier Inc. All rights reserved.

  16. High functional nano materials for ophthalmic lenses containing silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) and silicon 2,9,16,23-tetra-tert-butyl-29H31 H-phthalocyanine dihydroxide.

    Science.gov (United States)

    Sung, A-Young; Kim, Tae-Hun

    2014-11-01

    High functional ophthalmic lens materials, poly(HEMA-co-GMA)s were prepared by the copolymerization of HEMA, MMA, NVP, EDGMA and GMA in the presence of SiNc [silicon 2,3-naphthalocyanine bis(trihexylsilyloxide)] and SiPc (silicon 2,9,16,23-tetra-tert-butyl-29H31H-phthalocyanine dihydroxyde). Also, the physical and optical characteristics of the produced polymers were analyzed to investigate UV-blocking capabilities of these functional ophthalmic dyes and their applicability as materials for colored hydrogel contact lenses. For G_SN samples to which GMA was added to the Ref._SN combination, the transmittance for visible ray, UV-B and UV-A was in the range of 86.0-89.4%, 63.0-67.6% and 62.5-66.0% respectively. Also, for G_SP samples, the transmittance for visible ray, UV-B and UV-A was in the range of 85.2-87.0%, 70.0-72.6 and 68.0-70.2% respectively. The measurement of the spectral transmittance showed that both SiNc and SiPc absorbed a small amount of UV light, but the absorption pattern for UV light differed for each material. Based on the results, the addition of SiNc and SiPc to ophthalmic polymer materials can be used for various purposes in colored ophthalmic lens that are capable of offering protection from UV and infrared light without significant change of the physical properties.

  17. Discovery of 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride as a deoxofluorinating agent with high thermal stability as well as unusual resistance to aqueous hydrolysis, and its diverse fluorination capabilities including deoxofluoro-arylsulfinylation with high stereoselectivity.

    Science.gov (United States)

    Umemoto, Teruo; Singh, Rajendra P; Xu, Yong; Saito, Norimichi

    2010-12-29

    Versatile, safe, shelf-stable, and easy-to-handle fluorinating agents are strongly desired in both academic and industrial arenas, since fluorinated compounds have attracted considerable interest in many areas, such as drug discovery, due to the unique effects of fluorine atoms when incorporated into molecules. This article describes the synthesis, properties, and reactivity of many substituted and thermally stable phenylsulfur trifluorides, in particular, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (Fluolead, 1k), as a crystalline solid having surprisingly high stability on contact with water and superior utility as a deoxofluorinating agent compared to current reagents, such as DAST and its analogues. The roles of substituents on 1k in thermal and hydrolytic stability, fluorination reactivity, and the high-yield fluorination mechanism it undergoes have been clarified. In addition to fluorinations of alcohols, aldehydes, and enolizable ketones, 1k smoothly converts non-enolizable carbonyls to CF(2) groups, and carboxylic groups to CF(3) groups, in high yields. 1k also converts C(=S) and CH(3)SC(=S)O groups to CF(2) and CF(3)O groups, respectively, in high yields. In addition, 1k effects highly stereoselective deoxofluoro-arylsulfinylation of diols and amino alcohols to give fluoroalkyl arylsulfinates and arylsulfinamides, with complete inversion of configuration at fluorine and the simultaneous, selective formation of one conformational isomer at the sulfoxide sulfur atom. Considering the unique and diverse properties, relative safety, and ease of handling of 1k in addition to its convenient synthesis, it is expected to find considerable use as a novel fluorinating agent in both academic and industrial arenas.

  18. Simultaneous liquid-liquid extraction of dibenzyl disulfide, 2,6-di-tert-butyl-p-cresol, and 1,2,3-benzotriazole from power transformer oil prior to GC and HPLC determination.

    Science.gov (United States)

    Jaber, Abdul Muttaleb Yousef; Mehanna, Nemr Ahmed; Abulkibash, Abdalla Mahmoud

    2012-03-01

    2,6-Di-tert-butyl-p-cresol (DBPC), dibenzyl disulfide (DBDS), and 1,2,3-benzotriazole (BTA) are additives that may be found concomitantly in the oil matrix of power transformer. DBPC and DBDS act as antioxidants while, BTA is a corrosion inhibitor that protects copper conductors inside the transformer unit from corrosion. A powerful analytical method is, therefore, required to determine these additives at trace levels in the transformer oil. This work describes a unique single liquid-liquid extraction pretreatment step prior to the determination of the components by gas chromatography (GC) and high-performance liquid chromatography (HPLC) techniques. The optimum volume ratio used in the pretreatment step was determined as 5:2:5 for mineral oil/n-hexane/acetonitrile, respectively. Relatively, the method is simple and quick with a minimal use of solvents. Analytical results indicate that the method is relatively sensitive, accurate, and precise for each of the three components in fresh and used mineral oil. The calibration curves for the three components demonstrate a significant increase in sensitivities. Detection limits found were, 100 mg L(-1) (0.01% w/v), 0.80 mg L(-1) , and 2.04 mg L(-1) for DBPC, DBDS, and BTA, respectively. The Student's t values determined at 95% confidence level indicate that there is no significant difference between the experimental means obtained by this method and the standard method for each component. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. EFFECT OF DE-tert-BUTYLATION AND FUNCTIONALIZATION WITH AMINE GROUPS AT THE UPPER RIM OF p-tert-BUTYLCALIX[4]ARENE TO THE EXTRACTABILITY FOR Cr3+, Cd2+ and Pb2+ IONS

    Directory of Open Access Journals (Sweden)

    Firdaus Firdaus

    2010-06-01

    Full Text Available The effects to the extractability forwards Cr3+, Cd2+, and Pb2+ ions of de-tert-butylation and functionalization with amine groups at the upper rim of p-tert-butylcalix[4]arene had been studied by applied the p-tert-butylcalix[4]arene (1, tetrahydroxycalix[4]arene (2, and p-(aminobutoxycalixarene (3 compounds as extractants for the heavy metals ions. The extraction involved optimise of three parameters, i.e. pH, time, and concentration of extractants. The extraction degrees of the heavy metals ions at optimum conditions were compared each other to decide the effects. Compound 1 showed high extractability to Cr3+ and Pb2+ ions over Cd2+ ion, but compound 2 as the debutylated product of compound 1 showed low extractability to the all of the heavy metals ions. Compound 3 as product of etherification with butyl groups of the lower rim followed functionalization with amine groups of the upper rim of compound 1 showed high extractability to Pb2+, but low to Cr3+ and Cd2+. Pursuant to the facts it was concluded that debutylation of compound 1 to compound 2 causing decrease drastically of extractability to the heavy metals ions; functionalization of the upper with amine groups as ionophore (compound 3 causing increase of the extractability to Pb2+ ion and decrease of the extractability to Cr3+ with increasing of separation factor value β(Pb2+/Cr3+ from 1.74 by compound 1 to 48.00 by compound 3. By slope analysis, the extracted species and mechanisms of the extractions have been confirmed.   Keywords: p-tert-butylcalix[4]arene, debutylation, p-(aminobutoxycalix[4]arene, extractability, heavy metals, extraction mechanisms.

  20. In Vitro Formation of 8-hydroxy-2-deoxyguanosine (8-OHdG in Calf Thymus DNA upon Treatment of 2-deoxyguanosine with Propyl Gallate and 2,6-di-tert-butyl-p-benzoquinone

    Directory of Open Access Journals (Sweden)

    Budiawan Budiawan

    2015-12-01

    Full Text Available Oxidative DNA damage caused by propyl gallate (PG and 2,6-di-tert-butyl-p-benzoquinone (BHT-quinone, a metabolite of butylated hydroxytoluene (BHT was analyzed from the 8-hydroxy-2¢-deoxyguanosine (8-OHdG formation in calf thymus DNA and DNA base, 2¢-deoxyguanosine (dG. PG in the presence of CuCl2 increased the 8-OHdG formation in calf thymus DNA by around 9.17 times as compared to the control (untreated DNA. In the presence of CuCl2 at 1.28×10-5 M, the 8-OHdG per dG ratio resulting from the reaction of dG with PG at various concentrations (20–150 ppm ranged from 75.50 to 312.06 8-OHdG per 105 dG. The 8-OHdG formation increased when the PG concentration was increased from 20 ppm to 80 ppm, and then, it began to plateau around 80 ppm. On the other hand, BHT-quinone increased the formation of 8-OHdG in the presence of CuCl2 by 0.05 times as compared to the control (untreated DNA. LC-MS/MS analysis was used to identify the molecular structure of 8-OHdG, which had a base peak (M+. + 1 at m/z = 284 and two main fragments at m/z = 167.9 and m/z = 139.9.

  1. 7-tert-Butyl-6-(4-chloro-phenyl)-2-thioxo-2,3-dihydro-1H-pyrido[2,3-d]pyrimidin-4-one, a classic polymodal inhibitor of transient receptor potential vanilloid type 1 with a reduced liability for hyperthermia, is analgesic and ameliorates visceral hypersensitivity.

    Science.gov (United States)

    Nash, Mark S; McIntyre, Peter; Groarke, Alex; Lilley, Elliot; Culshaw, Andrew; Hallett, Allan; Panesar, Moh; Fox, Alyson; Bevan, Stuart

    2012-08-01

    The therapeutic potential of transient receptor potential vanilloid type 1 (TRPV1) antagonists for chronic pain has been recognized for more than a decade. However, preclinical and clinical data revealed that acute pharmacological blockade of TRPV1 perturbs thermoregulation, resulting in hyperthermia, which is a major hurdle for the clinical development of these drugs. Here, we describe the properties of 7-tert-butyl-6-(4-chloro-phenyl)-2-thioxo-2,3-dihydro-1H-pyrido[2,3-d]pyrimidin-4-one (BCTP), a TRPV1 antagonist with excellent analgesic properties that does not induce significant hyperthermia in rodents at doses providing maximal analgesia. BCTP is a classic polymodal inhibitor of TRPV1, blocking activation of the human channel by capsaicin and low pH with IC(50) values of 65.4 and 26.4 nM, respectively. Similar activity was observed with rat TRPV1, and the inhibition by BCTP was competitive and reversible. BCTP also blocked heat-induced activation of TRPV1. In rats, the inhibition of capsaicin-induced mechanical hyperalgesia was observed with a D(50) value of 2 mg/kg p.o. BCTP also reversed visceral hypersensitivity and somatic inflammatory pain, and using a model of neuropathic pain in TRPV1 null mice we confirmed that its analgesic properties were solely through the inhibition of TRPV1. We were surprised to find that BCTP administered orally induced only a maximal 0.6°C increase in core body temperature at the highest tested doses (30 and 100 mg/kg), contrasting markedly with N-[4-({6-[4-(trifluoromethyl)phenyl]pyrimidin-4-yl}oxy)-1,3-benzothiazol-2-yl]acetamide (AMG517), a clinically tested TRPV1 antagonist, which induced marked hyperthermia (>1°C) at doses eliciting submaximal reversal of capsaicin-induced hyperalgesia. The combined data indicate that TRPV1 antagonists with a classic polymodal inhibition profile can be identified where the analgesic action is separated from the effects on body temperature.

  2. Activity-Dependent Calcium, Oxygen, and Vascular Responses in a Mouse Model of Familial Hemiplegic Migraine Type 1

    DEFF Research Database (Denmark)

    Khennouf, Lila; Gesslein, Bodil; Lind, Barbara Lykke

    2016-01-01

    after CSD. The CSD-induced Ca2+ changes were mitigated by the CaV2.1 gating modifier, tert-butyl dihydroquinone. Interpretation: Our findings suggest that tissue anoxia might be a mechanism for prolonged aura in FHM1. Reduced Ca2+ signals during normal network activity in FHM1 as compared to WT mice may...

  3. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium; Determinacion de la capacidad extractiva del p-ter-butilocalix[8]areno octa-fosfinoilado hacia iones uranilo de un medio acuo-acido salino

    Energy Technology Data Exchange (ETDEWEB)

    Serrano V, E. C.

    2011-07-01

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO{sub 3}-3.5 NaNO{sub 3}) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10{sup -4} M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10{sup -4} M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO{sub 2}){sub 2}B{sub 8}bL{sup 8}(NO{sub 3}){sub 4}(H{sub 2}O){sub 4}CHCl{sub 3}(CH{sub 3}OH){sub 3} the methanol molecules come from its purification. It is proposed that B{sub 8}bL{sup 8} calixarene in

  4. Structure/activity Relationship of Thapsigargin Inhibition on the Purified Golgi/secretory Pathway Ca2+/Mn2+ Transport ATPase (SPCA1a)

    DEFF Research Database (Denmark)

    Jialin, Chen; de Raeymaecker, Joren; Hovgaard, Jannik Brøndsted

    2017-01-01

    activity. Moreover, SPCA1a is blocked by μM concentrations of commonly used SERCA1a inhibitors thapsigargin (Tg), cyclopiazonic acid (CPA) and 2,5-di-tert-butyl hydroquinone (BHQ). Since tissue-specific targeting of SERCA2b by Tg analogues is considered for prostate cancer therapy, the inhibition of SPCA1a...

  5. 1-tert-butyl-3-[6-(3,5-dimethoxy-phenyl)-2-(4-diethylamino-butylamino)-pyrido[2,3-d]pyrimidin-7-yl]-urea (PD173074), a selective tyrosine kinase inhibitor of fibroblast growth factor receptor-3 (FGFR3), inhibits cell proliferation of bladder cancer carrying the FGFR3 gene mutation along with up-regulation of p27/Kip1 and G1/G0 arrest.

    Science.gov (United States)

    Miyake, Makito; Ishii, Masazumi; Koyama, Naoki; Kawashima, Kiyotaka; Kodama, Tetsuro; Anai, Satoshi; Fujimoto, Kiyohide; Hirao, Yoshihiko; Sugano, Kokichi

    2010-03-01

    Activating mutation of the fibroblast growth factor receptor-3 (FGFR3) gene is known as a key molecular event in both oncogenesis and cell proliferation of low-grade noninvasive human bladder urothelial carcinoma (UC), which is characterized by frequent intravesical recurrence. In this study, we investigated the antitumor potentiality of 1-tert-butyl-3-[6-(3,5-dimethoxy-phenyl)-2-(4-diethylamino-butylamino)-pyrido[2,3-d]pyrimidin-7-yl]-urea (PD173074), a small-molecule FGFR3-selective tyrosine kinase inhibitor (TKI), as a therapeutic modality using eight UC cell lines. In our in vitro cell proliferation assay, PD173074 suppressed cell proliferation remarkably in two cell lines, namely, UM-UC-14 and MGHU3, which expressed mutated FGFR3 protein. In contrast, the other six cell lines expressing wild-type FGFR3 or without FGFR3 expression were resistant to PD173074 treatment. Cell cycle analysis revealed the growth inhibitory effect of PD173074 was associated with arrest at G(1)-S transition in a dose-depending manner. Furthermore, we observed an inverse relationship between Ki-67 and p27/Kip1 expression after PD173074 treatment, suggesting that up-regulation of p27 recruited UC cells harboring activating FGFR3 mutations in G(1) that was analogous with the other receptor TKIs acting on the epidermal growth factor receptors. In the mouse xenograft models using subcutaneously transplanted UM-UC-14 and MGHU3, orally administered PD173074 suppressed tumor growth and induced apoptotic changes comparable with the results of our in vitro assay. These findings elucidated the effectiveness of molecular targeted approach for bladder UC harboring FGFR3 mutations and the potential utility to decrease the intravesical recurrence of nonmuscle invasive bladder UC after transurethral surgical resection.

  6. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Zafer Yeşilel, Okan [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Büyükgüngör, Orhan [Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-05-15

    methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Highlights: • Four new 2D and 3D coordination polymers with 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers. • The structural diversity depending on ligands and coordination number of metal centers. • Fluorescent sensor for the detection of acetone.

  7. Characteristics of Oxidative Storage Stability of Canola Fatty Acid Methyl Ester Stabilised with Antioxidants

    Directory of Open Access Journals (Sweden)

    Tirto Prakoso

    2012-11-01

    Full Text Available The storage effects on the oxidation characteristics of fatty acid methyl ester of canola oil (CME were investigated in this study. CME stabilised with two antioxidants, i.e. 2,6-di-tert-bytyl-p-cresol (BHT and 6,6-di-tert-butyl-2, 2’-methylendi-p-cresol (BPH, was stored at 20, 40 and 60°C. The oxidation stability data were measured by the Rancimat test method and it was found that both BHT and BPH addition increased the oxidation resistance of the CME. The results showed that when BPH or BHT was added at a concentration of 100 ppm, the oxidation induction period of the neat CME samples increased from 5.53 h to 6.93 h and 6.14 h, respectively. Comparing both antioxidants, BPH proved to be more effective in increasing the oxidation resistance when both antioxidants were added at the same concentration. Furthermore, the oxidation induction time decreased linearly with the storage time. It was shown that the oxidation occurred rapidly in the first 8 weeks of storage. Later, a kinetic study was undertaken and first-order kinetics were applied to explain the oxidation characteristics of the CME added with antioxidants. This kinetic study focused on exploiting the activation energy values obtained from the Arrhenius equations. Also, the oxidation effects on other quality parameters, including acid value, peroxide value, kinematic viscosity, and water content, were examined.

  8. N-tert-Butyl-2-methylpropanamide

    Directory of Open Access Journals (Sweden)

    Kelly A. Kluge

    2011-08-01

    Full Text Available The title compound, C8H17NO, crystallizes with two independent molecules in the asymmetric unit. In the crystal, intermolecular N—H...O hydrogen bonding is observed between neighboring molecules, forming continuous molecular chains along the c-axis direction.

  9. The glutamate receptor GluR5 agonist (S)-2-amino-3-(3-hydroxy-7,8-dihydro-6H-cyclohepta[d]isoxazol-4-yl)propionic acid and the 8-methyl analogue

    DEFF Research Database (Denmark)

    Clausen, Rasmus Prætorius; Naur, Peter; Kristensen, Anders Skov

    2009-01-01

    The design, synthesis, and pharmacological characterization of a highly potent and selective glutamate GluR5 agonist is reported. (S)-2-Amino-3-((RS)-3-hydroxy-8-methyl-7,8-dihydro-6H-cyclohepta[d]isoxazol-4-yl)propionic acid (5) is the 8-methyl analogue of (S)-2-amino-3-(3-hydroxy-7,8-dihydro-6H......-cyclohepta[d]isoxazol-4-yl)propionic acid ((S)-4-AHCP, 4). Compound 5 displays an improved selectivity profile compared to 4. A versatile stereoselective synthetic route for this class of compounds is presented along with the characterization of the binding affinity of 5 to ionotropic glutamate receptors (i......GluRs). Functional characterization of 5 at cloned iGluRs using a calcium imaging assay and voltage-clamp recordings show a different activation of GluR5 compared to (S)-glutamic acid (Glu), kainic acid (KA, 1), and (S)-2-amino-3-(3-hydroxy-5-tert-butyl-4-isoxazolyl)propionic acid ((S)-ATPA, 3) as previously...

  10. Nuclease Activity via Self-Activation and Anticancer Activity of Mononuclear Copper(II) Complex: Novel Role of Tertiary Butyl Group in the Ligand Frame

    OpenAIRE

    Ghosh, Kaushik; Kumar, Pramod; Mohan, Varun; Singh, Udai P.; Kasiri, Sahba; Mandal, Subhrangsu S.

    2012-01-01

    Copper complex [Cu(tBuPhimp)(Cl)] (1) derived from tridentate ligand tBuPhimpH having N2O donors was synthesized and molecular structure was determined. Phenoxyl radical complex was generated in solution at room temperature using Ce(IV) salt. Nuclease activity and anticancer activity of 1 was investigated. Roles of tert-butyl group and singlet oxygen in DNA cleavage activity were also discussed.

  11. tert-Butyl 3-(8-bromo-4H,10H-1,2-oxazolo[4,3-c][1]benzoxepin-10-yl-2-methyl-1H-indole-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Ankur Trigunait

    2010-08-01

    Full Text Available In the title compound, C25H23BrN2O4, the seven-membered ring adopts a twisted-boat conformation. The indole ring system is planar within 0.021 (2 Å and the ester group [–C(=O—O—C–] is almost coplanar with it [dihedral angle = 3.0 (2°]. The conformation of the ester group is influenced by intramolecular C—H...O interactions. In the crystal structure, molecules are linked into chains along the b axis by C—H...N hydrogen bonds.

  12. tert-Butyl (2S,3R,4R-7′-bromo-4-methyl-2′,5-dioxo-4,5-dihydro-3H-spiro[furan-2,3′-indoline]-3-carboxylate

    Directory of Open Access Journals (Sweden)

    Chen-Hong Meng

    2017-03-01

    Full Text Available In the title compound, C17H18BrNO5, the furan ring has an envelope conformation with the carboxylate substituted C atom as the flap. The planar indoline ring is inclined to the mean plane of the furan ring by 87.5 (2°. In the crystal, molecules are linked by N—H...O and C—H...O hydrogen bonds forming chains propagating along the a-axis direction.

  13. The glutamate receptor GluR5 agonist (S)-2-amino-3-(3-hydroxy-7,8-dihydro-6H-cyclohepta[d]isoxazol-4-yl)propionic acid and the 8-methyl analogue: synthesis, molecular pharmacology, and biostructural characterization.

    Science.gov (United States)

    Clausen, Rasmus P; Naur, Peter; Kristensen, Anders S; Greenwood, Jeremy R; Strange, Mette; Bräuner-Osborne, Hans; Jensen, Anders A; Nielsen, Anne Sophie T; Geneser, Ulla; Ringgaard, Lone M; Nielsen, Birgitte; Pickering, Darryl S; Brehm, Lotte; Gajhede, Michael; Krogsgaard-Larsen, Povl; Kastrup, Jette S

    2009-08-13

    The design, synthesis, and pharmacological characterization of a highly potent and selective glutamate GluR5 agonist is reported. (S)-2-Amino-3-((RS)-3-hydroxy-8-methyl-7,8-dihydro-6H-cyclohepta[d]isoxazol-4-yl)propionic acid (5) is the 8-methyl analogue of (S)-2-amino-3-(3-hydroxy-7,8-dihydro-6H-cyclohepta[d]isoxazol-4-yl)propionic acid ((S)-4-AHCP, 4). Compound 5 displays an improved selectivity profile compared to 4. A versatile stereoselective synthetic route for this class of compounds is presented along with the characterization of the binding affinity of 5 to ionotropic glutamate receptors (iGluRs). Functional characterization of 5 at cloned iGluRs using a calcium imaging assay and voltage-clamp recordings show a different activation of GluR5 compared to (S)-glutamic acid (Glu), kainic acid (KA, 1), and (S)-2-amino-3-(3-hydroxy-5-tert-butyl-4-isoxazolyl)propionic acid ((S)-ATPA, 3) as previously demonstrated for 4. An X-ray crystallographic analysis of 4 and computational analyses of 4 and 5 bound to the GluR5 agonist binding domain (ABD) are presented, including a watermap analysis, which suggests that water molecules in the agonist binding site are important selectivity determinants.

  14. High-temperature measurements of the reactions of OH with small methyl esters: methyl formate, methyl acetate, methyl propanoate, and methyl butanoate.

    Science.gov (United States)

    Lam, King-Yiu; Davidson, David F; Hanson, Ronald K

    2012-12-20

    The overall rate constants for the reactions of hydroxyl radicals (OH) with four small methyl esters, namely methyl formate (CH(3)OCHO), methyl acetate (CH(3)OC(O)CH(3)), methyl propanoate (CH(3)OC(O)C(2)H(5)), and methyl butanoate (CH(3)OC(O)C(3)H(7)), were investigated behind reflected shock waves using UV laser absorption of OH radicals near 306.69 nm. Test gas mixtures of individual methyl esters and tert-butyl hydroperoxide (TBHP), a fast source of OH at elevated temperatures, diluted in argon were shock-heated to temperatures spanning from 876 to 1371 K at pressures near 1.5 atm. The overall rate constants were determined by matching the measured OH time-histories with the computed profiles from the comprehensive chemical kinetic mechanisms of Dooley et al. (2010) and Dooley et al. (2008), which were originally developed for the oxidation of methyl formate and methyl butanoate, respectively. These measured values can be expressed in Arrhenius form as k(CH(3)OCHO+OH) = 2.56 × 10(13) exp(-2026/T) cm(3) mol(-1) s(-1), k(CH(3)OC(O)CH(3)+OH) = 3.59 × 10(13) exp(-2438/T) cm(3) mol(-1) s(-1), k(CH(3)OC(O)C(2)H(5)+OH) = 6.65 × 10(13) exp(-2539/T) cm(3) mol(-1) s(-1), and k(CH(3)OC(O)C(3)H(7)+OH) = 1.13 × 10(14) exp(-2515/T) cm(3) mol(-1) s(-1) over the temperature ranges studied. Detailed error analyses were performed to estimate the overall uncertainties of these reactions, and the estimated (2σ) uncertainties were found to be ±29% at 913 K and ±18% at 1289 K for k(CH(3)OCHO+OH), ± 29% at 930 K and ±17% at 1299 K for k(CH(3)OC(O)CH(3)+OH), ± 25% at 909 K and ±17% at 1341 K for k(CH(3)OC(O)C2H(5)+OH), and ±24% at 925 K and ±16% at 1320 K for k(CH(3)OC(O)C(3)H(7)+OH). We believe these are the first direct high-temperature rate constant measurements for the reactions of OH with these small methyl esters. These measured rate constants were also compared with the estimated values employed in different comprehensive kinetic mechanisms. Additionally, the

  15. A radical pathway in catecholase activity with nickel(II) complexes of phenol based "end-off" compartmental ligands.

    Science.gov (United States)

    Ghosh, Totan; Adhikary, Jaydeep; Chakraborty, Prateeti; Sukul, Pradip K; Jana, Mahendra Sekhar; Mondal, Tapan Kumar; Zangrando, Ennio; Das, Debasis

    2014-01-14

    Seven dinuclear and one dinuclear based dicyanamide bridged polymeric Ni(II) complexes of phenol based compartmental ligands (HL(1)-HL(4)) have been synthesized with the aim to investigate their catecholase-like activity and to evaluate the most probable mechanistic pathway involved in this process. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analyses namely [Ni2(L(2))(SCN)3(H2O)(CH3OH)] (), [Ni2(L(4))(SCN)3(CH3OH)2] (), [Ni2(L(2))(SCN)2(AcO)(H2O)] (), [Ni2(L(4))(SCN)(AcO)2] (), [Ni2(L(2))(N3)3(H2O)2] (), [Ni2(L(4))(N3)3(H2O)2] (), [Ni2(L(1))(AcO)2(N(CN)2)]n () and [Ni2(L(3))(AcO)2(N(CN)2)] (), [SCN = isothiocyanate, AcO = acetate, N3 = azide, and N(CN)2 = dicyanamide anion; L(1-4) = 2,6-bis(R2-iminomethyl)-4-R1-phenolato, where R1 = methyl and tert-butyl, R2 = N,N-dimethyl ethylene for L(1-2) and R1 = methyl and tert-butyl, R2 = 2-(N-ethyl) pyridine for L(3-4)]. A UV-vis spectrophotometric study using 3,5-di-tert butylcatechol (3,5-DTBC) reveals that all the complexes are highly active in catalyzing the aerobic oxidation of (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in methanol medium with the formation of hydrogen peroxide. An EPR study confirms the generation of radicals during the catalysis. Cyclic voltammetric studies of the complexes in the presence and absence of 3,5-DTBC have been performed. Reduction of Ni(II) to Ni(I) and that of the imine bond of the ligand system have been detected at ∼-1.0 V and ∼-1.5 V, respectively. Coulometric separation of the species at -1.5 V followed by the EPR study at 77 K confirms the species as an organic radical and thus most probably reduced imine species. Spectroelectrochemical analysis at -1.5 V clearly indicates the oxidation of 3,5-DTBC and thus suggests that the radical pathway is supposed to be responsible for the catecholase-like activity exhibited by the nickel complexes. The ligand centred radical generation has further been

  16. Effect of Water Clustering on the Activity of Candida antarctica Lipase B in Organic Medium

    Directory of Open Access Journals (Sweden)

    Sindrila Dutta Banik

    2017-07-01

    Full Text Available The effect of initial water activity of MTBE (methyl tert-butyl ether medium on CALB (Candida antarctica lipase B catalyzed esterification reaction is investigated using experimental methods and classical molecular dynamics (MD simulations. The experimental kinetic studies show that the initial reaction rate of CALB-catalyzed esterification reaction between butyric acid and ethanol decreases with increasing initial water activity of the medium. The highest rate of esterification is observed at the lowest water activity studied. MD simulations were performed to gain a molecular insight on the effect of initial water activity on the rate of CALB-catalyzed reaction. Our results show that hydration has an insignificant effect on the structure and flexibility of CALB. Rather, it appears that water molecules bind to certain regions (“hot spots” on the CALB surface and form clusters. The size of the water clusters at these hot spot regions gradually increase and expand with increasing water activity. Consequently, the surface area of CALB covered by the water molecules also increases. Specifically, our results indicate that a particular water cluster located close to the active site partially cover the binding pocket of substrate at high water activity. As a consequence, the effective concentration of substrate at the catalytic site decreases. Therefore, the reaction rate slows down with increasing water activity, which correlates well with the observed decrease in the experimentally determined initial reaction rate.

  17. Effect of ionic liquids on (vapor + liquid) equilibrium behavior of (water + 2-methyl-2-propanol)

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Lianzhong; Qiao Bingbang; Ge Yun; Deng Dongshun [College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310014 (China); Ji Jianbing [College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310014 (China)], E-mail: jjb@zjut.edu.cn

    2009-01-15

    Isobaric T, x, y data were reported for ternary systems of {l_brace}water + 2-methyl-2-propanol (tert-butyl alcohol, TBA) + ionic liquid (IL){r_brace} at p = 100 kPa. When the mole fraction of TBA on IL-free basis was fixed at 0.95, measurements were performed at IL mass fractions from 0.6 down to 0.05, in a way of repeated synthesis. The vapor-phase compositions were obtained by analytical methods and the liquid-phase compositions were calculated with the aid of mass balances. Activity coefficients of water and TBA were obtained without the need of a thermodynamic model of the liquid-phase. Six ILs, composed of an anion chosen from [OAc]{sup -} or [Cl]{sup -}, and a cation from [emim]{sup +}, or [bmim]{sup +}, or [hmim]{sup +}, were studied. Relative volatility and activity coefficients were presented in relation with the IL mole fraction, showing the effect of the ILs on a molar basis. The effect of the ILs on relative volatility of TBA to water was depicted by the effect of anions and cations on, respectively, the activity coefficients of water and TBA. The results indicated that, among the six ILs studied, [emim][Cl] has the most significant effect on enhancement of the relative volatility, which reaches a value of 7.2 at an IL mass fraction of 0.58. Another IL, [emim][OAc], has also significant effect, with an appreciable value of 5.2 for the relative volatility when the IL mass fraction is 0.6. Considering the relatively low viscosity and melting point of [emim][OAc], it might be a favorable candidate as solvent for the separation of water and TBA by extractive distillation. Simultaneous correlation by the NRTL model was presented for both systems of (water + ethanol + IL) and (water + TBA + IL), using consistent binary parameters for water and IL.

  18. Thermodynamic activity-based intrinsic enzyme kinetic sheds light on enzyme-solvent interactions.

    Science.gov (United States)

    Grosch, Jan-Hendrik; Wagner, David; Nistelkas, Vasilios; Spieß, Antje C

    2017-01-01

    The reaction medium has major impact on biocatalytic reaction systems and on their economic significance. To allow for tailored medium engineering, thermodynamic phenomena, intrinsic enzyme kinetics, and enzyme-solvent interactions have to be discriminated. To this end, enzyme reaction kinetic modeling was coupled with thermodynamic calculations based on investigations of the alcohol dehydrogenase from Lactobacillus brevis (LbADH) in monophasic water/methyl tert-butyl ether (MTBE) mixtures as a model solvent. Substrate concentrations and substrate thermodynamic activities were varied separately to identify the individual thermodynamic and kinetic effects on the enzyme activity. Microkinetic parameters based on concentration and thermodynamic activity were derived to successfully identify a positive effect of MTBE on the availability of the substrate to the enzyme, but a negative effect on the enzyme performance. In conclusion, thermodynamic activity-based kinetic modeling might be a suitable tool to initially curtail the type of enzyme-solvent interactions and thus, a powerful first step to potentially understand the phenomena that occur in nonconventional media in more detail. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:96-103, 2017. © 2016 American Institute of Chemical Engineers.

  19. Substituted Amides of Pyrazine-2-carboxylic acids: Synthesis and Biological Activity

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2002-03-01

    Full Text Available Condensation of 6-chloro-, 5-tert-butyl- or 6-chloro-5-tert-butylpyrazine-2-carboxylic acid chloride with ring substituted anilines yielded a series of amides, which were tested for their in vitro antimycobacterial, antifungal and photosynthesis-inhibiting activities. The highest antituberculotic activity (72% inhibition against Mycobacterium tuberculosis and the highest lipophilicity (log P = 6.85 were shown by the 3,5-bistrifluoromethylphenyl amide of 5-tert-butyl-6-chloropyrazine-2-carboxylic acid (2o. The 3-methylphenyl amides of 6-chloro- and 5-tert-butyl-6-chloro-pyrazine-2-carboxylic acid (2d and 2f exhibited only a poor in vitro antifungal effect (MIC = 31.25-500 μmol·dm-3 against all strains tested, although the latter was the most active antialgal compound (IC50 = 0.063 mmol·dm-3. The most active inhibitor of oxygen evolution rate in spinach chloroplasts was the (3,5-bis-trifluoromethylphenylamide of 6-chloropyrazine-2-carboxylic acid (2m, IC50 = 0.026 mmol·dm-3.

  20. Competitive and hindering effects of natural organic matter on the adsorption of MTBE onto activated carbons and zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Hung, H.W.; Lin, T.F.; Baus, C.; Sacher, F.; Brauch, H.J. [National Cheng Kung University, Tainan (Taiwan). Dept. of Environmental Engineering

    2005-12-15

    Equilibrium and kinetic adsorption of methyl tert-butyl ether (MTBE) onto three coal-based activated carbons, one coconut-based activated carbon, and two zeolites are elucidated in this study. Natural organic matter (NOM) and MTBE competed for the adsorption of activated carbons to different extents. The Ideal Adsorbed Solution Theory (lAST) combined with the equivalent background compound (EBC) model can adequately describe the NOM competition and predict the isotherms of MTBE onto the activated carbons. No competitive adsorption was observed for one of the zeolites, mordenite, due to the molecular effect. Besides, the aperture size, and the SiO{sub 2}/Al{sub 2}O3 ratio of the zeolite may also play an important role in the adsorption of MTBE from the aqueous phase. The surface diffusion model accurately simulated the transport of MTBE within the adsorbents employed in different water matrices. For all the activated carbons tested, the surface diffusivity of MTBE in natural water was nearly equal to that in deionized water, indicating that no apparently hindering effect occurs. A much slower adsorption kinetic of mordenite in natural water was observed since the opening apertures on mordenite may be appreciably hindered and blocked by NOM.

  1. Structure--activity relationships in cephalosporins prepared from penicillins. 1. 7beta-Acylamino derivatives of 3-benzyl- and 3-(3-pyridylmethyl)ceph-3-em-4-carboxylic acids.

    Science.gov (United States)

    Brain, E G; Eglington, A J; Nayler, J H; Osborne, N F; Pearson, M J; Smale, T C; Southgate, R; Tolliday, P; Basker, M J; Sutherland, R

    1977-08-01

    tert-Butyl 7beta-aminoceph-3-em-4-carboxylates carrying either benzyl or 3-pyridylmethyl substituents at position 3 have been prepared by a multistep modification of the penicillin nucleus. Acylation of either amine, followed by deprotection, gave a range of new cephalosporins. The relationship between structure and antibacterial activity is discussed. D-Phenylglycine proved to be a preferred side chain in both series.

  2. Growth Inhibition and DNA Damage Induced by X-Phenols in Yeast: A Quantitative Structure-Activity Relationship Study.

    Science.gov (United States)

    Negritto, M Cristina; Valdez, Clarissa; Sharma, Jasmine; Rosenberg, Christa; Selassie, Cynthia R

    2017-12-31

    Phenolic compounds and their derivatives are ubiquitous constituents of numerous synthetic and natural chemicals that exist in the environment. Their toxicity is mostly attributed to their hydrophobicity and/or the formation of free radicals. In a continuation of the study of phenolic toxicity in a systematic manner, we have examined the biological responses of Saccharomyces cerevisiae to a series of mostly monosubstituted phenols utilizing a quantitative structure-activity relationship (QSAR) approach. The biological end points included a growth assay that determines the levels of growth inhibition induced by the phenols as well as a yeast deletion (DEL) assay that assesses the ability of X-phenols to induce DNA damage or DNA breaks. The QSAR analysis of cell growth patterns determined by IC50 and IC80 values indicates that toxicity is delineated by a hydrophobic, parabolic model. The DEL assay was then utilized to detect genomic deletions in yeast. The increase in the genotoxicity was enhanced by the electrophilicity of the phenolic substituents that were strong electron donors as well as by minimal hydrophobicity. The electrophilicities are represented by Brown's sigma plus values that are a variant of the Hammett sigma constants. A few mutant strains of genes involved in DNA repair were separately exposed to 2,6-di-tert-butyl-4-methyl-phenol (BHT) and butylated hydroxy anisole (BHA). They were subsequently screened for growth phenotypes. BHA-induced growth defects in most of the DNA repair null mutant strains, whereas BHT was unresponsive.

  3. Activation of carboxylic acids by pyrocarbonates. Synthesis of symmetric anhydrides and esters of N-protected amino acids using dialkyl pyrocarbonates as condensing reagents.

    Science.gov (United States)

    Pozdnev, V F

    1992-11-01

    Activation of carboxylic acids was achieved via dialkyl pyrocarbonates (ROCO)2O, R = C2H5, i-C3H7, sec-C4H9, tert.-C4H9) in aprotic solvents in the presence tertiary amines. A convenient procedure for the preparation of carboxylic acid anhydrides from carboxylic acids and di-tert.-butyl pyrocarbonate in the presence of pyridine is reported. Analogously, di-isopropyl- or diethyl pyrocarbonate may be used in the presence of N-methylmorpholine (triethylamine). With pyridine, di-isopropyl- or diethyl pyrocarbonate carboxylic acids form isopropyl- or ethyl esters, respectively. A wide variety of esters were prepared in good yields in a one-pot procedure from carboxylic acids, including N-protected amino acids, and alcohols or from phenols by means of di-tert.-butyl pyrocarbonate in the presence of pyridine (Boc2O-pyridine system). t-Butyl esters of carboxylic acids were obtained by the same procedure with 4-dimethylaminopyridine. In the absence of carboxylic acid, with 4-dimethylaminopyridine Boc2O and alcohols generate alkyl tert.-butyl carbonates.

  4. 4-tert-Butyl-3′,4′-bis(4-methylphenyl-3,4-dihydro-1H,4′H-spiro[naphthalene-2,5′-[1,2]oxazol]-1-one

    Directory of Open Access Journals (Sweden)

    Mohamed Akhazzane

    2011-07-01

    Full Text Available In the title compound, C30H31NO2, the cyclohexanone ring in the naphthalene fused-ring system adopts a half-chair conformation, presumably due to conjugation of the benzene ring. The naphthalene ring system makes dihedral angles of 86.63 (7, 65.15 (8 and 63.18 (8° with respect to the two methylbenzene planes and the 1,2-oxazole ring system. Intermolecular C—H...O and C—H...N hydrogen bonding and C—H...π interactions stabilize the crystal structure. The H atoms of the two methyl groups of the methylphenyl groups are disordered over two positions with equal occupancies.

  5. Studies on the separation of {sup 89}Sr(II) from irradiated yttria target using 4, 4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) by solvent extraction technique

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Debasish; Vithya, Jayagopal; Kumar, Ramalingam; Venkata Subramani, Canchipuram Ramamoorthy; Vasudeva Rao, Polur Ranga [Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam (India). Chemistry Group

    2016-07-01

    The radioisotope {sup 89}Sr as {sup 89}SrCl{sub 2} is medically useful for bone pain palliation and is produced in fast reactors using the {sup 89}Y(n, p){sup 89}Sr reaction. A procedure for isolation of the radionuclide {sup 89}Sr by chemical processing of the irradiated Y{sub 2}O{sub 3} target has been standardised and trial runs have been carried out at the Fast Breeder Test Reactor (FBTR), Kalpakkam. The chemical processing of the irradiated Y{sub 2}O{sub 3} target involves (i) the removal of target Y(III) by TBP extraction and (ii) further purification of the separated {sup 89}Sr fraction by cationic exchange chromatography. However a selective isolation of {sup 89}Sr by the Sr-specific crown ether makes the above chemical processing faster and relatively simple. This work presents a study on the selective removal of Sr from the irradiated target dissolver solution using the Sr-specific crown ether 4,4{sup '}(5{sup '}) di-tert-butyl-cyclohexano-18-crown-6 (DtBuCH18C6) in octanol medium. The separation behaviour of the other impurities such as Ce(IV), Y(III), Tb(III), Eu(III), Zn(II), Mn(II) and Rb(I) present along with Sr(II) in the irradiated sample was also investigated. The method of separation by using the crown ether DtBuCH18C6 is proved to be a potential tool for the purification of {sup 89}Sr(II) source produced from yttria target in fast reactors.

  6. The DNA methylation profile of activated human natural killer cells.

    Science.gov (United States)

    Wiencke, John K; Butler, Rondi; Hsuang, George; Eliot, Melissa; Kim, Stephanie; Sepulveda, Manuel A; Siegel, Derick; Houseman, E Andres; Kelsey, Karl T

    2016-05-03

    Natural killer (NK) cells are now recognized to exhibit characteristics akin to cells of the adaptive immune system. The generation of adaptive memory is linked to epigenetic reprogramming including alterations in DNA methylation. The study herein found reproducible genome wide DNA methylation changes associated with human NK cell activation. Activation led predominately to CpG hypomethylation (81% of significant loci). Bioinformatics analysis confirmed that non-coding and gene-associated differentially methylated sites (DMS) are enriched for immune related functions (i.e., immune cell activation). Known DNA methylation-regulated immune loci were also identified in activated NK cells (e.g., TNFA, LTA, IL13, CSF2). Twenty-one loci were designated high priority and further investigated as potential markers of NK activation. BHLHE40 was identified as a viable candidate for which a droplet digital PCR assay for demethylation was developed. The assay revealed high demethylation in activated NK cells and low demethylation in naïve NK, T- and B-cells. We conclude the NK cell methylome is plastic with potential for remodeling. The differentially methylated region signature of activated NKs revealed similarities with T cell activation, but also provided unique biomarker candidates of NK activation, which could be useful in epigenome-wide association studies to interrogate the role of NK subtypes in global methylation changes associated with exposures and/or disease states.

  7. Mercury methylation and bacterial activity associated to tropical phytoplankton

    Energy Technology Data Exchange (ETDEWEB)

    Coelho-Souza, Sergio A. [Laboratorio de Tracadores Wolfgang Pfeiffer, SL 62, Instituto de Biofisica Carlos Chagas Filho, Bloco G, Ilha do Fundao, Universidade Federal do Rio de Janeiro (IBCCF/UFRJ), RJ, CEP 21949-900 (Brazil); Guimaraes, Jean R.D. [Laboratorio de Tracadores Wolfgang Pfeiffer, SL 62, Instituto de Biofisica Carlos Chagas Filho, Bloco G, Ilha do Fundao, Universidade Federal do Rio de Janeiro (IBCCF/UFRJ), RJ, CEP 21949-900 (Brazil)]. E-mail: jeanrdg@biof.ufrj.br; Mauro, Jane B.N. [Laboratorio de Tracadores Wolfgang Pfeiffer, SL 62, Instituto de Biofisica Carlos Chagas Filho, Bloco G, Ilha do Fundao, Universidade Federal do Rio de Janeiro (IBCCF/UFRJ), RJ, CEP 21949-900 (Brazil); Miranda, Marcio R. [Laboratorio de Tracadores Wolfgang Pfeiffer, SL 62, Instituto de Biofisica Carlos Chagas Filho, Bloco G, Ilha do Fundao, Universidade Federal do Rio de Janeiro (IBCCF/UFRJ), RJ, CEP 21949-900 (Brazil); Azevedo, Sandra M.F.O. [Laboratorio de Ecofisiologia e Toxicologia de Cianobacterias, IBCCF/UFRJ, RJ (Brazil)

    2006-07-01

    The methylated form of mercury (Hg), methylmercury (MeHg), is one of the most toxic pollutants. Biotic and/or abiotic methylation, often associated to sulfate-reducing bacteria metabolism, occurs in aquatic environments and in many tropical areas, mostly in the periphyton associated to floating macrophyte roots. Data about mercury methylation by phytoplankton are scarce and the aim of this study was to verify the biotic influence in the methylation process in Microcystis aeruginosa and Sineccocystis sp. laboratory strains and in natural populations of phytoplankton from two different aquatic systems, the mesotrophic Ribeirao das Lajes reservoir and hypereutrophic oligohaline Jacarepagua lagoon, Rio de Janeiro state, Brazil. Adapted radiochemical techniques were used to measure sulfate-reduction, mercury methylation and bacterial activity in phytoplankton samples. Methyl-{sup 203}Hg formation from added inorganic {sup 203}Hg and {sup 3}H-Leucine uptake were measured by liquid scintillation as well as sulfate-reduction, estimated as H{sub 2} {sup 35}S produced from added Na{sub 2} {sup 35}SO{sub 4}. There was no significant difference in low methylation potentials (0.37%) among the two cyanobacterium species studied in laboratory conditions. At Ribeirao das Lajes reservoir, there was no significant difference in methylation, bacterial activity and sulfate-reduction of surface sediment between the sampling points. Methylation in sediments (3-4%) was higher than in phytoplankton (1.5%), the opposite being true for bacterial activity (sediment mean 6.6 against 150.3 nmol gdw{sup -1} h{sup -1} for phytoplankton samples). At Jacarepagua lagoon, an expressive bacterial activity (477.1 x 10{sup 3} nmol gdw{sup -1} h{sup -1} at a concentration of 1000 nM leucine) and sulfate-reduction ({approx}21% H{sub 2} {sup 35}S trapped) associated to phytoplankton (mostly cyanobacteria M. aeruginosa) was observed, but mercury methylation was not detected.

  8. Study of the kinetics of palladium catalysts with 2-metoxy-naphtyl-diferrocenyl-, 2-tert-butyl-oxiphenyl-diferrocenyl-phosphine and 1,1’-diphenyl-phosphin-ferrocene ligands

    Directory of Open Access Journals (Sweden)

    Alibek Khabiyev

    2014-08-01

    Full Text Available The article presents results of the study on kinetic of palladium catalyst with 2-metoxy-naphtyl-diferrocenyl-, 2-tret-butyl-oxiphenyl-diferrocenyl-phosphin and 1,1’-diphenyl-phosphin-ferrocen ligands in Suzuki-Miyara test-reactions. The advantage of Suzuki reactions in difference from other cross-coupling reactions is the use of insensitive to water and oxygen thermostable organoboron compounds. As boronic acid was used phenylboronic acid and as weak base – potassium phosphate. All used catalysts showed good activity with arylbromides and weak activity with arylchlorides.

  9. Gymnaster koraiensis and its major components, 3,5-di-O-caffeoylquinic acid and gymnasterkoreayne B, reduce oxidative damage induced by tert-butyl hydroperoxide or acetaminophen in HepG2 cells

    Directory of Open Access Journals (Sweden)

    Eun Hye Jho

    2013-10-01

    Full Text Available We investigated the protective effects of Gymnaster koraiensisagainst oxidative stress-induced hepatic cell damage. We usedtwo different cytotoxicity models, i.e., the administration oftert-butyl hydroperoxide (t-BHP and acetaminophen, in HepG2cells to evaluate the protective effects of G. koraiensis. The ethylacetate (EA fraction of G. koraiensis and its major compound,3,5-di-O-caffeoylquinic acid (DCQA, exerted protective effectsin the t-BHP-induced liver cytotoxicity model. The EA fractionand DCQA ameliorated t-BHP-induced reductions in GSHlevels and exhibited free radical scavenging activity. The EAfraction and DCQA also significantly reduced t-BHP-inducedDNA damage in HepG2 cells. Furthermore, the hexane fractionof G. koraiensis and its major compound, gymnasterkoreayne B(GKB, exerted strong hepatoprotection in the acetaminopheninducedcytotoxicity model. CYP 3A4 enzyme activity wasstrongly inhibited by the extract, hexane fraction, and GKB. Thehexane fraction and GKB ameliorated acetaminophen-inducedreductions in GSH levels and protected against cell death. [BMBReports 2013; 46(10: 513-518

  10. Large-scale synthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by a stereoselective carbonyl reductase with high substrate concentration and product yield.

    Science.gov (United States)

    Liu, Zhi-Qiang; Hu, Zhong-Liang; Zhang, Xiao-Jian; Tang, Xiao-Ling; Cheng, Feng; Xue, Ya-Ping; Wang, Ya-Jun; Wu, Lin; Yao, Dan-Kai; Zhou, Yi-Teng; Zheng, Yu-Guo

    2017-05-01

    To biosynthesize the (3R,5S)-CDHH in an industrial scale, a newly synthesized stereoselective short chain carbonyl reductase (SCR) was successfully cloned and expressed in Escherichia coli. The fermentation of recombinant E. coli harboring SCR was carried out in 500 L and 5000 L fermenters, with biomass and specific activity of 9.7 g DCW/L, 15749.95 U/g DCW, and 10.97 g DCW/L, 19210.12 U/g DCW, respectively. The recombinant SCR was successfully applied for efficient production of (3R,5S)-CDHH. The scale-up synthesis of (3R,5S)-CDHH was performed in 5000 L bioreactor with 400 g/L of (S)-CHOH at 30°C, resulting in a space-time yield of 13.7 mM/h/g DCW, which was the highest ever reported. After isolation and purification, the yield and d.e. of (3R,5S)-CDHH reached 97.5% and 99.5%, respectively. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:612-620, 2017. © 2017 American Institute of Chemical Engineers.

  11. The chemical behavior of terminally tert-butylated polyolefins

    Directory of Open Access Journals (Sweden)

    Dagmar Klein

    2015-07-01

    Full Text Available The chemical behavior of various oligoenes 2 has been studied. The catalytic hydrogenation of diene 3 yielded monoene 4. Triene 7 was hydrogenated to diene 8, monoene 9 and saturated hydrocarbon 10. Bromine addition to 3 and 7 yielded the dibromides 17 and 18, respectively, i.e., the oligoene system has been attacked at its terminal olefinic carbon atoms. Analogously, the higher vinylogs 19 and 20 yielded the 1,8- and 1,10-bromine adduts 23 and 24, respectively, when less than 1 equivalent of bromine was employed. Treatment of tetraene 19 with excess bromine provided tetrabromide 25. In epoxidation reactions, both with meta-chloroperbenzoic acid (MCPBA and dimethyldioxirane (DMDO two model oligoenes were studied: triene 7 and tetraene 19. Whereas 7 furnished the rearrangement product 31 with MCPBA, it yielded the symmetrical epoxide 32 with DMDO. Analogously, 19 was converted to mono-epoxide 33 with MCPBA and to 34 with DMDO. Diels–Alder addition of 7 with N-phenyltriazolinedione (PTAD did not take place. Extension of the conjugated π-system to the next higher vinylog, 19, caused NPTD-addition to the symmetrical adduct 37 in good yield. Comparable results were observed on adding NPTD (equivalent amount to pentaene 20 and hexaene 21. Using 36 in excess provided the 2:1-adduct 40 from 21 and led to a complex mixture of adducts from heptaene 22. With tetracyanoethylene (TCNE as the dienophile, tetraolefin 19 yielded the symmetrical adduct 43, although the reaction temperature had to be increased. Pentaene 20 and hexaene 21 led to corresponding results, adducts 44 and 45 being produced in acceptable yields. With nonaene 42 and TCNE the 2:1-adduct 48 was generated according to its spectroscopic data. Exploratory photochemical studies were carried out with tetraene 19 as the model compound. On irradiation this reacted with oxygen to the stable endo-peroxide 52.

  12. Diaqua[μ-11,23-di-tert-butyl-3,7,15,19-tetraazatricyclo[19.3.1.19,13]tetracosa-1(25,2,6,9,11,13(26,14,19,21,23-dodecaene-25,26-diolato-κ4N3,N7,O25,O26:κ4N15,N19,O25,O26]dicopper(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Qiang Xu

    2012-08-01

    Full Text Available In the dinuclear title complex, [Cu2(C30H38N4O2(H2O2](ClO42, the coordination cation has crystallographically imposed twofold rotational symmetry. The CuII ion is five-coordinated by two N and two O atoms from the macrocylic ligand and one O atom from a water molecule, forming a square-pyramidal N2O3 geometry with the water molecule in the apical position. The distance between the two CuII atoms is 3.0930 (5 Å. Hydrogen bonds between water molecules and between water molecules and perchlorate anions assemble two cations and four anions into discrete supermolecules of S4 symmetry. Intramolecular O—H...N hydrogen bonds are also observed. The perchlorate anion and the tert-butyl group are disordered over two positions, with occupancies of the major positions of 0.527 (11 and 0.592 (9, respectively.

  13. Mn(II) complexes of different nuclearity: synthesis, characterization and catecholase-like activity.

    Science.gov (United States)

    Chakraborty, Prateeti; Majumder, Ishani; Banu, Kazi Sabnam; Ghosh, Bipinbihari; Kara, Hulya; Zangrando, Ennio; Das, Debasis

    2016-01-14

    Two "end-off" compartmental ligands, 2-formyl-4-chloro-6-N-ethylmorpholine-iminomethyl-phenol (HL1) and 2-formyl-4-methyl-6-N-ethylpyrrolidine-iminomethyl-phenol (HL2) have been designed and three complexes of Mn(ii), one mono-, one di- and a polynuclear, namely Mn(L1)(SCN)2(H2O)] (), [Mn2(L1)(OAc)2](BPh4)] (), and [Mn2(L2)(OAc)2(dca)]n () have been synthesized and structurally characterized. Variable temperature magnetic studies of and have been performed and data analyses reveal that Mn centers are antiferromagnetic coupled with J = -9.15 cm(-1) and J = -46.89, respectively. Catecholase activity of all the complexes has been investigated using 3,5-di-tert-butyl catechol (3,5-DTBC). All are highly active and the activity order on the basis of the kcat value is > > . In order to unveil whether the metal centered redox participation or the radical pathway is responsible for the catecholase-like activity of the complexes, detailed EPR and cyclic voltammetric (CV) studies have been performed. In addition to the six-line EPR spectrum characteristic to Mn(ii), an additional peak at g ∼ 2 is observed when the EPR study is done with the mixture of 3,5-DTBC and the catalyst, suggesting the formation of an organic radical, most likely ligand centered. The CV experiment with the mixture of 3,5-DTBC and the catalyst reveals ligand centered reduction rather than reduction of Mn(ii) to Mn(i). It is thus inferred that complexes show catecholase-like activity due to radical generation.

  14. Hydrogen Sulfide Releasing 2-Mercaptoacrylic Acid-Based Derivative Possesses Cytoprotective Activity in a Small Intestine of Rats with Medication-Induced Enteropathy

    Directory of Open Access Journals (Sweden)

    Yulia Sklyarova

    2017-10-01

    Full Text Available Small intestinal injury is known to be one of the most commonly appearing pathologies, resulting in the use of medications such as: nonsteroidal anti-inflammatory drugs (NSAIDs, antitumor drugs and angiotensin-converting enzyme (ACE inhibitors. The principal objective of this study is to evaluate the action of a novel mercaptoacrylic acid derivative able to release H2S on parameters of NO-synthase system and oxidative stress. Inducing enteropathy, three types of medications were used: indomethacin, an NSAID (35 mg/kg; methotrexate, an antitumor drug (10 mg/kg; and enalapril, an ACE inhibitor (2 mg/kg/day. 2-[(4-chlorophenyl-carbamoyl-methyl]-3-(3,5-di-tert-butyl-4-hydroxyphenyl-acrylic acid (2C3DHTA was introduced based on the background of medication-induced enteropathy (10 mg/kg/day. The survey showed that malondialdehyde (MDA concentration, myeloperoxidase (MPO activity, superoxide dismutase (SOD, catalase, and NO-synthases (NOS were determined in the small intestinal mucosa. The increase in inducible NO-synthase (iNOS activity was due to indomethacin and methotrexate administration. Constitutive NO-synthase (cNOS activity was decreased by an ACE-inhibitor. The cytoprotective effect was demonstrated by 2C3DHTA, which returned iNOS activity to its control level and increased cNOS activity. The enterotoxic action of studied medication was accompanied by the development of oxidative stress manifested, activity of MPO was increased. MPO activity and manifestations of oxidative stress were decreased by 2C3DHTA. Effects of 2C3DHTA can be explained by the action of H2S, released from this compound in the gastrointestinal (GI system.

  15. Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridine-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

    Energy Technology Data Exchange (ETDEWEB)

    Carreno, Alexander; Vega, Andres, E-mail: ichavez@uc.cl [Departamento de Ciencias Quimicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Santiago (Chile); Zarate, Ximena; Schott, Eduardo [Lab. Bionanotecnologia, Departamento de Ciencias Quimico-Biologicas, Universidad Bernardo O' Higgins, Santiago (Chile); Gacitua, Manuel; Valenzuela, Ninnette; Manriquez, Juan M.; Chavez, Ivonne [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago (Chile); Preite, Marcelo [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago (Chile)

    2014-07-01

    (E)-2-{[(2-Aminopyridine-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, {sup 1}H-NMR, {sup 13}C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer. (author)

  16. Macrolactone Nuiapolide, Isolated from a Hawaiian Marine Cyanobacterium, Exhibits Anti-Chemotactic Activity

    Science.gov (United States)

    Mori, Shogo; Williams, Howard; Cagle, Davey; Karanovich, Kristopher; Horgen, F. David; Smith, Roger; Watanabe, Coran M. H.

    2015-01-01

    A new bioactive macrolactone, nuiapolide (1) was identified from a marine cyanobacterium collected off the coast of Niihau, near Lehua Rock. The natural product exhibits anti-chemotactic activity at concentrations as low as 1.3 μM against Jurkat cells, cancerous T lymphocytes, and induces a G2/M phase cell cycle shift. Structural characterization of the natural product revealed the compound to be a 40-membered macrolactone with nine hydroxyl functional groups and a rare tert-butyl carbinol residue. PMID:26473885

  17. Iron optimization for Fenton-driven oxidation of MTBE-spent granular activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Scott G. Huling; Patrick K. Jones; Tony R. Lee [U.S. Environmental Protection Agency, Ada, OK (United States). Office of Research and Development, National Risk Management Research Laboratory

    2007-06-01

    Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was accomplished through the addition of iron (Fe) and hydrogen peroxide (H{sub 2}O{sub 2}) (15.9 g/L; pH 3). The GAC used was URV, a bituminous-coal based carbon. The Fe concentration in GAC was incrementally varied (1020-25 660 mg/kg) by the addition of increasing concentrations of Fe solution (FeSO4{center_dot}7H{sub 2}O). MTBE degradation in Fe-amended GAC increased by an order of magnitude over Fe-unamended GAC and H{sub 2}O{sub 2} reaction was predominantly (99%) attributed to GAC-bound Fe within the porous structure of the GAC. Imaging and microanalysis of GAC particles indicated limited penetration of Fe into GAC. The optimal Fe concentration was 6710 mg/kg (1020 mg/kg background; 5690 mg/kg amended Fe) and resulted in the greatest MTBE removal and maximum Fe loading oxidation efficiency (MTBE oxidized (g)/Fe loaded to GAC(mg/Kg)). At lower Fe concentrations, the H{sub 2}O{sub 2} reaction was Fe limited. At higher Fe concentrations, the H{sub 2}O{sub 2} reaction was not entirely Fe limited, and reductions in GAC surface area, GAC pore volume, MTBE adsorption, and Fe loading oxidation efficiency were measured. Results are consistent with nonuniform distribution of Fe, pore blockage in H{sub 2}O{sub 2} transport, unavailable Fe, and limitations in H{sub 2}O{sub 2} diffusive transport, and emphasize the importance of optimal Fe loading. 22 refs., 6 figs., 2 tabs.

  18. Nanotechnology in environmental remediation: degradation of volatile organic compounds (VOCs) over visible-light-active nanostructured materials.

    Science.gov (United States)

    Selvaraj, Rengaraj; Al-Kindy, Salma M Z; Silanpaa, Mika; Kim, Younghun

    2014-01-01

    Volatile organic compounds (VOCs) are major pollutants and are considered to be one of the most important contaminants generated by human beings living in urban and industrial areas. Methyl tert-butyl ether (MTBE) is a VOC that has been widely used as a gasoline additive to reduce VOC emissions from motor vehicles. However, new gasoline additives like MTBE are having negative environmental impacts. Recent survey reports clearly show that groundwater is often polluted owing to leakage of petroleum products from underground storage tanks. MTBE is highly soluble in water (e.g., 0.35-0.71 M) and has been detected at high concentrations in groundwater. The presence of MTBE in groundwater poses a potential health problem. The documented effects of MTBE exposure are headaches, vomiting, diarrhea, fever, cough, muscle aches, sleepiness, disorientation, dizziness, and skin and eye irritation. To address these problems, photocatalytic treatment is the preferred treatment for polluted water. In the present work, a simple and template-free solution phase synthesis method has been developed for the preparation of novel cadmium sulfide (CdS) hollow microspheres using cadmium nitrate and thioacetamide precursors. The synthesized products have been characterized by a variety of methods, including X-ray powder diffraction, high-resolution scanning electron microscopy (HR-SEM), X-ray photoelectron spectroscopy, and UV-visible diffused reflectance spectroscopy. The HR-SEM measurements revealed the spherical morphology of the CdS microspheres, which evolved by the oriented aggregation of the primary CdS nanocrystals. Furthermore, studies of photocatalytic activity revealed that the synthesized CdS hollow microspheres exhibit an excellent photocatalytic performance in rapidly degrading MTBE in aqueous solution under visible light illumination. These results suggest that CdS microspheres will be an interesting candidate for photocatalytic detoxification studies under visible light

  19. Presence of DNA methyltransferase activity and CpC methylation in Drosophila melanogaster.

    Science.gov (United States)

    Panikar, Chitra S; Rajpathak, Shriram N; Abhyankar, Varada; Deshmukh, Saniya; Deobagkar, Deepti D

    2015-12-01

    Drosophila melanogaster lacks DNMT1/DNMT3 based methylation machinery. Despite recent reports confirming the presence of low DNA methylation in Drosophila; little is known about the methyltransferase. Therefore, in this study, we have aimed to investigate the possible functioning of DNA methyltransferase in Drosophila. The 14 K oligo microarray slide was incubated with native cell extract from adult Drosophila to check the presence of the methyltransferase activity. After incubation under appropriate conditions, the methylated oligo sequences were identified by the binding of anti 5-methylcytosine monoclonal antibody. The antibody bound to the methylated oligos was detected using Cy3 labeled secondary antibody. Methylation sensitive restriction enzyme mediated PCR was used to assess the methylation at a few selected loci identified on the array. It could be seen that a few of the total oligos got methylated under the assay conditions. Analysis of methylated oligo sequences provides evidence for the presence of de novo methyltransferase activity and allows identification of its sequence specificity in adult Drosophila. With the help of methylation sensitive enzymes we could detect presence of CpC methylation in the selected genomic regions. This study reports presence of an active DNA methyltransferase in adult Drosophila, which exhibits sequence specificity confirmed by presence of asymmetric methylation at corresponding sites in the genomic DNA. It also provides an innovative approach to investigate methylation specificity of a native methyltransferase.

  20. Synthesis and antinociceptive activity of methyl nicotinate | Erharuyi ...

    African Journals Online (AJOL)

    Methyl nicotinate (methyl-3-pyridinecarboxylate) is a methyl ester of nicotinic acid – a type of B vitamin called niacin. It was prepared by esterification of nicotinic acid by refluxing with methanol in the presence of concentrated sulphuric acid, esterification product obtained was extracted into organic solvent (chloroform) after ...

  1. Activation barriers for methylation of DNA bases by dimethyl sulfate

    Science.gov (United States)

    Eichler, Daniel R.; Papadantonakis, George A.

    2017-12-01

    The SN2 transition states of the methylation reaction of DNA bases with dimethyl sulfate were examined employing DFT/ M06-2X/6-31+G∗ and DFT/B3LYP-D3/6-311+G (2df, 2p) levels of theory. Solvation effects were examined using the conductor-like polarizable continuum model (CPCM). Calculation results and feedback from electrostatic potential maps show that in water, charge separation lowers the activation barriers relative to the gas phase for the reactions at N7 of guanine, N3 of adenine and cytosine. Also, the reaction at the O6 site of guanine is governed by steric interference and exhibits a higher activation barrier in water.

  2. Effects of nickel on DNA methyltransferase activity and genomic DNA methylation levels.

    Science.gov (United States)

    Lee, Y W; Broday, L; Costa, M

    1998-07-31

    Methylation of DNA plays an important role in organizing the genome into transcriptionally active and inactive zones. Nickel compounds cause chromatin condensation and DNA methylation in the transgenic gpt+ Chinese hamster cell line (G12). Here we show that nickel is an inhibitor of cytosine 5-methyltransferase activity in vivo and in vitro. In living cells, this inhibition is transient and following a recovery period after nickel treatment, Mtase activity slightly rebounds. Genomic DNA methylation levels are also somewhat decreased following nickel treatment, but with time, there is an elevation of total DNA methylation above basal levels and before any rebound of methyltransferase activity. These results suggest that nickel exposure can elevate total genomic DNA methylation levels even when DNA methyltransferase activity is depressed. These findings may explain the hypermethylation of senescence and tumor suppressor genes found during nickel carcinogenesis and support the model of a direct effect of Ni2+ on chromatin leading to de novo DNA methylation.

  3. Synthesis, Antimycobacterial, Antifungal and Photosynthesis-Inhibiting Activity of Chlorinated N-phenylpyrazine-2-carboxamides †

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2010-11-01

    Full Text Available A series of sixteen pyrazinamide analogues with the -CONH- linker connecting the pyrazine and benzene rings was synthesized by the condensation of chlorides of substituted pyrazinecarboxylic acids with ring-substituted (chlorine anilines. The prepared compounds were characterized and evaluated for their antimycobacterial and antifungal activity, and for their ability to inhibit photosynthetic electron transport (PET. 6-Chloro-N-(4-chlorophenylpyrazine-2-carboxamide manifested the highest activity against Mycobacterium tuberculosis strain H37Rv (65% inhibition at 6.25 μg/mL. The highest antifungal effect against Trichophyton mentagrophytes, the most susceptible fungal strain tested, was found for 6-chloro-5-tert-butyl-N-(3,4-dichlorophenylpyrazine-2-carboxamide (MIC = 62.5 μmol/L. 6-Chloro-5-tert-butyl-N-(4-chlorophenylpyrazine-2-carboxamide showed the highest PET inhibition in spinach chloroplasts (Spinacia oleracea L. chloroplasts (IC50 = 43.0 μmol/L. For all the compounds, the relationships between the lipophilicity and the chemical structure of the studied compounds as well as their structure-activity relationships are discussed.

  4. Synthesis Methyl Nitrophenyl Acrylate and Cytotoxic Activity Test against P388 Leukemia Cells

    Directory of Open Access Journals (Sweden)

    Teni Ernawati

    2015-03-01

    Full Text Available Synthesis of methyl nitrophenyl acrylate via modification of methyl trans-cinnamate had been done to improve its biological activity. The reaction of methyl trans-cinnamate with nitrating agent gave methyl 3-(2-nitrophenylacrylate and methyl 3-(4-nitrophenylacrylate with an ortho/para ratio of 1:8. Its structure was confirmed with 1H-NMR, 13C-NMR, FTIR, GC-MS. Biological activity of methyl 3-(4-nitrophenylacrylate and methyl 3-(2-nitrophenylacrylate assays was performed on Cancer cells against P388 Murine Leukemia with IC50= 7.98 μg/mL, IC50 = 27.78 μg/mL.

  5. Crystal structure of (2,4-di-tert-butyl-6-{[(6,6′-dimethyl-2′-oxido-1,1′-biphenyl-2-ylimino]methyl}phenolato-κ3O,N,O′bis(propan-2-olato-κOtitanium(IV

    Directory of Open Access Journals (Sweden)

    Liang Chen

    2014-09-01

    Full Text Available In the mononuclear TiIV title complex, [Ti(C29H33NO2(C3H6O2], the TiNO4 coordination polyhedron comprises an N-atom and two O-atom donors from the dianionic Schiff base ligand and two O-atom donors from monodentate isopropoxide anions. The stereochemistry is distorted trigonal–bipyramidal with the N-donor in an elongated axial site [Ti—N = 2.2540 (17 Å], the O-donors having normal Ti—O bond lengths [1.7937 (14 Å (axial–1.8690 (14 Å]. In the crystal, C—H...π interactions link molecules into centrosymmetric dimers.

  6. Potentiation of insulin release in response to amino acid methyl esters correlates to activation of islet glutamate dehydrogenase activity

    DEFF Research Database (Denmark)

    Kofod, Hans; Lernmark, A; Hedeskov, C J

    1986-01-01

    Column perifusion of mouse pancreatic islets was used to study the ability of amino acids and their methyl esters to influence insulin release and activate islet glutamate dehydrogenase activity. In the absence of L-glutamine, L-serine and the methyl ester of L-phenylalanine, but neither L...... glutamate dehydrogenase activity showed that only the two methyl esters of L-phenylalanine and L-serine activated the enzyme. It is concluded that the mechanism by which methyl esters of amino acids potentiate insulin release is most likely to be mediated by the activation of pancreatic beta-cell glutamate...

  7. Evaluation of alternariol and alternariol methyl ether for mutagenic activity in Salmonella typhimurium

    Energy Technology Data Exchange (ETDEWEB)

    Davis, V.M.; Stack, M.E. (Food and Drug Administration, Washington, DC (United States))

    1994-10-01

    Alternariol and alternariol methyl ether were tested in the Ames Salmonella typhimurium assay, and both were shown, with and without metabolic activation, to be nonmutagenic to strains TA98 and TA100. The finding of other investigators that alternariol methyl ether is weakly mutagenic to Ta98 without metabolic activation could have resulted from the presence of a small amount of one of the highly mutagenic altertoxins in the alternariol methyl ether originally tested. 9 refs., 3 figs., 1 tab.

  8. The impact of methylation quantitative trait loci (mQTLs) on active smoking-related DNA methylation changes.

    Science.gov (United States)

    Gao, Xu; Thomsen, Hauke; Zhang, Yan; Breitling, Lutz Philipp; Brenner, Hermann

    2017-01-01

    Methylation quantitative trait loci (mQTLs) are the genetic variants that may affect the DNA methylation patterns of CpG sites. However, their roles in influencing the disturbances of smoking-related epigenetic changes have not been well established. This study was conducted to address whether mQTLs exist in the vicinity of smoking-related CpG sites (± 50 kb) and to examine their associations with smoking exposure and all-cause mortality in older adults. We obtained DNA methylation profiles in whole blood samples by Illumina Infinium Human Methylation 450 BeadChip array of two independent subsamples of the ESTHER study (discovery set, n = 581; validation set, n = 368) and their corresponding genotyping data using the Illumina Infinium OncoArray BeadChip. After correction for multiple testing (FDR), we successfully identified that 70 out of 151 previously reported smoking-related CpG sites were significantly associated with 192 SNPs within the 50 kb search window of each locus. The 192 mQTLs significantly influenced the active smoking-related DNA methylation changes, with percentage changes ranging from 0.01 to 18.96%, especially for the weakly/moderately smoking-related CpG sites. However, these identified mQTLs were not directly associated with active smoking exposure or all-cause mortality. Our findings clearly demonstrated that if not dealt with properly, the mQTLs might impair the power of epigenetic-based models of smoking exposure to a certain extent. In addition, such genetic variants could be the key factor to distinguish between the heritable and smoking-induced impact on epigenome disparities. These mQTLs are of special importance when DNA methylation markers measured by Illumina Infinium assay are used for any comparative population studies related to smoking-related cancers and chronic diseases.

  9. Hemi-methylated DNA regulates DNA methylation inheritance through allosteric activation of H3 ubiquitylation by UHRF1.

    Science.gov (United States)

    Harrison, Joseph S; Cornett, Evan M; Goldfarb, Dennis; DaRosa, Paul A; Li, Zimeng M; Yan, Feng; Dickson, Bradley M; Guo, Angela H; Cantu, Daniel V; Kaustov, Lilia; Brown, Peter J; Arrowsmith, Cheryl H; Erie, Dorothy A; Major, Michael B; Klevit, Rachel E; Krajewski, Krzysztof; Kuhlman, Brian; Strahl, Brian D; Rothbart, Scott B

    2016-09-06

    The epigenetic inheritance of DNA methylation requires UHRF1, a histone- and DNA-binding RING E3 ubiquitin ligase that recruits DNMT1 to sites of newly replicated DNA through ubiquitylation of histone H3. UHRF1 binds DNA with selectivity towards hemi-methylated CpGs (HeDNA); however, the contribution of HeDNA sensing to UHRF1 function remains elusive. Here, we reveal that the interaction of UHRF1 with HeDNA is required for DNA methylation but is dispensable for chromatin interaction, which is governed by reciprocal positive cooperativity between the UHRF1 histone- and DNA-binding domains. HeDNA recognition activates UHRF1 ubiquitylation towards multiple lysines on the H3 tail adjacent to the UHRF1 histone-binding site. Collectively, our studies are the first demonstrations of a DNA-protein interaction and an epigenetic modification directly regulating E3 ubiquitin ligase activity. They also define an orchestrated epigenetic control mechanism involving modifications both to histones and DNA that facilitate UHRF1 chromatin targeting, H3 ubiquitylation, and DNA methylation inheritance.

  10. Thermo-responsive, UV-active poly(phenyl acrylate-b-poly(diethyl acrylamide block copolymers

    Directory of Open Access Journals (Sweden)

    M. Maric

    2013-12-01

    Full Text Available The homopolymerization of phenyl acrylate (PA was investigated for the first time by nitroxide mediated polymerization (NMP with the succinimidyl form of the SG1-based unimolecular initiator 2-[N-tert-butyl-2,2-(dimethylpropyl-aminooxy]propionic acid (BlocBuilder MA. The control of PPA homopolymerization was improved by the use of 15 mol% additional free nitroxide SG1 ([tert-butyl[1-(diethoxyphosphoryl-2,2-dimethylpropyl]amino]oxidanyl and dispersities, Mw/Mn, of around 1.2 were achieved. A PPA homopolymer was then successfully chain-extended with diethyl acrylamide (DEAAm to form a block copolymer of PPA-b-PDEAAm where the PDEAAm segment is thermo-responsive, while the PPA block is potentially UV-active. The thermo-responsive behavior of the block copolymer in 0.5 wt% aqueous solution was studied by UV-Vis spectrometry and dynamic light scattering (DLS, indicating cloud point temperatures of 26–30°C, close to that reported for PDEAAm homopolymers.

  11. On the role of steric clashes in methylation control of restriction endonuclease activity.

    Science.gov (United States)

    Mierzejewska, Karolina; Bochtler, Matthias; Czapinska, Honorata

    2016-01-08

    Restriction-modification systems digest non-methylated invading DNA, while protecting host DNA against the endonuclease activity by methylation. It is widely believed that the methylated DNA would not 'fit' into the binding site of the endonuclease in the productive orientation, and thus steric clashes should account for most of the protection. We test this concept statistically by grafting methyl groups in silico onto non-methylated DNA in co-crystal structures with restriction endonucleases. Clash scores are significantly higher for protective than non-protective methylation (P < 0.05% according to the Wilcoxon rank sum test). Structural data alone are sufficient to distinguish between protective and non-protective DNA methylation with 90% confidence and decision thresholds of 1.1 Å and 48 Å(3) for the most severe distance-based and cumulative volume-based clash with the protein, respectively (0.1 Å was deducted from each interatomic distance to allow for coordinate errors). The most severe clashes are more pronounced for protective methyl groups attached to the nitrogen atoms (N6-methyladenines and N4-methylcytosines) than for C5-methyl groups on cytosines. Cumulative clashes are comparable for all three types of protective methylation. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  12. Discovery of novel orally active anti-inflammatory N-phenylpyrazolyl-N-glycinyl-hydrazone derivatives that inhibit TNF-α production.

    Directory of Open Access Journals (Sweden)

    Renata B Lacerda

    Full Text Available Herein, we describe the synthesis and pharmacological evaluation of novel N-phenylpyrazolyl-N-glycinyl-hydrazone derivatives that were designed as novel prototypes of p38 mitogen-activated protein kinase (MAPK inhibitors. All of the novel synthesized compounds described in this study were evaluated for their in vitro capacity to inhibit tumor necrosis factor α (TNF-α production in cultured macrophages and in vitro MAPK p38α inhibition. The two most active anti-TNF-α derivatives, (E-2-(3-tert-butyl-1-phenyl-1H-pyrazol-5-ylamino-N'-((4-(2-morpholinoethoxynaphthalen-1-ylmethyleneacetohydrazide (4a and (E-2-(3-tert-butyl-1-phenyl-1H-pyrazol-5-ylamino-N'-(4-chlorobenzylideneacetohydrazide (4f, were evaluated to determine their in vivo anti-hyperalgesic profiles in carrageenan-induced thermal hypernociception model in rats. Both compounds showed anti-inflammatory and antinociceptive properties comparable to SB-203580 used as a standard drug, by oral route at a dose of 100 µmol/kg. This bioprofile is correlated with the ability of NAH derivatives (4a and (4f suppressing TNF-α levels in vivo by 57.3 and 55.8%, respectively.

  13. Identifying carcinogenic activity of methylated and non-methylated polycyclic aromatic hydrocarbons (PAHs) through electronic and topological indices

    CERN Document Server

    Braga, R S; Barone, P M V B

    2000-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are a class of planar molecules, abundant in urban environment, which can induce chemical carcinogenesis. Their carcinogenic power varies in a large range, from very strong carcinogens to inactive ones. In a previous study, we proposed a methodology to identify the PAHs carcinogenic activity exploring electronic and topological indices. In the present work, we show that it is possible to simplify that methodology and expand its applicability to include methylated PAHs compounds. Using very simple rules, we can predict their carcinogenic activity with high accuracy (approx 89%).

  14. Antimicrobial and Antimycobacterial Activities of Methyl Caffeate Isolated from Solanum torvum Swartz. Fruit.

    Science.gov (United States)

    Balachandran, Chandrasekhar; Duraipandiyan, Veeramuthu; Al-Dhabi, Naif Abdullah; Balakrishna, K; Kalia, Nitin Pal; Rajput, Vikrant Singh; Khan, Inshad Ali; Ignacimuthu, Savarimuthu

    2012-12-01

    Solanum torvum Swartz. (Solanaceae) fruit is traditionally used for the treatment of bacterial and fungal infections. The methanolic extract was subjected to activity guided fractionation by column chromatography over silica gel. The structure of the compound was elucidated using physical and spectroscopic data. The antimicrobial activity was screened using five Gram-positive bacteria, six Gram-negative bacteria, seven clinical isolates and four fungi. Antimycobacterial activity was screened against two Mycobacterium strains. The zone of inhibition by methyl caffeate ranged from 0 to 22 mm. The lowest minimum inhibitory concentration (MIC) values of methyl caffeate were: 50 μg/ml against P. vulgaris, 25 μg/ml against K. pneumoniae (ESBL-3971), 8 μg/ml against M. tuberculosis (H(37)Rv) and 8 μg/ml against M. tuberculosis (Rif(R)). Methyl caffeate showed moderate antimicrobial and prominent antimycobacterial activities. Methyl caffeate can be evaluated further for drug development.

  15. Plasticity of DNA methylation in mouse T cell activation and differentiation

    Directory of Open Access Journals (Sweden)

    Li Yan

    2012-05-01

    Full Text Available Abstract Background Circulating CD4+ T helper cells are activated through interactions with antigen presenting cells and undergo differentiation into specific T helper cell subsets depending on the type of antigen encountered. In addition, the relative composition of the circulating CD4+ T cell population changes as animals mature with an increased percentage of the population being memory/effector type cells. Results Here, we report on the highly plastic nature of DNA methylation at the genome-wide level as T cells undergo activation, differentiation and aging. Of particular note were the findings that DNA demethylation occurred rapidly following T cell activation and that all differentiated T cell populations displayed lower levels of global methylation than the non-differentiated population. In addition, T cells from older mice had a reduced level of DNA methylation, most likely explained by the increase in the memory/effector cell fraction. Although significant genome-wide changes were observed, changes in DNA methylation at individual genes were restricted to specific cell types. Changes in the expression of enzymes involved in DNA methylation and demethylation reflect in most cases the changes observed in the genome-wide DNA methylation status. Conclusion We have demonstrated that DNA methylation is dynamic and flexible in CD4+ T cells and changes rapidly both in a genome-wide and in a targeted manner during T cell activation, differentiation. These changes are accompanied by parallel changes in the enzymatic complexes that have been implicated in DNA methylation and demethylation implying that the balance between these opposing activities may play a role in the maintaining the methylation profile of a given cell type but also allow flexibility in a cell population that needs to respond rapidly to environmental signals.

  16. Replication timing-related and gene body-specific methylation of active human genes.

    Science.gov (United States)

    Aran, Dvir; Toperoff, Gidon; Rosenberg, Michael; Hellman, Asaf

    2011-02-15

    Understanding how the epigenetic blueprint of the genome shapes human phenotypes requires systematic evaluation of the complex interplay between gene activity and the different layers of the epigenome. Utilizing microarray-based techniques, we explored the relationships between DNA methylation, DNA replication timing and gene expression levels across a variety of human tissues and cell lines. The analyses revealed unequal methylation levels among early- and late-replicating fractions of the genome: late-replicating DNA was hypomethylated compared with early-replicating DNA. Moreover, late-replicating regions were gradually demethylated with cell divisions, whereas the methylation of early-replicating regions was better maintained. As active genes concentrate at early-replicating regions, they are overall hypermethylated relative to inactive genes. Accordingly, we show that the previously reported positive correlation between gene-body methylation (methylation of the transcribed portion of genes) and gene expression is restricted to proliferative tissues and cell lines, whereas in tissues containing few proliferating cells, active and inactive genes have similar methylation levels. We further show that active gene bodies are hypermethylated not only compared with inactive gene bodies, but also compared with their flanking sequences. This specific hypermethylation of the active gene bodies is severely disrupted in cells of an immunodeficiency, centromeric region instability, facial anomalies (ICF) syndrome patient bearing mutated DNA methyltransferase 3B (DNMT3B). Our data show that a high methylation level is preferentially maintained in active gene bodies through independent cellular processes. Rather than serving as a distinctive mark between active and inactive genes, gene-body methylation appears to serve a vital, currently unknown function in active genes.

  17. ANAEROBIC DEGRADATION OF MTBE TO TBA IN GROUND WATER AT GASOLINE SPILL SITES IN ORANGE COUNTY, CALIFORNIA

    Science.gov (United States)

    Although tert-Butyl Alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared to the concentrations of the conventional fuel oxygenate Methyl tert-Butyl Ether (MTBE). In t...

  18. BDNF Methylation and Maternal Brain Activity in a Violence-Related Sample.

    Directory of Open Access Journals (Sweden)

    Dominik A Moser

    Full Text Available It is known that increased circulating glucocorticoids in the wake of excessive, chronic, repetitive stress increases anxiety and impairs Brain-Derived Neurotrophic Factor (BDNF signaling. Recent studies of BDNF gene methylation in relation to maternal care have linked high BDNF methylation levels in the blood of adults to lower quality of received maternal care measured via self-report. Yet the specific mechanisms by which these phenomena occur remain to be established. The present study examines the link between methylation of the BDNF gene promoter region and patterns of neural activity that are associated with maternal response to stressful versus non-stressful child stimuli within a sample that includes mothers with interpersonal violence-related PTSD (IPV-PTSD. 46 mothers underwent fMRI. The contrast of neural activity when watching children-including their own-was then correlated to BDNF methylation. Consistent with the existing literature, the present study found that maternal BDNF methylation was associated with higher levels of maternal anxiety and greater childhood exposure to domestic violence. fMRI results showed a positive correlation of BDNF methylation with maternal brain activity in the anterior cingulate (ACC, and ventromedial prefrontal cortex (vmPFC, regions generally credited with a regulatory function toward brain areas that are generating emotions. Furthermore we found a negative correlation of BDNF methylation with the activity of the right hippocampus. Since our stimuli focus on stressful parenting conditions, these data suggest that the correlation between vmPFC/ACC activity and BDNF methylation may be linked to mothers who are at a disadvantage with respect to emotion regulation when facing stressful parenting situations. Overall, this study provides evidence that epigenetic signatures of stress-related genes can be linked to functional brain regions regulating parenting stress, thus advancing our understanding of

  19. The influence of metabolic syndrome, physical activity and genotype on catechol-O-methyl transferase promoter-region methylation in schizophrenia.

    Science.gov (United States)

    Lott, S A; Burghardt, P R; Burghardt, K J; Bly, M J; Grove, T B; Ellingrod, V L

    2013-06-01

    The catechol-O-methyl transferase (COMT) 158Val/Met variant has been suggested to play a role in COMT function. Epigenetic regulation of COMT may further influence the prevalence of metabolic syndrome in these patient populations. This study examined the correlation between COMT promoter methylation and metabolic syndrome in schizophrenia patients receiving atypical antipsychotic (AAP) therapy. DNA was extracted from peripheral blood samples of schizophrenia subjects screened for metabolic syndrome. Pyrosequencing was used to analyze two methylation sites of the soluble COMT (COMT-s) promoter region. Associations between AAP use, lifestyle variables, metabolic syndrome and COMT genotype with peak methylation values were analyzed. Data are reported in 85 subjects. Methylation on CpG site 1 had a mean of 79.08% (±4.71) and it was 12.43% (±1.19) on site 2. COMT genotype proved to be an indicator of COMT methylation status on site 1 (F(2, 84)=5.78, P=0.0044) and site 2 (F(2, 84),=3.79, P=0.027). A significant negative correlation between physical activity and COMT promoter region methylation was found in Val/Val homozygous patients (site 1: P=0.013 and site 2: P=0.019). Those homozygous for Met/Met showed a positive correlation between promoter site methylation and physical activity (site 1: P=0.027, site 2: P=0.005), and between CpG site methylation and metabolic syndrome (site 1: P=0.002; site 2: P=0.001). The results of this study suggest that COMT promoter region methylation is largely influenced by COMT genotype and that physical activity plays a significant role in epigenetic modulation of COMT.

  20. Cryopreservation induces temporal DNA methylation epigenetic changes and differential transcriptional activity in Ribes germplasm.

    Science.gov (United States)

    Johnston, Jason W; Benson, Erica E; Harding, Keith

    2009-02-01

    The physiological and molecular mechanisms associated with acclimation and survival have been examined in four Ribes genotypes displaying differential cryotolerance. Changes in DNA methylation, nucleic acid and nucleoside composition were determined during acclimation and recovery of in vitro shoot-meristems from cryopreservation. DNA methylation was induced in the tolerant genotype, while demethylation was evident in sensitive genotypes. This response initially occurred during sucrose simulated acclimation, with progressive changes as shoots recovered from successive stages of the encapsulation-dehydration protocol. These methylation patterns existed in the initial vegetative cycle but regressed to control values following subculture, indicating the changes in DNA methylation to be a reversible epigenetic mechanism. RNA levels indicating transcriptional activity during the acclimation of nodal tissue are inversely linked to methylation changes, where activity appears to be up-regulated in the cryosensitive genotypes. Conversely, cryopreserved shoots show increased levels of both RNA and DNA methylation in the cryotolerant genotypes. Other nucleosides show post-transcriptional activity corresponds with tolerance during acclimation and cryopreservation. These observations connect physiological attributes to differential molecular changes in Ribes, the implications of which are discussed in relation to cryopreservation-induced apoptosis and genetic stability.

  1. Activities of natural methyl farnesoids on pupariation and metamorphosis of Drosophila melanogaster.

    Science.gov (United States)

    Jones, Grace; Jones, Davy; Li, Xiaobo; Tang, Lingfeng; Ye, Li; Teal, Peter; Riddiford, Lynn; Sandifer, Courtney; Borovsky, Dov; Martin, Jean-Rene

    2010-10-01

    Methyl farnesoate (MF) and juvenile hormone (JH III), which bind with high affinity to the receptors USP and MET, respectively, and bisepoxy JH III (bisJH III) were assessed for several activities during Drosophila larval development, and during prepupal development to eclosed adults. Dietary MF and JH III were similarly active, and more active than bisJH III, in lengthening larval development prior to pupariation. However, the order of activity was changed (JH III>bisJH III>MF) with respect to preventing prepupae from eclosing as normal adults, whether administered in the larval diet or as topically applied at the white puparium stage. If endogenous production of all three larval methyl farnesoids was suppressed by a strongly driven RNAi against HMGCR in the corpora allata cells, most larvae did not attain pupariation. Farnesol (which has no demonstrated life-necessary function in larval life except in corpora allata cells as a precursor to methyl farnesoid biosynthesis) when incorporated into the diet rescued attainment of pupariation in a dose-dependent manner, presumably by rescuing endogenous production of all three hormones. A more mild suppression of endogenous methyl farnesoid production enabled larval attainment of pupariation. However, in this background dietary MF had increased activity in preventing puparia from attaining normal adult eclosion. The physiological relevance of using exogenous methyl farnesoids to block prepupal development to normally eclosed adults was tested by, instead, protecting in prepupae the endogenous titer of methyl farnesoids. JH esterase normally increases during the mid-late prepupal stage, presumably to clear endogenous methyl farnesoids. When JH esterase was inhibited with an RNAi, it prevented attainment of adult eclosion. Cultured adult corpora allata from male and female Aedes aegypti released both MF and JH III, and the A. aegypti nuclear receptor USP bound MF with nanomolar affinity. These A. aegypti data support the

  2. Probing the active site of aromatase with 2-methyl-substituted androstenedione analogs.

    Science.gov (United States)

    Numazawa, Mitsuteru; Watari, Yoko; Yamada, Keiko; Umemura, Nao; Handa, Wakako

    2003-08-01

    To gain insight into the spatial nature of the androstenedione (AD) binding (active) site of aromatase in relation to the catalytic function of the enzyme, we synthesized 2,2-dimethylAD (4), 2beta- and 2alpha-methylADs (5 and 6), 19-oxygenated derivatives of compounds 4 and 6, and 2-methyleneAD (17), and we then tested their inhibitory activity as well as their aromatase reaction (aromatization for 2-methyl and 2-methylene analogs or 19-oxygenation for 2,2-dimethyl steroids) with human placental aromatase. 2-Methyl and 2-methylene steroids 5, 6, and 17 were good competitive inhibitors of aromatase (K(i)=22-68nM), but less effective compared to the 2,2-dimethyl analog 4 (K(i)=8.8nM), indicating that a combination of 2beta- and 2alpha-methyl moieties is essential for the formation of a thermodynamically stable inhibitor-aromatase complex. A series of 2alpha-methyl steroids were good substrates for aromatase, whereas 2beta-methyl steroid 5 was an extremely poor substrate, and a series of 2,2-dimethyl steroids did not serve as substrate, suggesting that a 2beta-methyl moiety of the 2,2-dimethyl and 2beta-methyl steroids would prevent the aromatase reaction probably due to steric hindrance in each case. The 2-methylene compound 17 was also aromatized to produce 2-methylestrogen with a low conversion rate where the 1,4-diene structure may have been created before the C(10)-C(19) bond cleavage. Kinetic analysis of the aromatization of androgens revealed that a good substrate was not essentially a good inhibitor for aromatase.

  3. Layered metal laurates as active catalysts in the methyl/ethyl esterification reactions of lauric acid

    Energy Technology Data Exchange (ETDEWEB)

    Lisboa, Fabio da Silva; Cordeiro, Claudiney S.; Wypych, Fernando, E-mail: wypych@ufpr.br [Centro de Pesquisas em Quimica Aplicada (CEPESQ), Departamento de Quimica, Universidade Federal do Parana, Curitiba, PR (Brazil); Gardolinski, Jose Eduardo F. da Costa [Laboratorio de Analise de Minerais e Rochas (LAMIR), Departamento de Geologia, Universidade Federal do Parana, Curitiba, PR (Brazil)

    2012-07-01

    In this work we report the synthesis, characterization and investigation of the catalytic activity of layered copper(II), manganese(II), lanthanum(III) and nickel(II) laurates in the methyl and ethyl esterification reactions of lauric acid. In the methyl esterification, conversions between 80 and 90% were observed for all catalysts, while for the ethyl esterification only manganese laurate showed reasonable catalytic activity, with conversions close to 75%. Reuse of copper and lanthanum laurates in three cycles of reaction was also investigated and both catalysts preserved the structure and retained catalytic activity close to that observed for the first reaction cycle. (author)

  4. The role of mesopores in MTBE removal with granular activated carbon.

    Science.gov (United States)

    Redding, Adam M; Cannon, Fred S

    2014-06-01

    This activated carbon research appraised how pore size and empty-bed contact time influenced the removal of methyl tert-butyl ether (MTBE) at part-per-billion (ppb) concentrations when MTBE was the sole organic impurity. The study compared six granular activated carbons (GACs) from three parent sources; these GACs contained a range of pore volume distributions and had uniform slurry pHs of 9.7-10.4 (i.e. the carbons' bulk surface chemistries were basic). Several of these activated carbons had been specifically tailored for enhanced sorption of trace organic compounds. In these tests, MTBE was spiked into deionized-distilled water (∼pH 7); MTBE loading was measured by isotherms and by rapid small-scale column tests (RSSCTs) that simulated full-scale empty-bed contact times of 7, 14, and 28 min. The results showed that both ultra-fine micropores and small-diameter mesopores were important for MTBE adsorption. Specifically, full MTBE loading during RSSCTs bore a strong correlation (R(2) = 0.94) to the product (mL/g × mL/g) of pore volume ≤4.06 Å wide and pore volume between ∼22 Å and ∼59 Å wide. This correlation was greater than for the product of any other pore volume combinations. Also, this product exhibited a stronger correlation than for just one or the other of these two pore ranges. This multiplicative relationship implied that both of these pore sizes were important for the optimum GAC performance of these six carbons (i.e. favorable mass transfer coupled with favorable sorption). The authors also compared MTBE mass loading during RSSCTs (μg MTBE/g GAC) to isotherm capacity (μg MTBE/g GAC). This RSSCT loading "efficiency" ranged from 28% to 96% for the six GACs; this efficiency correlated most strongly to pores that were 14-200 Å wide (R(2) = 0.94). This correlation indicated that only those carbons with a sufficient volume of 14-200 Å pores could adsorb MTBE to the extent that would be predicted from isotherm data. Copyright

  5. Biodegradation of triclosan and formation of methyl-triclosan in activated sludge under aerobic conditions

    DEFF Research Database (Denmark)

    Chen, Xijuan; Nielsen, Jeppe Lund; Furgal, Karolina

    2011-01-01

    of triclosan- methyl was investigated in activated sludge from a standard activated sludge WWTP equipped with enhanced biological phosphorus removal. The removal was found to occur mainly under aerobic conditions while under anoxic (nitrate reducing) and anaerobic conditions rather low removal rates were...

  6. hTERT promoter activity and CpG methylation in HPV-induced carcinogenesis

    NARCIS (Netherlands)

    de Wilde, J.; Kooter, J.M.; Overmeer, R.M.; Kramer, D.; Meijer, C.J.L.M.; Snijders, P.J.F.; Steenbergen, R.D.M.

    2010-01-01

    Background: Activation of telomerase resulting from deregulated hTERT expression is a key event during high-risk human papillomavirus (hrHPV)-induced cervical carcinogenesis. In the present study we examined hTERT promoter activity and its relation to DNA methylation as one of the potential

  7. Catalysis in a porous molecular capsule: activation by regulated access to sixty metal centers spanning a truncated icosahedron.

    Science.gov (United States)

    Kopilevich, Sivil; Gil, Adrià; Garcia-Ratés, Miquel; Bonet-Ávalos, Josep; Bo, Carles; Müller, Achim; Weinstock, Ira A

    2012-08-08

    The 30 cationic {Mo(V)2O4(acetate)}(+) units linking 12 negatively charged pentagonal "ligands," {(Mo(VI))Mo(VI)5O21(H2O)6}(6-) of the porous metal-oxide capsule, [{Mo(VI)6O21(H2O)6}12{Mo(V)2O4(acetate)}30](42-) provide active sites for catalytic transformations of organic "guests". This is demonstrated using a well-behaved model reaction, the fully reversible cleavage and formation of methyl tert-butyl ether (MTBE) under mild conditions in water. Five independent lines of evidence demonstrate that reactions of the MTBE guests occur in the ca. 6 × 10(3) Å(3) interior of the spherical capsule. The Mo atoms of the {Mo(V)2O4(acetate)}(+) linkers--spanning an ca. 3-nm truncated icosahedron--are sterically accessible to substrate, and controlled removal of their internally bound acetate ligands generates catalytically active {Mo(V)2O4(H2O)2}(2+) units with labile water ligands, and Lewis- and Brønsted-acid properties. The activity of these units is demonstrating by kinetic data that reveal a first-order dependence of MTBE cleavage rates on the number of acetate-free {Mo(V)2O4(H2O)2}(2+) linkers. DFT calculations point to a pathway involving both Mo(V) centers, and the intermediacy of isobutene in both forward and reverse reactions. A plausible catalytic cycle--satisfying microscopic reversibility--is supported by activation parameters for MTBE cleavage, deuterium and oxygen-18 labeling studies, and by reactions of deliberately added isobutene and of a water-soluble isobutene analog. More generally, pore-restricted encapsulation, ligand-regulated access to multiple structurally integral metal-centers, and options for modifying the microenvironment within this new type of nanoreactor, suggest numerous additional transformations of organic substrates by this and related molybdenum-oxide based capsules.

  8. Activity of cell wall degrading glycanases in methyl jasmonate-induced leaf abscission in Kalanchoe blossfeldiana

    Directory of Open Access Journals (Sweden)

    Marian Saniewski

    2013-12-01

    Full Text Available It was found previously that methyl jasmonate (JA-Me induced leaf abscission in Kalanchoe blossfeldiana. In present studies it was shown that JA-Me markedly increased the total activities of cellulase, polygalacturonase, pectinase and xylanase in petioles, but did not affect activities of these enzymes in the blades and apical part of shoots of K. blossfeldiana. These results suggest that methyl jasmonate promotes the degradation of cell wall polysaccharides in the abscission zone and in this way induces leaf abscission in Kalanchoe blossfeldiana.

  9. In vitro anticancer activity of methyl caffeate isolated from Solanum torvum Swartz. fruit.

    Science.gov (United States)

    Balachandran, C; Emi, N; Arun, Y; Yamamoto, Y; Ahilan, B; Sangeetha, B; Duraipandiyan, V; Inaguma, Yoko; Okamoto, Akinao; Ignacimuthu, S; Al-Dhabi, N A; Perumal, P T

    2015-12-05

    The present study was undertaken to investigate the anticancer activity of methyl caffeate isolated from Solanum torvum Swartz. fruit and to explore the molecular mechanisms of action in MCF-7 cells. Cytotoxic properties of hexane, ethyl acetate and methanol extracts were carried out against MCF-7 cells using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. Ethyl acetate extract showed good cytototoxic activities compared to hexane and methanol extracts. Methyl caffeate was isolated from the ethyl acetate extract using column chromatography. Cytotoxic properties of methyl caffeate was investigated against MCF-7, A549, COLO320, HepG-2 and Vero cells. The compound showed potent cytotoxic properties against MCF-7 cells compared to A549, COLO320 and HepG-2 cells. Methyl caffeate significantly reduced cell proliferation and increased formation of fragmented DNA and apoptotic body in MCF-7 cells. Bcl-2, Bax, Bid, p53, caspase-3, PARP and cytochrome c release were detected by western blot analysis. The activities of caspases-3 and PARP gradually increased after the addition of isolated compound. Bcl-2 protein was down regulated; Bid and Bax were up regulated after the treatment with methyl caffeate. Molecular docking studies showed that the compound bound stably to the active sites of poly (ADP-ribose) polymerase-1 (PARP1), B cell CLL/lymphoma-2 (BCL-2), E3 ubiquitin-protein ligase (MDM2) and tubulin. The results strongly suggested that methyl caffeate induced apoptosis in MCF-7 cells via caspase activation through cytochrome c release from mitochondria. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  10. Effect of salinity on mercury methylating benthic microbes and their activities in Great Salt Lake, Utah

    Science.gov (United States)

    Boyd, Eric S.; Yu, Ri-Qing; Barkay, Tamar; Hamilton, Trinity L.; Baxter, Bonnie K.; Naftz, David L.; Marvin-DiPasquale, Mark

    2017-01-01

    Surface water and biota from Great Salt Lake (GSL) contain some of the highest documented concentrations of total mercury (THg) and methylmercury (MeHg) in the United States. In order to identify potential biological sources of MeHg and controls on its production in this ecosystem, THg and MeHg concentrations, rates of Hg(II)-methylation and MeHg degradation, and abundances and compositions of archaeal and bacterial 16 rRNA gene transcripts were determined in sediment along a salinity gradient in GSL. Rates of Hg(II)-methylation were inversely correlated with salinity and were at or below the limits of detection in sediment sampled from areas with hypersaline surface water. The highest rates of Hg(II)-methylation were measured in sediment with low porewater salinity, suggesting that benthic microbial communities inhabiting less saline environments are supplying the majority of MeHg in the GSL ecosystem. The abundance of 16S rRNA gene transcripts affiliated with the sulfate reducer Desulfobacterium sp. was positively correlated with MeHg concentrations and Hg(II)-methylation rates in sediment, indicating a potential role for this taxon in Hg(II)-methylation in low salinity areas of GSL. Reactive inorganic Hg(II) (a proxy used for Hg(II) available for methylation) and MeHg concentrations were inversely correlated with salinity. Thus, constraints imposed by salinity on Hg(II)-methylating populations and the availability of Hg(II) for methylation are inferred to result in higher MeHg production potentials in lower salinity environments. Benthic microbial MeHg degradation was also most active in lower salinity environments. Collectively, these results suggest an important role for sediment anoxia and microbial sulfate reducers in the production of MeHg in low salinity GSL sub-habitats and may indicate a role for salinity in constraining Hg(II)-methylation and MeHg degradation activities by influencing the availability of Hg(II) for methylation.

  11. JPC-2997, a new aminomethylphenol with high in vitro and in vivo antimalarial activities against blood stages of Plasmodium.

    Science.gov (United States)

    Birrell, Geoffrey W; Chavchich, Marina; Ager, Arba L; Shieh, Hong-Ming; Heffernan, Gavin D; Zhao, Wenyi; Krasucki, Peter E; Saionz, Kurt W; Terpinski, Jacek; Schiehser, Guy A; Jacobus, Laura R; Shanks, G Dennis; Jacobus, David P; Edstein, Michael D

    2015-01-01

    4-(tert-Butyl)-2-((tert-butylamino)methyl)-6-(6-(trifluoromethyl)pyridin-3-yl)-phenol (JPC-2997) is a new aminomethylphenol compound that is highly active in vitro against the chloroquine-sensitive D6, the chloroquine-resistant W2, and the multidrug-resistant TM90-C2B Plasmodium falciparum lines, with 50% inhibitory concentrations (IC50s) ranging from 7 nM to 34 nM. JPC-2997 is >2,500 times less cytotoxic (IC50s > 35 μM) to human (HepG2 and HEK293) and rodent (BHK) cell lines than the D6 parasite line. In comparison to the chemically related WR-194,965, a drug that had advanced to clinical studies, JPC-2997 was 2-fold more active in vitro against P. falciparum lines and 3-fold less cytotoxic. The compound possesses potent in vivo suppression activity against Plasmodium berghei, with a 50% effective dose (ED50) of 0.5 mg/kg of body weight/day following oral dosing in the Peters 4-day test. The radical curative dose of JPC-2997 was remarkably low, at a total dose of 24 mg/kg, using the modified Thompson test. JPC-2997 was effective in curing three Aotus monkeys infected with a chloroquine- and pyrimethamine-resistant strain of Plasmodium vivax at a dose of 20 mg/kg daily for 3 days. At the doses administered, JPC-2997 appeared to be well tolerated in mice and monkeys. Preliminary studies of JPC-2997 in mice show linear pharmacokinetics over the range 2.5 to 40 mg/kg, a low clearance of 0.22 liters/h/kg, a volume of distribution of 15.6 liters/kg, and an elimination half-life of 49.8 h. The high in vivo potency data and lengthy elimination half-life of JPC-2997 suggest that it is worthy of further preclinical assessment as a partner drug. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  12. N-Methylated α-Amino Acids And Peptides: Synthesis And Biological Activity.

    Science.gov (United States)

    Di Gioia, Maria Luisa; Leggio, Antonella; Malagrinò, Francesca; Romio, Emanuela; Siciliano, Carlo; Liguori, Angelo

    2016-01-01

    The simplest and minimal modification of a single amino acid or peptide bonds is represented by N-methylation. This can improve the pharmacokinetic properties of biologically active peptides as well as resulting in analogues that show specific biological activity such as enzyme inhibitors, receptor antagonists and agonists, building blocks in combinatorial chemistry for the screening of new potential drugs. Further, structural and conformational studies performed with N-methylated analogues of natural amino acids and peptides enabled to (i) produce stable foldamers with different topology with respect to the helix of natural and endogenous peptides, (ii) confer to modified peptides high stability against proteases and (iii) enhance lipophilicity and bioavailability for pharmacological purposes. Consequentially, it is crucial to provide optically pure N-methyl-amino acids and N-methylated peptides with a large supply. The present report will focus on the results obtained in the last decade in the field of chemical synthetic methodologies for the N-methylation of amino acids.

  13. Synthesis of a high specific activity methyl sulfone tritium isotopologue of fevipiprant (NVP-QAW039).

    Science.gov (United States)

    Luu, Van T; Goujon, Jean-Yves; Meisterhans, Christian; Frommherz, Matthias; Bauer, Carsten

    2015-05-15

    The synthesis of a triple tritiated isotopologue of the CRTh2 antagonist NVP-QAW039 (fevipiprant) with a specific activity >3 TBq/mmol is described. Key to the high specific activity is the methylation of a bench-stable dimeric disulfide precursor that is in situ reduced to the corresponding thiol monomer and methylated with [(3)H3]MeONos having per se a high specific activity. The high specific activity of the tritiated active pharmaceutical ingredient obtained by a build-up approach is discussed in the light of the specific activity usually to be expected if hydrogen tritium exchange methods were applied. Copyright © 2015 John Wiley & Sons, Ltd.

  14. Microalgal fatty acid methyl ester a new source of bioactive compounds with antimicrobial activity

    Directory of Open Access Journals (Sweden)

    Arumugham Suresh

    2014-09-01

    Full Text Available Objective: To evaluate fatty acid composition and the antimicrobial activity of the major fraction of fatty acid methyl ester (FAME extracts from three microalgae collected from freshwater lakes in Theni District, Tamil Nadu, India. Methods: Antimicrobial study was carried out by well diffusion method against bacterial as well as fungal pathogens such as Escherichia coli, Staphylococcus aureus, Enterobacter sp., Klebsiella sp., Salmonella typhi, Fusarium sp., Cryptococcus sp., Candida sp., and Aspergillus niger and Aspergillus flavus. The FAME profiles were determined through gas chromatography with a flame ionization detector. Results: The FAME was found to be radial effective in inhibiting the radial growth of both bacterial and fungal pathogens. The FAME extracts exhibited the antibacterial activity against three clinical pathogens, namely, Escherichia coli, Salmonella typhi and Enterobacter sp. with the maximum zone of inhibition of 12.0 mm, 12.0 mm and 11.0 mm, respectively. The FAME showed moderate antifungal activity against Cryptococcus sp. (11.8 mm, Aspergillus niger (10.5 mm, Candida sp. (11.8 mm and Fusarium sp. (10.4 mm. Gas chromatography-flame ionization detector analysis revealed about 30 different FAMEs. Conclusions: We assume that the observed antimicrobial potency may be due to the abundance of erucic acid methyl ester (C22:0, arachidic acid methyl ester (C20:0, palmitic acid methyl ester (C16:0, cis-11-eicosenoicmethyl ester (C20:1, cis-11, 14-eicosadienoic acid methyl ester (C20:2 and linolenic acid methyl ester (C18:3 in FAMEs which appears to be promising to treat microbial diseases.

  15. Interplay between active chromatin marks and RNA-directed DNA methylation in Arabidopsis thaliana.

    Directory of Open Access Journals (Sweden)

    Maxim V C Greenberg

    2013-11-01

    Full Text Available DNA methylation is an epigenetic mark that is associated with transcriptional repression of transposable elements and protein-coding genes. Conversely, transcriptionally active regulatory regions are strongly correlated with histone 3 lysine 4 di- and trimethylation (H3K4m2/m3. We previously showed that Arabidopsis thaliana plants with mutations in the H3K4m2/m3 demethylase JUMONJI 14 (JMJ14 exhibit a mild reduction in RNA-directed DNA methylation (RdDM that is associated with an increase in H3K4m2/m3 levels. To determine whether this incomplete RdDM reduction was the result of redundancy with other demethylases, we examined the genetic interaction of JMJ14 with another class of H3K4 demethylases: lysine-specific demethylase 1-like 1 and lysine-specific demethylase 1-like 2 (LDL1 and LDL2. Genome-wide DNA methylation analyses reveal that both families cooperate to maintain RdDM patterns. ChIP-seq experiments show that regions that exhibit an observable DNA methylation decrease are co-incidental with increases in H3K4m2/m3. Interestingly, the impact on DNA methylation was stronger at DNA-methylated regions adjacent to H3K4m2/m3-marked protein-coding genes, suggesting that the activity of H3K4 demethylases may be particularly crucial to prevent spreading of active epigenetic marks. Finally, RNA sequencing analyses indicate that at RdDM targets, the increase of H3K4m2/m3 is not generally associated with transcriptional de-repression. This suggests that the histone mark itself--not transcription--impacts the extent of RdDM.

  16. Pharmacological activity of 2,3,8-tri-O-methyl ellagic acid isolated ...

    African Journals Online (AJOL)

    SERVER

    2007-08-20

    Aug 20, 2007 ... Full Length Research Paper. Pharmacological activity of 2,3,8-tri-O-methyl ellagic acid isolated from the stem bark of Irvingia gabonensis. George, I. Ndukwe 1* and Yimin Zhao2. 1Department of Chemistry, Ahmadu Bello University, Zaria, Nigeria. 2Beijing Institute of Pharmacology and Toxicology, Beijing, ...

  17. Activities of natural methyl farnesoids on pupariation and metamorphosis of Drosophila melanogaster

    Science.gov (United States)

    Methyl farnesoate (MF) and juvenile hormone (JH III), which respectively bind to the receptors USP and MET, and bisepoxy JH III (bisJHIII) were assessed for several activities during Drosophila larval development, and during prepupal development to eclosed adults. Dietary MF and JH III were similar...

  18. Conjugates of methylated cyclodextrin derivatives and hydroxyethyl starch (HES: Synthesis, cytotoxicity and inclusion of anaesthetic actives

    Directory of Open Access Journals (Sweden)

    Lisa Markenstein

    2014-12-01

    Full Text Available The mono-6-deoxy-6-azides of 2,6-di-O-methyl-β-cyclodextrin (DIMEB and randomly methylated-β-cyclodextrin (RAMEB were conjugated to propargylated hydroxyethyl starch (HES by Cu+-catalysed [2 + 3] cycloaddition. The resulting water soluble polymers showed lower critical solution temperatures (LCST at 52.5 °C (DIMEB-HES and 84.5 °C (RAMEB-HES, respectively. LCST phase separations could be completely avoided by the introduction of a small amount of carboxylate groups at the HES backbone. The methylated CDs conjugated to the HES backbone exhibited significantly lower cytotoxicities than the corresponding monomeric CD derivatives. Since the binding potentials of these CD conjugates were very high, they are promising candidates for new oral dosage forms of anaesthetic actives.

  19. hTERT promoter activity and CpG methylation in HPV-induced carcinogenesis

    Directory of Open Access Journals (Sweden)

    Snijders Peter JF

    2010-06-01

    Full Text Available Abstract Background Activation of telomerase resulting from deregulated hTERT expression is a key event during high-risk human papillomavirus (hrHPV-induced cervical carcinogenesis. In the present study we examined hTERT promoter activity and its relation to DNA methylation as one of the potential mechanisms underlying deregulated hTERT transcription in hrHPV-transformed cells. Methods Using luciferase reporter assays we analyzed hTERT promoter activity in primary keratinocytes, HPV16- and HPV18-immortalized keratinocyte cell lines and cervical cancer cell lines. In the same cells as well as cervical specimens we determined hTERT methylation by bisulfite sequencing analysis of the region spanning -442 to +566 (relative to the ATG and quantitative methylation specific PCR (qMSP analysis of two regions flanking the hTERT core promoter. Results We found that in most telomerase positive cells increased hTERT core promoter activity coincided with increased hTERT mRNA expression. On the other hand basal hTERT promoter activity was also detected in telomerase negative cells with no or strongly reduced hTERT mRNA expression levels. In both telomerase positive and negative cells regulatory sequences flanking both ends of the core promoter markedly repressed exogenous promoter activity. By extensive bisulfite sequencing a strong increase in CpG methylation was detected in hTERT positive cells compared to cells with no or strongly reduced hTERT expression. Subsequent qMSP analysis of a larger set of cervical tissue specimens revealed methylation of both regions analyzed in 100% of cervical carcinomas and 38% of the high-grade precursor lesions, compared to 9% of low grade precursor lesions and 5% of normal controls. Conclusions Methylation of transcriptionally repressive sequences in the hTERT promoter and proximal exonic sequences is correlated to deregulated hTERT transcription in HPV-immortalized cells and cervical cancer cells. The detection of DNA

  20. Design, Synthesis, and Safener Activity of Novel Methyl (R-N-Benzoyl/Dichloroacetyl-Thiazolidine-4-Carboxylates

    Directory of Open Access Journals (Sweden)

    Li-Xia Zhao

    2018-01-01

    Full Text Available A series of novel methyl (R-N-benzoyl/dichloroacetyl-thiazolidine-4-carboxylates were designed by active substructure combination. The title compounds were synthesized using a one-pot route from l-cysteine methyl ester hydrochloride, acyl chloride, and ketones. All compounds were characterized by IR, 1H NMR, 13C NMR, and HRMS. The structure of 4q was determined by X-ray crystallography. The biological tests showed that the title compounds protected maize from chlorimuron-ethyl injury to some extent. The ALS activity assay showed that the title compounds increased the ALS activity of maize inhibited by chlorimuron-ethyl. Molecular docking modeling demonstrated that Compound 4e competed against chlorimuron-ethyl to combine with the herbicide target enzyme active site, causing the herbicide to be ineffective.

  1. Synthesis, Characterization and Antimicrobial Activity of Imidazole Derivatives Based on 2-chloro-7-methyl-3-formylquinoline

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    R. H. Parab

    2012-01-01

    Full Text Available A series of oxazole and thereof imidazole derivatives were prepared from 2-chloro-7-methyl-3-formyl quinoline. The structures of all synthesized compounds were elucidated by elemental, IR, 1HNMR, 13CNMR spectra. Supplementary to these, they were assayed in vitro for their antimicrobial activity; it was revealed that some synthesized derivatives were exhibiting competent biological activity against both gram negative and gram positive bacterial species and fungal microorganisms.

  2. New Enantiomerically Pure Alkylimido Mo-Based Complexes. Synthesis, Characterization, and Activity as Chiral Olefin Metathesis Catalysts

    Science.gov (United States)

    Pilyugina, Tatiana S.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    Molybdenum olefin metathesis catalysts that contain aliphatic 1-phenylcyclohexylimido (NPhCy) and 2-phenyl-2-adamantylimido (NPhAd) groups and (S)-Biphen or (R)-Trip)(THF) ligands (Biphen = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate; Trip = 3,3′-bis(2,4,6-triisopropylphenyl)-2,2′-binaphtholate) have been prepared. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross-metathesis of substituted norborneols with styrene were compared to the results obtained with the only known alkylimido catalyst Mo(NAd)(CHCMe2Ph)[(S)-Biphen]. The activities and enantioselectivities provided by these new chiral complexes vary significantly, but in virtually all instances explored were not superior to the adamantylimido analogs. PMID:19079732

  3. Chromogenic radical based optical sensor membrane for screening of antioxidant activity.

    Science.gov (United States)

    Steinberg, Ivana Murković; Milardović, Stjepan

    2007-03-15

    Solid-state optical sensor membranes based on immobilised chromogenic radicals for the assessment of antioxidant activity have been studied. Two stable lipophilic chromogenic radicals, DPPH (2,2-diphenyl-1-picrylhydrazyl radical) and galvinoxyl radical, GV, (2,6-di-tert-butyl-alpha-(3,5-di-tert-butyl-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy radical), were immobilised in plasticised PVC films and screened for suitability as indicators of antioxidative activity. The spectrophotometric characterisation of the polymer films containing immobilised free radicals was performed, and the response of the immobilised free radicals toward standard antioxidants was studied. It has been demonstrated that the immobilised radicals retain their reactivity towards antioxidants and the results suggest that the reactivity of immobilised radicals is comparable to standard solution-based DPPH assays. Polymer films containing immobilised DPPH radical respond to standard antioxidants in aqueous solutions by changing colour irreversibly from purple (absorption maximum at 520nm) to yellow. The initial slopes of the response curves to the phenolic antioxidant gallic acid, obtained in the 1-50mM concentration range, gave a linear calibration plot in a 1min exposure cuvette test. The polymer films were used to screen antioxidative activity of beverage and food samples known to contain antioxidants, such as black and green tea, coffee, red wine, fruit juice, olive oil and sunflower oil. It has been demonstrated that a rapid and simple qualitative screening test of untreated samples is possible using a test strip based on immobilised DPPH radical.

  4. Physical properties and biological activities of hesperetin and naringenin in complex with methylated β-cyclodextrin

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    Waratchada Sangpheak

    2015-12-01

    Full Text Available The aim of this work is to improve physical properties and biological activities of the two flavanones hesperetin and naringenin by complexation with β-cyclodextrin (β-CD and its methylated derivatives (2,6-di-O-methyl-β-cyclodextrin, DM-β-CD and randomly methylated-β-CD, RAMEB. The free energies of inclusion complexes between hesperetin with cyclodextrins (β-CD and DM-β-CD were theoretically investigated by molecular dynamics simulation. The free energy values obtained suggested a more stable inclusion complex with DM-β-CD. The vdW force is the main guest–host interaction when hesperetin binds with CDs. The phase solubility diagram showed the formation of a soluble complex of AL type, with higher increase in solubility and stability when hesperetin and naringenin were complexed with RAMEB. Solid complexes were prepared by freeze-drying, and the data from differential scanning calorimetry (DSC confirmed the formation of inclusion complexes. The data obtained by the dissolution method showed that complexation with RAMEB resulted in a better release of both flavanones to aqueous solution. The flavanones-β-CD/DM-β-CD complexes demonstrated a similar or a slight increase in anti-inflammatory activity and cytotoxicity towards three different cancer cell lines. The overall results suggested that solubilities and bioactivities of both flavanones were increased by complexation with methylated β-CDs.

  5. Effect of benomyl and thiophanate-methyl on metabolic activities of Rhizoctonia solani Kühn.

    Science.gov (United States)

    Kataria, H R; Grover, R K

    1976-01-01

    Effect of benomyl and thiophanate-methyl on various metabolic activities of Rhizoctonia solani was investigated. Both fungitoxicants strongly reduced endogenous whole cell and mitochondrial respiration by inhibiting one or the other key enzymes of electron transport chain; the activity of cytochrome oxidase being most markedly inhibited. Incorporation of 3II-thymidine was reduced by both while there was little or no inhibition in the rate of incorporation of 14C-uracil and 14C-leucine. Cell permeability was not affected to any appreciable extent and there was a little release of cellular components from the treated cells only at prolonged incubation. It is concluded that benomyl and thiophanate-methyl have a similar mode of action which primarily involves inhibition of respiratory activities, and as a consequence the biosynthesis of DNA is reduced.

  6. Substituted Pyrazinecarboxamides: Synthesis and Biological Evaluation

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    Katarina Kralova

    2006-03-01

    Full Text Available Condensation of the corresponding chlorides of some substituted pyrazine-2-carboxylic acids (pyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 5-tert-butylpyrazine-2-carboxylic acid or 5-tert-butyl-6-chloropyrazine-2-carboxylic acid withvarious ring-substituted aminothiazoles or anilines yielded a series of amides. Thesyntheses, analytical and spectroscopic data of thirty newly prepared compounds arepresented. Structure-activity relationships between the chemical structures and the anti-mycobacterial, antifungal and photosynthesis-inhibiting activity of the evaluatedcompounds are discussed. 3,5-Bromo-4-hydroxyphenyl derivatives of substitutedpyrazinecarboxylic acid, 16-18, have shown the highest activity against Mycobacteriumtuberculosis H37Rv (54-72% inhibition. The highest antifungal effect againstTrichophyton mentagrophytes, the most susceptible fungal strain tested, was found for5-tert-butyl-6-chloro-N-(4-methyl-1,3-thiazol-2-ylpyrazine-2-carboxamide (8, MIC =31.25 μmol·mL-1. The most active inhibitors of oxygen evolution rate in spinachMolecules 2006, 11 243 chloroplasts were the compounds 5-tert-butyl-6-chloro-N-(5-bromo-2-hydroxyphenyl- pyrazine-2-carboxamide (27, IC50 = 41.9 μmol·L-1 and 5-tert-butyl-6-chloro-N-(1,3- thiazol-2-yl-pyrazine-2-carboxamide (4, IC50 = 49.5 μmol·L-1.

  7. Impact of sulfate deprivation and H2S exposure on the metabolites of the activated methyl cycle in Chinese cabbage

    NARCIS (Netherlands)

    Tseng, M.-H.; Yang, C.K.; Stuiver, C.E.E.; Chang, C.‐C.; De Kok, L.J.; De Kok, L.J.; Hawkesford, M.J.; Haneklaus, S.H.; Schnug, E.

    2017-01-01

    The activated methyl cycle is a central metabolic pathway used to generate (and recycle) several important sulfur-containing metabolites including methionine, S-adenosylmethionine (SAM) and S-adenosylhomocysteine (SAH) and enable methylation. We have developed a precise and sensitive method for the

  8. PTPRG inhibition by DNA methylation and cooperation with RAS gene activation in childhood acute lymphoblastic leukemia.

    Science.gov (United States)

    Xiao, Jianqiao; Lee, Seung-Tae; Xiao, Yuanyuan; Ma, Xiaomei; Houseman, E Andres; Hsu, Ling-I; Roy, Ritu; Wrensch, Margaret; de Smith, Adam J; Chokkalingam, Anand; Buffler, Patricia; Wiencke, John K; Wiemels, Joseph L

    2014-09-01

    While the cytogenetic and genetic characteristics of childhood acute lymphoblastic leukemias (ALL) are well studied, less clearly understood are the contributing epigenetic mechanisms that influence the leukemia phenotype. Our previous studies and others identified gene mutation (RAS) and DNA methylation (FHIT) to be associated with the most common cytogenetic subgroup of childhood ALL, high hyperdiploidy (having five more chromosomes). We screened DNA methylation profiles, using a genome-wide high-dimension platform of 166 childhood ALLs and 6 normal pre-B cell samples and observed a strong association of DNA methylation status at the PTPRG locus in human samples with levels of PTPRG gene expression as well as with RAS gene mutation status. In the 293 cell line, we found that PTPRG expression induces dephosphorylation of ERK, a downstream RAS target that may be critical for mutant RAS-induced cell growth. In addition, PTPRG expression is upregulated by RAS activation under DNA hypomethylating conditions. An element within the PTPRG promoter is bound by the RAS-responsive transcription factor RREB1, also under hypomethylating conditions. In conclusion, we provide evidence that DNA methylation of the PTPRG gene is a complementary event in oncogenesis induced by RAS mutations. Evidence for additional roles for PTPR family member genes is also suggested. This provides a potential therapeutic target for RAS-related leukemias as well as insight into childhood ALL etiology and pathophysiology. © 2014 UICC.

  9. Methylation of DACT2 promotes papillary thyroid cancer metastasis by activating Wnt signaling.

    Directory of Open Access Journals (Sweden)

    Zhiyan Zhao

    Full Text Available Thyroid cancer is the most common endocrine malignant disease and the incidence is increasing. DACT2 was found frequently methylated in human lung cancer and hepatocellular carcinoma. To explore the epigenetic change and the role of DACT2 in thyroid cancer, 7 thyroid cancer cell lines, 10 cases of non-cancerous thyroid tissue samples and 99 cases of primary thyroid cancer samples were involved in this study. DACT2 was expressed and unmethylated in K1, SW579, FTC-133, TT, W3 and 8505C cell lines. Loss of expression and complete methylation was found in TPC-1 cells. Restoration of DACT2 expression was induced by 5-aza-2'deoxycytidine treatment. It demonstrates that the expression of DACT2 was regulated by promoter region methylation. In human primary papillary thyroid cancer, 64.6% (64/99 was methylated and methylation of DACT2 was related to lymph node metastasis (p<0.01. Re-expression of DACT2 suppresses cell proliferation, invasion and migration in TPC-1 cells. The activity of TCF/LEF was inhibited by DACT2 in wild-type or mutant β-catenin cells. The activity of TCF/LEF was increased by co-transfecting DACT2 and Dvl2 in wild-type or mutant β-catenin cells. Overexpression of wild-type β-catenin promotes cell migration and invasion in DACT2 stably expressed cells. The expression of β-catenin, c-myc, cyclinD1 and MMP-9 were decreased and the level of phosphorylated β-catenin (p-β-catenin was increased after restoration of DACT2 expression in TPC-1 cells. The expression of β-catenin, c-myc, cyclinD1 and MMP-9 were increased and the level of p-β-catenin was reduced after knockdown of DACT2 in W3 and SW579 cells. These results suggest that DACT2 suppresses human papillary thyroid cancer growth and metastasis by inhibiting Wnt signaling. In conclusion, DACT2 is frequently methylated in papillary thyroid cancer. DACT2 expression was regulated by promoter region methylation. DACT2 suppresses papillary thyroid cancer proliferation and metastasis

  10. Facile synthesis of thick films of poly(methyl methacrylate), poly(styrene), and poly(vinyl pyridine) from Au surfaces.

    Science.gov (United States)

    Saha, Sampa; Bruening, Merlin L; Baker, Gregory L

    2011-08-01

    Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO(2) substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO(2) stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO(2) under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from noncross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to ∼100 °C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 h. At temperatures >100 °C, the polymer brush layers delaminate as large area films.

  11. Optical and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole and isocyanide, ethylenediamine, and diethyldithiocarbamate ligands

    Science.gov (United States)

    Katlenok, E. A.; Kinzhalov, M. A.; Eremina, A. A.; Balashev, K. P.

    2017-05-01

    The influence of donor-acceptor properties of tert-butyl-, 2.6-dimethylphenyl-, and 4-bromophenyl-isocyanides (BuNC, XylNC, BpNC), ethylenediamine (En), and diethyldithiocarbamate ions (Dtc-) on the 1H and 13C NMR, IR, optical, and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole is studied. Enhancement of the donor properties of BpNC, XylNC, BuNC, En, and Dtc- ligands leads to a bathochromic shift of metal-to-ligand charge transfer (MLCT) bands and to a decrease in the difference between the one-electron oxidation and reduction potentials of complexes. The bathochromic shift of the low-temperature phosphorescence of complexes in frozen (77 K) solutions with increasing donor properties of BpNC, XylNC, BuNC, En, and Dtc-ligands is caused by a decrease in the admixture of MLCT to the intraligand excited state of {Ir(bptz)2}. Quenching of the phosphorescence of complexes in liquid solutions is attributed to the thermally-induced population of excited d- d* states with subsequent nonradiative deactivation.

  12. Restriction-modification system with methyl-inhibited base excision and abasic-site cleavage activities.

    Science.gov (United States)

    Fukuyo, Masaki; Nakano, Toshiaki; Zhang, Yingbiao; Furuta, Yoshikazu; Ishikawa, Ken; Watanabe-Matsui, Miki; Yano, Hirokazu; Hamakawa, Takeshi; Ide, Hiroshi; Kobayashi, Ichizo

    2015-03-11

    The restriction-modification systems use epigenetic modification to distinguish between self and nonself DNA. A modification enzyme transfers a methyl group to a base in a specific DNA sequence while its cognate restriction enzyme introduces breaks in DNA lacking this methyl group. So far, all the restriction enzymes hydrolyze phosphodiester bonds linking the monomer units of DNA. We recently reported that a restriction enzyme (R.PabI) of the PabI superfamily with half-pipe fold has DNA glycosylase activity that excises an adenine base in the recognition sequence (5'-GTAC). We now found a second activity in this enzyme: at the resulting apurinic/apyrimidinic (AP) (abasic) site (5'-GT#C, # = AP), its AP lyase activity generates an atypical strand break. Although the lyase activity is weak and lacks sequence specificity, its covalent DNA-R.PabI reaction intermediates can be trapped by NaBH4 reduction. The base excision is not coupled with the strand breakage and yet causes restriction because the restriction enzyme action can impair transformation ability of unmethylated DNA even in the absence of strand breaks in vitro. The base excision of R.PabI is inhibited by methylation of the target adenine base. These findings expand our understanding of genetic and epigenetic processes linking those in prokaryotes and eukaryotes. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  13. 4-tert-Butyl-2-[2-(1,3,3-trimethylindolin-2-ylideneethylidene]cyclohexanone

    Directory of Open Access Journals (Sweden)

    Graeme J. Gainsford

    2011-05-01

    Full Text Available The title molecule, C23H31NO, has two alternative cyclohexanone configurations at the 4-position in a ratio of 0.663 (3:0.337 (3. The plane of the five-membered planar ring in the indolin-2-ylidene subtends an angle of 2.19 (7° with its fused aromatic ring, an angle of 16.24 (8° with the plane of the major cyclohexanone configuration and an angle of 8.54 (15° with the bridging planar ethylidene C atoms. These last atoms subtend an angle of 8.37 (16° with the mean plane through the major cyclohexanone configuration. The molecules pack approximately parallel to the (overline{1}01 plane via C—H...π and C—H...O interactions.

  14. tert-Butyl 2-{[5-(4-cyanophenylpyridin-3-yl]sulfonyl}acetate

    Directory of Open Access Journals (Sweden)

    H. C. Devarajegowda

    2014-04-01

    Full Text Available In the title compound, C18H18N2O4S, the dihedral angle between the aromatic rings is 33.71 (9° and an intramolecular C—H...O hydrogen bond closes an S(6 ring. In the crystal, molecules are linked by C—H...O and C—H...N hydrogen bonds to generate a three-dimensional network. A very weak aromatic π–π stacking interction is also observed [centroid–centroid separation = 3.9524 (10 Å].

  15. N-(Fluoren-9-ylmethoxycarbonyl-l-aspartic acid 4-tert-butyl ester

    Directory of Open Access Journals (Sweden)

    Kazuhiko Yamada

    2009-11-01

    Full Text Available The bond distances and bond angles of the title compound, C23H25NO6, are consistent with values typically found for fluoren-9-ylmethoxycarbonyl-protected amino acids. The conformations of the backbone and the side chain are slightly different from those of l-aspartic acid. The crystal structure exhibits two intermolecular hydrogen bonds, forming a two-dimensional sheet structure parallel to the ab plane.

  16. 3-tert-Butyl-4-oxo-3,4-dihydrophthalazin-1-yl 3,5-dimethylbenzoate

    Directory of Open Access Journals (Sweden)

    Dao-Xin Wu

    2008-01-01

    Full Text Available The title compound, C21H22N2O3, was synthesized by the reaction of tert-butylhydrazine with phthalic anhydride and further O-benzoylation of the resulting intermediate by 3,5-dimethylbenzoyl chloride. Intermolecular C—H...O=C interactions link the molecules into layers.

  17. 4,4′-Di-tert-butyl-2,2′-bipyridine

    Directory of Open Access Journals (Sweden)

    Tatiana R. Amarante

    2009-08-01

    Full Text Available In the title compound, C18H24N2, the molecular unit adopts a trans conformation around the central C—C bond [N—C—C—N torsion angle of 179.2 (3°], with the two aromatic rings almost coplanar [dihedral angle of only 0.70 (4°]. The crystal packing is driven by co-operative contacts involving weak C—H...N and C—H...π interactions, and also the need to fill effectively the available space.

  18. 4,6-Di-tert-butyl-2,3-di-hydroxy-benzalde-hyde.

    Science.gov (United States)

    Arsenyev, Max; Baranov, Eugene; Chesnokov, Sergey; Abakumov, Gleb

    2013-01-01

    The title compound, C15H22O3, crystallizes with two independent mol-ecules in the asymmetric unit. In each mol-ecule, one hy-droxy group (at position 2) is involved in an intra-molecular O-H⋯O hydrogen bond, and another one (at position 3) exhibits bifurcated hydrogen-bonding being involved in intra- and inter-molecular O-H⋯O inter-actions. In the crystal, O-H⋯O hydrogen bonds link alternating independent mol-ecules into chains running along [010].

  19. 4,6-Di-tert-butyl-2,3-dihydroxybenzaldehyde

    Directory of Open Access Journals (Sweden)

    Max Arsenyev

    2013-10-01

    Full Text Available The title compound, C15H22O3, crystallizes with two independent molecules in the asymmetric unit. In each molecule, one hydroxy group (at position 2 is involved in an intramolecular O—H...O hydrogen bond, and another one (at position 3 exhibits bifurcated hydrogen-bonding being involved in intra- and intermolecular O—H...O interactions. In the crystal, O—H...O hydrogen bonds link alternating independent molecules into chains running along [010].

  20. NecroX-7 prevents oxidative stress-induced cardiomyopathy by inhibition of NADPH oxidase activity in rats

    Energy Technology Data Exchange (ETDEWEB)

    Park, Joonghoon; Park, Eok; Ahn, Bong-Hyun; Kim, Hyoung Jin [LG Life Sciences Ltd., R and D Park, Daejeon, 305-380 (Korea, Republic of); Park, Ji-hoon [Department of Biochemistry, School of Medicine, Chungnam National University, Daejeon, 301-747 (Korea, Republic of); Koo, Sun Young; Kwak, Hyo-Shin; Park, Heui Sul; Kim, Dong Wook; Song, Myoungsub; Yim, Hyeon Joo; Seo, Dong Ook [LG Life Sciences Ltd., R and D Park, Daejeon, 305-380 (Korea, Republic of); Kim, Soon Ha, E-mail: shakim@lgls.com [LG Life Sciences Ltd., R and D Park, Daejeon, 305-380 (Korea, Republic of)

    2012-08-15

    Oxidative stress is one of the causes of cardiomyopathy. In the present study, NecroXs, novel class of mitochondrial ROS/RNS scavengers, were evaluated for cardioprotection in in vitro and in vivo model, and the putative mechanism of the cardioprotection of NecroX-7 was investigated by global gene expression profiling and subsequent biochemical analysis. NecroX-7 prevented tert-butyl hydroperoxide (tBHP)-induced death of H9C2 rat cardiomyocytes at EC{sub 50} = 0.057 μM. In doxorubicin (DOX)-induced cardiomyopathy in rats, NecroX-7 significantly reduced the plasma levels of creatine kinase (CK-MB) and lactate dehydrogenase (LDH) which were increased by DOX treatment (p < 0.05). Microarray analysis revealed that 21 genes differentially expressed in tBHP-treated H9C2 cells were involved in ‘Production of reactive oxygen species’ (p = 0.022), and they were resolved by concurrent NecroX-7 treatment. Gene-to-gene networking also identified that NecroX-7 relieved cell death through Ncf1/p47phox and Rac2 modulation. In subsequent biochemical analysis, NecroX-7 inhibited NADPH oxidase (NOX) activity by 53.3% (p < 0.001). These findings demonstrate that NecroX-7, in part, provides substantial protection of cardiomyopathy induced by tBHP or DOX via NOX-mediated cell death. -- Highlights: ► NecroX-7 prevented tert-butyl hydroperoxide-induced in vitro cardiac cell death. ► NecroX-7 ameliorated doxorubicin-induced in vivo cardiomyopathy. ► NecroX-7 prevented oxidative stress and necrosis-enriched transcriptional changes. ► NecroX-7 effectively inhibited NADPH oxidase activation. ► Cardioprotection of Necro-7 was brought on by modulation of NADPH oxidase activity.

  1. Atrazine exposure decreases the activity of DNMTs, global DNA methylation levels, and dnmt expression.

    Science.gov (United States)

    Wirbisky-Hershberger, Sara E; Sanchez, Oscar F; Horzmann, Katharine A; Thanki, Devang; Yuan, Chongli; Freeman, Jennifer L

    2017-11-01

    Atrazine, a herbicide used on agricultural crops is widely applied in the Midwestern United States as well as other areas of the globe. Atrazine frequently contaminates potable water supplies and is a suspected endocrine disrupting chemical. Previous studies have reported morphological, hormonal, and molecular alterations due to developmental and adulthood atrazine exposure; however, studies examining epigenetic alterations are limited. In this study, the effects of atrazine exposure on DNA methyltransferase (DNMT) activity and kinetics were evaluated. Global DNA methylation levels and dnmt expression in zebrafish larvae exposed to 0, 3, or 30 parts per billion (ppb) atrazine throughout embryogenesis was then assessed. Results indicate that atrazine significantly decreased the activity of maintenance DNMTs and that the inhibition mechanism can be described using non-competitive Michaelis-Menten kinetics. Furthermore, results show that an embryonic atrazine exposure decreases global methylation levels and the expression of dnmt4 and dnmt5. These findings indicate that atrazine exposure can decrease the expression and activity of DNMTs, leading to decreased DNA methylation levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. New Synthesis and Antiparasitic Activity of Model 5-Aryl-1-methyl-4-nitroimidazoles

    Directory of Open Access Journals (Sweden)

    Mustafa M. El-Abadelah

    2009-07-01

    Full Text Available A number of 5-aryl-1-methyl-4-nitroimidazoles 5a-f have been synthesized in good yields by the Suzuki coupling reaction between 5-chloro-1-methyl-4-nitroimidazole (3 and arylboronic acids 4a-f, aided by dichlorobis-(triphenylphosphinepalladium(II, K2CO3, and tetrabutylammonium bromide in water at 70-80 °C. Compounds 5a-f were characterized by elemental analysis, NMR and MS spectral data. On the basis of in vitro screening data, 5-(3-chlorophenyl-1-methyl-4-nitro-1H-imidazole (5fexhibited potent lethal activity against Entamoeba histolytica and Giardia intestinalis with IC50 = 1.47 µM/mL, a value lower by a factor of two than that of the standard drug, metronidazole. The boosted activity of 5f was not accompanied by any increased cytotoxicity.The rest of the series also exhibited potent antiparasitic activity with IC50 valuesin the 1.72-4.43 µM/mL range. The cytotoxicity of the derivatives 5c and 5e was increased compared to the precursor compound, metronidazole, although they remain non-cytotoxic at concentrations much higher than the antiparasitic concentration of the two derivatives.

  3. Using DNA-Stable Isotope Probing to Identify MTBE- and TBA-Degrading Microorganisms in Contaminated Groundwater

    Science.gov (United States)

    Key, Katherine C.; Sublette, Kerry L.; Duncan, Kathleen; Mackay, Douglas M.; Scow, Kate M.; Ogles, Dora

    2014-01-01

    Although the anaerobic biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with 13C5-MTBE, 13C1-MTBE (only methoxy carbon labeled), or13C4-TBA. 13C-DNA and 12C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert-butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading 13C-labeled MTBE and TBA in situ and the 13C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three13C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with 13C, suggesting that they were involved in processing carbon from the tert-butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with 13C. It is likely that members of this genus were secondary degraders cross-feeding on 13C-labeled metabolites such as acetate. PMID:25525320

  4. Acid activated montmorillonite as catalysts in methyl esterification reactions of lauric acid.

    Science.gov (United States)

    Zatta, Leandro; Ramos, Luiz Pereira; Wypych, Fernando

    2012-01-01

    The catalytic activity of acid activated montmorillonite in the esterification of free fatty acids (FFA) is reported. Standard Montmorillonite (MMT) type STx-1 provided by the Clay Mineral Society repository was activated using phosphoric, nitric and sulphuric acids under different conditions and the resulting materials were characterized and evaluated as catalysts in the methyl esterification of lauric acid. Blank reactions carried out in the absence of any added catalyst presented conversions of 32.64, 69.79 and 79.23%, for alcohol:lauric acid molar ratios of 60:1, 12:1 and 6:1, respectively. In the presence of the untreated clay and using molar ratios of 12:1 and 6:1 with 12% of catalyst, conversions of 70.92 and 82.30% were obtained, respectively. For the acid activated clays, conversions up to 93.08% of lauric acid to methyl laurate were obtained, much higher than those observed for the thermal conversion or using untreated montmorillonite. Relative good correlations were observed between the catalytic activity and the development of acid sites and textural properties of the resulting materials. Therefore, a simple acid activation was able to improve the catalytic activity and produce clay catalysts that are environmental friendly, cost effective, noncorrosive and reusable.

  5. Ellagic acid and its methyl-derivatives inhibit a newly found nitratase activity.

    Science.gov (United States)

    Léger, Claude L; Torres-Rasgado, Enrique; Fouret, Gilles; Lauret, Céline; Carbonneau, Marie-Annette

    2010-02-01

    We have recently shown that low density lipoprotein (LDL) was able to denitrate albumin-bound 3-NO(2)-Tyr residues and to concomitantly release NO(3)(-) through a Ca(2+)-dependent process that has been ascribed to a specific protein structure. A lipophilic food component (gamma-tocopherol), which is easily loaded into LDL has been found to totally inhibit denitrating activity. We presently found that ellagic acid (EA) and its methylated derivatives, 4,4'O-methyl- and 3,3'O-methyl-ellagic acids (MeEA1 and MeEA2, respectively), amphipathic phenolic components of certain fruits and beverages, were also able to inhibit this activity, with a total inhibition for EA and a 60% inhibition for MeEA1 and MeEA2. EA exhibited the highest affinity for protein plasma, whereas a higher affinity of MeEA1 and MeEA2 (with MeEA1 > MeEA2) than EA was found for lipoprotein fractions, suggesting that the inhibition-driving property is protein affinity. As a result of this nitratase-inhibition property EA and its natural metabolite MeEA2 may have a beneficial role in special physiopathological conditions.

  6. Synthesis of 1-isopropyl-3-acyl-5-methyl-benzimidazolone Derivatives and Their Antimicrobial Activity

    Directory of Open Access Journals (Sweden)

    Shaopeng Wei

    2013-03-01

    Full Text Available A series of N-acylated analogues of 1-isopropyl-3-acyl-5-methyl-benzimidazolone were synthesized. Bioassay results indicated that analogues 5-07 and 5-19 exhibited the most potency against Bacillus cereus, Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. Analogues 5-02, 5-07, 5-12, 5-15, 5-19, 5-20 and 5-25 could effectively inhibit the spore germination of Botrytis cinerea. The relationship between structure and their antimicrobial activity (SAR has also been discussed according to aliphatic acids and aromatic acids derivatives, respectively. This implied that the N-acylated derivatives of 5-methyl-benzimidazolone might be potential antimicrobial agents.

  7. Structure/activity Relationship of Thapsigargin Inhibition on the Purified Golgi/secretory Pathway Ca2+/Mn2+ Transport ATPase (SPCA1a)

    DEFF Research Database (Denmark)

    Jialin, Chen; de Raeymaecker, Joren; Hovgaard, Jannik Brøndsted

    2017-01-01

    activity. Moreover, SPCA1a is blocked by μM concentrations of commonly used SERCA1a inhibitors thapsigargin (Tg), cyclopiazonic acid (CPA) and 2,5-di-tert-butyl hydroquinone (BHQ). Since tissue-specific targeting of SERCA2b by Tg analogues is considered for prostate cancer therapy, the inhibition of SPCA1a......, but with lower affinity to the same homologous cavity as on the membrane surface of SERCA1a. The lower Tg affinity may depend on a more flexible binding cavity in SPCA1a, with low contributions of the Tg O-3, O-8 and O-10 chains to the binding energy. Conversely, the protein interaction of the Tg O-2 side chain...

  8. Glucocorticoid receptor activation selectively hampers N-methyl-d-aspartate receptor dependent hippocampal synaptic plasticity in vitro.

    NARCIS (Netherlands)

    Wiegert, O.; Pu, Z.; Shor, S.; Joëls, M.; Krugers, H.

    2005-01-01

    Corticosterone and exposure to stressful experiences have been reported to decrease hippocampal synaptic plasticity, in particular when relatively mild stimulation paradigms-presumably activating predominantly N-methyl-d-aspartate receptors-are being used. Using various stimulation paradigms and

  9. Biological activities of essential oils of Endlicheria citriodora, a methyl geranate-rich lauraceae

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Klenicy K.L.; Veiga-Junior, Valdir F., E-mail: valdirveiga@ufam.edu.br [Departamento de Quimica, Instituto de Ciencias Exatas, Universidade Federal do Amazonas, Manaus - AM (Brazil); Pedrosa, Tatiana do Nascimento; Vasconcellos, Marne Carvalho de; Lima, Emerson Silva [Faculdade de Ciencias Farmaceuticas, Universidade Federal do Amazonas, Manaus, AM (Brazil)

    2013-09-01

    The essential oils of branches and leaves of Endlicheria citiodora were obtained by hydrodistillation and analysed using GC-FID, GC-MS and both NMR {sup 13}C and {sup 1}H, resulting in the identification of methyl geranate as major constituent (93%) in both oils. Cytotoxicity, tyrosinase-inhibition and antioxidant activities were studied and characterized. High antioxidant potential (15.52 and 13.53 {mu}g/mL), low cytotoxicity and tyrosinase inhibition (53.85%) were observed. This is the first paper reporting the biological activities and composition of the essential oils of this species. (author)

  10. Cyclical DNA Methylation and Histone Changes Are Induced by LPS to Activate COX-2 in Human Intestinal Epithelial Cells.

    Directory of Open Access Journals (Sweden)

    Tiziana Angrisano

    Full Text Available Bacterial lipopolysaccharide (LPS induces release of inflammatory mediators both in immune and epithelial cells. We investigated whether changes of epigenetic marks, including selected histone modification and DNA methylation, may drive or accompany the activation of COX-2 gene in HT-29 human intestinal epithelial cells upon exposure to LPS. Here we describe cyclical histone acetylation (H3, methylation (H3K4, H3K9, H3K27 and DNA methylation changes occurring at COX-2 gene promoter overtime after LPS stimulation. Histone K27 methylation changes are carried out by the H3 demethylase JMJD3 and are essential for COX-2 induction by LPS. The changes of the histone code are associated with cyclical methylation signatures at the promoter and gene body of COX-2 gene.

  11. Antihyperglycemic activity and antidiabetic effect of methyl caffeate isolated from Solanum torvum Swartz. fruit in streptozotocin induced diabetic rats.

    Science.gov (United States)

    Gandhi, Gopalsamy Rajiv; Ignacimuthu, Savarimuthu; Paulraj, Michael Gabriel; Sasikumar, Ponnusamy

    2011-11-30

    Natural remedies from medicinal plants are considered to be effective and safe alternatives to treat diabetes mellitus. Solanum torvum Swartz. fruit is widely used in the traditional system of medicine to treat diabetes. In the present study methyl caffeate, isolated from S. torvum fruit, was screened for its efficacy in controlling diabetes in animal models. Antihyperglycemic effect of methyl caffeate was studied in normal glucose-fed rats. The effects of oral administration of methyl caffeate (10, 20 and 40 mg/kg) for 28 days on body weight, fasting blood glucose, plasma insulin, hemoglobin, glycated hemoglobin, total protein, hepatic glycogen and carbohydrate metabolism enzymes in streptozotocin induced diabetic rats were investigated. Histological observations in the pancreas and GLUT4 expression in skeletal muscles were also studied. Methyl caffeate at 40 mg/kg significantly prevented the increase in blood glucose level after glucose administration at 60 min in comparison to the hyperglycemic control group. In streptozotocin induced diabetic rats, methyl caffeate produced significant reduction in blood glucose and increased body weight. The levels and/or activities of other biochemical parameters were near normal due to treatment with methyl caffeate. Methyl caffeate treated diabetic rats showed upregulation of GLUT4 and regeneration of β-cells in the pancreas. These results substantiated that methyl caffeate possessed hypoglycemic effect, and it could be developed into a potent oral antidiabetic drug. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Antifungal and antioxidant activity of fatty acid methyl esters from vegetable oils

    Directory of Open Access Journals (Sweden)

    MARIA E.A. PINTO

    2017-08-01

    Full Text Available ABSTRACT Fatty acid methyl esters (FAMEs were obtained from vegetable oils of soybean, corn and sunflower. The current study was focused on evaluating the antifungal activity of FAMEs mainly against Paracoccidioides spp., as well as testing the interaction of these compounds with commercial antifungal drugs and also their antioxidant potential. FAMEs presented small IC50 values (1.86-9.42 μg/mL. All three FAMEs tested showed antifungal activity against isolates of Paracoccidioides spp. with MIC values ranging from 15.6-500 µg/mL. Sunflower FAMEs exhibited antifungal activity that extended also to other genera, with an MIC of 15.6 μg/mL against Candida glabrata and C. krusei and 31.2 μg/mL against C. parapsilosis. FAMEs exhibited a synergetic effect with itraconazole. The antifungal activity of the FAMEs against isolates of Paracoccidioides spp. is likely due to the presence of methyl linoleate, the major compound present in all three FAMEs. The results obtained indicate the potential of FAMEs as sources for antifungal and antioxidant activity.

  13. Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study.

    Science.gov (United States)

    Li, Youji; Li, Xiaodong; Li, Junwen; Yin, Jing

    2006-03-01

    TiO2-coated activated carbon (AC) grain (TiO2/AC) was prepared through hydrolytic precipitation of TiO2 from Tetrabutylorthotitanate and following heat treatment. The TiO2/AC was characterized by BET, SEM, XRD and optical absorption spectroscopy. The samples were employed as catalysts for methyl orange photocatalytic oxidation degradation in aqueous suspension, used as probe reaction. The kinetics of methyl orange photodegradation was analyzed. The results indicate that BET surface area of TiO2-coated ACs decreased drastically in comparison with the original AC with increasing TiO2 coatings by more than 1 doped cycle. Nano-TiO2 particles were dispersed on the AC with the size of 20-40 nm. Crystalline TiO2 doped onto AC was from anatase to rutile with increase of heat-treatment temperature. The TiO2/AC was shown high photoactivity for the photodegradation of methyl orange (MO) dyestuff in aqueous solution under UV irradiation. The kinetics of photocatalytic MO dyestuff degradation was found to follow a pseudo-first-order rate law. It was observed that the presence of the AC enhanced the photoefficiency of the titanium dioxide catalyst. Different amount of TiO2 coatings induced different increases in the apparent first-order rate constant of the process. The kinetic behavior could be described in terms of a modified Langmuir-Hinshelwood model. The values of the adsorption equilibrium constants for the organic molecules, KC, and for the rate constants, kc, were certainly dependent on TiO2 content. At 47wt% TiO2 coatings with the highest rate constant, the KC and kc was 0.1116l mmol(-1) and 0.1872 mmol l(-1) min(-1), respectively. The mechanism of methyl orange degradation was discussed in terms of the titanium dioxide photosensitization by the AC.

  14. Planar chiral (η6-arene)Cr(CO)3 containing carboxylic acid derivatives: synthesis and use in the preparation of organometallic analogues of the antibiotic platensimycin.

    Science.gov (United States)

    Patra, Malay; Merz, Klaus; Metzler-Nolte, Nils

    2012-01-07

    With more and more organometallic compounds receiving attention for applications in medicinal organometallic chemistry, the need arises for stereoselective syntheses of more complicated structures containing organometallic moieties, for example as isosteric substitutes for organic drug candidates. Herein, the synthesis and characterization of both diastereomers of a planar chiral (η(6)-arene)Cr(CO)(3) containing carboxylic acid derivative, namely, 3-{η(6)-(1, 2, 3, 4-tetrahydro-1-endo/exo-methyl-2-oxonaphthalen-1-yl)-tricarbonylchromium(0)}propanoic acid (7 and 8) is reported. The molecular structures of both were confirmed by single crystal X-ray diffraction. The degree of diastereoselectivity in Cr(CO)(3) complexation with methyl/tert-butyl-3-(1,2,3,4-tetrahydro-1-methyl-2-oxonaphthalen-1-yl)propanoate (4a/4b) vs. the Michael addition of methyl/tert-butyl acrylate to (η(6)-1-methyl-2-tetralone)Cr(CO)(3) (9) was also examined. In the latter case the alkylation was found to be completely diastereoselective and gave methyl/tert-butyl-3-{η(6)-(1, 2, 3, 4-tetrahydro-1-endo-methyl-2-oxonaphthalen-1-yl)-tricarbonylchromium (0)}propanoate (5a and 5b) in excellent yield. Both the carboxylic acids 7 and 8 were coupled with the aminoresorcyclic acid core to achieve diastereomeric bioorganometallics 15a and 15b based on the naturally occurring antibiotic platensimycin lead structure (1a, see Fig. 1). The newly synthesized bioorganometallics were tested against various Gram-positive and Gram-negative bacterial strains but show no promising antibacterial activity.

  15. Anatase TiO{sub 2} hierarchical nanospheres with enhanced photocatalytic activity for degrading methyl orange

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Liqin; Xu, Wence [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Zhu, Shengli, E-mail: slzhu@tju.edu.cn [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Cui, Zhenduo [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Yang, Xianjin [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin, 300072 (China); Inoue, Akihisa [School of Materials Science and Engineering, Tianjin University, Tianjin, 300072 (China); International Institute of Green Materials, Josai International University, Togane, 283-8555 (Japan)

    2016-02-15

    Anatase TiO{sub 2} hierarchical nanospheres were synthesized through a simple way combining dealloying and hydrothermal methods. The photocatalytic activity of the obtained products and Degussa P25 were evaluated by the degradation of methyl orange (MO) aqueous solution at different initial pH values and concentrations. The anatase TiO{sub 2} hierarchical nanospheres exhibited excellent photocatalytic activity for the degradation of methyl orange under ultraviolet–visible light irradiation. The photocatalytic efficiency of the anatase TiO{sub 2} increased with the decrease of pH at first then decreased and it also decreased with the increase of MO concentration. The superior photocatalytic performance of anatase TiO{sub 2} hierarchical nanospheres is attributed to its crystal phase, microstructure, and particularly surface acidity. The enhancement of surface acidity reduces the electron–hole pair recombination, and further increases the photocatalytic efficiency. - Highlights: • Anatase TiO{sub 2} nanospheres was prepared by chemical dealloying method. • The anatase TiO{sub 2} nanospheres exhibited good photocatalytic activity. • Sulfate ions adsorbed on TiO{sub 2} was beneficial for the photocatalytic performance.

  16. Control of anthracnose disease via increased activity of defence related enzymes in 'Hass' avocado fruit treated with methyl jasmonate and methyl salicylate.

    Science.gov (United States)

    Glowacz, Marcin; Roets, Nico; Sivakumar, Dharini

    2017-11-01

    Development of anthracnose disease caused by Colletotrichum gloeosporioides Penz. is one of the major issues within the avocado supply chain. Exposure to methyl jasmonate (MeJA) and methyl salicylate (MeSA) vapours at 10 and 100µmoll(-1) was investigated as an alternative solution to commercial fungicide - prochloraz® that is currently being used by the industry. The incidence of anthracnose disease was found to be significantly reduced in 'Hass' avocado fruit treated with MeJA or MeSA vapours, especially at 100μmoll(-1). The mechanism involved enhanced activity of defence related enzymes, i.e. chitinase, β-1,3-glucanase and PAL, and higher content of epicatechin. Copyright © 2017. Published by Elsevier Ltd.

  17. 1-Methyl-3-octylimidazolium Chloride—Sorption and Primary Biodegradation Analysis in Activated Sewage Sludge

    Directory of Open Access Journals (Sweden)

    Monika Paszkiewicz

    2009-11-01

    Full Text Available Ionic liquids (ILs are known to be non-volatile and thus to have low potential for atmospheric contamination or intoxication of humans by inhalation. However ILs have the potential to contaminate soil and water as they might be water soluble and can be sorbed onto solids. The investigation of possible natural ways of reducing the concentration of ILs in the environment is of high importane, especially because the requirement for biodegradable chemicals increases, together with pressure for reduction of incineration and landfill waste. It was found that the upper concentration threshold for primary biodegradation of 1-methyl-3-octylimidazolium chloride is 0.2 mM. At higher concentrations the dehydrogenase activity of the cells dropped markedly, indicating that the IL inhibits cell activity. This concentration is in good agreement with the minimal inhibitory concentration of the same compound found for a series of bacteria and fungi by this research group. The sorption of 1-methyl-3-octylimidazolium chloride was found to be significant, and the sorption coefficient was determined to be 98.2 L kg-1.

  18. Methylated Cytokinins from the Phytopathogen Rhodococcus fascians Mimic Plant Hormone Activity1[OPEN

    Science.gov (United States)

    Radhika, Venkatesan; Ueda, Nanae; Tsuboi, Yuuri; Kojima, Mikiko; Kikuchi, Jun; Kudo, Takuji; Sakakibara, Hitoshi

    2015-01-01

    Cytokinins (CKs), a class of phytohormones that regulate plant growth and development, are also synthesized by some phytopathogens to disrupt the hormonal balance and to facilitate niche establishment in their hosts. Rhodococcus fascians harbors the fasciation (fas) locus, an operon encoding several genes homologous to CK biosynthesis and metabolism. This pathogen causes unique leafy gall symptoms reminiscent of CK overproduction; however, bacterial CKs have not been clearly correlated with the severe symptoms, and no virulence-associated unique CKs or analogs have been identified. Here, we report the identification of monomethylated N6-(∆2-isopentenyl)adenine and dimethylated N6-(∆2-isopentenyl)adenine (collectively, methylated cytokinins [MeCKs]) from R. fascians. MeCKs were recognized by a CK receptor and up-regulated type-A ARABIDOPSIS THALIANA RESPONSE REGULATOR genes. Treatment with MeCKs inhibited root growth, a hallmark of CK action, whereas the receptor mutant was insensitive. MeCKs were retained longer in planta than canonical CKs and were poor substrates for a CK oxidase/dehydrogenase, suggesting enhanced biological stability. MeCKs were synthesized by S-adenosyl methionine-dependent methyltransferases (MT1 and MT2) that are present upstream of the fas genes. The best substrate for methylation was isopentenyl diphosphate. MT1 and MT2 catalyzed distinct methylation reactions; only the MT2 product was used by FAS4 to synthesize monomethylated N6-(∆2-isopentenyl)adenine. The MT1 product was dimethylated by MT2 and used as a substrate by FAS4 to produce dimethylated N6-(∆2-isopentenyl)adenine. Chemically synthesized MeCKs were comparable in activity. Our results strongly suggest that MeCKs function as CK mimics and play a role in this plant-pathogen interaction. PMID:26251309

  19. Methylated Cytokinins from the Phytopathogen Rhodococcus fascians Mimic Plant Hormone Activity.

    Science.gov (United States)

    Radhika, Venkatesan; Ueda, Nanae; Tsuboi, Yuuri; Kojima, Mikiko; Kikuchi, Jun; Kudo, Takuji; Sakakibara, Hitoshi

    2015-10-01

    Cytokinins (CKs), a class of phytohormones that regulate plant growth and development, are also synthesized by some phytopathogens to disrupt the hormonal balance and to facilitate niche establishment in their hosts. Rhodococcus fascians harbors the fasciation (fas) locus, an operon encoding several genes homologous to CK biosynthesis and metabolism. This pathogen causes unique leafy gall symptoms reminiscent of CK overproduction; however, bacterial CKs have not been clearly correlated with the severe symptoms, and no virulence-associated unique CKs or analogs have been identified. Here, we report the identification of monomethylated N(6)-(∆(2)-isopentenyl)adenine and dimethylated N(6)-(∆(2)-isopentenyl)adenine (collectively, methylated cytokinins [MeCKs]) from R. fascians. MeCKs were recognized by a CK receptor and up-regulated type-A ARABIDOPSIS THALIANA RESPONSE REGULATOR genes. Treatment with MeCKs inhibited root growth, a hallmark of CK action, whereas the receptor mutant was insensitive. MeCKs were retained longer in planta than canonical CKs and were poor substrates for a CK oxidase/dehydrogenase, suggesting enhanced biological stability. MeCKs were synthesized by S-adenosyl methionine-dependent methyltransferases (MT1 and MT2) that are present upstream of the fas genes. The best substrate for methylation was isopentenyl diphosphate. MT1 and MT2 catalyzed distinct methylation reactions; only the MT2 product was used by FAS4 to synthesize monomethylated N(6)-(∆(2)-isopentenyl)adenine. The MT1 product was dimethylated by MT2 and used as a substrate by FAS4 to produce dimethylated N(6)-(∆(2)-isopentenyl)adenine. Chemically synthesized MeCKs were comparable in activity. Our results strongly suggest that MeCKs function as CK mimics and play a role in this plant-pathogen interaction. © 2015 American Society of Plant Biologists. All Rights Reserved.

  20. Synthesis, Structure and Properties of Various Molecules Based on the 4,8,12-trioxa-4,8,12,12c-tetrahydrodibenzo[cd,mn]pyrene System With an Evaluation of the Effect Differing Molecular Substitution Patterns Has on the Space Group Symmetry

    DEFF Research Database (Denmark)

    Faldt, André; Krebs, Frederik C; Thorup, Niels

    1997-01-01

    4,8,12-Trioxa-4,8,12,12c-tetrahydrodibenzo [cd,mn]pyrene (3),2,6,10-tri-tert-butyl-4,8,12 -trioxa-4,8,12,12c-tetrahydrodibenzo [cd,mn]pyrene (11) and 2,6,10-tri-tert-butyl-4,8,12-trioxa-12c -methyl-4,8,12,12c -tetrahydrodibenzo[cd,mn]pyrene (12)have been synthesised and their crystal structures d...

  1. Regulation of GLUT4 activity in myotubes by 3-O-methyl-d-glucose.

    Science.gov (United States)

    Shamni, Ofer; Cohen, Guy; Gruzman, Arie; Zaid, Hilal; Klip, Amira; Cerasi, Erol; Sasson, Shlomo

    2017-10-01

    The rate of glucose influx to skeletal muscles is determined primarily by the number of functional units of glucose transporter-4 (GLUT4) in the myotube plasma membrane. The abundance of GLUT4 in the plasma membrane is tightly regulated by insulin or contractile activity, which employ distinct pathways to translocate GLUT4-rich vesicles from intracellular compartments. Various studies have indicated that GLUT4 intrinsic activity is also regulated by conformational changes and/or interactions with membrane components and intracellular proteins in the vicinity of the plasma membrane. Here we show that the non-metabolizable glucose analog 3-O-methyl-d-glucose (MeGlc) augmented the rate of hexose transport into myotubes by increasing GLUT4 intrinsic activity without altering the content of the transporter in the plasma membrane. This effect was not a consequence of ATP depletion or hyperosmolar stress and did not involve Akt/PKB or AMPK signal transduction pathways. MeGlc reduced the inhibitory potency (increased Ki) of indinavir, a selective inhibitor of GLUT4, in a dose-dependent manner. Kinetic analyses indicate that MeGlc induced changes in GLUT4 or GLUT4 complexes within the plasma membrane, which enhanced the hexose transport activity and reduced the potency of indinavir inhibition. Finally, we present a simple kinetic analysis for screening and discovering low molecular weight compounds that augment GLUT4 activity. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Preparation and characterization of silver nanoparticles in methyl cellulose matrix and their antibacterial activity

    Science.gov (United States)

    Kolarova, Katerina; Samec, Daniel; Kvitek, Ondrej; Reznickova, Alena; Rimpelova, Silvie; Svorcik, Vaclav

    2017-06-01

    In this work we present in situ preparation of silver nanoparticles (NPs) by reduction of silver nitrate by methyl cellulose (MC). The aim of this study was to prepare a stable solution of MC-Ag, convert it to solid film, redissolve it and determine how this process influences the form and properties of the prepared NPs. MC was analysed by UV-vis spectrometry, transmission electron microscopy and X-ray photoelectron spectroscopy; it was studied in forms of a solution and as a solid film. We also evaluated the antibacterial activity and material properties of prepared films. Our results indicate that the size and distribution of particles are not negatively influenced by the conversion process. These findings can be used for preparation of antibacterial films or as a way of nanoparticle storage.

  3. Two-year drinking water carcinogenicity study of methyl tertiary-butyl ether (MTBE) in Wistar rats.

    Science.gov (United States)

    Dodd, Darol; Willson, Gabrielle; Parkinson, Horace; Bermudez, Edilberto

    2013-07-01

    Methyl tertiary-butyl ether (MTBE) has been used as a gasoline additive to reduce tailpipe emissions and its use has been discontinued. There remains a concern that drinking water sources have been contaminated with MTBE. A two-year drinking water carcinogenicity study of MTBE was conducted in Wistar rats (males, 0, 0.5, 3, 7.5 mg ml(-1); and females, 0, 0.5, 3, and 15 mg ml(-1)). Body weights were unaffected and water consumption was reduced in MTBE-exposed males and females. Wet weights of male kidneys were increased at the end of two years of exposure to 7.5 mg ml(-1) MTBE. Chronic progressive nephropathy was observed in males and females, was more severe in males, and was exacerbated in the high MTBE exposure groups. Brain was the only tissue with a statistically significant finding of neoplasms. One astrocytoma (1/50) was found in a female rat (15 mg ml(-1)). The incidence of brain astrocytomas in male rats was 1/50, 1/50, 1/50 and 4/50 for the 0, 0.5, 3 and 7.5 mg ml(-1) exposure groups, respectively. This was a marginally significant statistical trend, but not statistically significant when pairwise comparisons were made or when multiple comparisons were taken into account. The incidence of astrocytoma fell within historical control ranges for Wistar rats, and the brain has not been identified as a target organ following chronic administration of MTBE, ethyl tert-butyl ether, or tertiary butyl alcohol (in drinking water) to mice and rats. We conclude that the astrocytomas observed in this study are not associated with exposure to MTBE. Copyright © 2011 John Wiley & Sons, Ltd.

  4. Effect of methyl parathion on the muscle and brain acetylcholinesterase activity of matrinxã (Brycon cephalus

    Directory of Open Access Journals (Sweden)

    Almeida Luciana Cristina de

    2005-01-01

    Full Text Available Farming of the freshwater fish is emerging in Brazil and many species from the wild are promising. The teleost matrinxã (Brycon cephalus holds several characteristics such as fast growth rate, high commercial value and adaptability to artificial raring conditions, which make it a promising species for commerce. The use of pesticides in aquatic environment is frequent in Brazil, and methyl parathion is very common in aquaculture. We have determined the enzymatic activity of acetyl cholinesterase in white muscle and brain of matrinxã exposed to 2ppm of environmental methyl parathion for 24 hours. There was 64% and 69% of acetyl cholinesterase inhibition in muscle and brain respectively. These activities were not recovered after 8 days from exposure to this pesticide. It can be concluded that acetyl cholinesterase from those tissues was inhibited by small amounts of methyl parathion, and the main effect was observed in the brain.

  5. Methyl caffeate as an alpha-glucosidase inhibitor from Solanum torvum fruits and the activity of related compounds.

    Science.gov (United States)

    Takahashi, Keisuke; Yoshioka, Yasuyuki; Kato, Eisuke; Katsuki, Shigeki; Iida, Osamu; Hosokawa, Keizo; Kawabata, Jun

    2010-01-01

    In screening experiments for rat intestinal alpha-glucosidase (sucrase and maltase) inhibitors in 325 plants cultivated in Japan's southern island, of Tanegashima, marked inhibition against both sucrase and maltase was found in the extract of the fruit of Solanum torvum. Enzyme-assay guided fractionation of the extract led to the isolation of methyl caffeate (1) as a rat intestinal sucrase and maltase inhibitor. We examined 13 caffeoyl derivatives for sucrase- and maltase-inhibitory activities. The results showed that methyl caffeate (1) had a most favorable structure for both sucrase and maltase inhibition, except for a higher activity of methyl 3,4,5-trihydroxycinnamate (14) against sucrase. Its moderate inhibitory action against alpha-glucosidase provides a prospect for antidiabetic usage of S. torvum fruit.

  6. Cytotoxic and cell transforming activities of the fungicide methyl thiophanate on BALB/c 3T3 cells in vitro.

    Science.gov (United States)

    Perocco, P; Del Ciello, C; Mazzullo, M; Rocchi, P; Ferreri, A M; Paolini, M; Pozzetti, L; Cantelli-Forti, G

    1997-11-27

    Cytotoxic and cell-transforming activities of methyl thiophanate a systemic fungicide capable of entering plant cells and thus controlling fungal diseases that have already started were studied in an in vitro medium-term (6-8 weeks) experimental model utilizing BALB/c 3T3 cells. Cells were exposed to the chemical, dissolved in dimethyl sulfoxide, in the absence or presence of an exogenous metabolizing system derived from rat livers supplemented with cofactors (S9 mix). In the absence of metabolic activation, methyl thiophanate exerted cytotoxic activity, evidenced through the formation of cell colonies, at low doses (> 10 micrograms/ml). However, the cytotoxic activity was greatly reduced by the S9 mix-induced metabolic activation of the chemical. Without bioactivation, cell-transforming potential, evidenced through the induction of transformation foci, was observable only at the highest (weakly toxic) dose employed (25 micrograms/ml). On the contrary, in the presence of metabolic activation, the cell-transforming activity was detectable at all tested doses (i.e. from 20 to 200 micrograms/ml) and it was particularly evident in a level-II transformation amplification test when the cells were allowed to perform active proliferative activity. These results, providing further information on the activity of methyl thiophanate in multistep carcinogenesis as possible genotoxic and/or co-carcinogenic agent, may contribute to better evaluate the oncogenic risk to man.

  7. Pectin Methyl Esterase Activity Change in Intermediate Moisture Sun-Dried Figs after Storage

    Directory of Open Access Journals (Sweden)

    Dilek Demirbüker Kavak

    2015-12-01

    Full Text Available Intermediate moisture fruits can be obtained by rehydrating dried fruits. Intermediate moisture fruits are suitable for direct consumption compared to dry fruits and can be directly used in the production of various products such as bakery products, dairy products and candies. Aim of this study is to compare the pectin methyl esterase (PME activity of intermediate moisture figs which causes softening of the texture and to compare their microbial stability after 3 months storage period. For this purpose, dried figs were rehydrated in 30 and 80° C water until they reach 30% moisture content. Rehydrated samples were stored for 3 months at +4°C. Results showed that there was no statistically significant difference between the control samples and the samples rehydrated at 80°C according to the total viable counts. At the end of the storage period, results of residual PME activity in control samples was 24.1 μmol COOH min-1g-1, while it was found 17.4 μmol COOH min-1g-1 in samples rehydrated at 80°C. As a result rehydration conducted at 80°C provided 28% reduction in PME activity compared to the control samples rehydrated at 30°C, although it did not affect the microbial load significantly after storage.

  8. Customer exposure to MTBE, TAME, C6 alkyl methyl ethers, and benzene during gasoline refueling.

    Science.gov (United States)

    Vainiotalo, S; Peltonen, Y; Ruonakangas, A; Pfäffli, P

    1999-01-01

    We studied customer exposure during refueling by collecting air samples from customers' breathing zone. The measurements were carried out during 4 days in summer 1996 at two Finnish self-service gasoline stations with "stage I" vapor recovery systems. The 95-RON (research octane number) gasoline contained approximately 2.7% methyl tert-butyl ether (MTBE), approximately 8.5% tert-amyl methyl ether (TAME), approximately 3.2% C6 alkyl methyl ethers (C6 AMEs), and 0.75% benzene. The individual exposure concentrations showed a wide log-normal distribution, with low exposures being the most frequent. In over 90% of the samples, the concentration of MTBE was higher (range MTBE values were well below the short-term (15 min) threshold limits set for occupational exposure (250-360 mg/m3). At station A, the geometric mean concentrations in individual samples were 3.9 mg/m3 MTBE and 2. 2 mg/m3 TAME. The corresponding values at station B were 2.4 and 1.7 mg/m3, respectively. The average refueling (sampling) time was 63 sec at station A and 74 sec at station B. No statistically significant difference was observed in customer exposures between the two service stations. The overall geometric means (n = 167) for an adjusted 1-min refueling time were 3.3 mg/m3 MTBE and 1.9 mg/m3 TAME. Each day an integrated breathing zone sample was also collected, corresponding to an arithmetic mean of 20-21 refuelings. The overall arithmetic mean concentrations in the integrated samples (n = 8) were 0.90 mg/m3 for benzene and 0.56 mg/m3 for C6 AMEs calculated as a group. Mean MTBE concentrations in ambient air (a stationary point in the middle of the pump island) were 0.16 mg/m3 for station A and 0.07 mg/m3 for station B. The mean ambient concentrations of TAME, C6 AMEs, and benzene were 0.031 mg/m3, approximately 0.005 mg/m3, and approximately 0.01 mg/m3, respectively, at both stations. The mean wind speed was 1.4 m/sec and mean air temperature was 21 degreesC. Of the gasoline refueled during the

  9. Lead Selection of a New Aminomethylphenol, JPC-3210, for Malaria Treatment and Prevention.

    Science.gov (United States)

    Chavchich, Marina; Birrell, Geoffrey W; Ager, Arba L; MacKenzie, Donna O; Heffernan, Gavin D; Schiehser, Guy A; Jacobus, Laura R; Shanks, G Dennis; Jacobus, David P; Edstein, Michael D

    2016-05-01

    Structure-activity relationship studies of trifluoromethyl-substituted pyridine and pyrimidine analogues of 2-aminomethylphenols (JPC-2997, JPC-3186, and JPC-3210) were conducted for preclinical development for malaria treatment and/or prevention. Of these compounds, JPC-3210 [4-(tert-butyl)-2-((tert-butylamino)methyl)-6-(5-fluoro-6-(trifluoromethyl)pyridin-3-yl)phenol] was selected as the lead compound due to superior in vitro antimalarial activity against multidrug-resistant Plasmodium falciparum lines, lower in vitro cytotoxicity in mammalian cell lines, longer plasma elimination half-life, and greater in vivo efficacy against murine malaria. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  10. Synthesis, Characterization and Antimicrobial Activity of 5-(4-Methyl piperazinyl methylene-8-hydroxy quinoline and its Various Metal Chelates

    Directory of Open Access Journals (Sweden)

    I. J. Patel

    2006-01-01

    Full Text Available 5-Chloromethyl-8-quinolinol was condensed with 4-methyl piperazine in presence of sodium bicarbonate. The resulting 5-(4-methyl piper-azinylmethylene-8-quinolinol (MPQ was characterized by elemental analysis and spectral studies. The transition metal chelates viz Cu+2, Ni+2, Co+2, Mn+2, Zn+2, Cd+2, and Fe+3 of MPQ were prepared and characterized by metal-ligand (M:L ratio, IR and reflectance spectroscopies and magnetic properties. The antifungal activity of MPQ and its metal chelates was screened against various fungi. The results show that all these samples are good antifungal agents.

  11. Synthesis, Antifungal Activity and Structure-Activity Relationships of Novel 3-(Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic Acid Amides

    Directory of Open Access Journals (Sweden)

    Shijie Du

    2015-05-01

    Full Text Available A series of novel 3-(difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid amides were synthesized and their activities were tested against seven phytopathogenic fungi by an in vitro mycelia growth inhibition assay. Most of them displayed moderate to excellent activities. Among them N-(2-(5-bromo-1H-indazol-1-ylphenyl-3-(difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide (9m exhibited higher antifungal activity against the seven phytopathogenic fungi than boscalid. Topomer CoMFA was employed to develop a three-dimensional quantitative structure-activity relationship model for the compounds. In molecular docking, the carbonyl oxygen atom of 9m could form hydrogen bonds towards the hydroxyl of TYR58 and TRP173 on SDH.

  12. Destruction of methyl bromide sorbed to activated carbon by thiosulfate and electrolysis

    Science.gov (United States)

    Methyl bromide is widely used as a fumigant for post-harvest and quarantine uses at port facilities due to the low treatment times required, but it is vented to the atmosphere after its use. Due to the potential contributions of methyl bromide to stratospheric ozone depletion, technologies for the c...

  13. Semisynthesis, cytotoxicity, antiviral activity, and drug interaction liability of 7-O-methylated analogues of flavonolignans from milk thistle.

    Science.gov (United States)

    Althagafy, Hanan S; Graf, Tyler N; Sy-Cordero, Arlene A; Gufford, Brandon T; Paine, Mary F; Wagoner, Jessica; Polyak, Stephen J; Croatt, Mitchell P; Oberlies, Nicholas H

    2013-07-01

    Silymarin, an extract of the seeds of milk thistle (Silybum marianum), is used as an herbal remedy, particularly for hepatoprotection. The main chemical constituents in silymarin are seven flavonolignans. Recent studies explored the non-selective methylation of one flavonolignan, silybin B, and then tested those analogues for cytotoxicity and inhibition of both cytochrome P450 (CYP) 2C9 activity in human liver microsomes and hepatitis C virus infection in a human hepatoma (Huh7.5.1) cell line. In general, enhanced bioactivity was observed with the analogues. To further probe the biological consequences of methylation of the seven major flavonolignans, a series of 7-O-methylflavonolignans were generated. Optimization of the reaction conditions permitted selective methylation at the phenol in the 7-position in the presence of each metabolite's 4-5 other phenolic and/or alcoholic positions without the use of protecting groups. These 7-O-methylated analogues, in parallel with the corresponding parent compounds, were evaluated for cytotoxicity against Huh7.5.1 cells; in all cases the monomethylated analogues were more cytotoxic than the parent compounds. Moreover, parent compounds that were relatively non-toxic and inactive or weak inhibitors of hepatitis C virus infection had enhanced cytotoxicity and anti-HCV activity upon 7-O-methylation. Also, the compounds were tested for inhibition of major drug metabolizing enzymes (CYP2C9, CYP3A4/5, UDP-glucuronsyltransferases) in pooled human liver or intestinal microsomes. Methylation of flavonolignans differentially modified inhibitory potency, with compounds demonstrating both increased and decreased potency depending upon the compound tested and the enzyme system investigated. In total, these data indicated that monomethylation modulates the cytotoxic, antiviral, and drug interaction potential of silymarin flavonolignans. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Exogenous Methyl Jasmonate Treatment Increases Glucosinolate Biosynthesis and Quinone Reductase Activity in Kale Leaf Tissue

    Science.gov (United States)

    Ku, Kang-Mo; Jeffery, Elizabeth H.; Juvik, John A.

    2014-01-01

    Methyl jasmonate (MeJA) spray treatments were applied to the kale varieties ‘Dwarf Blue Curled Vates’ and ‘Red Winter’ in replicated field plantings in 2010 and 2011 to investigate alteration of glucosinolate (GS) composition in harvested leaf tissue. Aqueous solutions of 250 µM MeJA were sprayed to saturation on aerial plant tissues four days prior to harvest at commercial maturity. The MeJA treatment significantly increased gluconasturtiin (56%), glucobrassicin (98%), and neoglucobrassicin (150%) concentrations in the apical leaf tissue of these genotypes over two seasons. Induction of quinone reductase (QR) activity, a biomarker for anti-carcinogenesis, was significantly increased by the extracts from the leaf tissue of these two cultivars. Extracts of apical leaf tissues had greater MeJA mediated increases in phenolics, glucosinolate concentrations, GS hydrolysis products, and QR activity than extracts from basal leaf tissue samples. The concentration of the hydrolysis product of glucoraphanin, sulforphane was significantly increased in apical leaf tissue of the cultivar ‘Red Winter’ in both 2010 and 2011. There was interaction between exogenous MeJA treatment and environmental conditions to induce endogenous JA. Correlation analysis revealed that indole-3-carbanol (I3C) generated from the hydrolysis of glucobrassicin significantly correlated with QR activity (r = 0.800, Pkale leaf tissues of both cultivars in 2011. Correlation analysis of these results indicated that sulforaphane, NI3C, neoascorbigen, I3C, and diindolylmethane were all significantly correlated with QR activity. Thus, increased QR activity may be due to combined increases in phenolics (quercetin and kaempferol) and GS hydrolysis product concentrations rather than by individual products alone. PMID:25084454

  15. Maintaining methylation activities during salt stress. The involvement of adenosine kinase.

    Science.gov (United States)

    Weretilnyk, E A; Alexander, K J; Drebenstedt, M; Snider, J D; Summers, P S; Moffatt, B A

    2001-02-01

    Synthesis of the compatible osmolyte Gly betaine is increased in salt-stressed spinach (Spinacia oleracea). Gly betaine arises by oxidation of choline from phosphocholine. Phosphocholine is synthesized in the cytosol by three successive S-adenosyl-Met-dependent N-methylations of phosphoethanolamine. With each transmethylation, a molecule of S-adenosylhomo-Cys (SAH) is produced, a potent inhibitor of S-adenosyl-Met-dependent methyltransferases. We examined two enzymes involved in SAH metabolism: SAH hydrolase (SAHH) catabolizes SAH to adenosine plus homo-Cys and adenosine kinase (ADK) converts adenosine to adenosine monophosphate. In vitro SAHH and ADK activities increased incrementally in extracts from leaves of spinach plants subjected to successively higher levels of salt stress and these changes reflected increased levels of SAHH and ADK protein and transcripts. Another Gly betaine accumulator, sugar beet (Beta vulgaris), also showed salt-responsive increases in SAHH and ADK activities and protein whereas tobacco (Nicotiana tabacum) and canola (Brassica napus), which do not accumulate Gly betaine, did not show comparable changes in these enzymes. In spinach, subcellular localization positions SAHH and ADK in the cytosol with the phospho-base N-methyltransferase activities. Because SAHH activity is inhibited by its products, we propose that ADK is not a stress-responsive enzyme per se, but plays a pivotal role in sustaining transmethylation reactions in general by serving as a coarse metabolic control to reduce the cellular concentration of free adenosine. In support of this model, we grew Arabidopsis under a short-day photoperiod that promotes secondary cell wall development and found both ADK activity and transcript levels to increase severalfold.

  16. TWO-PARAMETER ISOTHERMS OF METHYL ORANGE SORPTION BY PINECONE DERIVED ACTIVATED CARBON

    Directory of Open Access Journals (Sweden)

    M. R. Samarghandi ، M. Hadi ، S. Moayedi ، F. Barjasteh Askari

    2009-10-01

    Full Text Available The adsorption of a mono azo dye methyl-orange (MeO onto granular pinecone derived activated carbon (GPAC, from aqueous solutions, was studied in a batch system. Seven two-parameter isotherm models Langmuir, Freundlich, Dubinin-Radushkevic, Temkin, Halsey, Jovanovic and Hurkins-Jura were used to fit the experimental data. The results revealed that the adsorption isotherm models fitted the data in the order of Jovanovic (X2=1.374 > Langmuir > Dubinin-Radushkevic > Temkin > Freundlich > Halsey > Hurkins-Jura isotherms. Adsorption isotherms modeling showed that the interaction of dye with activated carbon surface is localized monolayer adsorption. A comparison of kinetic models was evaluated for the pseudo-second order, Elovich and Lagergren kinetic models. Lagergren first order model was found to agree well with the experimental data (X2=9.231. In order to determine the best-fit isotherm and kinetic models, two error analysis methods of Residual Mean Square Error and Chi-square statistic (X2 were used to evaluate the data.

  17. The effect of methyl-donated hydrogen bonding on active site conformations of hyaluronate lyase

    Science.gov (United States)

    Migues, Angela N.; Vergenz, Robert A.; Moore, Kevin B.

    2010-03-01

    Geometric evidence shows a val-A252 methyl-donated (MD) hydrogen bond (HB) in hyaluronate lyase (Streptococcus pneumoniae) interacts with nearby NH--O and OH--O HBs, distorting active-site helical structure. Results for model fragment A248-254 are based on experimental heavy atom positions with ab initio hydrogen atoms. The MDHB, with (H-O distance, donor-H-O angle) = (2.3å; 174^o), exhibits more favorable geometry than thr-A253 OH--O HB (1.8å; 170^o) to the same ala-249 C=O. Consequently, thr-253 N-H--O interaction is forced closer to lys-250 C=O than ala-249 C=O(2.6 versus 2.7å). A novel method has been developed to quantify the effects of atomic diplacements on motions of neighboring helices. A coordinate system was established to track the movement of specific residues and to ascertain the effect of such motions on active site conformations.

  18. Anti-inflammatory activity of methyl palmitate and ethyl palmitate in different experimental rat models

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Noha M. [Department of Pharmacology and Toxicology, Faculty of Pharmacy, Egyptian Russian University, Cairo (Egypt); El-Demerdash, Ebtehal [Department of Pharmacology and Toxicology, Faculty of Pharmacy, Ain Shams University, Cairo (Egypt); Abdel-Rahman, Hanaa M. [Department of Pharmacology and Toxicology, Faculty of Pharmacy, Egyptian Russian University, Cairo (Egypt); Algandaby, Mardi M. [Department of Biology (Botany), Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia); Al-Abbasi, Fahad A. [Department of Biochemistry, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia); Abdel-Naim, Ashraf B., E-mail: abnaim@pharma.asu.edu.eg [Department of Pharmacology and Toxicology, Faculty of Pharmacy, Ain Shams University, Cairo (Egypt)

    2012-10-01

    Methyl palmitate (MP) and ethyl palmitate (EP) are naturally occurring fatty acid esters reported as inflammatory cell inhibitors. In the current study, the potential anti-inflammatory activity of MP and EP was evaluated in different experimental rat models. Results showed that MP and EP caused reduction of carrageenan-induced rat paw edema in addition to diminishing prostaglandin E2 (PGE2) level in the inflammatory exudates. In lipopolysaccharide (LPS)-induced endotoxemia in rats, MP and EP reduced plasma levels of tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6). MP and EP decreased NF-κB expression in liver and lung tissues and ameliorated histopathological changes caused by LPS. Topical application of MP and EP reduced ear edema induced by croton oil in rats. In the same animal model, MP and EP reduced neutrophil infiltration, as indicated by decreased myeloperoxidase (MPO) activity. In conclusion, this study demonstrates the effectiveness of MP and EP in combating inflammation in several experimental models. -- Highlights: ► Efficacy of MP and EP in combating inflammation was displayed in several models. ► MP and EP reduced carrageenan-induced rat paw edema and prostaglandin E2 level. ► MP and EP decreased TNF-α and IL-6 levels in experimental endotoxemia. ► MP and EP reduced NF-κB expression and histological changes in rat liver and lung. ► MP and EP reduced croton oil-induced ear edema and neutrophil infiltration.

  19. Exogenous methyl jasmonate regulates cytokinin content by modulating cytokinin oxidase activity in wheat seedlings under salinity.

    Science.gov (United States)

    Avalbaev, Azamat; Yuldashev, Ruslan; Fedorova, Kristina; Somov, Kirill; Vysotskaya, Lidiya; Allagulova, Chulpan; Shakirova, Farida

    2016-02-01

    The treatment of 4-days-old wheat seedlings with methyl jasmonate (MeJA) in concentration optimal for their growth (0.1 μM) resulted in a rapid transient almost two-fold increase in the level of cytokinins (CKs). MeJA-induced accumulation of CKs was due to inhibition of both cytokinin oxidase (CKX) (cytokinin oxidase/dehydrogenase, EC 1.5.99.12) gene expression and activity of this enzyme. Pretreatment of wheat seedlings with MeJA decreased the growth-retarding effect of sodium chloride salinity and accelerated growth recovery after withdrawal of NaCl from the incubation medium. We speculate that this protective effect of the hormone might be due to MeJA's ability to prevent the salinity-induced decline in CK concentration that was caused by inhibition of gene expression and activity of CKX in wheat seedlings. The data might indicate an important role for endogenous cytokinins in the implementation of growth-promoting and protective effects of exogenous MeJA application on wheat plants. Copyright © 2015 Elsevier GmbH. All rights reserved.

  20. Labdanolic acid methyl ester (LAME) exerts anti-inflammatory effects through inhibition of TAK-1 activation.

    Science.gov (United States)

    Cuadrado, Irene; Cidre, Florencia; Herranz, Sandra; Estevez-Braun, Ana; de las Heras, Beatriz; Hortelano, Sonsoles

    2012-01-01

    Labdane derivatives obtained from the diterpenoid labdanediol suppressed NO and PGE(2) production in LPS-stimulated RAW 264.7 macrophages. However, mechanisms involved in these inhibitory effects are not elucidated. In this study, we investigated the signaling pathways involved in the anti-inflammatory effects of labdanolic acid methyl ester (LAME) in peritoneal macrophages and examined its therapeutic effect in a mouse endotoxic shock model. LAME reduced the production of NO and PGE(2) in LPS-activated macrophages. This effect involved the inhibition of NOS-2 and COX-2 gene expression, acting at the transcription level. Examination of the effects of the diterpene on NF-κB signaling showed that LAME inhibits the phosphorylation of IκBα and IκBβ, preventing their degradation and the nuclear translocation of the NF-κB p65 subunit. Moreover, inhibition of MAPK signaling was also observed. A further experiment revealed that LAME inhibited the phosphorylation of transforming growth factor-β (TGF-β)-activated kinase 1 (TAK1), an upstream signaling molecule required for IKK and mitogen-activated protein kinases (MAPKs) activation. Inflammatory cytokines such as IL-6, TNF-α and IP-10 were downregulated in the presence of this compound after stimulation with LPS. Additionally, LAME also improved survival in a mouse model of endotoxemia and reduced the circulatory levels of cytokines (IL-6, TNF-α). In conclusion, these results indicate that labdane diterpene LAME significantly attenuates the pro-inflammatory response induced by LPS both in vivo and in vitro. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. Enhanced Photocatalytic Activity for Degradation of Methyl Orange over Silica-Titania

    Directory of Open Access Journals (Sweden)

    Yaping Guo

    2011-01-01

    Full Text Available Silica-modified titania (SMT powders with different atomic ratios of silica to titanium (Rx were successfully synthesized by a simple ultrasonic irradiation technique. The prepared samples were characterized by X-ray diffraction (XRD, FT-IR spectroscopy, transmission electron microscopy (TEM, X-ray photoelectron spectroscopy (XPS, and ultraviolet visible spectroscopy. The specific surface area was measured according to BET theory. Results indicate that the addition of silica to titania can suppress the crystalline size growth and the transformation of anatase phase to rutile phase of titania, enlarge specific surface area of the titania particles, and result in a blue shift of absorption edge compared to pure titania. The photocatalytic activity of the SMT samples was evaluated by decolorizing methyl orange aqueous solutions under UV-visible light irradiation. It was found in our study that this activity was affected by silica content, calcination temperature, H2SO4, and oxidants such as KIO4, (NH42S2O8 and H2O2. The results reveal that the photocatalytic activity of 0.1-SMT catalyst is the best among all samples calcined at 550°C for 1 h and it is 1.56 times higher than that of Degussa P-25 titania, which is a widely used commercial TiO2 made by Germany Degussa company and has been most widely used in industry as photocatalyst, antiultraviolet product, and thermal stabilizer. The optimal calcination temperature for preparation was 550°C. The photocatalytic activity of SMT samples is significantly enhanced by H2SO4 solution treatment and oxidants.

  2. Fibrillarin methylates H2A in RNA polymerase I trans-active promoters in Brassica oleracea

    Directory of Open Access Journals (Sweden)

    lloyd eLoza-Muller

    2015-11-01

    Full Text Available Fibrillarin is a well conserved methyltransferase involved in several if not all of the more than 100 methylations sites in rRNA which are essential for proper ribosome function. It is mainly localized in the nucleoli and Cajal bodies inside the cell nucleus where it exerts most of its functions. In plants, fibrillarin binds directly the guide RNA together with Nop56, Nop58 and 15.5ka proteins to form a snoRNP complex that selects the sites to be methylated in pre-processing of ribosomal RNA. Recently, the yeast counterpart NOP1 was found to methylate histone H2A in the nucleolar regions. Here we show that plant fibrillarin can also methylate histone H2A. In Brassica floral meristem cells the methylated histone H2A is mainly localized in the nucleolus but unlike yeast or human cells it also localize in the periphery of the nucleus. In specialized transport cells the pattern is altered and it exhibits a more diffuse staining in the nucleus for methylated histone H2A as well as for fibrillarin. Here we also show that plant fibrillarin is capable of interacting with H2A and carry out its methylation in the rDNA promoter.

  3. Induction of Methyl Tertiary Butyl Ether (MTBE)-Oxidizing Activity in Mycobacterium vaccae JOB5 by MTBE

    OpenAIRE

    Johnson, Erika L.; Smith, Christy A.; O'Reilly, Kirk T.; Hyman, Michael R.

    2004-01-01

    Alkane-grown cells of Mycobacterium vaccae JOB5 cometabolically degrade the gasoline oxygenate methyl tertiary butyl ether (MTBE) through the activities of an alkane-inducible monooxygenase and other enzymes in the alkane oxidation pathway. In this study we examined the effects of MTBE on the MTBE-oxidizing activity of M. vaccae JOB5 grown on diverse nonalkane substrates. Carbon-limited cultures were grown on glycerol, lactate, several sugars, and tricarboxylic acid cycle intermediates, both ...

  4. Studies of Ca2+ ATPase (SERCA) inhibition.

    Science.gov (United States)

    Inesi, Giuseppe; Hua, Suming; Xu, Cheng; Ma, Hailun; Seth, Malini; Prasad, Anand M; Sumbilla, Carlota

    2005-12-01

    The Ca(2+) transport ATPase of intracellular membranes (SERCA) can be inhibited by a series of chemical compounds such as Thapsigargin (TG), 2,5-di(tert-butyl)hydroquinone (DBHQ) and 1,3-dibromo-2,4,6-tris (methyl-isothio-uronium) benzene (Br(2)-TITU). These compounds have specific binding sites in the ATPase protein, and different mechanisms of inhibition. On the other hand, SERCA gene silencing offers a convenient and specific method for suppression of SERCA activity in cells. The physiological and pharmacological implications of SERCA inhibition are discussed.

  5. Alphaproteobacteria dominate active 2-methyl-4-chlorophenoxyacetic acid herbicide degraders in agricultural soil and drilosphere.

    Science.gov (United States)

    Liu, Ya-Jun; Liu, Shuang-Jiang; Drake, Harold L; Horn, Marcus A

    2011-04-01

    2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a widely used phenoxyalkanoic acid herbicide and subject to aerobic microbial degradation. Earthworms stimulate both growth and activity of MCPA-degrading bacteria in soil. Thus, active MCPA degraders in soil and drilosphere (i.e. burrow walls, gut content and cast) were assessed by 16S rRNA stable isotope probing in soil columns under experimental conditions designed to minimize laboratory incubation biases. Agriculturally relevant concentrations of [(13) C]MCPA (20 µg g(dw) (-1)) were degraded in soil within 23 and 27 days in the presence and absence of earthworms respectively. Total 16S rRNA analysis revealed 73 operational taxonomic units indicative of active Acidobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Cyanobacteria, Firmicutes, Gemmatimonadetes, Planctomycetes, Proteobacteria and Verrucomicrobia in soil and drilosphere derived material. Seven operational taxonomic units indicative of Alpha-, Beta-, Gammaproteobacteria and Firmicutes consumed MCPA-[(13) C]. Dominant consumers of MCPA-[(13) C] were Alphaproteobacteria (Sphingomonadaceae and Bradyrhizobiaceae) in soil and drilosphere. Beta- (Comamonadaceae) and Gammaproteobacteria (Xanthomonadaceae) were also important MCPA-[(13) C] consumers in burrow walls only, indicating that earthworms favour betaproteobacterial MCPA degraders. In oxic microcosms with bulk soil, burrow walls and cast, 20 and 300-400 µg g(dw) (-1) [(13) C]MCPA were consumed within 24 h and 20 days respectively. Gut contents did not facilitate the degradation of [(13) C]MCPA. Sphingomonadaceae dominated MCPA-[(13) C] consumers in bulk soil and burrow wall microcosms, while Beta- and Gammaproteobacteria (Burkholderiacea, Comamonadaceae, Oxalobacteraceae and Xanthomonadaceae) dominated MCPA-[(13) C] consumers in microcosms of cast, indicating that the latter taxa are prone to respond to MCPA in cast. The collective data indicated that Alphaproteobacteria are major MCPA degraders in

  6. Biomimetic synthesis of silver nanoparticles and evaluation of their catalytic activity towards degradation of methyl orange

    Science.gov (United States)

    Manjari Mishra, Pravat; Bihari Pani, Khirod

    2017-11-01

    This paper described the significant effect of process variables like reductant concentrations, substrate concentration, reaction pH and reaction temperature on the size, morphology and yield of the silver nanoparticles (AgNPs) synthesized using aqueous leaf extract of a medicinal plant Momordica charantia (Bitter guard). By means of UV–vis spectroscopy, XRD analysis, TEM analysis and Fluorescence analysis, it is observed that the reaction solution containing 10‑3 M of AgNO3 of pH 5.3  +  10 ml of aqueous leaf extract at normal room temperature, was optimum for synthesis of stable, polydisperse, predominantly spherical AgNPs with average size of 12.15 nm. FT-IR and TEM studies confirmed the stability of AgNPs was due to the capping of phytoconstituents present in the leaf extract. The aqueous solution of leaf extract containing AgNPs showed remarkable catalytic activity towards degradation of methyl orange (MO) in aqueous medium.

  7. Increased antioxidant activity and polyphenol metabolites in methyl jasmonate treated mung bean (Vigna radiata sprouts

    Directory of Open Access Journals (Sweden)

    Li LI

    Full Text Available Abstract Mung bean sprouts are a popular health food both in China and worldwide. We determined the optimal concentration of exogenous methyl jasmonate (MeJA for the promotion of the sprouting in mung beans (Vigna radiata. The 1,1-diphenyl-2- picrylhydrazyl radical (DPPH scavenging test showed that MeJA application resulted in significantly improved antioxidant capacity in the sprouts 72 h later. Measurement of total polyphenols in MeJA-treated beans from 0 to 168 h, using Folin–Ciocalteu colorimetry, showed that the polyphenols changing was significantly correlated with antioxidant activity. The main polyphenols isovitexin, kaempferol-3-O-rutinoside, daidzein, genistein, isoquercitrin, p-coumaric acid, and caffeic acid were quantified using high-performance liquid chromatography (HPLC/QqQ MS and partial least squares discriminant analysis (PLS-DA. MeJA promoted the production of polyphenols, metabolites, and antioxidants in the sprouts; therefore, its use may allow sprouts to be prepared more quickly or increase their nutritional value.

  8. Fracture-induced mechanophore activation and solvent healing in poly(methyl methacrylate)

    Science.gov (United States)

    Celestine, Asha-Dee N.

    Damage detection is a highly desirable functionality in engineering materials. The potential of using mechanophores, stress-sensitive molecules, as material stress sensors has been established through tensile, compressive and shear tests. Spiropyran (SP) has been the chosen mechanophore and this molecule undergoes a ring opening reaction (activation) upon the application of mechanical stress. This activation is accompanied by a change in color and fluorescence as the colorless SP is converted to the highly colored merocyanine (MC) form. One requirement for SP activation in bulk polymers is large scale plastic deformation. In order to induce this plastic deformation during fracture testing of SP-linked brittle polymers such as poly(methyl methacrylate) (PMMA), rubber nanoparticles can be incorporated into the matrix material. These nanoparticles facilitate the increased shear yielding necessary for SP activation during mechanical testing. Cross-linked SP-PMMA, containing 7.3 wt% rubber nanoparticles is synthesized via a free radical polymerization. Specimens of this material are fabricated for Single Edge Notch Tension (SENT) testing. The rubber toughened SP-PMMA specimens are first prestretched to approximately 35% axial strain to align the spiropyran molecules in the direction of applied force and thus increase the likelihood of fracture-induced activation. After prestretching the specimens are pre-notched and irradiated with 532 nm wavelength light to revert the colored merocyanine to the colorless spiropyran form. Specimens are then fracture tested to failure using the SENT test. The evolution of mechanophore activation is monitored via in situ fluorescence imaging and inspection of the specimens after testing. Activation of the SP is observed ahead of the crack tip and along the propagated crack. Also, the degree of activation is found to increase with crack growth and the size of the activation zone is linearly correlated to the size of the plastic zone ahead

  9. THE ROLE OF VALENCE AND METHYLATION STATE ON THE ACTIVITY OF ARSENIC DURING MITOSIS

    Science.gov (United States)

    Trivalent methylated arsenicals are much more potent DNA damaging agents, clastogens, and large deletion mutagens than are their inorganic and pentavalent counterparts. Previously we had noticed that many of the arsenicals induced "c-type" anaphases characteristic of spindle pois...

  10. Remifentanil directly activates human N-methyl-D-aspartate receptors expressed in Xenopus laevis oocytes

    NARCIS (Netherlands)

    Hahnenkamp, Klaus; Nollet, Joke; van Aken, Hugo K.; Buerkle, Hartmut; Halene, Tobias; Schauerte, Svenja; Hahnenkamp, Anke; Hollmann, Markus W.; Strümper, Danja; Durieux, Marcel E.; Hoenemann, Christian W.

    2004-01-01

    BACKGROUND: Clinical studies suggest that intraoperative administration of the clinical remifentanil formulation Ultiva (GlaxoWellcome GmbH & Co, Bad Oldesloe, Germany) increases postoperative pain and postoperative analgesic requirements, but mechanisms remain unclear. N-methyl-D-aspartate (NMDA)

  11. Labdanolic acid methyl ester (LAME) exerts anti-inflammatory effects through inhibition of TAK-1 activation

    Energy Technology Data Exchange (ETDEWEB)

    Cuadrado, Irene [Departamento de Farmacología, Facultad de Farmacia, Universidad Complutense, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Cidre, Florencia; Herranz, Sandra [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain); Estevez-Braun, Ana [Instituto Universitario de Bio-Orgánica “Antonio González”. Universidad de La Laguna. Avda. Astrofísico Fco. Sánchez 2. 38206. La Laguna, Tenerife (Spain); Instituto Canario de Investigaciones del Cáncer (ICIC) (Spain); Heras, Beatriz de las, E-mail: lasheras@farm.ucm.es [Departamento de Farmacología, Facultad de Farmacia, Universidad Complutense, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Hortelano, Sonsoles, E-mail: shortelano@isciii.es [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain)

    2012-01-01

    Labdane derivatives obtained from the diterpenoid labdanediol suppressed NO and PGE{sub 2} production in LPS-stimulated RAW 264.7 macrophages. However, mechanisms involved in these inhibitory effects are not elucidated. In this study, we investigated the signaling pathways involved in the anti-inflammatory effects of labdanolic acid methyl ester (LAME) in peritoneal macrophages and examined its therapeutic effect in a mouse endotoxic shock model. LAME reduced the production of NO and PGE{sub 2} in LPS-activated macrophages. This effect involved the inhibition of NOS-2 and COX-2 gene expression, acting at the transcription level. Examination of the effects of the diterpene on NF-κB signaling showed that LAME inhibits the phosphorylation of IκBα and IκBβ, preventing their degradation and the nuclear translocation of the NF-κB p65 subunit. Moreover, inhibition of MAPK signaling was also observed. A further experiment revealed that LAME inhibited the phosphorylation of transforming growth factor-β (TGF-β)-activated kinase 1 (TAK1), an upstream signaling molecule required for IKK and mitogen-activated protein kinases (MAPKs) activation. Inflammatory cytokines such as IL-6, TNF-α and IP-10 were downregulated in the presence of this compound after stimulation with LPS. Additionally, LAME also improved survival in a mouse model of endotoxemia and reduced the circulatory levels of cytokines (IL-6, TNF-α). In conclusion, these results indicate that labdane diterpene LAME significantly attenuates the pro-inflammatory response induced by LPS both in vivo and in vitro. Highlights: ► LAME reduced the production of NO and PGE{sub 2} in LPS-activated macrophages. ► IL-6, TNF-α and IP-10 were also inhibited by LAME. ► Inhibition of TAK-1 activation is the mechanism involved in this process. ► LAME improved survival in a mouse model of endotoxemia. ► LAME reduced the circulatory levels of cytokines (IL-6, TNF-α).

  12. 1-tert-butyl-3-[6-(3,5-dimethoxy-phenyl)-2-(4-diethylamino-butylamino)-pyrido[2,3-d]pyrimidin-7-yl]-urea (PD173074), a selective tyrosine kinase inhibitor of fibroblast growth factor receptor-3 (FGFR3), inhibits cell proliferation of bladder cancer carrying the FGFR3 gene mutation along with up-regulation of p27/Kip1 and G1/G0 arrest

    National Research Council Canada - National Science Library

    Miyake, Makito; Ishii, Masazumi; Koyama, Naoki; Kawashima, Kiyotaka; Kodama, Tetsuro; Anai, Satoshi; Fujimoto, Kiyohide; Hirao, Yoshihiko; Sugano, Kokichi

    2010-01-01

    Activating mutation of the fibroblast growth factor receptor-3 (FGFR3) gene is known as a key molecular event in both oncogenesis and cell proliferation of low-grade noninvasive human bladder urothelial carcinoma (UC...

  13. Determination of S-methyl-, S-propyl-, and S-propenyl-L-cysteine sulfoxides by gas chromatography-mass spectrometry after tert-butyldimethylsilylation.

    Science.gov (United States)

    Tsuge, Kouichiro; Kataoka, Mieko; Seto, Yasuo

    2002-07-31

    A gas chromatographic-mass spectrometric method for the determination of S-methyl-L-cysteine sulfoxide (1), S-propyl-L-cysteine sulfoxide (2), and S-propenyl-L-cysteine sulfoxide (3), specific marker compounds in the genus Allium, is described. The target amino acids were converted to the tert-butyldimethylsilyl derivatives. The products were silylated on the amino and carboxyl groups and on an additional oxygen atom and were separated on a nonpolar capillary column. That incorporation of three tert-butyldimethylsilyl groups had occurred was verified by mass spectrometry, which gave an m/z 302 fragment as base peak (amino acid side chain eliminated ion) and m/z 436 (1), 464 (2), or 462 (3) as major peaks (tert-butyl function eliminated ion), by electron impact ionization. The detection limits for 1 and 2 under selected ion monitoring at m/z 436 (1) and m/z 464 (2), respectively, were determined to be 0.3 and 1.8 ng per injection. To clean up the analytes from the solvent extract of onion, as a representative food material, onion, the sample solution was subjected to combined solid phase extraction. The eluate from a Sep-Pak C(18) cartridge was applied to a Bond Elut SCX cartridge (H(+) form), followed by washing with 0.1 M hydrochloric acid and elution with 0.5 M ammonia. From a simulated matrix solution containing 5% sucrose, 1 and 2 were extracted quantitatively, and the detection yield was approximately 75%. The contents of 1, 2, and 3 in commercial onion were estimated to be 0.3, 3.1, and 3.0 mg, respectively, per gram of fresh weight.

  14. Prenatal polycyclic aromatic hydrocarbon, adiposity, peroxisome proliferator-activated receptor (PPAR γ methylation in offspring, grand-offspring mice.

    Directory of Open Access Journals (Sweden)

    Zhonghai Yan

    Full Text Available Greater levels of prenatal exposure to polycyclic aromatic hydrocarbon (PAH have been associated with childhood obesity in epidemiological studies. However, the underlying mechanisms are unclear.We hypothesized that prenatal PAH over-exposure during gestation would lead to weight gain and increased fat mass in offspring and grand-offspring mice. Further, we hypothesized that altered adipose gene expression and DNA methylation in genes important to adipocyte differentiation would be affected.Pregnant dams were exposed to a nebulized PAH mixture versus negative control aerosol 5 days a week, for 3 weeks. Body weight was recorded from postnatal day (PND 21 through PND60. Body composition, adipose cell size, gene expression of peroxisome proliferator-activated receptor (PPAR γ, CCAAT/enhancer-binding proteins (C/EBP α, cyclooxygenase (Cox-2, fatty acid synthase (FAS and adiponectin, and DNA methylation of PPAR γ, were assayed in both the offspring and grand-offspring adipose tissue.Offspring of dams exposed to greater PAH during gestation had increased weight, fat mass, as well as higher gene expression of PPAR γ, C/EBP α, Cox2, FAS and adiponectin and lower DNA methylation of PPAR γ. Similar differences in phenotype and DNA methylation extended through the grand-offspring mice.Greater prenatal PAH exposure was associated with increased weight, fat mass, adipose gene expression and epigenetic changes in progeny.

  15. Structure-activity relationship of daptomycin analogues with substitution at (2S, 3R) 3-methyl glutamic acid position.

    Science.gov (United States)

    Lin, Du'an; Lam, Hiu Yung; Han, Wenbo; Cotroneo, Nicole; Pandya, Bhaumik A; Li, Xuechen

    2017-02-01

    Daptomycin is a highly effective lipopeptide antibiotic against Gram-positive pathogens. The presence of (2S, 3R) 3-methyl glutamic acid (mGlu) in daptomycin has been found to be important to the antibacterial activity. However the role of (2S, 3R) mGlu is yet to be revealed. Herein, we reported the syntheses of three daptomycin analogues with (2S, 3R) mGlu substituted by (2S, 3R) methyl glutamine (mGln), dimethyl glutamic acid and (2S, 3R) ethyl glutamic acid (eGlu), respectively, and their antibacterial activities. The detailed synthesis of dimethyl glutamic acid was also reported. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Do TE activity and counteracting genome defenses, RNAi and methylation, shape the sex lives of smut fungi?

    Science.gov (United States)

    Laurie, John D; Linning, Rob; Wong, Philip; Bakkeren, Guus

    2013-04-01

    The availability of three genomes from smut fungi differing in mating, TE load, and genome defense mechanisms, allowed a comparative analyses and a discussion on evolutionary forces shaping them. A complex balance of selective forces seems at play. A bipolar mating system in Ustilago hordei promotes selfing, advantageous for successful niche occupation but favoring accumulation of repetitive DNA, including TEs. TE activity may have caused genome variations necessary for these obligate parasites under high host selection pressures. Higher TE activity is balanced by genome defenses through recombination, RNAi, methylation and RIP mutagenesis. In tetrapolar U. maydis, lacking silencing and possibly methylation mechanisms, reduced inbreeding potential favors removal of repetitive DNA, presumably by its highly-efficient recombination system.

  17. Modification of the association between recreational physical activity and survival after breast cancer by promoter methylation in breast cancer-related genes.

    Science.gov (United States)

    McCullough, Lauren E; Chen, Jia; Cho, Yoon Hee; Khankari, Nikhil K; Bradshaw, Patrick T; White, Alexandra J; Teitelbaum, Susan L; Terry, Mary Beth; Neugut, Alfred I; Hibshoosh, Hanina; Santella, Regina M; Gammon, Marilie D

    2017-02-21

    Mechanisms underlying the inverse association between physical activity and survival after breast cancer are unresolved, but DNA methylation may play a role. We hypothesized that promoter methylation of breast cancer-related genes, as well as global methylation, may modify the association between prediagnostic recreational physical activity (RPA) and breast cancer mortality. Using a population-based sample of 1254 women diagnosed with first primary breast cancer, we examined modification of the RPA-mortality association by gene-specific promoter methylation and global methylation. Average lifetime RPA was assessed from menarche to diagnosis through structured in-home interviews. Promoter methylation of 13 breast cancer-related genes was evaluated in archived tumor by methylation-specific polymerase chain reaction and MethyLight assay. Global methylation in white blood cell DNA was determined at long interspersed nucleotide element 1 and by the luminometric methylation assay. After approximately 15 years of follow-up, 486 patients had died, and 186 of the deaths were breast cancer-related. We used Cox proportional hazards regression to estimate HRs and 95% CIs as well as likelihood ratio tests to assess multiplicative interactions. All-cause mortality was lower only among physically active women with methylated promoter of APC (HR 0.60, 95% CI 0.40-0.80), CCND2 (HR 0.56, 95% CI 0.32-0.99), HIN (HR 0.55, 95% CI 0.38-0.80), and TWIST1 (HR 0.28, 95% CI 0.14-0.56) in tumors, but not among those with unmethylated tumors (significant interaction p breast cancer that is associated with RPA may be more pronounced in women with promoter tumor methylation in biologically plausible genes.

  18. Brain-derived neurotrophic factor modulates hippocampal synaptic transmission by increasing N-methyl-d-aspartic acid receptor activity

    OpenAIRE

    Levine, Eric S; Crozier, Robert A.; Black, Ira B.; Plummer, Mark R.

    1998-01-01

    Neurotrophins (NTs) have recently been found to regulate synaptic transmission in the hippocampus. Whole-cell and single-channel recordings from cultured hippocampal neurons revealed a mechanism responsible for enhanced synaptic strength. Specifically, brain-derived neurotrophic factor augmented glutamate-evoked, but not acetylcholine-evoked, currents 3-fold and increased N-methyl-d-aspartic acid (NMDA) receptor open probability. Activation of trkB NT receptors was critical, as glutamate curr...

  19. Covalent binding of quinones activates the Ah receptor in Hepa1c1c7 cells.

    Science.gov (United States)

    Abiko, Yumi; Puga, Alvaro; Kumagai, Yoshito

    2015-12-01

    Highly reactive quinone species produced by photooxidation and/or metabolic activation of mono- or bi-aromatic hydrocarbons modulate cellular homeostasis and electrophilic signal transduction pathways through the covalent modification of proteins. Polycyclic aromatic hydrocarbons, but not mono- or bi-aromatic hydrocarbons, are well recognized as ligands for the aryl hydrocarbon receptor (AhR). However, quinone species produced from mono- and bi-aromatic hydrocarbons could potentially cause AhR activation. To clarify the AhR response to mono- and bi-aromatic hydrocarbon quinones, we studied Cyp1a1 (cytochrome P450 1A1) induction and AhR activation by these quinones. We detected Cyp1a1 induction during treatment with quinones in Hepa1c1c7 cells, but not their parent compounds. Nine of the twelve quinones with covalent binding capability for proteins induced Cyp1a1. Cyp1a1 induction mediated by 1,2-naphthoquinone (1,2-NQ), 1,4-NQ, 1,4-benzoquinone (1,4-BQ) and tert-butyl-1,4-BQ was suppressed by a specific AhR inhibitor and was not observed in c35 cells, which do not have a functional AhR. These quinones stimulated AhR nuclear translocation and interaction with the AhR nuclear translocator. Interestingly, 1,2-NQ covalently modified AhR, which was detected by an immunoprecipitation assay using a specific antibody against 1,2-NQ, resulting in enhancement of xenobiotic responsive element (XRE)-derived luciferase activity and binding of AhR to the Cyp1a1 promoter region. While mono- and bi-aromatic hydrocarbons are generally believed to be poor ligands for AhR and hence unable to induce Cyp1a1, our study suggests that the quinones of these molecules are able to modify AhR and activate the AhR/XRE pathway, thereby inducing Cyp1a1. Since we previously reported that 1,2-NQ and tert-butyl-1,4-BQ also activate NF-E2-related factor 2, it seems likely that some of quinones are bi-functional inducers for phase-I and phase-II reaction of xenobiotics.

  20. Synthesis of 4-methyl-1,2,3-thiadiazole derivatives via Ugi reaction and their biological activities.

    Science.gov (United States)

    Zuo, Xiang; Mi, Na; Fan, Zhijin; Zheng, Qingxiang; Zhang, Haike; Wang, Huan; Yang, Zhikun

    2010-03-10

    The Ugi reaction is a green and rapid one-pot reaction for lead derivation. To develop novel candidate pesticides with diverse biological activities, two series of 4-methyl-1,2,3-thiadiazole derivatives containing active substructures of 3-chloro-4-methylphenyl or 3-fluoro-4-methylphenyl, respectively, were rationally designed and synthesized via Ugi reaction according to the principle of combinations of bioactive substructures. All of the structures of newly synthesized compounds were confirmed by proton nuclear magnetic resonance and high-resolution mass spectrometry. Biological activities of the target compounds including fungicide activity, antivirus activity in vitro and in vivo, and systemic acquired resistance were evaluated systematically. The results indicated that derivatives containing 3-(trifluoromethyl)phenyl and 2-methylphenyl possessed a potential wide spectrum of fungicidal activity. Derivatives containing 3-(trifluoromethyl)phenyl and 4-hydroxyphenyl possessed good potential direct antivirus activities against tobacco mosaic virus (TMV) in vitro, and the replacement of Cl atom by F atom improved their direct inhibition activities against TMV in vitro. Derivatives containing phenyl, 2-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl, 3-nitrophenyl, 4-nitrophenyl, 2-methylphenyl, and 4-hydroxyphenyl possessed good potential bioactivities in vivo including protection, inactivation, curative, and induction activities against TMV. These studies indicate that the newly synthesized 4-methyl-1,2,3-thiadiazole derivatives possessed good potential bioactivities, and a combination of bioactive substructures via Ugi reaction was an effective way to find bioactive compounds for novel pesticide development.

  1. Heavy-ion radiation induces both activation of multiple endogenous transposable elements and alterations in DNA methylation in rice

    Science.gov (United States)

    Zhang, Meng; Sun, Yeqing; Li, Xishan; Xiaolin, Cui; Li, Xiang

    2012-07-01

    Space radiation represents a complex environmental condition in which several interacting factors such as electron, neutron, proton, heavy-ion are involved, which may provoke stress responses and jeopardize genome integrity. Given the inherent property of epigenetic modifications to respond to intrinsic aswell as external perturbations, it is conceivable that epigenetic markers like DNA methylation and transposition may undergo alterations in response to space radiation. Cytosine DNA methylation plays important roles in maintaining genome stability and controlling gene expression. A predominant means for Transposable elements (TEs) to cause genetic instability is via their transpositional activation. To find the detailed molecular characterization of the nature of genomic changes induced by space radiation, the seeds of rice were exposed to 0.02, 0.2, 1, 2 and 20 Gy dose of ^{12}C heavy-ion radiation, respectively. We found that extensive alteration in both DNA methylation and gene expression occurred in rice plants after different dose of heavy-ion radiation. Here we shown that heavy-ion radiation has induced transposition of mPing and Tos17 in rice, which belong to distinct classes including the miniature inverted terminal repeat TEs (MITEs) and long-terminal repeat (LTR) retrotransposons, respectively. mPing and Tos17 mobility were found to correlate with cytosine methylation alteration detected by MSAP and genetic variation detected by AFLP. The result showed that at least in some cases transposition of TEs was associated with cytosine demethylation within the elements. Our results implicate that the heavy-ion radiation represents a potent mutagenic agent that can cause genomic instabilities by eliciting transposition of endogenous TEs in rice. Keywords: Heavy-ion radiation, DNA methylation, Transposable elements, mPing, Tos17

  2. Multiple resistance to pirimiphos-methyl and bifenthrin in Tribolium castaneum involves the activity of lipases, esterases, and laccase2.

    Science.gov (United States)

    Julio, Alison Henrique Ferreira; Gigliolli, Adriana Aparecida Sinópolis; Cardoso, Kátia Aparecida Kern; Drosdoski, Sandro Daniel; Kulza, Rodrigo Amaral; Seixas, Flávio Augusto Vicente; Ruvolo-Takasusuki, Maria Claudia Colla; de Souza, Cristina Giatti Marques; Lapenta, Ana Silvia

    2017-05-01

    Several recent studies have elucidated the molecular mechanisms that confer insecticide resistance on insect pests. However, little is known about multiple resistance in red flour beetle (Tribolium castaneum) at molecular level. The multiple resistance is characterized as resistance to different classes of insecticides that have different target sites, and is mediated by several enzymatic systems. In this study, we investigated the biochemical and molecular mechanisms involved in multiple resistance of T. castaneum to bifenthrin (pyrethroid [Pyr]) and pirimiphos-methyl (organophosphate [Org]). We used artificial selection, biochemical and in silico approaches including structural computational biology. After five generations of artificial selection in the presence of bifenthrin (F5Pyr) or pirimiphos-methyl (F5Org), we found high levels of multiple resistance. The hierarchical enzymatic cluster revealed a pool of esterases (E), lipases (LIPs) and laccase2 (LAC2) potentially contributing to the resistance in different ways throughout development, after one or more generations in the presence of insecticides. The enzyme-insecticide interaction network indicated that E2, E3, LIP3, and LAC2 are enzymes potentially required for multiple resistance phenotype. Kinetic analysis of esterases from F5Pyr and F5Org showed that pirimiphos-methyl and specially bifenthrin promote enzyme inhibition, indicating that esterases mediate resistance by sequestering bifenthrin and pirimiphos-methyl. Our computational data were in accordance with kinetic results, indicating that bifenthrin has higher affinity at the active site of esterase than pirimiphos-methyl. We also report the capability of these insecticides to modify the development in T. castaneum. Our study provide insights into the biochemical mechanisms employed by T. castaneum to acquire multiple resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Inhibition of aromatase activity by methyl sulfonyl PCB metabolites in primary culture of human mammary fibroblasts

    Energy Technology Data Exchange (ETDEWEB)

    Berg, M. van den; Heneweer, M.; Geest, M. de; Sanderson, T. [Inst. for Risk Assessment Sciences and Utrecht Univ. (Netherlands); Jong, P. de [St. Antonius Hospital, Nieuwegein (Netherlands); Bergman, A. [Stockholm Univ., Stockholm (Sweden)

    2004-09-15

    Methyl sulfonyl PCB metabolites (MeSO2-PCBs) are persistent contaminants and are ubiquitously present in humans and the environment. Lipophilicity of MeSO2- PCB metabolites is similar to the parent compounds and they have been detected in human milk, adipose, liver and lung tissue. 4- MeSO2-PCB-149 is the most abundant PCB metabolite in human adipose tissue and milk at a level of 1.5 ng/g lipids. Human blood concentration of 4-MeSO2-PCB-149 is approximately 0.03 nM. 3- MeSO2-PCB-101 is the predominant PCB metabolite in muscle and blubber in wildlife, such as otter, mink and grey seal. In the environment, they have been linked to chronic and reproductive toxicity in exposed mink. Additionaly, some MeSO{sub 2}-PCBs have been shown to be glucocorticoid receptor (GR) antagonists. Since approximately 60% of all breast tumors are estrogen responsive, exposure to compounds that are able to alter estrogen synthesis through interference with the aromatase enzyme, can lead to changes in estrogen levels and possibly to accelerated or inhibit breast tumor growth. Therefore, it is important to identify exogenous compounds that can alter aromatase activity in addition to those compounds which have direct interaction with the estrogen receptor (ER). Aromatase (CYP19) comprises the ubiquitous flavoprotein, NADPH-cytochrome P450 reductase, and a unique cytochrome P450 that is exclusively expressed in estrogen producing cells. Previous studies have revealed that expression of the aromatase gene is regulated in a species- and tissue specific manner. In healthy breast tissue, the predominantly active aromatase promoter region I.4 is regulated by glucocorticoids and class I cytokines. Therefore, it is important to investigate possible aromatase inhibiting properties of MeSO{sub 2}-PCBs (as anti glucocorticoids?) in relevant human tissues. We used primary human mammary fibroblasts because of their role in breast cancer development. We compared the results in primary fibroblasts with

  4. Synthesis, structural investigations, and anti-cancer activity of new methyl indole-3-carboxylate derivatives

    Science.gov (United States)

    Niemyjska, Maria; Maciejewska, Dorota; Wolska, Irena; Truszkowski, Paweł

    2012-10-01

    Two new methyl indole-3-carboxylate derivatives: methyl 1-(3'-indolylmethane)-indole-3-carboxylate (1), and methyl 1-(1'-benzenosulfonyl-3'-indolylmethane)-indole-3-carboxylate (2) were synthesized. They are interesting as the analogs of 3,3'-diindolylmethane, which is intensively tested as a potent antitumor agent. Their solid-state structure was characterized using 13C CP/MAS NMR or X-ray diffraction measurements. Molecular modeling was used as a help in the structure elucidation. The solid-state NMR spectroscopy showed only one stable conformer of 1, but the X-ray diffraction results indicate that compound 2 crystallizes in the triclinic space group P-1 with two molecules, A and B, in the asymmetric unit. Both compounds inhibited the growth of melanoma, renal and breast cancers cell lines.

  5. Screening SIRT1 Activators from Medicinal Plants as Bioactive Compounds against Oxidative Damage in Mitochondrial Function

    Directory of Open Access Journals (Sweden)

    Yi Wang

    2016-01-01

    Full Text Available Sirtuin type 1 (SIRT1 belongs to the family of NAD+ dependent histone deacetylases and plays a critical role in cellular metabolism and response to oxidative stress. Traditional Chinese medicines (TCMs, as an important part of natural products, have been reported to exert protective effect against oxidative stress in mitochondria. In this study, we screened SIRT1 activators from TCMs and investigated their activities against mitochondrial damage. 19 activators were found in total by in vitro SIRT1 activity assay. Among those active compounds, four compounds, ginsenoside Rb2, ginsenoside F1, ginsenoside Rc, and schisandrin A, were further studied to validate the SIRT1-activation effects by liquid chromatography-mass spectrometry and confirm their activities against oxidative damage in H9c2 cardiomyocytes exposed to tert-butyl hydroperoxide (t-BHP. The results showed that those compounds enhanced the deacetylated activity of SIRT1, increased ATP content, and inhibited intracellular ROS formation as well as regulating the activity of Mn-SOD. These SIRT1 activators also showed moderate protective effects on mitochondrial function in t-BHP cells by recovering oxygen consumption and increasing mitochondrial DNA content. Our results suggested that those compounds from TCMs attenuated oxidative stress-induced mitochondrial damage in cardiomyocytes through activation of SIRT1.

  6. In vitro radical scavenging activity of two Columbian Magnoliaceae

    Science.gov (United States)

    Puertas M., Miguel A.; Mesa v., Ana M.; Sáez v., Jairo A.

    2005-08-01

    The recent interest in the conservation of the tropical forest is due, at least in part, to the potential economic and health benefits that can be exploited from several plants. This report shows the in vitro antioxidant activity of some fractions isolated from leaves of two Columbian Magnoliaceae, Talauma hernandezii G. Lozano-C and Dugandiodendron yarumalense Lozano. The activity was determined using the radical monocation 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS·+) and the stable free radical 2-2-diphenyl-1-picrylhydrazyl (DPPH·), as part of general biological screening of these plants. The antioxidant capacity obtained from fractions was similar to those of α-tocopherol, tert-butylated hydroxyanisole (BHA), and ascorbic acid. The most active scavenger extract was the fraction 7 (TAA = 48.6 mmol Trolox/kg extract and IC50 ≤ 0.01 kg extract/mmol DPPH); and the least active was the fraction 1 (TAA = 11.23 mmol Trolox/kg extract and IC50 = 0.21 kg extract/mmol DPPH) all of them isolated from D. yarumalense. These results suggest that these plants can be attractive as source of antioxidant compounds with the ability to reduce radicals like ATBS and DPPH.

  7. Antioxidant Activity of Phytic Acid in Lipid Model System

    Directory of Open Access Journals (Sweden)

    Marijana Sakač

    2010-01-01

    Full Text Available Free radicals formed during thermal (60 °C, 24 h and catalytic (Fe2+ ions, room temperature (23±1 °C, 3 h oxidative degradation of hydroperoxyde-enriched soybean oil (HESO were stabilized in the presence of spin trap N-tert-butyl-α-phenylnitrone (PBN and detected by electron spin resonance (ESR spectrometry. In both thermal and catalytic oxidation of HESO, the same hyperfine coupling parameters (aN=14.75 G and aH β=2.80 G confirmed the generation of PBN-OOL/-OL spin adducts. The antiradical activity (AA of phytic acid, in the 0.076–0.30 mM concentration range, was tested by measuring its ability to inhibit the generation of PBN-OOL/-OL spin adducts during thermal and catalytic oxidation of HESO. Phytic acid did not inhibit the thermal oxidation of HESO and showed no effect in the β-carotene bleaching test (AOA. Contrary to this, phytic acid exhibited antioxidant effect on the catalytic oxidation of HESO by chelating Fe2+ ions. The mechanism of antioxidant activity was confirmed by the results of chelating activity on Fe2+ in Fe2+-ferrozine test where a dose-dependent chelating activity of phytic acid was obtained.

  8. Methyl bromide release from activated carbon and the soil/water/carbon interface

    Science.gov (United States)

    Methyl Bromide (MB) is a major source of stratospheric bromine radical, a known depletor of ozone. The use of ozone-depleting chemicals, including MB, is regulated by the Montreal Protocol. Critical uses of MB are permitted, such as when postharvest fumigation is mandated by an importing country. Fo...

  9. Increased intragenic IGF2 methylation is associated with repression of insulator activity and elevated expression in serous ovarian carcinoma

    Directory of Open Access Journals (Sweden)

    Zhiqing eHuang

    2013-05-01

    Full Text Available Overexpression of insulin-like growth factor-II (IGF2 is a prominent characteristic of many epithelial ovarian malignancies. IGF2 imprinting and transcription are regulated in part through DNA methylation, which in turn regulates binding of the insulator protein, CTCF, within the IGF2/H19 imprint center. We have shown that IGF2 overexpression in ovarian cancer is associated with hypermethylation of CTCF binding sites within the IGF2/H19 imprint center. The aim of this study was to investigate the methylation and binding capacity of a novel putative CTCF binding motif located intragenic to IGF2 and determine how this relates to IGF2 expression. In 35 primary serous epithelial ovarian cancer specimens, methylation of two CpGs, including one within the core binding motif and another adjacent to this motif, was higher in the 18 cancers with elevated IGF2 expression versus 10 with low expression (avg. 68.2% vs. 38.5%; p<0.0001. We also found that the CpG site within the CTCF binding motif is hypermethylated in male gametes (>92%; avg. 93.2%; N=16. We confirmed binding of CTCF to this region in ovarian cancer cells, as well as the paralog of CTCF, BORIS, which is frequently overexpressed in cancers. The unmethylated CTCF binding motif has insulator activity in cells that express CTCF or BORIS, but not in cells that express both CTCF and BORIS. These intragenic CpG dinucleotides comprise a novel paternal germline imprint mark and are located in a binding motif for the insulator protein CTCF. Methylation of the CpG dinucleotides is positively correlated with IGF2 transcription, supporting that increased methylation represses insulator function. These combined results suggest that methylation and CTCF binding at this region play important roles in regulating the level of IGF2 transcription. Our data have revealed a novel epigenetic regulatory element within the IGF2/H19 imprinted domain that is highly relevant to aberrant IGF2 expression in ovarian

  10. The anti-dermatophyte activity of Commiphora molmol.

    Science.gov (United States)

    Mahboubi, Mohaddese; Kashani, Leila Mohammad Taghizadeh

    2016-01-01

    Commiphora molmol Engl (Burseraceae) or myrrh has been traditionally used for the treatment of skin fungal infections. This study evaluates the antifungal activity of myrrh ethanol extract and essential oil against skin dermatophytes. The antifungal evaluations were performed by the food poisoning technique (250 ppm) and micro-broth dilution assay (800-6.25 µg/mL) against Trichophyton rubrum, T. mentagrophytes, Microsporum canis, M. gypseum, and T. verrucosum. The chemical composition of myrrh oil and ethanol extract was analyzed by GC and GC-MS. Furanoeudesma 1,3-diene and menthofuran were the main components of myrrh oil, while 2-tert-butyl-1,4-naphthoquinone, benzenemethanol,3-methoxy-α-phenyl, and curzerene were the main components of myrrh ethanol extract. The inhibitory effect of myrrh oil and ethanol extract against dermatophytes were 43.1-61.6% and 12.5-27.5%, respectively. The MIC and MFC values of myrrh oil were 25-100 and 25-200 µg/mL while these amounts for ethanol extract were 25-400 and 25-400 µg/mL, respectively. Therefore, myrrh oil had higher antifungal activity than that of the ethanol extract. Both extracts showed good anti-elastase activity. The results of our investigation confirmed the traditional uses of C. molmol as a poultice for the treatment of cutaneous fungal infections.

  11. Controlling enzymatic activity by immobilization on graphene oxide

    Science.gov (United States)

    Bolibok, Paulina; Wiśniewski, Marek; Roszek, Katarzyna; Terzyk, Artur P.

    2017-04-01

    In this study, graphene oxide (GO) has been applied as a matrix for enzyme immobilization. The protein adsorption capacity of GO is much higher than of other large surface area carbonaceous materials. Its structure and physicochemical properties are reported beneficial also for enzymatic activity modifications. The experimental proof was done here that GO-based biocatalytic systems with immobilized catalase are modifiable in terms of catalyzed reaction kinetic constants. It was found that activity and stability of catalase, considered here as model enzyme, closely depend on enzyme/GO ratio. The changes in kinetic parameters can be related to secondary structure alterations. The correlation between enzyme/GO ratio and kinetic and structure parameters is reported for the first time and enables the conscious control of biocatalytic processes and their extended applications. The biological activity of obtained biocatalytic systems was confirmed in vitro by the use of functional test. The addition of immobilized catalase improved the cells' viability after they were exposed to hydrogen peroxide and tert-butyl-hydroperoxide used as source of reactive oxygen species.

  12. Stilbenoids remodel the DNA methylation patterns in breast cancer cells and inhibit oncogenic NOTCH signaling through epigenetic regulation of MAML2 transcriptional activity.

    Science.gov (United States)

    Lubecka, Katarzyna; Kurzava, Lucinda; Flower, Kirsty; Buvala, Hannah; Zhang, Hao; Teegarden, Dorothy; Camarillo, Ignacio; Suderman, Matthew; Kuang, Shihuan; Andrisani, Ourania; Flanagan, James M; Stefanska, Barbara

    2016-07-01

    DNA hypomethylation was previously implicated in cancer progression and metastasis. The purpose of this study was to examine whether stilbenoids, resveratrol and pterostilbene thought to exert anticancer effects, target genes with oncogenic function for de novo methylation and silencing, leading to inactivation of related signaling pathways. Following Illumina 450K, genome-wide DNA methylation analysis reveals that stilbenoids alter DNA methylation patterns in breast cancer cells. On average, 75% of differentially methylated genes have increased methylation, and these genes are enriched for oncogenic functions, including NOTCH signaling pathway. MAML2, a coactivator of NOTCH targets, is methylated at the enhancer region and transcriptionally silenced in response to stilbenoids, possibly explaining the downregulation of NOTCH target genes. The increased DNA methylation at MAML2 enhancer coincides with increased occupancy of repressive histone marks and decrease in activating marks. This condensed chromatin structure is associated with binding of DNMT3B and decreased occupancy of OCT1 transcription factor at MAML2 enhancer, suggesting a role of DNMT3B in increasing methylation of MAML2 after stilbenoid treatment. Our results deliver a novel insight into epigenetic regulation of oncogenic signals in cancer and provide support for epigenetic-targeting strategies as an effective anticancer approach. © The Author 2016. Published by Oxford University Press.

  13. Changes in protein kinase C during vitellogenesis in the crayfish Cherax quadricarinatus--possible activation by methyl farnesoate.

    Science.gov (United States)

    Soroka, Y; Sagi, A; Khalaila, I; Abdu, U; Milner, Y

    2000-05-01

    During ovarian maturation in the crayfish Cherax quadricarinatus, changes in ovarian protein kinase C (PKC) isoenzymes take place in parallel to yolk accumulation (as shown by immunoblot analysis). Significant changes were recorded in the amounts of specific isoenzymes and in their distribution between the cytosol and the membranes. Ovarian maturation was accompanied by the appearance of high- and low-molecular-weight immunoreactive PKC isoenzyme species. Among the isoenzymes tested, PKC alpha was the most clearly activated during ovarian maturation, as shown by significant translocation from the cytosol to the particulate fraction and the appearance of high-molecular-weight species. Moreover, a similar picture was obtained in the ovaries of intersex individuals upon induction of secondary vitellogenesis by androgenic gland ablation. Immunohistological staining showed PKC alpha to be localized mainly in the cytosol of premature oocytes, whereas in later maturation stages, it was concentrated around the nucleus in a vesicular structure and in the oocyte membrane. In secondary vitellogenic stages, PKC was localized in the plasma membrane and apparently in follicular cells. In addition, its activity was demonstrated by in vitro phosphorylation assays of a crayfish ovarian homogenate. Activation of total PKC phosphorylation of histone, an external substrate, was induced by phosphatidylserine plus 12-O-tetradecanoylphorbol-13-acetate (TPA) or methyl farnesoate. Both TPA and methyl farnesoate stimulated activation of PKC alpha in organ culture, causing its translocation from the cytosol to the membranes and inducing autophosphorylation of threonine residues. The changes in PKC isoenzymes during ovarian maturation in the crayfish suggest their involvement in this process as well as a possible regulatory role for methyl farnesoate through a direct effect on some PKC isoenzymes.

  14. Synthesis of Hindered Anilines: Three-Component Coupling of Arylboronic Acids, tert-Butyl Nitrite, and Alkyl Bromides.

    Science.gov (United States)

    Fisher, David J; Shaum, James B; Mills, C Landon; Read de Alaniz, Javier

    2016-10-07

    The synthesis of sterically hindered amines has been a significant challenge in organic chemistry. Herein, we report a modular, three-component coupling that constructs two carbon-nitrogen bonds including a sterically hindered C sp 3 -N bond using commercially available materials. This process uses an earth-abundant copper catalyst and mild reaction conditions, allowing access to a variety of complex aromatic amines.

  15. Synthesis of Hindered Anilines: Three-Component Coupling of Arylboronic Acids, tert-Butyl Nitrite, and Alkyl Bromides.

    OpenAIRE

    Fisher, DJ; Shaum, JB; Mills, CL; Read de Alaniz, J

    2016-01-01

    The synthesis of sterically hindered amines has been a significant challenge in organic chemistry. Herein, we report a modular, three-component coupling that constructs two carbon-nitrogen bonds including a sterically hindered Csp(3)-N bond using commercially available materials. This process uses an earth-abundant copper catalyst and mild reaction conditions, allowing access to a variety of complex aromatic amines.

  16. N-tert-Butyl-2-[4-(dimethylaminophenyl]imidazo[1,2-a]pyrazin-3-amine

    Directory of Open Access Journals (Sweden)

    Zeenat Fatima

    2013-04-01

    Full Text Available In the title compound, C18H23N5, the imidazole ring makes a dihedral angles of 3.96 (8 and 19.02 (8°, respectively, with the pyrazine and benzene rings while the dihedral angle between the pyrazine and benzene rings is 16.96 (7°. In the crystal, molecules are linked via N—H...N hydrogen bonds, forming chains along [010]. These chains are linked by C—H...N hydrogen bonds, forming two-dimensional networks lying parallel to (001.

  17. tert-Butyl N-((1S-2-hydroxy-1-{N′-[(1E-4-methoxybenzylidene]hydrazinecarbonyl}ethylcarbamate

    Directory of Open Access Journals (Sweden)

    Alessandra C. Pinheiro

    2011-07-01

    Full Text Available The molecule of the title compound, C16H23N3O5, is twisted about the chiral C atom, the dihedral angle formed between the amide residues being 79.6 (3°. The conformation about the imine bond [1.278 (5 Å] is E. In the crystal, O—H...O and N—H...O hydrogen bonding between the hydroxy, amine and carbonyl groups leads to the formation of supramolecular layers, which stack along the c-axis direction.

  18. 4,6-Di-tert-butyl-2,3-di­hydroxy­benzalde­hyde

    Science.gov (United States)

    Arsenyev, Max; Baranov, Eugene; Chesnokov, Sergey; Abakumov, Gleb

    2013-01-01

    The title compound, C15H22O3, crystallizes with two independent mol­ecules in the asymmetric unit. In each mol­ecule, one hy­droxy group (at position 2) is involved in an intra­molecular O—H⋯O hydrogen bond, and another one (at position 3) exhibits bifurcated hydrogen-bonding being involved in intra- and inter­molecular O—H⋯O inter­actions. In the crystal, O—H⋯O hydrogen bonds link alternating independent mol­ecules into chains running along [010]. PMID:24098244

  19. 2-tert-Butyl-1-(4-nitroamino-1,2,5-oxadiazol-3-yldiazene 1-oxide

    Directory of Open Access Journals (Sweden)

    Xiang-Zhi Li

    2012-07-01

    Full Text Available In the title compound, C6H10N6O4, the nitroamine –NHNO2 substituent and the C–N=N(→ O unit of the other substituent of the oxadiazole ring are nearly coplanar with the five-membered ring [dihedral angles = 5.7 (1 and 3.0 (1°]. The amino group of the –NHNO2 substituent is a hydrogen-bond donor to the two-coordinate N atom of the C—N=N(→ O unit.

  20. CMTM5 exhibits tumor suppressor activity through promoter methylation in oral squamous cell carcinoma

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Heyu [Central Laboratory, Peking University School of Stomatology, Beijing (China); Nan, Xu [Center for Human Disease Genomics, Department of Immunology, Key Laboratory of Medical Immunology, Ministry of Health, School of Basic Medical Sciences, Peking University, Beijing (China); Li, Xuefen [Central Laboratory, Peking University School of Stomatology, Beijing (China); Chen, Yan; Zhang, Jianyun [Department of Oral Pathology, Peking University School of Stomatology, Beijing (China); Sun, Lisha [Central Laboratory, Peking University School of Stomatology, Beijing (China); Han, Wenlin [Center for Human Disease Genomics, Department of Immunology, Key Laboratory of Medical Immunology, Ministry of Health, School of Basic Medical Sciences, Peking University, Beijing (China); Li, Tiejun, E-mail: litiejun22@vip.sina.com [Department of Oral Pathology, Peking University School of Stomatology, Beijing (China)

    2014-05-02

    Highlights: • Down-regulation of CMTM5 expression in OSCC tissues was found. • The promoter methylation status of CMTM5 was measured. • CMTM5-v1 inhibited cell proliferation and migration and induced apoptosis. • CMTM5 might act as a putative tumor suppressor gene in OSCC. - Abstract: Oral squamous cell carcinoma (OSCC) is one of the most common types of malignancies in the head and neck region. CKLF-like MARVEL transmembrane domain-containing member 5 (CMTM5) has been recently implicated as a tumor suppressor gene in several cancer types. Herein, we examined the expression and function of CMTM5 in oral squamous cell carcinoma. CMTM5 was down-regulated in oral squamous cell lines and tumor samples from patients with promoter methylation. Treatment with the demethylating agent 5-aza-2′-deoxycytidine restored CMTM5 expression. In the OSCC cell lines CAL27 and GNM, the ectopic expression of CMTM5-v1 strongly inhibited cell proliferation and migration and induced apoptosis. In addition, CMTM5-v1 inhibited tumor formation in vivo. Therefore, CMTM5 might act as a putative tumor suppressor gene through promoter methylation in oral squamous cell carcinoma.

  1. Chemiluminescence resonance energy transfer biosensing platform for site-specific determination of DNA methylation and assay of DNA methyltransferase activity using exonuclease III-assisted target recycling amplification.

    Science.gov (United States)

    Chen, Chun; Li, Baoxin

    2014-04-15

    Site-specific determination of DNA methylation and assay of MTase activity can be used for determining specific cancer types, providing insights into the mechanism of gene repression, and developing novel drugs to treat methylation-related diseases. Herein, we develop a simple and highly sensitive chemiluminescence (CL) biosensing platform for site-specific determination of DNA methylation using Exonuclease III (Exo III)-assisted target recycling signal amplification. After bisulfite treatment of mixture of methylated DNA and unmethylated DNA, methylated DNA can hybridize with fluorescein (FAM)-labeled probe DNA to form double-stranded DNA (dsDNA), removing the FAM-labeled probe DNA from the surface of grapheme oxide, and the chemiluminescence resonance energy transfer (CRET) sensing signal can be observed and then amplified using Exo III-based recycling strategy. The biosensing platform exhibits excellent high sensitivity, and it can ever distinguish as low as 0.002% methylation level from the mixture, which is superior to most currently reported methods used for DNA methylation assay. In addition, the proposed method can also be used to sensitively assay MTase activity with determination limit of 0.007 U/mL. This CL biosensing offers the advantages of being facile, sensitive, rapid and cost-effective. These features make the system promising for future use for early cancer diagnosis and discover of new anticancer drugs. © 2013 Published by Elsevier B.V.

  2. Active Fragment of Veronica ciliata Fisch. Attenuates t-BHP-Induced Oxidative Stress Injury in HepG2 Cells through Antioxidant and Antiapoptosis Activities

    Directory of Open Access Journals (Sweden)

    Yiran Sun

    2017-01-01

    Full Text Available Excessive amounts of reactive oxygen species (ROS in the body are a key factor in the development of hepatopathies such as hepatitis. The aim of this study was to assess the antioxidation effect in vitro and hepatoprotective activity of the active fragment of Veronica ciliata Fisch. (VCAF. Antioxidant assays (DPPH, superoxide, and hydroxyl radicals scavenging were conducted, and hepatoprotective effects through the application of tert-butyl hydroperoxide- (t-BHP- induced oxidative stress injury in HepG2 cells were evaluated. VCAF had high phenolic and flavonoid contents and strong antioxidant activity. From the perspective of hepatoprotection, VCAF exhibited a significant protective effect on t-BHP-induced HepG2 cell injury, as indicated by reductions in cytotoxicity and the levels of ROS, 8-hydroxydeoxyguanosine (8-OHdG, and protein carbonyls. Further study demonstrated that VCAF attenuated the apoptosis of t-BHP-treated HepG2 cells by suppressing the activation of caspase-3 and caspase-8. Moreover, it significantly decreased the levels of ALT and AST, increased the activities of acetyl cholinesterase (AChE, glutathione (GSH, superoxide dismutase (SOD, and catalase (CAT, and increased total antioxidative capability (T-AOC. Collectively, we concluded that VCAF may be a considerable candidate for protecting against liver injury owing to its excellent antioxidant and antiapoptosis properties.

  3. α-amino-3-hydroxy-5-methyl-4-isoxazoleproprionic acid receptor activation protects against phencyclidine-induced caspase-3 activity by activating voltage-gated calcium channels.

    Science.gov (United States)

    Timpe, Jennifer M; Wang, Cheng Z; Kim, Jisoo; Johnson, Kenneth M

    2014-12-01

    Phencyclidine (PCP) is a noncompetitive, open channel blocker of the N-methyl-D-aspartate (NMDA) receptor-ion channel complex. When administered to immature animals, it is known to cause apoptotic neurodegeneration in several regions, and this is followed by olanzapine-sensitive, schizophrenia-like behaviors in late adolescence and adulthood. Clarification of its mechanism of action could yield data that would help to inform the treatment of schizophrenia. In our initial experiments, we found that α-amino-3-hydroxy-5-methyl-4-isoxazoleproprionic acid (AMPA) inhibited PCP-induced apoptosis in organotypic neonatal rat brain slices in a concentration-dependent and 6-cyano-7-nitroquinoxaline-2,3-dione-sensitive manner. Calcium signaling pathways are widely implicated in apoptosis, and PCP prevents calcium influx through NMDA receptor channels. We therefore hypothesized that AMPA could protect against this effect by activation of voltage-dependent calcium channels (VDCCs). In support of this hypothesis, pretreatment with the calcium channel blocker cadmium chloride eliminated AMPA-mediated protection against PCP. Furthermore, the L-type VDCC inhibitor nifedipine (10 µM) fully abrogated the effects of AMPA, suggesting that L-type VDCCs are required for AMPA-mediated protection against PCP-induced neurotoxicity. Whereas the P/Q-type inhibitor ω-agatoxin TK (200 nM) reduced AMPA protection by 51.7%, the N-type VDCC inhibitor ω-conotoxin (2 µM) had no effect. Decreased AMPA-mediated protection following cotreatment with K252a, a TrkB inhibitor, suggests that brain-derived neurotrophic factor signaling plays an important role. By analogy, these results suggest that activation of L-type, and to a lesser extent P/Q-type, VDCCs might be advantageous in treating conditions associated with diminished NMDAergic activity during early development. © 2014 Wiley Periodicals, Inc.

  4. Synthesis, antimicrobial and anti-biofilm activities of novel Schiff base analogues derived from methyl-12-aminooctadec-9-enoate.

    Science.gov (United States)

    Mohini, Y; Prasad, R B N; Karuna, M S L; Poornachandra, Y; Ganesh Kumar, C

    2014-11-15

    A novel library of Schiff base analogues (5a-q) were synthesized by the condensation of methyl-12-aminooctadec-9-enoate and different substituted aromatic aldehydes. The synthesized compounds were thoroughly characterized by spectroscopic techniques (FT-IR, (1)H NMR, (13)C NMR, ESI-MS and HRMS). The Schiff base analogues with different substitutions were screened for in vitro antibacterial activity against 7 different bacterial strains. Among these, the compounds with electron withdrawing substituent, namely chlorine (5a) and electron donating substituents, namely hydroxy (5 n) and methoxy (5 o), were found to exhibit excellent to good antimicrobial activities (MIC value 9-18 μM) against Staphylococcus aureus MTCC 96, Staphylococcus aureus MLS-16 MTCC 2940 and Bacillus subtilis MTCC 121. The products were also screened for anti-biofilm and MBC (Minimum Bactericidal Concentration) activities which exhibited promising activities. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. DNA methylation in an enhancer region of the FADS cluster is associated with FADS activity in human liver.

    Science.gov (United States)

    Howard, Timothy D; Mathias, Rasika A; Seeds, Michael C; Herrington, David M; Hixson, James E; Shimmin, Lawrence C; Hawkins, Greg A; Sellers, Matthew; Ainsworth, Hannah C; Sergeant, Susan; Miller, Leslie R; Chilton, Floyd H

    2014-01-01

    Levels of omega-6 (n-6) and omega-3 (n-3), long chain polyunsaturated fatty acids (LcPUFAs) such as arachidonic acid (AA; 20:4, n-6), eicosapentaenoic acid (EPA; 20:5, n-3) and docosahexaenoic acid (DHA; 22:6, n-3) impact a wide range of biological activities, including immune signaling, inflammation, and brain development and function. Two desaturase steps (Δ6, encoded by FADS2 and Δ5, encoded by FADS1) are rate limiting in the conversion of dietary essential 18 carbon PUFAs (18C-PUFAs) such as LA (18:2, n-6) to AA and α-linolenic acid (ALA, 18:3, n-3) to EPA and DHA. GWAS and candidate gene studies have consistently identified genetic variants within FADS1 and FADS2 as determinants of desaturase efficiencies and levels of LcPUFAs in circulating, cellular and breast milk lipids. Importantly, these same variants are documented determinants of important cardiovascular disease risk factors (total, LDL, and HDL cholesterol, triglycerides, CRP and proinflammatory eicosanoids). FADS1 and FADS2 lie head-to-head (5' to 5') in a cluster configuration on chromosome 11 (11q12.2). There is considerable linkage disequilibrium (LD) in this region, where multiple SNPs display association with LcPUFA levels. For instance, rs174537, located ∼ 15 kb downstream of FADS1, is associated with both FADS1 desaturase activity and with circulating AA levels (p-value for AA levels = 5.95 × 10(-46)) in humans. To determine if DNA methylation variation impacts FADS activities, we performed genome-wide allele-specific methylation (ASM) with rs174537 in 144 human liver samples. This approach identified highly significant ASM with CpG sites between FADS1 and FADS2 in a putative enhancer signature region, leading to the hypothesis that the phenotypic associations of rs174537 are likely due to methylation differences. In support of this hypothesis, methylation levels of the most significant probe were strongly associated with FADS1 and, to a lesser degree, FADS2 activities.

  6. DNA methylation in an enhancer region of the FADS cluster is associated with FADS activity in human liver.

    Directory of Open Access Journals (Sweden)

    Timothy D Howard

    Full Text Available Levels of omega-6 (n-6 and omega-3 (n-3, long chain polyunsaturated fatty acids (LcPUFAs such as arachidonic acid (AA; 20:4, n-6, eicosapentaenoic acid (EPA; 20:5, n-3 and docosahexaenoic acid (DHA; 22:6, n-3 impact a wide range of biological activities, including immune signaling, inflammation, and brain development and function. Two desaturase steps (Δ6, encoded by FADS2 and Δ5, encoded by FADS1 are rate limiting in the conversion of dietary essential 18 carbon PUFAs (18C-PUFAs such as LA (18:2, n-6 to AA and α-linolenic acid (ALA, 18:3, n-3 to EPA and DHA. GWAS and candidate gene studies have consistently identified genetic variants within FADS1 and FADS2 as determinants of desaturase efficiencies and levels of LcPUFAs in circulating, cellular and breast milk lipids. Importantly, these same variants are documented determinants of important cardiovascular disease risk factors (total, LDL, and HDL cholesterol, triglycerides, CRP and proinflammatory eicosanoids. FADS1 and FADS2 lie head-to-head (5' to 5' in a cluster configuration on chromosome 11 (11q12.2. There is considerable linkage disequilibrium (LD in this region, where multiple SNPs display association with LcPUFA levels. For instance, rs174537, located ∼ 15 kb downstream of FADS1, is associated with both FADS1 desaturase activity and with circulating AA levels (p-value for AA levels = 5.95 × 10(-46 in humans. To determine if DNA methylation variation impacts FADS activities, we performed genome-wide allele-specific methylation (ASM with rs174537 in 144 human liver samples. This approach identified highly significant ASM with CpG sites between FADS1 and FADS2 in a putative enhancer signature region, leading to the hypothesis that the phenotypic associations of rs174537 are likely due to methylation differences. In support of this hypothesis, methylation levels of the most significant probe were strongly associated with FADS1 and, to a lesser degree, FADS2 activities.

  7. Prognostic Significance of Activated Leukocyte Cell Adhesion Molecule (ALCAM in Association with Promoter Methylation of the ALCAM Gene in Breast Cancer

    Directory of Open Access Journals (Sweden)

    Young Ju Jeong

    2018-01-01

    Full Text Available Activated leukocyte cell adhesion molecule (ALCAM has been implicated in tumorigenesis. In this study, we studied DNA methylation status of the ALCAM gene using pyrosequencing in breast cancer tissues. We analyzed the association between the methylation status of the ALCAM gene and its expression. Also, the effects of inflammation on the ALCAM gene methylation and its expression were investigated. The ALCAM gene methylation was associated with the ALCAM transcripts in tumor tissues. The methylation status of the ALCAM gene was not significantly different between tumor and normal tissues. The level of ALCAM transcripts was associated with the expression of TNFα, NF-κB p50, IL-4, and intratumoral inflammation. The IHC expression of ALCAM was associated with histologic grade, HER2 overexpression and molecular subtype. The expression of TNFα, NF-κB p50, and IL-4 showed significant association with the clinicopathologic characteristics. In conclusion, the ALCAM gene methylation was related to the level of ALCAM transcripts. Also, the level of ALCAM transcripts was associated with the inflammatory markers in breast cancer. Our results suggest that the methylation of the ALCAM gene contributes to the decreased expression of ALCAM. Also, ALCAM is linked to the inflammatory response in breast cancer.

  8. Synthesis and Antimicrobial and Antioxidant Activities of Some New 5-(2-Methyl-1H-indol-3-yl-1,3,4-oxadiazol-2-amine Derivatives

    Directory of Open Access Journals (Sweden)

    Anand R. Saundane

    2013-01-01

    Full Text Available A series of 5-(2-methyl-1H-indol-3-yl-1,3,4-oxadiazol-2-amine derivatives (3–5 were synthesized. These previously unknown compounds were characterized by spectral studies and elemental analysis. These compounds were evaluated for their antimicrobial and antioxidant activities. Among all the compounds tested 5d exhibited promising antibacterial, antifungal, radical scavenging, and ferric ions (Fe3+ reducing antioxidant power (FRAP activities, whereas the compounds 3b, 4c, and 5e exhibited good FRAP and metal chelating activities. In general compounds containing chloro and methyl substituent exhibited better antimicrobial and antioxidant activities.

  9. Biotransformation of Bicyclic Halolactones with a Methyl Group in the Cyclohexane Ring into Hydroxylactones and Their Biological Activity.

    Science.gov (United States)

    Wińska, Katarzyna; Grabarczyk, Małgorzata; Mączka, Wanda; Żarowska, Barbara; Maciejewska, Gabriela; Dancewicz, Katarzyna; Gabryś, Beata; Szumny, Antoni; Anioł, Mirosław

    2016-10-31

    The aim of this study was the chemical synthesis of a series of halo- and unsaturated lactones, as well as their microbial transformation products. Finally some of their biological activities were assessed. Three bicyclic halolactones with a methyl group in the cyclohexane ring were obtained from the corresponding γ,δ-unsaturated ester during a two-step synthesis. These lactones were subjected to screening biotransformation using twenty two fungal strains. These strains were tested on their ability to transform halolactones into new hydroxylactones. Among the six strains able to catalyze hydrolytic dehalogenation, only two ( Fusarium equiseti , AM22 and Yarrowia lipolytica , AM71) gave a product in a high yield. Moreover, one strain ( Penicillium wermiculatum , AM30) introduced the hydroxy group on the cyclohexane ring without removing the halogen atom. The biological activity of five of the obtained lactones was tested. Some of these compounds exhibited growth inhibition against bacteria, yeasts and fungi and deterrent activity against peach-potato aphid.

  10. Cytotoxic, thrombolytic, membrane stabilizing and anti-oxidant activities of Hygrophila schulli

    Directory of Open Access Journals (Sweden)

    Md. Abu Sufian

    2015-08-01

    Full Text Available The crude methanol extract of Hygrophila schulli and its petroleum ether, chloroform, ethyl acetate and aqueous soluble Kupchan partitionates were investigated for in vitro cytotoxic, thrombolytic, membrane stabilizing and anti-oxidant activities. In the brine shrimp lethality bioassay, the petroleum ether soluble extract of H. schulli showed significant cytotoxicity (LC50 = 0.1 µg/mL and LC90 = 15 µg/mL as compared to vincristine sulfate (LC50 = 0.4 µg/mL and LC90 = 9 µg/mL. Among all the partitionates, chloroform soluble fraction demonstrated the highest thrombolytic activity with 10.5% clot lyses. Moreover, in hypotonic- and heat-induced conditions, the chloroform soluble extractive inhibited hemolysis of human erythrocyte by 113.7% and 14.3%, respectively as compared to 71.9% and 42.2% demonstrated by standard acetylsalicylic acid. On the other hand, in anti-oxidant activity test, chloroform soluble fraction revealed mild antioxidant activity (IC50 = 195.1 µg/mL as compared to standard tert-butyl-1-hydroxytoluene (IC50 = 27.5 µg/mL.

  11. H3 lysine 4 is acetylated at active gene promoters and is regulated by H3 lysine 4 methylation.

    Directory of Open Access Journals (Sweden)

    Benoit Guillemette

    2011-03-01

    Full Text Available Methylation of histone H3 lysine 4 (H3K4me is an evolutionarily conserved modification whose role in the regulation of gene expression has been extensively studied. In contrast, the function of H3K4 acetylation (H3K4ac has received little attention because of a lack of tools to separate its function from that of H3K4me. Here we show that, in addition to being methylated, H3K4 is also acetylated in budding yeast. Genetic studies reveal that the histone acetyltransferases (HATs Gcn5 and Rtt109 contribute to H3K4 acetylation in vivo. Whilst removal of H3K4ac from euchromatin mainly requires the histone deacetylase (HDAC Hst1, Sir2 is needed for H3K4 deacetylation in heterochomatin. Using genome-wide chromatin immunoprecipitation (ChIP, we show that H3K4ac is enriched at promoters of actively transcribed genes and located just upstream of H3K4 tri-methylation (H3K4me3, a pattern that has been conserved in human cells. We find that the Set1-containing complex (COMPASS, which promotes H3K4me2 and -me3, also serves to limit the abundance of H3K4ac at gene promoters. In addition, we identify a group of genes that have high levels of H3K4ac in their promoters and are inadequately expressed in H3-K4R, but not in set1Δ mutant strains, suggesting that H3K4ac plays a positive role in transcription. Our results reveal a novel regulatory feature of promoter-proximal chromatin, involving mutually exclusive histone modifications of the same histone residue (H3K4ac and H3K4me.

  12. Synthesis and evaluation of [{sup 123}I]labelled analogues of the partial inverse agonist Ro 15-4513 for the study of diazepam-insensitive benzodiazepine receptors

    Energy Technology Data Exchange (ETDEWEB)

    Katsifis, Andrew E-mail: akx@ansto.gov.au; Mardon, Karine; McPhee, Meredith; Mattner, Filomena; Dikic, Branko; Ridley, Damon

    1999-08-01

    The imidazobenzodiazepines ethyl 8-iodo-5,6 dihydro-5-methyl-6-oxo-4H-imidazo[1,5a][1,4] benzodiazepine-3-carboxylate 1 and tert-butyl 8-iodo-5,6 dihydro-5-methyl-6-oxo-4H-imidazo [1,5a][1,4] benzodiazepine-3-carboxylate 2 were prepared to study the diazepam-insensitive (DI) benzodiazepine receptor (BZR) subtype. The [{sup 123}I] analogues were prepared via iododestannylation reactions in radiochemical yields of 70-80% and a specific activity >2,500 Ci/mmol. The tert-butyl analogue [{sup 123}I]-2 exhibited nanomolar affinity for BZRs in homogenate membranes of rat cerebellum with K{sub d} values for the diazepam-sensitive (DS) and DI receptors of 3.18{+-}0.58 and 13.55{+-}2.72 nM, respectively. The B{sub max} for cerebellar DS and DI receptors were 1,276{+-}195 and 518{+-}26 fmol/mg protein, respectively.

  13. Antimutagenic constituents of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) with potential cancer chemopreventive activity.

    Science.gov (United States)

    Chen, Huang-Hui; Chiang, Wenchang; Chang, Jang-Yang; Chien, Ya-Lin; Lee, Ching-Kuo; Liu, Ko-Jiunn; Cheng, Yen-Ting; Chen, Ting-Fang; Kuo, Yueh-Hsiung; Kuo, Ching-Chuan

    2011-06-22

    Adlay has long been used in traditional Chinese medicine and as a nourishing food. The acetone extract of adlay hull had previously been demonstrated to possess potent antimutagenic activity. The aims of this study were to identify the antimutagenic constituents from adlay hull by using Ames antimutagenic activity-guide isolation procedures and to investigate their chemopreventive efficacies in cultured cells. The results demonstrated that six compounds showing great antimutagenic activity were identified by spectroscopic methods and by comparison with authentic samples to be p-hydroxybenzaldehyde, vanillin, syringaldehyde, trans-coniferylaldehyde, sinapaldehyde, and coixol. Two of them, trans-coniferylaldehyde and sinapaldehyde, exhibit relatively potent scavenging of DPPH radicals, inhibit TPA stimulated superoxide anion generation in neutrophil-like leukocytes, and induce Nrf2/ARE-driven luciferase activity in HSC-3 cells. Moreover, trans-coniferylaldehyde possesses cytoprotective efficacy against tert-butyl hydroperoxide-induced DNA double-strand breaks in cultured cells, and the chemopreventive potency induced by trans-coniferylaldehyde may be through the activation of kinase signals, including p38, ERK1/2, JNK, MEK1/2, and MSK1/2. In summary, we first identified six antimutagenic constituents from adlay hull. Among them, trans-coniferylaldehyde would be a highly promising agent for cancer chemoprevention and merits further investigation.

  14. Preparation, characterization, and photocatalytic activity of sulfate-modified titania for degradation of methyl orange under visible light.

    Science.gov (United States)

    Parida, K M; Sahu, N; Biswal, N R; Naik, B; Pradhan, A C

    2008-02-15

    Hydrated titania was prepared by a sol-gel method, taking tetraisopropyl orthotitanate as starting material, and then promoted with different weight percentages of sulfate by an incipient wetness impregnation method. The materials were characterized by various advanced techniques such as PXRD, BET surface area, N(2) adsorption-desorption measurements, FTIR, and SEM. Analytical results demonstrated that TiO(2) is mesoporous in nature, and sulfate modification could inhibit the phase transformation and enhance the thermal stability of TiO(2). It was also found that sulfate modification could reduce the crystallite size and increase the specific surface area of the catalysts. The degradation of methyl orange under solar radiation was investigated to evaluate the photocatalytic activity of these materials. Effects of different parameters such as pH of the solution, amount of catalyst, additives, and kinetics were investigated. At 2.5 wt% sulfate loading, the average percentage of degradation of methyl orange was nearly two times than that of neat TiO(2). The photocatalytic degradation followed first-order kinetics.

  15. Protein complex interactor analysis and differential activity of KDM3 subfamily members towards H3K9 methylation.

    Directory of Open Access Journals (Sweden)

    Michael Brauchle

    Full Text Available Histone modifications play an important role in chromatin organization and gene regulation, and their interpretation is referred to as epigenetic control. The methylation levels of several lysine residues in histone tails are tightly controlled, and JmjC domain-containing proteins are one class of broadly expressed enzymes catalyzing methyl group removal. However, several JmjC proteins remain uncharacterized, gaps persist in understanding substrate recognition, and the integration of JmjC proteins into signaling pathways is just emerging. The KDM3 subfamily is an evolutionarily conserved group of histone demethylase proteins, thought to share lysine substrate specificity. Here we use a systematic approach to compare KDM3 subfamily members. We show that full-length KDM3A and KDM3B are H3K9me1/2 histone demethylases whereas we fail to observe histone demethylase activity for JMJD1C using immunocytochemical and biochemical approaches. Structure-function analyses revealed the importance of a single amino acid in KDM3A implicated in the catalytic activity towards H3K9me1/2 that is not conserved in JMJD1C. Moreover, we use quantitative proteomic analyses to identify subsets of the interactomes of the 3 proteins. Specific interactor candidates were identified for each of the three KDM3 subfamily members. Importantly, we find that SCAI, a known transcriptional repressor, interacts specifically with KDM3B. Taken together, we identify substantial differences in the biology of KDM3 histone demethylases, namely enzymatic activity and protein-protein interactions. Such comparative approaches pave the way to a better understanding of histone demethylase specificity and protein function at a systems level and are instrumental in identifying the more subtle differences between closely related proteins.

  16. Antioxidant activity of Nepeta nuda L. ssp. nuda essential oil rich in nepetalactones from Greece.

    Science.gov (United States)

    Gkinis, George; Bozin, Biljana; Mimica-Dukic, Neda; Tzakou, Olga

    2010-10-01

    Essential oils from air-dried leaves and verticillasters of Nepeta nuda ssp. nuda from Greece were analyzed by means of gas chromatography-flame ionization detection and gas chromatography-mass spectrometry. The dominant constituent in the verticillaster oils was 4aα,7α,7aß-nepetalactone (75.7%). The main metabolites of the leaf oil were 1,8-cineole (16.7%), 4aα,7α,7aß-nepetalactone (24.7%), and caryophyllene oxide (16.3%). The oils were examined for their antioxidant activity. Neutralization of stable 2,2-diphenyl-1-picrylhydrazyl radical ranged from 10.83% (2.50 μg/mL) to 58.64% (50.00 μg/mL) for verticillaster oil and from 6.25% (2.50 μg/mL) to 57.79% (50.00 μg/mL) for leaf oil. The essential oil from verticillasters had significant effects on lipid peroxidation (in the range of 41.18-59.23%), compared to tert-butylated hydroxytoluene (37.04%). In contrast, the essential oil from leaves exhibited pro-oxidant activity at the highest concentration applied.

  17. Metabolite Profile Resulting from the Activation/Inactivation of 1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine and 2-Methyltetrahydro-β-carboline by Oxidative Enzymes

    Directory of Open Access Journals (Sweden)

    Tomás Herraiz

    2013-01-01

    Full Text Available Metabolic enzymes are involved in the activation/deactivation of the 1-methyl-4-phenyl-1,2,3,6-tetrahydropyiridine (MPTP neurotoxin and its naturally occurring analogs 2-methyltetrahydro-β-carbolines. The metabolic profile and biotransformation of these protoxins by three enzymes, monoamine oxidase (MAO, cytochrome P450, and heme peroxidases (myeloperoxidase and lactoperoxidase, were investigated and compared. The metabolite profile differed among the enzymes investigated. MAO and heme peroxidases activated these substances to toxic pyridinium and β-carbolinium species. MAO catalyzed the oxidation of MPTP to 1-methyl-4-phenyl-2,3-dihydropyridinium cation (MPDP+, whereas heme peroxidases catalyzed the oxidation of MPDP+ to 1-methyl-4-phenylpyridinium (MPP+ and of 2-methyltetrahydro-β-carboline to 2-methyl-3,4-dihydro-β-carbolinium cation (2-Me-3,4-DHβC+. These substances were inactivated by cytochrome P450 2D6 through N-demethylation and aromatic hydroxylation (MPTP and aromatic hydroxylation (2-methyltetrahydro-β-carboline. In conclusion, the toxicological effects of these protoxins might result from a balance between the rate of their activation to toxic products (i.e., N-methylpyridinium-MPP+ and MPDP+- and N-methyl-β-carbolinium—βC+— by MAO and heme peroxidases and the rate of inactivation (i.e., N-demethylation, aromatic hydroxylation by cytochrome P450 2D6.

  18. Crude cacao Theobroma cacao extract reduces mutagenicity induced by benzo[a]pyrene through inhibition of CYP1A activity in vitro.

    Science.gov (United States)

    Ohno, Marumi; Sakamoto, Kentaro Q; Ishizuka, Mayumi; Fujita, Shoichi

    2009-08-01

    Polyphenols have been shown to have potent antioxidant activity, and therefore, food containing polyphenols is expected to contribute to the prevention of cancer. However, food contains not only polyphenols but also various other constituents. We used the Ames test to investigate the effects of crude extracts of whole cacao products, which are known to be rich in polyphenols, on the mutagenicity of benzo[a]pyrene (B[a]P) in Salmonella typhimurium strain TA 98 and tert-butyl hydroperoxide (t-BuOOH) in S. typhimurium strain TA 102. B[a]P induces mutagenicity by metabolic activation and t-BuOOH induces it by generation of free radicals. While white chocolate did not modulate the numbers of revertant colonies produced by B[a]P treatment, milk chocolate and cacao powder extracts did. On the other hand, surprisingly, none of the cacao products tested affected the number of revertant colonies when t-BuOOH was used as the mutagen. At maximum concentration (13.25 mg cacao powder/ml), the crude cacao powder extract reduced ethoxyresorufin O-deethylase activity to 17.4% of the control, suggesting that whole cacao products inhibit cytochrome P450 (CYP) 1A activity. In conclusion, inhibition of CYP1A activity by cacao products may prevent DNA damage by reducing metabolic activation of carcinogens. Copyright 2009 John Wiley & Sons, Ltd.

  19. Antibacterial activity of methylated egg white proteins against pathogenic G(+) and G(-) bacteria matching antibiotics.

    Science.gov (United States)

    Abdel-Shafi, Seham; Osman, Ali; Enan, Gamal; El-Nemer, Mona; Sitohy, Mahmoud

    2016-01-01

    Native egg white protein with high level of acidic amino acid residues (pI = 4.8) and hydrophilic nature was transformed into its methylated derivative (MEW), acquiring rather hydrophobic and basic character (pI = 8). The MIC of MEW against ten studied bacteria (G(+) and G(-)) ranged between 0.5 and 1 μg/disc matching or excelling the comparative values of some known specific antibiotics (ranging from 1 to 7.5 μg/disc). Combinations of MEW (1 MIC) and different ready-made disc concentrations of antibiotics indicated either nil, antagonistic or synergistic antimicrobial effect. Replacing the antibiotic Ciprofloxacin by gradual levels of MEW (20-100 %) proportionally increased the potentiality to induce bigger sized inhibition zones. MEW (1 MIC) could inhibit the growth of 6 G(+) and 4 G(-) pathogenic bacteria in their liquid broth media during 24 h at 37 °C, indicating its broad and wide specificity. TEM examination indicated the susceptibility of the two types of bacteria (G(+) and G(-)) to the antimicrobial action of MEW as manifested in different signs of cellular deformations, confirming its broad specificity and its mode of action was rather targeting the cell wall and cell membrane.

  20. Photo Degradation of Methyl Orange by Persulfate Activated with Zero Valent Iron

    Science.gov (United States)

    Munkoeva, V. A.; Sizykh, M. R.; Batoeva, A. A.

    2017-11-01

    The oxidative degradation of Methyl Orange (MO) subjected to direct photolysis (Solar) and various oxidative systems was studied. The comparative experiments have shown that MO conversion and mineralization increases in the following order: Solar ∼ Solar/Fe0 ∼ Solar/S2O82- concentrations of MO:S2O82-:Fe0, pH and temperature of the reaction medium) on the degree of MO conversion and mineralization was studied. The optimal pH and temperature of the reaction medium were 5.8 and 25°C, respectively. The rate of MO decomposition and mineralization increased proportionally to the initial concentration of the oxidant at the molar ratios [S2O82-] :[MO] ≤ 12. Judging by the nature of the kinetic curves, a further increase of this ratio is impractical. However, an increase in the oxidant concentration had a positive effect on the degrees of conversion and mineralization of total organic carbon (TOC). Thus, at the ratios of 12:1 and 48:1, the conversion efficiency of TOC was 23 and 60 %, respectively. The optimal concentration of Fe0 was 100 mg/l.

  1. UV-H2O2 degradation of methyl orange catalysed by H3PW12O40/activated clay.

    Science.gov (United States)

    Wei, Guangtao; Zhang, Linye; Wei, Tengyou; Luo, Qiyu; Tong, Zhangfa

    2012-01-01

    A catalyst consisting of phosphotungstic acid (H3PW12O40) combined with activated clay was prepared by the impregnation method, and an experiment was carried out to evaluate the catalytic activity of the H3PW12O40/activated clay for the degradation of methyl orange (MO) in the UV-H2O2 process. The degradation ratio of MO can be affected by H2O2 concentration, reaction time, catalyst dosage, pH and temperature. The reaction temperature should be controlled at less than 70 degrees C, and the catalyst has a wide applicable pH range in the UV-H2O2 process. Hydroxyl radicals were generated in the UV-H2O2 system under the action of H3PW12O40/activated clay, and MO was degraded by hydroxyl radicals. Compared with traditional catalysts used in UV-H2O2 systems, H3PW12O40/activated clay has certain advantages for its practical application.

  2. Silver halide/silver iodide@silver composite with excellent visible light photocatalytic activity for methyl orange degradation.

    Science.gov (United States)

    Zeng, Cuiyun; Tian, Baozhu; Zhang, Jinlong

    2013-09-01

    AgBr/AgI@Ag composite photocatalyst was prepared by a handy multistep route, including controllable double-jet precipitation to synthesize cubic AgBr microcrystals, ion exchange to form AgI on AgBr surface, and visible light reduction to generate Ag nanoparticles. UV-Vis diffuse reflectance and electrochemical impedance spectra demonstrated that AgBr/AgI composite structure not only favors forming more silver nanoparticles to harvest visible light but also facilitates the transfer of charge carriers when compared with pure AgBr. Beneficial from the synergistic effect of highly effective visible light harvest and electron-hole separation, AgBr/AgI@Ag shows higher photocatalytic activity for the degradation of methyl orange (MO) than AgBr, AgBr@Ag, and AgBr/AgBr. Copyright © 2013 Elsevier Inc. All rights reserved.

  3. A symmetric supercapacitor based on 30% poly (methyl methacrylate) grafted natural rubber (MG30) polymer and activated carbon electrodes

    Science.gov (United States)

    Zaki, Nur Hamizah Mohd; Mahmud, Zaidatul Salwa; Hassan, Oskar Hasdinor; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

    2017-08-01

    This article focuses on polymer-based gel electrolytes because basic features good self-standing characteristics, conductivity, and excellent window stability for supercapacitor devices when compared to aqueous electrolytes. Gel polymer electrolytes (GPEs) based on 30% poly (methyl methacrylate) grafted natural rubber (MG30) doped with ammonium triflate (NH4CF3SO3) and plasticized with ethylene carbonate (EC) were prepared by a solution casting method. Owing to being plasticized, the GPEs exhibit high room temperature ionic conductivity of 9.61×10-4 S.cm-1 at the composition of 26:14:60 wt% for MG30: NH4CF3SO3: EC. Linear sweep voltammogram study shows the highest conducting GPE exhibited electrochemical window stability of 2.7V. The GPEs has been employed to demonstrate the possibility of fabricating supercapacitor. Symmetric devices assembled using activated carbon as electrodes and GPEs (highest conducting) exhibit a specific capacitance of 32 F.g-1.

  4. Synthesis of copper sulfides with different morphologies in DMF and water: catalytic activity for methyl orange reduction

    Science.gov (United States)

    Rahmani, Alireza; Rahmani, Hossein; Zonouzi, Afsaneh

    2017-12-01

    Copper sulfides (covellite, digenite and djurleite) were synthesized using microwave irradiation. Copper acetate and thiourea were chosen as precursors and used at a fixed ratio. Crystalline phase and morphology (particles, spheres and inter-grown belts) were changed by only changing the synthetic media (water, DMF and a 1:1 V/V mixture of them). A domestic microwave oven was used at 1000 watt for only 20 s for each synthesis. The obtained samples were characterized using powder XRD, FESEM, and EDX; results were used to postulate the differences in phase and morphology of the obtained samples. All samples were tested as reduction catalysts for methyl orange degradation by NaBH4 and time-dependent UV–vis spectroscopy was used to compare their activity.

  5. Propolis in Kenya: Antioxidative and Radical Scavenging Activity in ...

    African Journals Online (AJOL)

    Dept. of Food Science & Technology

    2013-01-01

    Jan 1, 2013 ... disease and cancer [1]. Synthetic antioxidants, such as butylated hydroxyanisole. (BHA), butylated hydroxyltoluene (BHT), and tert-butyl hydroquinone (TBHQ), are widely used in the food industry because they are effective and less expensive than natural antioxidants. Their safety however, has been ...

  6. Active Razor Shell CaO Catalyst Synthesis for Jatropha Methyl Ester Production via Optimized Two-Step Transesterification

    Directory of Open Access Journals (Sweden)

    A. N. R. Reddy

    2017-01-01

    Full Text Available Calcium based catalysts have been studied as promising heterogeneous catalysts for production of methyl esters via transesterification; however a few were explored on catalyst synthesis with high surface area, less particle size, and Ca leaching analysis. In this work, an active Razor shell CaO with crystalline size of 87.2 nm, SBET of 92.63 m2/g, pore diameters of 37.311 nm, and pore volume of 0.613 cc/g was synthesized by a green technique “calcination-hydro aeration-dehydration.” Spectrographic techniques TGA/DTA, FTIR, SEM, XRD, BET&BJH, and PSA were employed for characterization and surface morphology of CaO. Two-step transesterification of Jatropha curcas oil was performed to evaluate CaO catalytic activity. A five-factor-five-level, two-block, half factorial, central composite design based response surface method was employed for experimental analysis and optimization of Jatropha methyl ester (JME yield. The regression model adequacy ascertained thru coefficient of determination (R2: 95.81%. A JME yield of 98.80% was noted at C (3.10 wt.%, M (54.24 mol./mol.%, T (127.87 min, H (51.31°C, and R (612 rpm. The amount of Ca leached to JME during 1st and 4th reuse cycles was 1.43 ppm ± 0.11 and 4.25 ppm ± 0.21, respectively. Higher leaching of Ca, 6.67 ppm ± 1.09, was found from the 5th reuse cycle due to higher dispersion of Ca2+; consequently JME yield reduces to 76.40%. The JME fuel properties were studied according to biodiesel standards EN 14214 and comply to use as green biodiesel.

  7. Active and efficient Co-N/C catalysts derived from cobalt porphyrin for selective oxidation of alkylaromatics

    Science.gov (United States)

    Chen, Yuan; Jie, Shanshan; Yang, Congqiang; Liu, Zhigang

    2017-10-01

    The development of highly active and efficient heterogeneous catalytic oxidation systems has become an attractive research area. In this study, nano cobalt-coordinated nitrogen-doped carbon catalysts (Co-N/C), which were prepared by the pyrolysis of cobalt porphyrin supported on carbon black precursor, were used as highly active catalysts for the oxidation of hydrocarbons with tert-butyl hydroperoxide as the oxidant. The results showed that the catalyst was efficient in the selective oxidation of a variety of saturated (including primary, secondary, and tertiary) Csbnd H bonds. The catalyst displayed the best catalytic performance, which was comparable to those for previously reported metal oxide catalysts and even better. The resultant Co-N/C catalysts were characterized in detail by XRD, nitrogen adsorption/desorption isotherms, TEM, SEM and XPS. The homogeneous distribution of the Co species and interactions between the Co-N species could improve the synergistic effect between the Cosbnd O, Cosbnd N and Nsbnd C species, which led to their excellent catalytic performance. A first order kinetics was observed for the reaction with the apparent activation energy for ethylbenzene oxidation was 22.2 ± 2.1 kJ mol-1.

  8. A Novel Strategy Towards the Asymmetric Synthesis of Orthogonally Funtionalised 2-N-Benzyl-N-α-methylbenzylamino- 5-carboxymethyl-cyclopentane-1-carboxylic acid.

    Directory of Open Access Journals (Sweden)

    Julio G. Urones

    2004-04-01

    Full Text Available The asymmetric synthesis of the orthogonally funtionalised compounds tert-butyl 2-N-benzyl-N-α-methylbenzylamino-5-methoxycarbonylmethylcyclopentane- 1-carboxylate and methyl 2-N-benzyl-N-α-methylbenzylamino-5–carboxymethylcyclo- pentane-1-carboxylate by a domino reaction of tert-butyl methyl (E,E-octa-2,6- diendioate with lithium N-α-methylbenzyl-N-benzylamide initiated by a Michael addition, subsequent 5-exo-trig intramolecular cyclisation and posterior selective hydrolysis with trifluoroacetic acid is reported.

  9. VTP as an Active Layer in a Vertical Organic Field Effect Transistor

    Science.gov (United States)

    Roslan, Nur Adilah; Abdullah, Shahino Mah; Halizan, Muhammad Zharfan Mohd; Bawazeer, Tahani M.; Alsenany, Nourah; Alsoufi, Mohammad S.; Majid, Wan Haliza Abdul; Supangat, Azzuliani

    2017-12-01

    In this letter, a p-type organic material from metal phthalocyanine (MPc) derivative, vanadyl 3,10,17,24-tetra-tert-butyl-1,8,15,22-tetrakis (dimethylamino)-29H,31H-phthalocyanine (VTP) has been utilized for fabrication of an organic electronic device. Prior to the fabrication of a vertical organic field effect transistor (VOFET), fundamental work in investigating the energy level of VTP has been done through determination of oxidation and reduction potentials. Energy levels of VTP were calculated based on the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of cyclic voltammetry (CV) and UV-vis analyses. Subsequently, the soluble VTP was employed as an active layer in VOFET with different thicknesses of 90.4 nm, 66.4 nm, and 52.1 nm. It is found that a device with 66.4 nm VTP's thickness showed the optimum performance, by giving the maximum current density and lowest threshold voltage of around 37 mA/cm2 and 7.1 V, respectively. The effects of the channel thickness on the semi-transparent VOFET devices are explained in this work.

  10. Novel Organotin(IV) Schiff Base Complexes with Histidine Derivatives: Synthesis, Characterization, and Biological Activity

    Science.gov (United States)

    Garza-Ortiz, Ariadna; Camacho-Camacho, Carlos; Sainz-Espuñes, Teresita; Rojas-Oviedo, Irma; Gutiérrez-Lucas, Luis Raúl; Gutierrez Carrillo, Atilano; Vera Ramirez, Marco A.

    2013-01-01

    Five novel tin Schiff base complexes with histidine analogues (derived from the condensation reaction between L-histidine and 3,5-di-tert-butyl-2-hydroxybenzaldehyde) have been synthesized and characterized. Characterization has been completed by IR and high-resolution mass spectroscopy, 1D and 2D solution NMR (1H, 13C  and 119Sn), as well as solid state 119Sn NMR. The spectroscopic evidence shows two types of structures: a trigonal bipyramidal stereochemistry with the tin atom coordinated to five donating atoms (two oxygen atoms, one nitrogen atom, and two carbon atoms belonging to the alkyl moieties), where one molecule of ligand is coordinated in a three dentate fashion. The second structure is spectroscopically described as a tetrahedral tin complex with four donating atoms (one oxygen atom coordinated to the metal and three carbon atoms belonging to the alkyl or aryl substituents), with one molecule of ligand attached. The antimicrobial activity of the tin compounds has been tested against the growth of bacteria in vitro to assess their bactericidal properties. While pentacoordinated compounds 1, 2, and 3 are described as moderate effective to noneffective drugs against both Gram-positive and Gram-negative bacteria, tetracoordinated tin(IV) compounds 4 and 5 are considered as moderate effective and most effective compounds, respectively, against the methicillin-resistant Staphylococcus aureus strains (Gram-positive). PMID:23864839

  11. Adsorption of Cu(2+) and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes.

    Science.gov (United States)

    Hou, Xiao-Xu; Deng, Qing-Fang; Ren, Tie-Zhen; Yuan, Zhong-Yong

    2013-12-01

    Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO3 activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu(2+) and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N2 adsorption, CO2 adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.

  12. 2C-Methyl-d-erythritol 4-phosphate enhances and sustains cyclodiphosphate synthase IspF activity

    Science.gov (United States)

    Bitok, J. Kipchirchir; Freel Meyers, Caren

    2012-01-01

    There is significant progress toward understanding catalysis throughout the essential MEP pathway to isoprenoids in human pathogens; however, little is known about pathway regulation. The present study begins by testing the hypothesis that isoprenoid biosynthesis is regulated via feedback inhibition of the fifth enzyme cyclodiphosphate IspF by downstream isoprenoid diphosphates. Here, we demonstrate recombinant E. coli IspF is not inhibited by downstream metabolites and isopentenyl diphosphate (IDP), dimethylallyl diphosphate (DMADP), geranyl diphosphate (GDP) and farnesyl diphosphate (FDP) under standard assay conditions. However, 2C-methyl-d-erythritol 4-phosphate (MEP), the product of reductoisomerase IspC and first committed MEP pathway intermediate, activates and sustains this enhanced IspF activity, and the IspF-MEP complex is inhibited by FDP. We further show that the methylerythritol scaffold itself, which is unique to this pathway, drives the activation and stabilization of active IspF. Our results suggest a novel feed-forward regulatory mechanism for 2Cmethyl-d-erythritol 2,4-cyclodiphosphate (MEcDP) production and support an isoprenoid biosynthesis regulatory mechanism via feedback inhibition of the IspF-MEP complex by FDP. The results have important implications for development of inhibitors against the IspF-MEP complex, which may be the physiologically relevant form of the enzyme. PMID:22839733

  13. Theoretical and Kinetic Tools for Selecting Effective Antioxidants: Application to the Protection of Omega-3 Oils with Natural and Synthetic Phenols.

    Science.gov (United States)

    Guitard, Romain; Nardello-Rataj, Véronique; Aubry, Jean-Marie

    2016-07-29

    Radical-scavenging antioxidants play crucial roles in the protection of unsaturated oils against autoxidation and, especially, edible oils rich in omega-3 because of their high sensitivity to oxygen. Two complementary tools are employed to select, among a large set of natural and synthetic phenols, the most promising antioxidants. On the one hand, density functional theory (DFT) calculations provide bond dissociation enthalpies (BDEs) of 70 natural (i.e., tocopherols, hydroxybenzoic and cinnamic acids, flavonoids, stilbenes, lignans, and coumarins) and synthetic (i.e., 2,6-di-tert-butyl-4-methylphenol (BHT), 3-tert-butyl-4-hydroxyanisol (BHA), and tert-butylhydroquinone (TBHQ)) phenols. These BDEs are discussed on the basis of structure-activity relationships with regard to their potential antioxidant activities. On the other hand, the kinetic rate constants and number of hydrogen atoms released per phenol molecule are measured by monitoring the reaction of phenols with 2,2-diphenyl-1-picrylhydrazyl (DPPH(•)) radical. The comparison of the results obtained with these two complementary methods allows highlighting the most promising antioxidants. Finally, the antioxidant effectiveness of the best candidates is assessed by following the absorption of oxygen by methyl esters of linseed oil containing 0.5 mmol L(-1) of antioxidant and warmed at 90 °C under oxygen atmosphere. Under these conditions, some natural phenols namely epigallocatechin gallate, myricetin, rosmarinic and carnosic acids were found to be more effective antioxidants than α-tocopherol.

  14. Theoretical and Kinetic Tools for Selecting Effective Antioxidants: Application to the Protection of Omega-3 Oils with Natural and Synthetic Phenols

    Directory of Open Access Journals (Sweden)

    Romain Guitard

    2016-07-01

    Full Text Available Radical-scavenging antioxidants play crucial roles in the protection of unsaturated oils against autoxidation and, especially, edible oils rich in omega-3 because of their high sensitivity to oxygen. Two complementary tools are employed to select, among a large set of natural and synthetic phenols, the most promising antioxidants. On the one hand, density functional theory (DFT calculations provide bond dissociation enthalpies (BDEs of 70 natural (i.e., tocopherols, hydroxybenzoic and cinnamic acids, flavonoids, stilbenes, lignans, and coumarins and synthetic (i.e., 2,6-di-tert-butyl-4-methylphenol (BHT, 3-tert-butyl-4-hydroxyanisol (BHA, and tert-butylhydroquinone (TBHQ phenols. These BDEs are discussed on the basis of structure–activity relationships with regard to their potential antioxidant activities. On the other hand, the kinetic rate constants and number of hydrogen atoms released per phenol molecule are measured by monitoring the reaction of phenols with 2,2-diphenyl-1-picrylhydrazyl (DPPH• radical. The comparison of the results obtained with these two complementary methods allows highlighting the most promising antioxidants. Finally, the antioxidant effectiveness of the best candidates is assessed by following the absorption of oxygen by methyl esters of linseed oil containing 0.5 mmol L−1 of antioxidant and warmed at 90 °C under oxygen atmosphere. Under these conditions, some natural phenols namely epigallocatechin gallate, myricetin, rosmarinic and carnosic acids were found to be more effective antioxidants than α-tocopherol.

  15. DNA Protecting Activities of Nymphaea nouchali (Burm. f Flower Extract Attenuate t-BHP-Induced Oxidative Stress Cell Death through Nrf2-Mediated Induction of Heme Oxygenase-1 Expression by Activating MAP-Kinases

    Directory of Open Access Journals (Sweden)

    Md Badrul Alam

    2017-09-01

    Full Text Available This study was performed to investigate the antioxidant activities of Nymphaea nouchali flower (NNF extract and the underlying mechanism using RAW 264.7 cells. The presence of gallic acid, catechin, epicatechin, epigallocatechin, epicatechin gallate, caffeic acid, quercetin, and apigenin in the NNF was confirmed by high-performance liquid chromatography (HPLC. The extract had a very potent capacity to scavenge numerous free radicals. NNF extract was also able to prevent DNA damage and quench cellular reactive oxygen species (ROS generation induced by tert-Butyl hydroperoxide (t-BHP with no signs of toxicity. The NNF extract was able to augment the expression of both primary and phase II detoxifying enzyme, resulting in combat the oxidative stress. This is accomplished by phosphorylation of mitogen-activated protein kinase (MAP kinase (p38 kinase and extracellular signal-regulated kinase (ERK followed by enhancing the nuclear translocation of the nuclear factor erythroid 2-related factor 2 (Nrf2. This attenuates cellular ROS generation and confers protection from cell death. Altogether, the results of current study revealed that Nymphaea nouchali flower could be a source of natural phytochemicals that could lead to the development of new therapeutic agents for preventing oxidative stress associated diseases and attenuating disease progression.

  16. Alkylphenol Activity against Candida spp. and Microsporum canis: A Focus on the Antifungal Activity of Thymol, Eugenol and O-Methyl Derivatives

    Directory of Open Access Journals (Sweden)

    Ynayara C. Lima

    2011-07-01

    Full Text Available In recent years there has been an increasing search for new antifungal compounds due to the side effects of conventional antifungal drugs and fungal resistance. The aims of this study were to test in vitro the activity of thymol, eugenol, estragole and anethole and some O-methyl-derivatives (methylthymol and methyleugenol against Candida spp. and Microsporum canis. The broth microdilution method was used to determine the minimum inhibitory concentration (MIC. The minimum fungicidal concentrations (MFC for both Candida spp. and M. canis were found by subculturing each fungal suspension on potato dextrose agar. Thymol, methylthymol, eugenol, methyl-eugenol, anethole, estragole and griseofulvin respectively, presented the following MIC values against M. canis: 4.8–9.7; 78–150; 39; 78–150; 78–150; 19–39 µg/mL and 0.006–2.5 mg/mL. The MFC values for all compounds ranged from 9.7 to 31 µg/mL. Concerning Candida spp, thymol, methylthymol, eugenol, methyleugenol, anethole, estragole and amphotericin, respectively, showed the following MIC values: 39; 620–1250; 150–620; 310–620; 620; 620–1250 and 0.25–2.0 mg/mL. The MFC values varied from 78 to 2500 µg/mL. All tested compounds thus showed in vitro antifungal activity against Candida spp. and M. canis. Therefore, further studies should be carried out to confirm the usefulness of these alkylphenols in vivo.

  17. Regulation of Active DNA Demethylation by a Methyl-CpG-Binding Domain Protein in Arabidopsis thaliana.

    Directory of Open Access Journals (Sweden)

    Qi Li

    2015-05-01

    Full Text Available Active DNA demethylation plays crucial roles in the regulation of gene expression in both plants and animals. In Arabidopsis thaliana, active DNA demethylation is initiated by the ROS1 subfamily of 5-methylcytosine-specific DNA glycosylases via a base excision repair mechanism. Recently, IDM1 and IDM2 were shown to be required for the recruitment of ROS1 to some of its target loci. However, the mechanism(s by which IDM1 is targeted to specific genomic loci remains to be determined. Affinity purification of IDM1- and IDM2- associating proteins demonstrated that IDM1 and IDM2 copurify together with two novel components, methyl-CpG-binding domain protein 7 (MBD7 and IDM2-like protein 1 (IDL1. IDL1 encodes an α-crystallin domain protein that shows high sequence similarity with IDM2. MBD7 interacts with IDM2 and IDL1 in vitro and in vivo and they form a protein complex associating with IDM1 in vivo. MBD7 directly binds to the target loci and is required for the H3K18 and H3K23 acetylation in planta. MBD7 dysfunction causes DNA hypermethylation and silencing of reporter genes and a subset of endogenous genes. Our results suggest that a histone acetyltransferase complex functions in active DNA demethylation and in suppression of gene silencing at some loci in Arabidopsis.

  18. Pretreatment of Parsley (Petroselinum crispum L.) Suspension Cultures with Methyl Jasmonate Enhances Elicitation of Activated Oxygen Species.

    Science.gov (United States)

    Kauss, H.; Jeblick, W.; Ziegler, J.; Krabler, W.

    1994-05-01

    Suspension-cultured cells of parsley (Petroselinum crispum L.) were used to demonstrate an influence of jasmonic acid methyl ester (JAME) on the elicitation of activated oxygen species. Preincubation of the cell cultures for 1 d with JAME greatly enhanced the subsequent induction by an elicitor preparation from cell walls of Phytophtora megasperma f. sp. glycinea (Pmg elicitor) and by the polycation chitosan. Shorter preincubation times with JAME were less efficient, and the effect was saturated at about 5 [mu]M JAME. Treatment of the crude Pmg elicitor with trypsin abolished induction of activated oxygen species, an effect similar to that seen with elicitation of coumarin secretion. These results suggest that JAME conditioned the parsley suspension cells in a time-dependent manner to become more responsive to elicitation, reminiscent of developmental effects caused by JAME in whole plants. It is interesting that pretreatment of the parsley cultures with 2,6-dichloroisonicotinic and 5-chlorosalicylic acid only slightly enhanced the elicitation of activated oxygen species, whereas these substances greatly enhanced the elicitation of coumarin secretion. Therefore, these presumed inducers of systemic acquired resistance exhibit a specificity different from JAME.

  19. Synthesis, characterization, thermal behavior and antimicrobial activity of 3-methyl benzoate complexes of transition metal with hydrazine

    Directory of Open Access Journals (Sweden)

    S. Mohanapriya

    2016-08-01

    Full Text Available Reaction of the ligands, 3-methyl benzoic acid (mbH and hydrazine with transition metal ions form the complexes of formulae, [M(N2H42(mb2].H2O where M = Co(II and Zn(II at pH = 5-6, [M(N2H4n(mb2].xH2O where M = Ni(II, n = 2, x = 0 at pH = 5 and M = Cd, n = 1, x = 1 at pH = 6. The same acid also forms metal carboxylates with zinc and copper of formula, [Zn(mb2H2O].H2O at pH = 6 and [Cu(mb2].H2O at pH = 5, respectively. The IR spectra of the complexes show that hydrazine is present as bridging bidentate ligand and the carboxylic acid as monodentate bridging carboxylate anion. The electronic spectra, magnetic moments and ESR spectral data suggest the coordination number. Thermal studies show that cobalt, zinc and nickel complexes containing hydrazine, and carboxylates of copper, zinc on their thermal decomposition form the corresponding metal oxides in nano size in the temperature range 755-815 °C. The antibacterial and antifungal activity show that both activities of the complexes are higher than that of the acid and among the complexes, cadmium compound shows more antimicrobial activity towards bacteria and fungi.

  20. Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

    Science.gov (United States)

    Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

    2017-10-01

    Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.

  1. Enhanced visible light photocatalytic activity of copper-doped titanium oxide-zinc oxide heterojunction for methyl orange degradation

    Science.gov (United States)

    Dorraj, Masoumeh; Alizadeh, Mahdi; Sairi, Nor Asrina; Basirun, Wan Jefrey; Goh, Boon Tong; Woi, Pei Meng; Alias, Yatimah

    2017-08-01

    A novel Cu-doped TiO2 coupled with ZnO nanoparticles (Cu-TiO2/ZnO) was prepared by sol-gel method and subsequent precipitation for methyl orange (MO) photodegradation under visible light irradiation. The compositions and shapes of the as-prepared Cu-TiO2/ZnO nanocomposites were characterized by photoluminescence spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV-vis diffuse reflectance spectra and Brunauer-Emmett-Teller adsorption isotherm techniques. The Cu-TiO2/ZnO nanocomposites showed considerably higher photocatalytic activity for MO removal from water under visible light irradiation than that of single-doped semiconductors. The effects of Cu-TiO2 and ZnO mass ratios on the photocatalytic reaction were also studied. A coupling percentage of 30% ZnO exhibited the highest photocatalytic activity. The enhanced photocatalytic activity of the Cu-TiO2/ZnO nanocomposites was mainly attributed to heterojunction formation, which allowed the efficient separation of photoinduced electron-hole pairs at the interface. Moreover, these novel nanocomposites could be recycled during MO degradation in a three-cycle experiment without evident deactivation, which is particularly important in environmental applications.

  2. Activated carbons from end-products of tree nut and tree fruit production as sorbents for removing methyl bromide in ventilation effluent from postharvest chamber fumigation

    Science.gov (United States)

    End-products of tree nuts and tree fruits grown in California, USA were evaluated for the ability to remove methyl bromide from the ventilation effluent of postharvest chamber fumigations. Activated carbon sorbents from walnut and almond shells as well as peach and prune pits were prepared using dif...

  3. Antioxidant activity of gallic acid and methyl gallate in triacylglycerols of Kilka fish oil and its oil-in-water emulsion.

    Science.gov (United States)

    Asnaashari, Maryam; Farhoosh, Reza; Sharif, Ali

    2014-09-15

    The anti-DPPH radical effect as well as anti-peroxide activity of gallic acid, methyl gallate, and α-tocopherol in a bulk Kilka fish oil and its oil-in-water emulsion stabilized by soy protein isolate at 55°C were investigated. Gallic acid with the lowest hydrophobicity (log P=-0.28) was found to be the most active antiradical agent (IC50=29.5 μM), followed by methyl gallate (IC50=38.0 μM, log P=-0.23) and α-tocopherol (IC50=105.3 μM, log P=0.70). The anti-peroxide activity in the bulk oil system decreased in the order of methyl gallate>gallic acid>α-tocopherol. In the emulsion system, methyl gallate still behaved better than gallic acid, but the highest activity belonged to α-tocopherol. Based on the calculation of a number of kinetic parameters, the antioxidants, in general, showed better performances in the bulk oil system than in the emulsion system. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Differential roles for MBD2 and MBD3 at methylated CpG islands, active promoters and binding to exon sequences.

    Science.gov (United States)

    Günther, Katharina; Rust, Mareike; Leers, Joerg; Boettger, Thomas; Scharfe, Maren; Jarek, Michael; Bartkuhn, Marek; Renkawitz, Rainer

    2013-03-01

    The heterogeneous collection of nucleosome remodelling and deacetylation (NuRD) complexes can be grouped into the MBD2- or MBD3-containing complexes MBD2-NuRD and MBD3-NuRD. MBD2 is known to bind to methylated CpG sequences in vitro in contrast to MBD3. Although functional differences have been described, a direct comparison of MBD2 and MBD3 in respect to genome-wide binding and function has been lacking. Here, we show that MBD2-NuRD, in contrast to MBD3-NuRD, converts open chromatin with euchromatic histone modifications into tightly compacted chromatin with repressive histone marks. Genome-wide, a strong enrichment for MBD2 at methylated CpG sequences is found, whereas CpGs bound by MBD3 are devoid of methylation. MBD2-bound genes are generally lower expressed as compared with MBD3-bound genes. When depleting cells for MBD2, the MBD2-bound genes increase their activity, whereas MBD2 plus MBD3-bound genes reduce their activity. Most strikingly, MBD3 is enriched at active promoters, whereas MBD2 is bound at methylated promoters and enriched at exon sequences of active genes.

  5. A TGFβ-PRMT5-MEP50 axis regulates cancer cell invasion through histone H3 and H4 arginine methylation coupled transcriptional activation and repression.

    Science.gov (United States)

    Chen, H; Lorton, B; Gupta, V; Shechter, D

    2017-01-19

    Protein arginine methyltransferase 5 (PRMT5) complexed with MEP50/WDR77 catalyzes arginine methylation on histones and other proteins. PRMT5-MEP50 activity is elevated in cancer cells and its expression is highly correlated with poor prognosis in many human tumors. We demonstrate that PRMT5-MEP50 is essential for transcriptional regulation promoting cancer cell invasive phenotypes in lung adenocarcinoma, lung squamous cell carcinoma and breast carcinoma cancer cells. RNA-Seq transcriptome analysis demonstrated that PRMT5 and MEP50 are required to maintain expression of metastasis and Epithelial-to-mesenchymal transition (EMT) markers and to potentiate an epigenetic mechanism of the TGFβ response. We show that PRMT5-MEP50 activity both positively and negatively regulates expression of a wide range of genes. Exogenous TGFβ promotes EMT in a unique pathway of PRMT5-MEP50 catalyzed histone mono- and dimethylation of chromatin at key metastasis suppressor and EMT genes, defining a new mechanism regulating cancer invasivity. PRMT5 methylation of histone H3R2me1 induced transcriptional activation by recruitment of WDR5 and concomitant H3K4 methylation at targeted genes. In parallel, PRMT5 methylation of histone H4R3me2s suppressed transcription at distinct genomic loci. Our decoding of histone methylarginine at key genes supports a critical role for complementary PRMT5-MEP50 transcriptional activation and repression in cancer invasion pathways and in response to TGFβ stimulation and therefore orients future chemotherapeutic opportunities.

  6. Field Confirmation and Monitoring Tools for Aerobic Bioremediation of TBA and MTBE

    Science.gov (United States)

    North, K.; Rasa, E.; Mackay, D. M.; Scow, K. M.; Hristova, K. R.

    2009-12-01

    We have been investigating in situ biotreatment of an existing tert-butyl alcohol (TBA) plume at Vandenberg AFB by recirculation/oxygenation and evaluating monitoring tools for microbial community composition and activity inside and outside of the treatment zone. Results indicate that recirculation/oxygenation by two pairs of recirculation wells is effective at adding oxygen and decreasing methyl tert-butyl ether (MTBE) and TBA concentrations to detection limits along the flowpaths predicted. Compound-specific isotope analyses (CSIA) of groundwater and microbial community analyses (extraction and analysis of DNA) of groundwater and sediments are underway for sampling locations along flowpaths inside and outside of the treatment zone to seek confirmation of in situ biodegradation. We are also evaluating a novel approach to compare the performance of microbial “traps” in characterizing microbial communities: groundwater from the aerobic treatment zone is extracted, separated and directed to multiple chambers located in an air-conditioned ex situ experimental setup. The “traps” under evaluation are in separate chambers; influent and effluent are monitored. The traps being evaluated include Bio-Trap® housings containing Bio-Sep® beads baited with MTBE or TBA labeled with 13C and various unbaited materials. Insights from the various monitoring approaches will be discussed and compared.

  7. Effect of H2 and redox condition on biotic and abiotic MTBE transformation

    Science.gov (United States)

    Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

    2006-01-01

    Laboratory studies conducted with surface water sediment from a methyl tert-butyl ether (MTBE)-contaminated site in South Carolina demonstrated that, under methanogenic conditions, [U-14C] MTBE was transformed to 14C tert-butyl alcohol (TBA) with no measurable production of 14CO2. Production of TBA was not attributed to the activity of methanogenic microorganisms, however, because comparable transformation of [U-14C] MTBE to 14C-TBA also was observed in heat-sterilized controls with dissolved H2 concentrations > 5 nM. The results suggest that the transformation of MTBE to TBA may be an abiotic process that is driven by biologically produced H2 under in situ conditions. In contrast, mineralization of [U-14C] MTBE to 14CO2 was completely inhibited by heat sterilization and only observed in treatments characterized by dissolved H2 concentrations MTBE transformation is influenced by in situ H2 concentrations and that in situ H2 concentrations may be an useful indicator of MTBE transformation pathways in ground water systems.

  8. Quantitative structure activity relationship (QSAR) of competitive N-methyl-D-aspartate (NMDA) antagonists

    Science.gov (United States)

    Korkut, Anil; Varnali, Tereza

    Glutamic acid is an excitatory amino acid neurotransmitter in the mammalian central nervous system and the NMDA molecule binds to NMDA-type glutamic acid receptors as a glutamic acid analogue, in vitro. The NMDA-type glutamic acid receptors are known for their function in many neural processes, such as neural plasticity, learning and memory. In addition, excessive NMDA receptor activity has been shown to be related to neurodegenerative diseases like epilepsy so the design of new NMDA antagonists has extra importance as potent drugs for various neural diseases. Potential antagonist molecules are usually synthesized and their activity is measured by experimental techniques. Here, computational chemistry methods are applied to develop a model, which allows one to predict the activity of potent competitive NMDA antagonists. First, various molecular parameters are calculated for a series of competitive NMDA antagonists with known activity values and those parameters are used to make a regression analysis which provides a model that relates the computationally calculated parameters to experimentally determined activity values. By the quantitative structure activity relationship (QSAR) model developed here, it is possible to predict the activity of a potent drug before its synthesis since only theoretically determined molecular parameters are used for the prediction.

  9. Preparation of TiO2 Nanoparticle Loaded MCM-41 and Study of Its Photo-Catalytic Activity Towards Decolorization of Methyl Orange.

    Science.gov (United States)

    Naik, Bhanudas; Hazra, Subhenjit; Dayananda, Desagani; Prasad, V S; Ghosh, Narendra Nath

    2015-09-01

    Here we report the synthesis of TiO2 nanoparticle loaded mesoporous MCM-41 photocatalysts for degradation of methyl orange dye in aqueous medium under sunlight exposure. TiO2 loaded MCM-41 was synthesized by impregnation method. Anatase form of TiO2 nanoparticles were formed in the porous matrix of the silicate MCM-41. The synthesized materials were characterized using powder X-ray diffraction method, surface area and porosimetry analysis; diffuse reflectance analysis, particle size analysis and transmission electron microscopy. The photocatalytic property of the synthesized materials were investigated towards the degradation of methyl orange under sunlight exposure and monitored by UV-visible spectrophotometer. Synthesized catalysts showed high photocatalytic activity for the degradation of methyl orange.

  10. Evaluation of antioxidant activity of loquat fruit (Eriobotrya japonica lindl.) skin and the feasibility of their application to improve the oxidative stability of soybean oil.

    Science.gov (United States)

    Delfanian, Mojtaba; Kenari, Reza Esmaeilzadeh; Sahari, Mohammad Ali

    2016-05-01

    The effects of ultrasound-assisted, supercritical CO2 and solvent extraction techniques on antioxidant activity of loqua (Eriobotrya japonica Lindl.) skin extract in oxidation stability of soybean oil was evaluated. The antioxidant efficacy of extracts was determined using 2, 2-diphenyl-1-picrylhydrazyl (DPPH(•)) radical scavenging capacity, β-carotene/linoleic acid, and Rancimat test system. Results showed that solvent extract of loquat fruit skin at 400 ppm had the highest antioxidant activity compared to ultrasound-assisted and supercritical CO2 extracts. Further, solvent extraction was the most effective method for extraction of phenolic compounds. Protective effects of extracts in stabilization of soybean oil during both frying and storage conditions were tested and compared to tert-butyl hydroquinone (TBHQ) by measuring their peroxide value, free fatty acids, conjugated dienes and trienes value. During frying process solvent extract of skin at 400 ppm (SOEA) exhibited stronger antioxidant activity in oil compared to other oil samples, but this antioxidant potential was lower than TBHQ in storage conditions. Present study showed that loquat fruit skin is a good source of natural antioxidant compounds, and has the potential to be used as a substitute for synthetic antioxidants in vegetable oils.

  11. Antimycobacterial Activities of Novel 5-(1H-1,2,3-TriazolylMethyl Oxazolidinones

    Directory of Open Access Journals (Sweden)

    Oludotun Adebayo Phillips

    2012-01-01

    Full Text Available The antibacterial activities of a series of triazolyl oxazolidinones against Mycobacterium tuberculosis strain in vitro and in vivo in a mice model are presented. Most active compounds were noncytotoxic against VERO cells with acceptable selectivity indexes (SI as measures of compound tolerability. Structure activity relationships (SARs revealed that analogs with alkylcarbonyl (IC90: < 0.2 to 0.422 μg/mL and arylcarbonyl (IC90: < 0.2 to 2.103 μg/mL groups at the piperazine 4N-position-displayed potent antimycobacterium activities, comparable to the methanesulfonyl (IC90: < 0.2 μg/mL analog, linezolid (IC90: < 0.2 μg/mL, and isoniazid (IC90: < 0.034 μg/mL. The furanylcarbonyl derivative also displayed potent activity, while the arylsulfonyl analogs were inactive. Of the triazolyl oxazolidinones, the morpholino (PH-27 derivative with medium bioavailability in plasma was most active in vivo, but relatively less efficacious than isoniazid.

  12. Intracellular and membrane-damaging activities of methyl gallate isolated from Terminalia chebula against multidrug-resistant Shigella spp.

    Science.gov (United States)

    Acharyya, Saurabh; Sarkar, Prodipta; Saha, Dhira R; Patra, Amarendra; Ramamurthy, T; Bag, Prasanta K

    2015-08-01

    Shigella spp. (Shigella dysenteriae, Shigella flexneri, Shigella boydii and Shigella sonnei) cause bacillary dysentery (shigellosis), which is characterized by bloody mucous diarrhoea. Although a variety of antibiotics have been effective for treatment of shigellosis, options are becoming limited due to globally emerging drug resistance. In the present study, in vitro antibacterial activity of methyl gallate (MG) isolated from Terminalia chebula was determined by performing MIC, minimal bactericidal concentration (MBC) and time-kill kinetic studies. Bacterial membrane-damaging activity of MG was determined by membrane perturbation and transmission electron microscopy (TEM). Cellular drug accumulation, cell infection and assessment of intracellular activities of MG and reference antibiotics were performed using HeLa cell cultures. The bactericidal activity of MG against multidrug-resistant (MDR) Shigella spp. in comparison with other commonly used drugs including fluoroquinolone was demonstrated here. TEM findings in the present study revealed that MG caused the total disintegration of inner and outer membranes, and leakage of the cytoplasmic contents of S. dysenteriae. The level of accumulation of MG and tetracycline in HeLa cells incubated for 24  h was relatively higher than that of ciprofloxacin and nalidixic acid (ratio of intracellular concentration/extracellular concentration of antibiotic for MG and tetracycline>ciprofloxacin and nalidixic acid). The viable number of intracellular S. dysenteriae was decreased in a time-dependent manner in the presence of MG (4 × MBC) and reduced to zero within 20  h. The significant intracellular activities of MG suggested that it could potentially be used as an effective antibacterial agent for the treatment of severe infections caused by MDR Shigella spp.

  13. Size-Dependent Photodynamic Activity of Gold Nanoparticles Conjugate of Water Soluble Purpurin-18-N-Methyl-D-Glucamine

    Directory of Open Access Journals (Sweden)

    Byambajav Lkhagvadulam

    2013-01-01

    Full Text Available Gold nanoparticles (GNPs conjugates of water soluble ionic photosensitizer (PS, purpurin-18-N-methyl-D-glucamine (Pu-18-NMGA, were synthesized using various molar ratios between HAuCl4 and Pu-18-NMGA without adding any particular reducing agents and surfactants. The PS-GNPs conjugates showed long wavelength absorption of range 702–762 nm, and their different shapes and diameters depend on the molar ratios used in the synthesis. In vitro anticancer efficacy of the PS-GNPs conjugates was investigated by MTT assay against A549 cells, resulting in higher photodynamic activity than that of the free Pu-18-NMGA. Among the PS-GNPs conjugates, the GNPs conjugate from the molar ratio of 1 : 2 (Au(III: Pu-18-NMGA exhibits the highest photodynamic activity corresponding to bigger size (~60 nm of the GNPs conjugate which could efficiently transport the PS into the cells than that of smaller size of the GNPs conjugate.

  14. Structure–Activity Relationship To Screen Ni–Bisphosphine Complexes for the Oxidative Coupling of CO2 and Ethylene

    KAUST Repository

    Al-Ghamdi, Miasser

    2017-03-07

    Density functional theory calculations have been used to investigate competition between inner- and outer-sphere reaction pathways in the oxidative coupling of CO2 and ethylene for a set of 12 Ni–bisphosphine complexes, in order to build a QSAR approach correlating catalyst structure to calculated energy barriers for CO2 activation. The ligands were selected to explore different substituents on the P atoms (cyclohexyl, phenyl, and tert-butyl) and different lengths of the tether connecting the P atoms, −(CH2)n– with n = 1–3. As expected, the conclusion is that the inner-sphere reaction pathway is favored with unhindered ligands, while the outer-sphere reaction pathway is favored with hindered ligands. To find a possible correlation with molecular descriptors, we started using the buried volume as a steric descriptor. A reasonable correlation could be found for the energy barrier along the inner-sphere pathway, while scarce correlation was found for the energy barrier along the outer-sphere pathway, indicating that the steric bulkiness of the ligand disfavors approach of CO2 to the metal center. Much stronger correlation between the ligand structure and the energy barrier along the inner-sphere pathway was achieved when the steric descriptor was augmented by an electronic descriptor, consisting of the partial charge on the Ni atom. The much better correlation suggests that bisphosphine ligands have a non-negligible electronic impact on the catalyst performance.

  15. Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

    Science.gov (United States)

    Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

    2015-11-15

    Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

    2007-07-18

    A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.

  17. Structure-activity relationship for quaternary ammonium compounds hybridized with poly(methyl methacrylate).

    Science.gov (United States)

    Melo, Leticia D; Palombo, Renata R; Petri, Denise F S; Bruns, Michael; Pereira, Edla M A; Carmona-Ribeiro, Ana M

    2011-06-01

    Hybrid films from poly (methylmethacrylate) (PMMA) and dioctadecyldimethylammonium bromide (DODAB), cetyltrimethylammonium bromide (CTAB), or tetrapropylammonium bromide (TPAB) were characterized by determination of wettability, ellipsometry, atomic force microscopy, active compounds diffusion to water, X-ray photoelectron spectroscopy (XPS) with determination of atomic composition on the films surface, and biocidal activity against Pseudomonas aeruginosa or Staphylococcus aureus. QAC mobility in the films increased from DODAB to CTAB to TPAB. Diffusion and optimal hydrophobic-hydrophilic balance imparted the highest bioactivity to CTAB. DODAB sustained immobilization at the film surface killed bacteria upon contact. TPAB ability to diffuse was useless because of its unfavorable hydrophobic-hydrophilic balance for bioactivity. © 2011 American Chemical Society

  18. Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol

    Energy Technology Data Exchange (ETDEWEB)

    Miyano, Yoshimori [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan)]. E-mail: miyano@chem.kusa.ac.jp; Kobashi, Takahiro [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Shinjo, Hiroshi [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Kumada, Shinya [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Watanabe, Yusuke [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Niya, Wataru [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Tateishi, Yoko [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan)

    2006-06-15

    Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol in the temperature range of 250 K to 330 K were measured by a gas stripping method and partial molar excess enthalpies were calculated from the activity coefficients. A rigorous formula for evaluating the Henry's law constants from the gas stripping measurements was used for the data reduction of these highly volatile mixtures. The uncertainty is about 2% for the Henry's law constants and 3% for the estimated infinite dilution activity coefficients. In the evaluation of the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and Poynting correction factor cannot be neglected, especially at higher temperatures. The estimated uncertainty of the infinite dilution activity coefficients includes 1% for nonideality.

  19. Enhanced visible light photocatalytic activity of copper-doped titanium oxide–zinc oxide heterojunction for methyl orange degradation

    Energy Technology Data Exchange (ETDEWEB)

    Dorraj, Masoumeh, E-mail: masidor20@gmail.com [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Alizadeh, Mahdi [UM Power Energy Dedicated Advanced Centre (UMPEDAC), Level 4 Wisma R& D, University of Malaya, Jalan Pantai Baharu, 59990 Kuala Lumpur (Malaysia); Sairi, Nor Asrina, E-mail: asrina@um.edu.my [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); University of Malaya Centre for Ionic Liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Basirun, Wan Jefrey [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Goh, Boon Tong [Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Woi, Pei Meng; Alias, Yatimah [Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); University of Malaya Centre for Ionic Liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia)

    2017-08-31

    Highlights: • The novel Cu-TiO{sub 2}/ZnO heterojunction nanocomposite was synthesized for the first time via a two-step process. • The Cu-TiO{sub 2}/ZnO heterostructured nanocomposite exhibited an enhanced visible-light-driven photocatalytic activity for MO degradation. • The heterostructured nanocomposite could be recycled during the degradation of MO in a three-cycle experiment with good stability. - Abstract: A novel Cu-doped TiO{sub 2} coupled with ZnO nanoparticles (Cu-TiO{sub 2}/ZnO) was prepared by sol-gel method and subsequent precipitation for methyl orange (MO) photodegradation under visible light irradiation. The compositions and shapes of the as-prepared Cu-TiO{sub 2}/ZnO nanocomposites were characterized by photoluminescence spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV–vis diffuse reflectance spectra and Brunauer–Emmett–Teller adsorption isotherm techniques. The Cu-TiO{sub 2}/ZnO nanocomposites showed considerably higher photocatalytic activity for MO removal from water under visible light irradiation than that of single-doped semiconductors. The effects of Cu-TiO{sub 2} and ZnO mass ratios on the photocatalytic reaction were also studied. A coupling percentage of 30% ZnO exhibited the highest photocatalytic activity. The enhanced photocatalytic activity of the Cu-TiO{sub 2}/ZnO nanocomposites was mainly attributed to heterojunction formation, which allowed the efficient separation of photoinduced electron−hole pairs at the interface. Moreover, these novel nanocomposites could be recycled during MO degradation in a three-cycle experiment without evident deactivation, which is particularly important in environmental applications.

  20. A new lead for nonpeptidic active-site-directed inhibitors of the severe acute respiratory syndrome coronavirus main protease discovered by a combination of screening and docking methods.

    Science.gov (United States)

    Kaeppler, Ulrich; Stiefl, Nikolaus; Schiller, Markus; Vicik, Radim; Breuning, Alexander; Schmitz, Werner; Rupprecht, Daniel; Schmuck, Carsten; Baumann, Knut; Ziebuhr, John; Schirmeister, Tanja

    2005-11-03

    The coronavirus main protease, M(pro), is considered to be a major target for drugs suitable for combating coronavirus infections including severe acute respiratory syndrome (SARS). An HPLC-based screening of electrophilic compounds that was performed to identify potential M(pro) inhibitors revealed etacrynic acid tert-butylamide (6a) as an effective nonpeptidic inhibitor. Docking studies suggested a binding mode in which the phenyl ring acts as a spacer bridging the inhibitor's activated double bond and its hydrophobic tert-butyl moiety. The latter is supposed to fit into the S4 pocket of the target protease. Furthermore, these studies revealed etacrynic acid amide (6b) as a promising lead for nonpeptidic active-site-directed M(pro) inhibitors. In a fluorimetric enzyme assay using a novel fluorescence resonance energy transfer (FRET) pair labeled substrate, compound 6b showed a K(i) value of 35.3 muM. Since the novel lead compound does not target the S1', S1, and S2 subsites of the enzyme's substrate-binding pockets, there is room for improvement that underlines the lead character of compound 6b.

  1. Lico A Enhances Nrf2-Mediated Defense Mechanisms against t-BHP-Induced Oxidative Stress and Cell Death via Akt and ERK Activation in RAW 264.7 Cells

    Directory of Open Access Journals (Sweden)

    Hongming Lv

    2015-01-01

    Full Text Available Licochalcone A (Lico A exhibits various biological properties, including anti-inflammatory and antioxidant activities. In this study, we investigated the antioxidative potential and mechanisms of Lico A against tert-butyl hydroperoxide- (t-BHP- induced oxidative damage in RAW 264.7 cells. Our results indicated that Lico A significantly inhibited t-BHP-induced cytotoxicity, apoptosis, and reactive oxygen species (ROS generation and reduced glutathione (GSH depletion but increased the glutamate-cysteine ligase modifier (GCLM subunit and the glutamate-cysteine ligase catalytic (GCLC subunit genes expression. Additionally, Lico A dramatically upregulated the antioxidant enzyme heme oxygenase 1 (HO-1 and nuclear factor erythroid 2-related factor 2 (Nrf2, which were associated with inducing Nrf2 nuclear translocation, decreasing Keap1 protein expression and increasing antioxidant response element (ARE promoter activity. Lico A also obviously induced the activation of serine/threonine kinase (Akt and extracellular signal-regulated kinase (ERK, but PI3K/Akt and ERK inhibitors treatment displayed clearly decreased levels of LicoA-induced Nrf2 nuclear translocation and HO-1 expression, respectively. Furthermore, Lico A treatment markedly attenuated t-BHP-induced oxidative damage, which was reduced by treatment with PI3K/Akt, ERK, and HO-1 inhibitors. Therefore, Lico A might have a protective role against t-BHP-induced cytotoxicity by modulating HO-1 and by scavenging ROS via the activation of the PI3K/Akt and ERK/Nrf2 signaling pathways.

  2. A "light-on" colorimetric assay for anion detection using the inhibitory effect of anions on the catalytic activity of metal nanoparticles for the degradation of methyl orange.

    Science.gov (United States)

    Lu, Lixia; Yang, Fan; Yang, Xiurong

    2014-12-07

    In this communication, we studied the inhibitory effects of anions on the catalytic activity of metal nanoparticles for the degradation of methyl orange (MO). Some anions have great affinity with specific metal nanoparticles, thus resulting in the change of surface state and inhibition of catalytic activity, which can be observed with the naked eye or manifested in the UV spectrum of MO for anion detection.

  3. Redox-active quinones induces genome-wide DNA methylation changes by an iron-mediated and Tet-dependent mechanism

    DEFF Research Database (Denmark)

    Zhao, Bailin; Yang, Ying; Wang, Xiaoli

    2014-01-01

    DNA methylation has been proven to be a critical epigenetic mark important for various cellular processes. Here, we report that redox-active quinones, a ubiquitous class of chemicals found in natural products, cancer therapeutics and environment, stimulate the conversion of 5 mC to 5 hmC in vivo...... diminished the 5 hmC increase. These results suggest an iron-regulated Tet-dependent DNA demethylation mechanism mediated by redox-active biomolecules....

  4. Murine T cell activation is regulated by surfen (bis-2-methyl-4-amino-quinolyl-6-carbamide)

    Energy Technology Data Exchange (ETDEWEB)

    Warford, Jordan, E-mail: jordan.warford@dal.ca [Department of Pathology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Doucette, Carolyn D., E-mail: carolyn.doucette@dal.ca [Department of Microbiology and Immunology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Hoskin, David W., E-mail: d.w.hoskin@dal.ca [Department of Pathology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Department of Microbiology and Immunology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Easton, Alexander S., E-mail: alexander.easton@dal.ca [Department of Pathology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Department of Microbiology and Immunology, Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada); Department of Surgery (Neurosurgery), Dalhousie University, Tupper Building, 5850 College Street, Halifax, Nova Scotia B3H 4R2 (Canada)

    2014-01-10

    Highlights: •Surfen is the first inhibitor of glycosaminoglycan function to be studied in murine T cells. •Surfen reduces T cell proliferation stimulated in vitro and in vivo. •Surfen reduces CD25 expression in T cells activated in vivo but not in vitro. •Surfen increases T cell proliferation when T cell receptor activation is bypassed. •Surfen’s effects are blocked by co-administration of heparin sulfate. -- Abstract: Surfen (bis-2-methyl-4-amino-quinolyl-6-carbamide) binds to glycosaminoglycans (GAGs) and has been shown to influence their function, and the function of proteoglycans (complexes of GAGs linked to a core protein). T cells synthesize, secrete and express GAGs and proteoglycans which are involved in several aspects of T cell function. However, there are as yet no studies on the effect of GAG-binding agents such as surfen on T cell function. In this study, surfen was found to influence murine T cell activation. Doses between 2.5 and 20 μM produced a graduated reduction in the proliferation of T cells activated with anti-CD3/CD28 antibody-coated T cell expander beads. Surfen (20 mg/kg) was also administered to mice treated with anti-CD3 antibody to activate T cells in vivo. Lymphocytes from surfen-treated mice also showed reduced proliferation and lymph node cell counts were reduced. Surfen reduced labeling with a cell viability marker (7-ADD) but to a much lower extent than its effect on proliferation. Surfen also reduced CD25 (the α-subunit of the interleukin (IL)-2 receptor) expression with no effect on CD69 expression in T cells treated in vivo but not in vitro. When receptor activation was bypassed by treating T cells in vitro with phorbyl myristate acetate (10 ng/ml) and ionomycin (100 ng/ml), surfen treatment either increased proliferation (10 μM) or had no effect (2.5, 5 and 20 μM). In vitro treatment of T cells with surfen had no effect on IL-2 or interferon-γ synthesis and did not alter proliferation of the IL-2 dependent cell

  5. Photoisomerization of azobenzene moiety in crosslinking polymer materials

    Science.gov (United States)

    Wang, Hui; Chen, Wei-Qiang; Jin, Feng; Dong, Xian-Zi; Zhao, Zhen-Sheng; Duan, Xuan-Ming

    2012-10-01

    In this study, a series of acryloyloxy-substituted azobenzene derivatives, 3-(tert-butyl)-4,4'-bisacryoloxy-azobenzene (tBu-Azo-AO), 3-(tert-butyl)-4,4'-bis[3-(acryoloxy)propoxy]-azobenzene (tBu-Azo-AO3) and 3-(tert-butyl)-4,4'-bis[6-(acryoloxy)hexyloxy]-azobenzene (tBu-Azo-AO6) were synthesized and employed as monomers to prepare polymer films by copolymerizing dipentaerythritol hexaacrylate (DPE-6A) and methyl methacrylate (MMA), respectively. When exposed to a nanosecond laser beam at the wavelength of 355 nm, ultraviolet-visible (UV-Vis) absorption spectra of the resultant polymer films with different irradiation time were monitored. On the basis of the absorbance of the π-π* electronic transition, the kinetics of trans-to-cis photoisomerization of three kinds of azobenzene moieties were demonstrated and found to be influenced by both the pump energy and azobenzene concentration.

  6. Activation of thalamocortical networks by the N-methyl-D-aspartate receptor antagonist phencyclidine: reversal by clozapine.

    Science.gov (United States)

    Santana, Noemí; Troyano-Rodriguez, Eva; Mengod, Guadalupe; Celada, Pau; Artigas, Francesc

    2011-05-15

    Noncompetitive N-methyl-D-aspartate receptor antagonists are widely used as pharmacological models of schizophrenia. Their neurobiological actions are still poorly understood, although the prefrontal cortex (PFC) appears as a key target area. We examined the effect of phencyclidine (PCP) on neuronal activity of the mediodorsal (MD) and centromedial (CM) thalamic nuclei, reciprocally connected with the PFC, using extracellular recordings (n = 50 neurons from 35 Wistar rats) and c-fos expression. Phencyclidine (.25 mg/kg intravenous [IV]) markedly disorganized the activity of MD/CM neurons, increasing (424%) and decreasing (41%) the activity of 57% and 20% of the recorded neurons, respectively (23% remained unaffected). Phencyclidine reduced delta oscillations (.15-4 Hz) as assessed by recording local field potentials. The subsequent clozapine administration (1 mg/kg IV) reversed PCP effects on neuronal discharge and delta oscillations. Double in situ hybridization experiments revealed that PCP (10 mg/kg intraperitoneal [IP]) markedly increased c-fos expression in glutamatergic neurons of several cortical areas (prefrontal, somatosensory, retrosplenial, entorhinal) and in thalamic nuclei, including MD/CM. Phencyclidine also increased c-fos expression in the amygdala; yet, it had a small effect in the hippocampus. Phencyclidine did not increase c-fos expression in gamma-aminobutyric acidergic cells except in hippocampus, amygdala, somatosensory, and retrosplenial cortices. Clozapine (5 mg/kg IP) had no effect by itself but significantly prevented PCP-induced c-fos expression. Phencyclidine likely exerts its psychotomimetic action by increasing excitatory neurotransmission in thalamo-cortico-thalamic networks involving, among others, PFC, retrosplenial, and somatosensory cortices. The antipsychotic action of clozapine includes, among other actions, an attenuation of the neuronal hyperactivity in thalamocortical networks. Copyright © 2011 Society of Biological

  7. Low concentrations of salicylic acid delay methyl jasmonate-induced leaf senescence by up-regulating nitric oxide synthase activity.

    Science.gov (United States)

    Ji, Yingbin; Liu, Jian; Xing, Da

    2016-09-01

    In plants, extensive efforts have been devoted to understanding the crosstalk between salicylic acid (SA) and jasmonic acid (JA) signaling in pathogen defenses, but this crosstalk has scarcely been addressed during senescence. In this study, the effect of SA application on methyl jasmonate (MeJA)-induced leaf senescence was assessed. We found that low concentrations of SA (1-50 μM) played a delayed role against the senescence promoted by MeJA. Furthermore, low concentrations of SA enhanced plant antioxidant defenses and restricted reactive oxygen species (ROS) accumulation in MeJA-treated leaves. When applied simultaneously with MeJA, low concentrations of SA triggered a nitric oxide (NO) burst, and the elevated NO levels were linked to the nitric oxide associated 1 (NOA1)-dependent pathway via nitric oxide synthase (NOS) activity. The ability of SA to up-regulate plant antioxidant defenses, reduce ROS accumulation, and suppress leaf senescence was lost in NO-deficient Atnoa1 plants. In a converse manner, exogenous addition of NO donors increased the plant antioxidant capacity and lowered the ROS levels in MeJA-treated leaves. Taken together, the results indicate that SA at low concentrations counteracts MeJA-induced leaf senescence through NOA1-dependent NO signaling and strengthening of the antioxidant defense. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  8. Enhanced decolorization of methyl orange in aqueous solution using iron-carbon micro-electrolysis activation of sodium persulfate.

    Science.gov (United States)

    Li, Peng; Liu, Zhipeng; Wang, Xuegang; Guo, Yadan; Wang, Lizhang

    2017-08-01

    Reactivity of sodium persulfate (PS) in the decolorization of methyl orange (MO) in aqueous solution using an iron-carbon micro-electrolysis (ICE) method was investigated. The effects of sodium persulfate doses, pH, Fe-to-C mass ratios, initial MO concentration as well as the reaction temperature were comprehensively studied in batch experiments. The ICE-PS coupled process was more suitable for wide ranges of pH, initial MO concentration and reaction temperature, accompanied by the reduction of Fe compared ICE. The MO removal efficiency improved substantially by ICE-PS technique, 76.03% for ICE and 91.27% for ICE-PS at experimental conditions of pH 3.0, Fe-to-C mass ratio 3:1, PS addition 10 mM and initial MO concentration 0.61 mM. Furthermore, the biodegradability index (BI) dramatically increased from 0.26 to 0.65. The binary hydroxyl and sulfate radicals that non-selectively degrade MO to the derivatives with small molecules are ascribed to ICE-PS method as detected by the UV-vis spectra. The PS activation resource was Fe2+ through the hydroxyl radical quenching reaction by the additive tert-butanol (TBA). This study provides an in-depth theoretical understanding of the development and wide commercial application of the ICE technology to refractory industrial dye wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Methyl-beta-cyclodextrin enhanced biodegradation of polycyclic aromatic hydrocarbons and associated microbial activity in contaminated soil.

    Science.gov (United States)

    Sun, Mingming; Luo, Yongming; Christie, Peter; Jia, Zhongjun; Li, Zhengao; Teng, Ying

    2012-01-01

    The contamination of soils by polycyclic aromatic hydrocarbons (PAHs) is a widespread environmental problem and the remediation of PAHs from these areas has been a major concern. The effectiveness of many in situ bioremediation systems may be constrained by low contaminant bioavailability due to limited aqueous solubility or a large magnitude of sorption. The objective of this research was to evaluate the effect of methyl-beta-cyclodextrin (MCD) on bioaugmentation by Paracoccus sp. strain HPD-2 of an aged PAH-contaminated soil. When 10% (W/W) MCD amendment was combined with bioaugmentation by the PAH-degrading bacterium Paracoccus sp. strain HPD-2, the percentage degradation of total PAHs was significantly enhanced up to 34.8%. Higher counts of culturable PAH-degrading bacteria and higher soil dehydrogenase and soil polyphenol oxidase activities were observed in 10% (W/W) MCD-assisted bioaugmentation soil. This MCD-assisted bioaugmentation strategy showed significant increases (p contaminated soil. The results suggest that MCD-aided bioaugmentation by Paracoccus sp. strain HPD-2 may be a promising practical bioremediation strategy for aged PAH-contaminated soils.

  10. Synthesis of New 2,5-Di-substituted 1,3,4-Oxadiazoles Bearing 2,6-Di-tert-butylphenol Moieties and Evaluation of Their Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Raied M. Shakir

    2014-03-01

    Full Text Available Eleven new 2,6-di-tert-butyl-4-(5-aryl-1,3,4-oxadiazol-2-ylphenols 5a–k were synthesized by reacting aryl hydrazides with 3,5-di-tert butyl 4-hydroxybenzoic acid in the presence of phosphorus oxychloride. The resulting compounds were characterized based on their IR, 1H-NMR, 13C-NMR, and HRMS data. 2,2-Diphenyl-1-picrylhydrazide (DPPH and ferric reducing antioxidant power (FRAP assays were used to test the antioxidant properties of the compounds. Compounds 5f and 5j exhibited significant free-radical scavenging ability in both assays.

  11. Methyl Bromide Buffer Zone Distances for Commodity and Structural Fumigation: Active Aeration, Horizontal Stacks, 8 Hours or Less

    Science.gov (United States)

    This document contains buffer zone tables required by certain methyl bromide commodity fumigant product labels that refer to Buffer Zone Lookup Tables located at epa.gov/pesticide-registration/mbcommoditybuffer on the label.

  12. Methyl Bromide Buffer Zone Distances for Commodity and Structural Fumigation: Active Aeration, No Stack, 8 Hours or Less

    Science.gov (United States)

    This document contains buffer zone tables required by certain methyl bromide commodity fumigant product labels that refer to Buffer Zone Lookup Tables located at epa.gov/pesticide-registration/mbcommoditybuffer on the label.

  13. Methyl Bromide Buffer Zone Distances for Commodity and Structural Fumigation: Active Aeration, No Stack, More than 8 Hours

    Science.gov (United States)

    This document contains buffer zone tables required by certain methyl bromide commodity fumigant product labels that refer to Buffer Zone Lookup Tables located at epa.gov/pesticide-registration/mbcommoditybuffer on the label.

  14. A novel synthetic Piper amide derivative NED-180 inhibits hyperpigmentation by activating the PI3K and ERK pathways and by regulating Ca2+ influx via TRPM1 channels.

    Science.gov (United States)

    Hwang, Eunson; Lee, Taek Hwan; Lee, Wook-Joo; Shim, Won-Sik; Yeo, Eui-Ju; Kim, Sanghee; Kim, Sun Yeou

    2016-01-01

    Piper amides have a characteristic, unsaturated amide group and exhibit diverse biological activities, including proliferation and differentiation of melanocytes, although the molecular mechanisms underlying its antimelanogenesis effect remain unknown. We screened a selected chemical library of newly synthesized Piper amide derivatives and identified (E)-3-(4-(tert-butyl)phenyl)-N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)acrylamide (NED-180) as one of the most potent compounds in suppressing melanogenesis. In murine melan-a melanocytes, NED-180 downregulated the expression of melanogenic regulatory proteins including tyrosinase, Tyrp1, Dct, and MITF. PI3K/Akt-dependent phosphorylation of GSK3β by NED-180 decreases MITF phosphorylation and inhibits melanogenesis without any effects on cytotoxicity and proliferation. Furthermore, topical application of NED-180 significantly ameliorated UVB-induced skin hyperpigmentation in guinea pigs. Interestingly, data obtained using calcium imaging techniques suggested that NED-180 reduced the TPA-induced activation of TRPM1 (melastatin), which could explain the NED-180-induced inhibition of melanogenesis. All things taken together, NED-180 triggers activation of multiple pathways, such as PI3K and ERK, and inhibits TRPM1/TRPV1, leading to inhibition of melanogenesis. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  15. MN1 overexpression is driven by loss of DNMT3B methylation activity in inv(16) pediatric AML.

    Science.gov (United States)

    Larmonie, N S D; Arentsen-Peters, T C J M; Obulkasim, A; Valerio, D; Sonneveld, E; Danen-van Oorschot, A A; de Haas, V; Reinhardt, D; Zimmermann, M; Trka, J; Baruchel, A; Pieters, R; van den Heuvel-Eibrink, M M; Zwaan, C M; Fornerod, M

    2017-09-11

    In acute myeloid leukemia (AML), specific genomic aberrations induce aberrant methylation, thus directly influencing the transcriptional programing of leukemic cells. Therefore, therapies targeting epigenetic processes are advocated as a promising therapeutic tool for AML treatment. However, to develop new therapies, a comprehensive understanding of the mechanism(s) driving the epigenetic changes as a result of acquired genetic abnormalities is necessary. This understanding is still lacking. In this study, we performed genome-wide CpG-island methylation profiling on pediatric AML samples. Six differentially methylated genomic regions within two genes, discriminating inv(16)(p13;q22) from non-inv(16) pediatric AML samples, were identified. All six regions had a hypomethylated phenotype in inv(16) AML samples, and this was most prominent at the regions encompassing the meningioma (disrupted in balanced translocation) 1 (MN1) oncogene. MN1 expression primarily correlated with the methylation level of the 3' end of the MN1 exon-1 locus. Decitabine treatment of different cell lines showed that induced loss of methylation at the MN1 locus can result in an increase of MN1 expression, indicating that MN1 expression is coregulated by DNA methylation. To investigate this methylation-associated mechanism, we determined the expression of DNA methyltransferases in inv(16) AML. We found that DNMT3B expression was significantly lower in inv(16) samples. Furthermore, DNMT3B expression correlated negatively with MN1 expression in pediatric AML samples. Importantly, depletion of DNMT3B impaired remethylation efficiency of the MN1 exon-1 locus in AML cells after decitabine exposure. These findings identify DNMT3B as an important coregulator of MN1 methylation. Taken together, this study shows that the methylation level of the MN1 exon-1 locus regulates MN1 expression levels in inv(16) pediatric AML. This methylation level is dependent on DNMT3B, thus suggesting a role for DNMT3B in

  16. Influence of N-methyl pyrrolidone on the activity of the pulp-dentine complex and bone

    OpenAIRE

    Gjoksi Bebeka

    2016-01-01

    AIM: To analyse the effect of systemic application of N methyl pyrrolidone (NMP) on the pulp dentine complex and on the jawbone of ovariectomized rats. METHOD: Female Sprague Dawley rats were randomly divided into a Sham operated group (Sham n = 6) and an oestrogen depletion by ovariectomy (OVX n = 12) group. In 6 of the ovariectomized animals N methyl pyrrolidone (NMP) in phosphate buffered saline (PBS) was administered systemically weekly by intraperitoneal injection (i.p.); the other 6 w...

  17. Development, Optimization, and Anti-diabetic Activity of Gliclazide-Loaded Alginate–Methyl Cellulose Mucoadhesive Microcapsules

    OpenAIRE

    Pal, Dilipkumar; Nayak, Amit Kumar

    2011-01-01

    The purpose of this work was to develop and optimize gliclazide-loaded alginate–methyl cellulose mucoadhesive microcapsules by ionotropic gelation using central composite design. The effect of formulation parameters like polymer blend ratio and cross-linker (CaCl2) concentration on properties of gliclazide-loaded alginate–methyl cellulose microcapsules like drug encapsulation efficiency and drug release were optimized. The optimized microcapsules were subjected to swelling, mucoadhesive, and ...

  18. Longterm performance of polyolefins in different environments including chlorinated water: antioxidant consumption and migration and polymer degradation

    OpenAIRE

    Lundbäck, Marie

    2005-01-01

    The long-term performance of stabilized polyolefins in different environments was studied with focus on antioxidant consumption and migration. Plaques of linear polyethylene (LPE) and branched polyethylene (BPE) were stabilized with Santonox® R (4,4'-Thiobis(6-tert-butyl-3-methylphenol)), Irganox® 1081 (2,2’-Thiobis(4-methyl-6-tertbutylphenol)), or Lowinox® 22M46 (2,2’-Methylenebis(6-tert-butyl-4-methylphenol)). The samples were aged in water and nitrogen at 75, 90 and 95°C. Antioxidant conce...

  19. DNA methylation

    DEFF Research Database (Denmark)

    Williams, Kristine; Christensen, Jesper; Helin, Kristian

    2012-01-01

    DNA methylation is involved in key cellular processes, including X-chromosome inactivation, imprinting and transcriptional silencing of specific genes and repetitive elements. DNA methylation patterns are frequently perturbed in human diseases such as imprinting disorders and cancer. The recent...... discovery that the three members of the TET protein family can convert 5-methylcytosine (5mC) into 5-hydroxymethylcytosine (5hmC) has provided a potential mechanism leading to DNA demethylation. Moreover, the demonstration that TET2 is frequently mutated in haematopoietic tumours suggests that the TET...... proteins are important regulators of cellular identity. Here, we review the current knowledge regarding the function of the TET proteins, and discuss various mechanisms by which they contribute to transcriptional control. We propose that the TET proteins have an important role in regulating DNA methylation...

  20. Molecular structure, quantum mechanical calculation and radical scavenging activities of (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds

    Science.gov (United States)

    Alaşalvar, Can; Soylu, Mustafa Serkan; Güder, Aytaç; Albayrak, Çiğdem; Apaydın, Gökhan; Dilek, Nefise

    2014-09-01

    In this study, (E)-4,6-dibromo-2-[(3,5-dimethylphenylimino)methyl]-3-methoxyphenol and (E)-4,6-dibromo-2-[(2,6-dimethylphenylimino)methyl]-3-methoxyphenol compounds have been synthesized and characterized by using X-ray crystallographic method, FT-IR and Density functional method. The molecular geometry, vibrational frequencies of the title compounds in the ground state have been calculated by using B3LYP with the 6-31G(d,p) basis set. The tautomeric form of the compounds has been demonstrated by using single crystal X-ray method, FT-IR spectrometer and DFT method. In addition, HOMO-LUMO energy gap, molecular electrostatic potential map and NBO analysis of the compounds are performed at B3LYP/6-31G(d,p) level. It may be remarked that the free radical scavenging activities of the title compounds were assessed using DPPHrad , DMPDrad +, and ABTSrad + assays. The obtained results show that especially compound 2 has effective DPPHrad (SC50 1.52 ± 0.14 μg/mL), DMPDrad + (SC50 1.22 ± 0.21 μg/mL), and ABTSrad + (SC50 3.32 ± 0.17 μg/mL) scavenging activities compared with standards (BHA, rutin, and trolox).