WorldWideScience

Sample records for tert-butyl ether degradation

  1. Method for determination of methyl tert-butyl ether and its degradation products in water

    Science.gov (United States)

    Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

    1997-01-01

    An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method

  2. 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...

  3. 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.

  4. Enhancement of methyl tert-butyl ether degradation by the addition of readily metabolizable organic substrates

    International Nuclear Information System (INIS)

    Chen Dongzhi; Chen Jianmeng; Zhong Weihong

    2009-01-01

    Supplements with readily metabolizable organic substrates were investigated to increase the biomass and enhance degradation of methyl tert-butyl ether (MTBE) due to the low biomass yield of MTBE which has been one of the factors for low-rate MTBE degradation. The influence of various organic substrates on the rate of aerobic degradation of methyl tert-butyl ether (MTBE) by Methylibium petroleiphilum PM1 was investigated, and only yeast extract (YE), beef extract and tryptone exhibited stimulatory effect. With the concentration of each substrate being 100 mg/L, the average MTBE removal rate could increase to 1.29, 1.20 and 1.04 mg/(L h), respectively, in comparison with 0.71 mg/(L h) when carried out in medium without addition. The stimulatory effects of YE addition, as well as induction period required by MTBE degradation, varied dramatically with the storage conditions, pre-culture medium and concentrations of the inoculums. The extent of stimulatory effects of YE might be closely related to the proportion of induction period in the total time of MTBE-degradation. The removal efficiency increased from about 50% to 90.5% with the addition of YE in a packed-bed reactor loaded with calcium alginate immobilized cells.

  5. 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)

  6. Draft Genome Sequence of Paenibacillus etheri sp. nov. SH7T, a Methyl Tert-Butyl Ether Degrader.

    Science.gov (United States)

    Purswani, Jessica; Guisado, Isabel M; Gonzalez-Lopez, Jesus; Pozo, Clementina

    2016-02-18

    We report here the draft genome sequence of Paenibacillus etheri sp. nov. SH7(T) (= CECT 8558(T) = DSM 29760(T)), isolated from a hydrocarbon-contaminated soil pilot plant in Granada, Spain. The bacterium was isolated and sequenced due to its methyl tert-butyl ether (MTBE)-degrading properties. Copyright © 2016 Purswani et al.

  7. Degradation of methyl tert-butyl ether by gel immobilized Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Chen, Dongzhi; Chen, Jianmeng; Zhong, Weihong; Cheng, Zhuowei

    2008-07-01

    Cells of Methylibium petroleiphilum PM1 were immobilized in gel beads to degrade methyl tert-butyl ether (MTBE). Calcium alginate, agar, polyacrylamide and polyvinvyl alcohol were screened as suitable immobilization matrices, with calcium alginate demonstrating the fastest MTBE-degradation rate. The rate was accelerated by 1.8-fold when the beads had been treated in physiological saline for 24h at 28 degrees C. MTBE degradation in mineral salts medium (MSM) was accompanied by the increase of biomass. The half-life of MTBE-degradation activity for the encapsulated cells stored at 28 degrees C was about 120 h, which was obviously longer than that of free cells (approximately 36 h). Efficient reusability of the beads up to 30 batches was achieved in poor nutrition solution as compared to only 6 batches in MSM. The immobilized cells could be operated in a packed-bed reactor for degradation of 10 mg L(-1) MTBE in groundwater with more than 99% removal efficiency at hydraulic retention time of 20 min. These results suggested that immobilized cells of PM1 in bioreactor might be applicable to a groundwater treatment system for the removal of MTBE.

  8. Effect of substrate interaction on the degradation of methyl tert-butyl ether, benzene, toluene, ethylbenzene, and xylene by Rhodococcus sp.

    Science.gov (United States)

    Lee, Eun-Hee; Cho, Kyung-Suk

    2009-08-15

    It was examined the substrate interactions of benzene (B), tolulene (T), ethylbenzene (E), xylene (X), and methyl tert-butyl ether (M) in binary, ternary, quaternary, and quinary mixtures by Rhodococcus sp. EH831 that could aerobically degrade all of five single components. The specific degradation rates (SDRs) of B, T, E, X, and M were 234, 913, 131, 184 and 139 micromol g-dry cell weight (DCW)(-1)h(-1), respectively. In binary, ternary, quaternary, and quinary mixtures of them, ethylbenzene was the strongest inhibitor for the other substrates, and methyl tert-butyl ether was the weakest inhibitor. Interestingly, no degradation of benzene and methyl tert-butyl ether was found in the coexistence of ethylbenzene. The degradation of benzene followed only after toluene became exhausted when both was present. Ethylbenzene was least inhibited by methyl tert-butyl ether and most inhibited by toluene.

  9. Involvement of a novel enzyme, MdpA, in methyl tert-butyl ether degradation in Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R

    2008-11-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr(59) distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum.

  10. Detection and Quantification of Methyl tert-Butyl Ether-Degrading Strain PM1 by Real-Time TaqMan PCR

    OpenAIRE

    Hristova, Krassimira R.; Lutenegger, Christian M.; Scow, Kate M.

    2001-01-01

    The fuel oxygenate methyl tert-butyl ether (MTBE), a widely distributed groundwater contaminant, shows potential for treatment by in situ bioremediation. The bacterial strain PM1 rapidly mineralizes and grows on MTBE in laboratory cultures and can degrade the contaminant when inoculated into groundwater or soil microcosms. We applied the TaqMan quantitative PCR method to detect and quantify strain PM1 in laboratory and field samples. Specific primers and probes were designed for the 16S ribos...

  11. Whole-genome analysis of the methyl tert-butyl ether-degrading beta-proteobacterium Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Kane, Staci R; Chakicherla, Anu Y; Chain, Patrick S G; Schmidt, Radomir; Shin, Maria W; Legler, Tina C; Scow, Kate M; Larimer, Frank W; Lucas, Susan M; Richardson, Paul M; Hristova, Krassimira R

    2007-03-01

    Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C(5) to C(12)) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an approximately 4-Mb circular chromosome and an approximately 600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (approximately 99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria.

  12. Whole-genorne analysis of the methyl tert-butyl ether-degrading beta-proteobacterium Methylibium petroleiphilum PM1

    Energy Technology Data Exchange (ETDEWEB)

    Kane, Staci R. [Lawrence Livermore National Laboratory (LLNL); Chakicherla, Anu Y. [Lawrence Livermore National Laboratory (LLNL); Chain, Patrick S. G. [Lawrence Livermore National Laboratory (LLNL); Schmidt, Radomir [University of California, Davis; Shin, M [U.S. Department of Energy, Joint Genome Institute; Legler, Tina C. [Lawrence Livermore National Laboratory (LLNL); Scow, Kate M. [University of California, Davis; Larimer, Frank W [ORNL; Lucas, Susan [Joint Genome Institute, Walnut Creek, California; Richardson, P M [U.S. Department of Energy, Joint Genome Institute; Hristova, Krassimira R. [University of California, Davis

    2007-03-01

    Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C, to C,,) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an similar to 4-Mb circular chromosome and an similar to 600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (similar to 99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria.

  13. Gene mdpC plays a regulatory role in the methyl-tert-butyl ether degradation pathway of Methylibium petroleiphilum strain PM1.

    Science.gov (United States)

    Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

    2015-04-01

    Among the few bacteria known to utilize methyl tert-butyl ether (MTBE) as a sole carbon source, Methylibium petroleiphilum PM1 is a well-characterized organism with a sequenced genome; however, knowledge of the genetic regulation of its MTBE degradation pathway is limited. We investigated the role of a putative transcriptional activator gene, mdpC, in the induction of MTBE-degradation genes mdpA (encoding MTBE monooxygenase) and mdpJ (encoding tert-butyl alcohol hydroxylase) of strain PM1 in a gene-knockout mutant mdpC(-). We also utilized quantitative reverse transcriptase PCR assays targeting genes mdpA, mdpJ and mdpC to determine the effects of the mutation on transcription of these genes. Our results indicate that gene mdpC is involved in the induction of both mdpA and mdpJ in response to MTBE and tert-butyl alcohol (TBA) exposure in PM1. An additional independent mechanism may be involved in the induction of mdpJ in the presence of TBA. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  14. Predicting methyl tert-butyl ether, tert-butyl formate, and tert-butyl alcohol levels in the environment using the fugacity approach.

    Science.gov (United States)

    Arp, Hans Peter H; Fenner, Kathrin; Schmidt, Torsten C

    2005-05-01

    Through its extensive use as a fuel oxygenate, methyl tert-butyl ether (MTBE) is found nearly ubiquitouslythroughout the environment. To better understand the environmental fate of MTBE, fugacity models are commonly used. However, models developed by the scientific community and by governmental bodies differ in their predictions of relative MTBE concentrations for relevant environmental compartments and of seasonal concentration variations; further, to date they have not considered the formation of transformation products. In this study, the sensitivity of predicted environmental concentrations of MTBE and its two major degradation products, tert-butyl formate (TBF) and tert-butyl alcohol (TBA), to all types of model input parameters is analyzed in a probabilistic sensitivity analysis. This analysis allowed for an assessment of the most influential parameters for predicting soil, water, and air concentrations and thereby provided insight into why previous modeling studies on MTBE differed. Further, the information from the sensitivity analysis was used to parametrize a multispecies transformation model for predicting European concentration levels of MTBE and, for the first time, TBF and TBA. Water and air concentrations of MTBE predicted with the transformation model were in good agreement with measurements of environmental samples. No studies are available on environmental TBF and TBA levels to compare with model predictions; however, the modeling results indicate that, in the water phase, TBA concentrations may reach appreciable levels. One major uncertainty identified regarding the prediction of TBA levels was the fraction of TBA formed from atmospheric MTBE and TBF.

  15. Effect of benzene and ethylbenzene on the transcription of methyl-tert-butyl ether degradation genes of Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

    2016-09-01

    Methyl-tert-butyl ether (MTBE) and its degradation by-product, tert-butyl alcohol (TBA), are widespread contaminants detected frequently in groundwater in California. Since MTBE was used as a fuel oxygenate for almost two decades, leaking underground fuel storage tanks are an important source of contamination. Gasoline components such as BTEX (benzene, toluene, ethylbenzene and xylenes) are often present in mixtures with MTBE and TBA. Investigations of interactions between BTEX and MTBE degradation have not yielded consistent trends, and the molecular mechanisms of BTEX compounds' impact on MTBE degradation are not well understood. We investigated trends in transcription of biodegradation genes in the MTBE-degrading bacterium, Methylibium petroleiphilum PM1 upon exposure to MTBE, TBA, ethylbenzene and benzene as individual compounds or in mixtures. We designed real-time quantitative PCR assays to target functional genes of strain PM1 and provide evidence for induction of genes mdpA (MTBE monooxygenase), mdpJ (TBA hydroxylase) and bmoA (benzene monooxygenase) in response to MTBE, TBA and benzene, respectively. Delayed induction of mdpA and mdpJ transcription occurred with mixtures of benzene and MTBE or TBA, respectively. bmoA transcription was similar in the presence of MTBE or TBA with benzene as in their absence. Our results also indicate that ethylbenzene, previously proposed as an inhibitor of MTBE degradation in some bacteria, inhibits transcription of mdpA, mdpJ and bmoAgenes in strain PM1.

  16. 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.

  17. Involvement of a Novel Enzyme, MdpA, in Methyl tert-Butyl Ether Degradation in Methylibium petroleiphilum PM1 ▿

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R.

    2008-01-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr59 distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum. PMID:18791002

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

    Directory of Open Access Journals (Sweden)

    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.

  19. Isolate PM1 populations are dominant and novel methyl tert-butyl ether-degrading bacterial in compost biofilter enrichments.

    Science.gov (United States)

    Bruns, M A; Hanson, J R; Mefford, J; Scow, K M

    2001-03-01

    The gasoline additive MTBE, methyl tert-butyl ether, is a widespread and persistent groundwater contaminant. MTBE undergoes rapid mineralization as the sole carbon and energy source of bacterial strain PM1, isolated from an enrichment culture of compost biofilter material. In this report, we describe the results of microbial community DNA profiling to assess the relative dominance of isolate PM1 and other bacterial strains cultured from the compost enrichment. Three polymerase chain reaction (PCR)-based profiling approaches were evaluated: denaturing gradient gel electrophoresis (DGGE) analysis of 230 bp 16S rDNA fragments; thermal gradient gel electrophoresis (TGGE) analysis of 575 bp 16S rDNA fragments; and non-denaturing polyacrylamide gel electrophoresis of 300-1,500 bp fragments containing 16S/23S ribosomal intergenic transcribed spacer (ITS) regions. Whereas all three DNA profiling approaches indicated that PM1-like bands predominated in mixtures from MTBE-grown enrichments, ITS profiling provided the most abundant and specific sequence data to confirm strain PM1's presence in the enrichment. Moreover, ITS profiling did not produce non-specific PCR products that were observed with T/DGGE. A further advantage of ITS community profiling over other methods requiring restriction digestion (e.g. terminal restriction fragment length polymorphisms) was that it did not require an additional digestion step or the use of automated sequencing equipment. ITS bands, excised from similar locations in profiles of the enrichment and PM1 pure culture, were 99.9% identical across 750 16S rDNA positions and 100% identical across 691 spacer positions. BLAST comparisons of nearly full-length 16S rDNA sequences showed 96% similarity between isolate PM1 and representatives of at least four different genera in the Leptothrix subgroup of the beta-Proteobacteria (Aquabacterium, Leptothrix, Rubrivivax and Ideonella). Maximum likelihood and parsimony analyses of 1,249 nucleotide

  20. Aerobic degradation of methyl tert-butyl ether in a closed symbiotic system containing a mixed culture of Chlorella ellipsoidea and Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Zhong, Weihong; Li, Yixiao; Sun, Kedan; Jin, Jing; Li, Xuanzhen; Zhang, Fuming; Chen, Jianmeng

    2011-01-30

    The contamination of groundwater by methyl tert-butyl ether (MTBE) is one of the most serious environmental problems around the world. MTBE degradation in a closed algal-bacterial symbiotic system, containing a mixed culture of Methylibium petroleiphilum PM1 and Chlorella ellipsoidea, was investigated. The algal-bacterial symbiotic system showed increased MTBE degradation. The MTBE-degradation rate in the mixed culture (8.808 ± 0.007 mg l(-1) d(-1)) was higher than that in the pure bacterial culture (5.664 ± 0.017 mg l(-1) d(-1)). The level of dissolved oxygen was also higher in the mixed culture than that in the pure bacterial culture. However, the improved efficiency of MTBE degradation was not in proportional to the biomass of the alga. The optimal ratio of initial cell population of bacteria to algae was 100:1. An immobilized culture of mixed bacteria and algae also showed higher MTBE degradation rate than the immobilized pure bacterial culture. A mixed culture with algae and PM1 immobilized separately in different gel beads showed higher degradation rate (8.496 ± 0.636 mg l(-1) d(-1)) than that obtained with algae and PM1 immobilized in the same gel beads (5.424 ± 0.010 mg l(-1) d(-1)). Copyright © 2010 Elsevier B.V. All rights reserved.

  1. 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.

  2. Whole-Genome Analysis of the Methyl tert-Butyl Ether-Degrading Beta-Proteobacterium Methylibium petroleiphilum PM1▿ †

    Science.gov (United States)

    Kane, Staci R.; Chakicherla, Anu Y.; Chain, Patrick S. G.; Schmidt, Radomir; Shin, Maria W.; Legler, Tina C.; Scow, Kate M.; Larimer, Frank W.; Lucas, Susan M.; Richardson, Paul M.; Hristova, Krassimira R.

    2007-01-01

    Methylibium petroleiphilum PM1 is a methylotroph distinguished by its ability to completely metabolize the fuel oxygenate methyl tert-butyl ether (MTBE). Strain PM1 also degrades aromatic (benzene, toluene, and xylene) and straight-chain (C5 to C12) hydrocarbons present in petroleum products. Whole-genome analysis of PM1 revealed an ∼4-Mb circular chromosome and an ∼600-kb megaplasmid, containing 3,831 and 646 genes, respectively. Aromatic hydrocarbon and alkane degradation, metal resistance, and methylotrophy are encoded on the chromosome. The megaplasmid contains an unusual t-RNA island, numerous insertion sequences, and large repeated elements, including a 40-kb region also present on the chromosome and a 29-kb tandem repeat encoding phosphonate transport and cobalamin biosynthesis. The megaplasmid also codes for alkane degradation and was shown to play an essential role in MTBE degradation through plasmid-curing experiments. Discrepancies between the insertion sequence element distribution patterns, the distributions of best BLASTP hits among major phylogenetic groups, and the G+C contents of the chromosome (69.2%) and plasmid (66%), together with comparative genome hybridization experiments, suggest that the plasmid was recently acquired and apparently carries the genetic information responsible for PM1's ability to degrade MTBE. Comparative genomic hybridization analysis with two PM1-like MTBE-degrading environmental isolates (∼99% identical 16S rRNA gene sequences) showed that the plasmid was highly conserved (ca. 99% identical), whereas the chromosomes were too diverse to conduct resequencing analysis. PM1's genome sequence provides a foundation for investigating MTBE biodegradation and exploring the genetic regulation of multiple biodegradation pathways in M. petroleiphilum and other MTBE-degrading beta-proteobacteria. PMID:17158667

  3. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

  5. 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...

  6. Aerobic biodegradation of methyl tert-butyl ether by aquifer bacteria from leaking underground storage tank sites.

    Science.gov (United States)

    Kane, S R; Beller, H R; Legler, T C; Koester, C J; Pinkart, H C; Halden, R U; Happel, A M

    2001-12-01

    The potential for aerobic methyl tert-butyl ether (MTBE) degradation was investigated with microcosms containing aquifer sediment and groundwater from four MTBE-contaminated sites characterized by oxygen-limited in situ conditions. MTBE depletion was observed for sediments from two sites (e.g., 4.5 mg/liter degraded in 15 days after a 4-day lag period), whereas no consumption of MTBE was observed for sediments from the other sites after 75 days. For sediments in which MTBE was consumed, 43 to 54% of added [U-(14)C]MTBE was mineralized to (14)CO(2). Molecular phylogenetic analyses of these sediments indicated the enrichment of species closely related to a known MTBE-degrading bacterium, strain PM1. At only one site, the presence of water-soluble gasoline components significantly inhibited MTBE degradation and led to a more pronounced accumulation of the metabolite tert-butyl alcohol. Overall, these results suggest that the effects of oxygen and water-soluble gasoline components on in situ MTBE degradation will vary from site to site and that phylogenetic analysis may be a promising predictor of MTBE biodegradation potential.

  7. 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.

  8. INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

    Science.gov (United States)

    Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

  9. Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, Francoise, E-mail: francoise.fayolle@ifpen.fr [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Durand, Jonathan [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Cheucle, Mathilde [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Rosell, Monica [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Michelland, Rory Julien [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Tracol, Jean-Philippe [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); Le Roux, Francoise [IFP Energies nouvelles, 1 et 4 avenue de Bois-Preau, 92852 Rueil-Malmaison (France); Grundman, Genevieve [Universite de Lyon, F-69622 Lyon (France); Universite Lyon 1, Villeurbanne (France); CNRS, UMR5557, Ecologie Microbienne (France); Atteia, Olivier [Institut EGID Bordeaux 3, 1 Allee Daguin 33607 Pessac Cedex (France); Richnow, Hans H. [Department of Isotope Biogeochemistry, Helmholtz Centre for Environmental Research - UFZ, Permoserstrasse 15, 04318 Leipzig (Germany); Dumestre, Alain [SERPOL, 2 chemin du Genie, BP 80, 69633 Venissieux Cedex (France); and others

    2012-01-30

    Highlights: Black-Right-Pointing-Pointer Ethyl tert-butyl ether (ETBE) (>300 mg L{sup -1}) found in a groundwater (gas-station). Black-Right-Pointing-Pointer No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. Black-Right-Pointing-Pointer MC-IFP culture degraded ETBE (0.91 mg L{sup -1} h{sup -1}) and BTEX (0.64 mg L{sup -1} h{sup -1}). Black-Right-Pointing-Pointer A pilot plant (2 m{sup 3}) inoculated with MC-IFP degraded ETBE in groundwater (15 Degree-Sign C). Black-Right-Pointing-Pointer ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 Multiplication-Sign 10{sup 6}ethB gene copies L{sup -1}). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L{sup -1}) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L{sup -1} h{sup -1} and BTEX: 0.64 and 0.82 mg L{sup -1} h{sup -1}, respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L{sup -1}). An on-site pilot plant (2 m{sup 3}) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant

  10. Study of an aquifer contaminated by ethyl tert-butyl ether (ETBE): Site characterization and on-site bioremediation

    International Nuclear Information System (INIS)

    Fayolle-Guichard, Françoise; Durand, Jonathan; Cheucle, Mathilde; Rosell, Mònica; Michelland, Rory Julien; Tracol, Jean-Philippe; Le Roux, Françoise; Grundman, Geneviève; Atteia, Olivier; Richnow, Hans H.; Dumestre, Alain

    2012-01-01

    Highlights: ► Ethyl tert-butyl ether (ETBE) (>300 mg L −1 ) found in a groundwater (gas-station). ► No significant carbon or hydrogen isotopic fractionation of ETBE along the plume. ► MC-IFP culture degraded ETBE (0.91 mg L −1 h −1 ) and BTEX (0.64 mg L −1 h −1 ). ► A pilot plant (2 m 3 ) inoculated with MC-IFP degraded ETBE in groundwater (15 °C). ► ethB gene (ETBE biodegradation) amplified during bioaugmentation (5 × 10 6 ethB gene copies L −1 ). - Abstract: Ethyl tert-butyl ether (ETBE) was detected at high concentration (300 mg L −1 ) in the groundwater below a gas-station. No significant carbon neither hydrogen isotopic fractionation of ETBE was detected along the plume. ETBE and BTEX biodegradation capacities of the indigenous microflora Pz1-ETBE and of a culture (MC-IFP) composed of Rhodococcus wratislaviensis IFP 2016, Rhodococcus aetherivorans IFP 2017 and Aquincola tertiaricarbonis IFP 2003 showed that ETBE and BTEX degradation rates were in the same range (ETBE: 0.91 and 0.83 mg L −1 h −1 and BTEX: 0.64 and 0.82 mg L −1 h −1 , respectively) but tert-butanol (TBA) accumulated transiently at a high level using Pz1-ETBE (74 mg L −1 ). An on-site pilot plant (2 m 3 ) filled with polluted groundwater and inoculated by MC-IFP, successfully degraded four successive additions of ETBE and gasoline. However, an insignificant ETBE isotopic fractionation was also accompanying this decrease which suggested the involvement of low fractionating-strains using EthB enzymes, but required of additional proofs. The ethB gene encoding a cytochrome P450 involved in ETBE biodegradation (present in R. aetherivorans IFP 2017) was monitored by quantitative real-time polymerase chain reaction (q-PCR) on DNA extracted from water sampled in the pilot plant which yield up to 5 × 10 6 copies of ethB gene per L −1 .

  11. 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...

  12. 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.

  13. 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 EC 50 ) 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.

  14. [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.

  15. 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)

  16. 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 (EC 50 ).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.

  17. 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.

  18. Treatment of methyl tert-butyl ether vapors in biotrickling filters. 1. Reactor startup, steady-state performance, and culture characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Fortin, N.Y.; Deshusses, M.A. [Univ. of California, Riverside, CA (United States). Dept. of Chemical and Environmental Engineering

    1999-09-01

    An aerobic microbial consortium able to biodegrade methyl tert-butyl ether (MTBE) was enriched in two waste air biotrickling filters after continuous operation for 6 months. After this acclimation phase, the two laboratory-scale biotrickling filters were able to degrade up to 50 g of MTBE per cubic meter of reactor per hour, a value comparable to other gasoline constituents. Such high performance could be sustained for at least 4--6 weeks. After the acclimation phase, the MTBE degrading biotrickling filters were characterized by their almost full conversion of MTBE to carbon dioxide and the absence of any degradation byproducts in either the gas or the liquid phase. They also exhibited a very high specific degradation activity per amount of biomass, and a low rate of biomass accumulation. An observed biomass yield of 0.1 g g{sup {minus}1} and a specific growth rate of 0.025 day{sup {minus}1} were determined for the biotrickling filter process culture. Further data on MTBE mass transfer and on the dynamic behavior of the biotrickling filter are presented in part 2 of this paper. Overall, the results demonstrate that MTBE can be effectively biodegraded under carefully controlled environmental conditions.

  19. Assessing soil ecotoxicity of methyl tert-butyl ether using earthworm bioassay; closed soil microcosm test for volatile organic compounds

    International Nuclear Information System (INIS)

    An, Youn-Joo

    2005-01-01

    An earthworm bioassay was conducted to assess ecotoxicity in methyl tert-butyl ether (MTBE)-amended soils. Ecotoxicity of MTBE to earthworms was evaluated by a paper contact method, natural field soil test, and an OECD artificial soil test. All tests were conducted in closed systems to prevent volatilization of MTBE out of test units. Test earthworm species were Perionyx excavatus and Eisenia andrei. Mortality and abnormal morphology of earthworms exposed to different concentrations of MTBE were examined. MTBE was toxic to both earthworm species and the severity of response increased with increasing MTBE concentrations. Perionyx excavatus was more sensitive to MTBE than Eisenia andrei in filter papers and two different types of soils. MTBE toxicity was more severe in OECD artificial soils than in field soils, possibly due to the burrowing behavior of earthworms into artificial soils. The present study demonstrated that ecotoxicity of volatile organic compounds such as MTBE can be assessed using an earthworm bioassay in closed soil microcosm with short-term exposure duration. - Earthworm bioassay can be a good protocol to assess soil ecotoxicity of volatile organic compounds such as MTBE

  20. 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.

  1. Degradation of methyl-tert-butyl ether (MTBE)

    Czech Academy of Sciences Publication Activity Database

    Cajthaml, Tomáš; Baldrian, Petr; Stoychev, I.; Nerud, František

    2004-01-01

    Roč. 53, - (2004), s. 208-209 ISSN 0964-8305. [International Bideterioration and Biodegradation Symposium /12./. Praha, 14.07.2002-18.07.2002] R&D Projects: GA MŠk LN00B030 Institutional research plan: CEZ:AV0Z5020903 Keywords : mtbe Subject RIV: EE - Microbiology, Virology Impact factor: 0.835, year: 2004

  2. Fatty acid methyl esters synthesis from non-edible vegetable oils using supercritical methanol and methyl tert-butyl ether

    International Nuclear Information System (INIS)

    Lamba, Neha; Modak, Jayant M.; Madras, Giridhar

    2017-01-01

    Highlights: • FAMEs were synthesized from non-edible oils using supercritical MeOH and MTBE. • Effect of time, temperature, pressure and molar ratio on conversions was studied. • Rate constants of reaction with methanol and MTBE differ by an order of magnitude. • Non-catalytic supercritical reactions are one order faster than acid catalyzed synthesis. - Abstract: Fatty acid methyl esters (FAMEs) are useful as biodiesel and have environmental benefits compared to conventional diesel. In this study, these esters were synthesized non-catalytically from non-edible vegetable oils: neem oil and mahua oil with two different methylating agents: methanol and methyl tert-butyl ether (MTBE). The effects of temperature, pressure, time and molar ratio on the conversion of triglycerides were studied. The temperature was varied in the range of 523–723 K with molar ratios upto 50:1 and a reaction time of upto 150 min. Conversion of neem and mahua oil to FAMEs with supercritical methanol was found to be 83% in 15 min and 99% in 10 min, respectively at 698 K. Further, a conversion of 46% of mahua oil and 59% of neem oil was obtained in 15 min at 723 K using supercritical MTBE. The rate constants evaluated using pseudo first order reaction kinetics were in the range of 4.7 × 10 −6 to 1.0 × 10 −3 s −1 for the investigated range of temperatures. The activation energies obtained were in the range of 62–113 kJ/mol for the reaction systems investigated. The supercritical synthesis was found to be superior to the catalytic synthesis of the corresponding FAMEs.

  3. Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Keun-Chan; Stringfellow, William T.

    2003-10-02

    Methyl tert-butyl ether (MTBE) is now one of the most common groundwater contaminants in the United States. Groundwater contaminated with MTBE is also likely to be contaminated with tert-butyl alcohol (TBA), because TBA is a component of commercial grade MTBE, TBA can also be used as a fuel oxygenate, and TBA is a biodegradation product of MTBE. In California, MTBE is subject to reporting at concentrations greater than 3 {micro}g/L. TBA is classified as a ''contaminant of current interest'' and has a drinking water action level of 12 {micro}g/L. In this paper, we describe the development and optimization of a simple, automated solid phase microextraction (SPME) method for the analysis of MTBE and TBA in water and demonstrate the applicability of this method for monitoring MTBE and TBA contamination in groundwater, drinking water, and surface water. In this method, the headspace (HS) of a water sample is extracted with a carboxen/polydimethylsiloxane SPME fiber, the MTBE and TBA are desorbed into a gas chromatograph (GC), and detected using mass spectrometry (MS). The method is optimized for the routine analysis of MTBE and TBA with a level of quantitation of 0.3 {micro}g/L and 4 {micro}g/L, respectively, in water. MTBE quantitation was linear for over two orders of concentration (0.3 {micro}g/L -80 {micro}g/L). TBA was found to be linear within the range of 4 {micro}g/L-7,900 {micro}g/L. The lower level of detection for MTBE is 0.03 {micro}g/L using this method. This SPME method using headspace extraction was found to be advantageous over SPME methods requiring immersion of the fiber into the water samples, because it prolonged the life of the fiber by up to 400 sample analyses. This is the first time headspace extraction SPME has been shown to be applicable to the measurement of both MTBE and TBA at concentrations below regulatory action levels. This method was compared with the certified EPA Method 5030/8260B (purge-and-trap/GC/MS) using split

  4. Volumetric Behaviour of the Ternary System (Methyl Tert-butyl ether + Methylbenzene + Butan-1-ol) and Its Binary sub-System (Methyl Tert-Butyl Ether + Butan-1-ol) within the Temperature Range (298.15–328.15) K

    Czech Academy of Sciences Publication Activity Database

    Morávková, Lenka; Troncoso, J.; Škvorová, M.; Havlica, Jaromír; Petrus, P.; Sedláková, Zuzana

    2015-01-01

    Roč. 90, NOV 2015 (2015), s. 59-70 ISSN 0021-9614 R&D Projects: GA ČR(CZ) GAP105/12/0664; GA MŠk(CZ) LD14094 Grant - others:GNIL(IT) 408 REGALIs (CN2012/120) Institutional support: RVO:67985858 Keywords : methylbenzene * density * methyl-tert-butyl ether Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.196, year: 2015

  5. 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.

  6. 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.

  7. 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.

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

    International Nuclear Information System (INIS)

    Cwiklinska, Aneta; Dzikowski, Tomasz; Szychowski, Dariusz; Kinart, Wojciech J.; Kinart, Cezary M.

    2007-01-01

    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 (Δln η) and excess energies of activation for viscous flow (ΔG *E ) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Auslaender, and McAllister. The results for Δln η and ΔG *E are discussed in terms of intermolecular interactions and structure of studied binary mixtures

  9. 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.

  10. 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.

  11. 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.

  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.

    2011-01-01

    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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 2 sorptiometry study. The XPS results confirmed the structure of the Pd CeO 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 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

  14. 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.

  15. Volumetric behaviour of the ternary liquid system composed of methyl tert-butyl ether, toluene, and isooctane at temperatures from (298.15 to 328.15) K: Experimental data and correlation

    International Nuclear Information System (INIS)

    Moravkova, L.; Wagner, Z.; Sedlakova, Z.; Linek, J.

    2010-01-01

    The densities and speeds of sound of (methyl tert-butyl ether {MTBE} + toluene + isooctane) were measured at four temperatures over the range (298.15 to 328.15) K and the respective values of excess volumes V m E and adiabatic compressibility κ S were calculated. The V m E and κ S values for the ternary and corresponding binaries were fitted to the Redlich-Kister equation considering various numbers of ternary constants. The necessary number of ternary constants needed to describe the system is discussed.

  16. Measurement of critical temperatures and critical pressures for binary mixtures of methyl tert-butyl ether (MTBE) + alcohol and MTBE + alkane

    International Nuclear Information System (INIS)

    Han, Kewei; Xia, Shuqian; Ma, Peisheng; Yan, Fangyou; Liu, Tao

    2013-01-01

    Highlights: • The critical properties of seven binary mixtures related to gasoline were measured. • The critical properties of the five systems containing MTBE were reported for the first time. • Binary interaction parameters were fitted by experimental data using PR EOS with Wong–Sandler mixing rule. • Redlich–Kister equation was used to correlate the experimental data. -- Abstract: A set of high-pressure view apparatus was designed for determining the critical properties of chemicals. In order to check the reliability of the apparatus, the critical temperatures (T c ) and critical pressures (P c ) of pure n-heptane, cyclohexane, methanol, ethanol, 1-propanol, methyl tert-butyl ether (MTBE), and binary mixture n-hexane + ethanol were measured. The experimental data were in good agreement with the literature data, which proves the reliability of the apparatus used in the work. The critical temperatures and critical pressures of five binary mixtures containing gasoline additive (MTBE + n-heptane, MTBE + cyclohexane, MTBE + methanol, MTBE + ethanol, MTBE + 1-propanol) were measured using the high-pressure view cell with visual observation. The critical temperatures and critical pressures for the five binary mixtures were all reported for the first time. In addition, the critical temperatures and critical pressures of the binary mixture n-heptane + cyclohexane (two of main components in gasoline) were also measured. All the critical lines for the mixtures studied are continuous which connect the critical points of the two pure components, indicating their phase diagrams belong to type I proposed by Scott and van Konynenburg. The critical points of these systems were calculated by the Peng–Robinson equation of state with the Wong–Sandler mixing rule. This model could calculate the critical properties of the mixtures well with the binary interaction parameter k ij obtained by fitting the experimental critical data. And the experimental data were all

  17. Volumetric and viscometric properties of binary mixtures of {l_brace}methyl tert-butyl ether (MTBE) + alcohol{r_brace} at several temperatures and p = 0.1 MPa: Experimental results and application of the ERAS model

    Energy Technology Data Exchange (ETDEWEB)

    Hoga, H.E. [Departamento de Engenharia Quimica, Centro Universitario da FEI, Avenida Humberto de Alencar, Castelo Branco 3972, 09850-901 Sao Bernardo do Campo, Sao Paulo (Brazil); Torres, R.B., E-mail: belchior@fei.edu.br [Departamento de Engenharia Quimica, Centro Universitario da FEI, Avenida Humberto de Alencar, Castelo Branco 3972, 09850-901 Sao Bernardo do Campo, Sao Paulo (Brazil)

    2011-08-15

    Highlights: > Binary mixtures of MTBE + alcohol have been studied. > Volumetric and viscometric properties have been determined at several temperatures. > Excess molar volumes have been used to test the applicability of the ERAS model. > The results are discussed in terms of chemical and structural effects. - Abstract: Densities and viscosities of binary mixtures of {l_brace}methyl tert-butyl ether (MTBE) + methanol, or +ethanol, or +1-propanol, or +2-propanol, or +1-butanol, or +1-pentanol, or +1-hexanol{r_brace} have been determined as a function of composition at several temperatures and atmospheric pressure. The temperatures studied were (293.15, 298.15, 303.15, and 308.15) K. The experimental results have been used to calculate the excess molar volume (V{sub m}{sup E}) and viscosity deviation ({Delta}{eta}). Both V{sub m}{sup E} and {Delta}{eta} values were negative over the entire range of mole fraction for all temperatures and systems studied. Moreover, the V{sub m}{sup E} values have been used to test the applicability of the Extended Real Associated Solution (ERAS) model.

  18. γ-aminobutyric acidA (GABAA) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 α1 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.

  19. Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol

    Czech Academy of Sciences Publication Activity Database

    Velychkivska, Nadiia; Bogomolova, Anna; Filippov, Sergey K.; Starovoytova, Larisa; Labuta, J.

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1419-1428 ISSN 0303-402X R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : phase separation * coil-globule transition * poly(vinyl methyl ether) Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  20. 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.

  1. 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.

  2. 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.

  3. 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...

  4. Isothermal Vapour-Liquid Equilibria in the Binary and Ternary Systems Composed of tert-Butyl Methyl Ether, 3,3-Dimethyl-2-butanone and 2,2-Dimethyl-1-propanol

    Czech Academy of Sciences Publication Activity Database

    Bernatová, Svatoslava; Pavlíček, Jan; Wichterle, Ivan

    2009-01-01

    Roč. 278, 1-2 (2009), s. 129-134 ISSN 0378-3812 R&D Projects: GA ČR GA104/07/0444 Institutional research plan: CEZ:AV0Z40720504 Keywords : alcohol * ether * ketone Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.857, year: 2009

  5. Regioselective synthesis of nitrosoimidazoheterocycles using tert-butyl nitrite.

    Science.gov (United States)

    Monir, Kamarul; Ghosh, Monoranjan; Jana, Sourav; Mondal, Pallab; Majee, Adinath; Hajra, Alakananda

    2015-08-28

    A simple and practical method has been developed for the regioselective nitrosylation of imidazopyridines via C(sp(2))-H bond functionalization using tert-butyl nitrite under mild reaction conditions in a short time. A library of 3-nitrosoimidazopyridines with broad functionalities was synthesized in near quantitative yields. The present protocol is also applicable to imidazo[2,1-b]thiazole and benzo[d]imidazo[2,1-b]thiazole.

  6. 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.

  7. 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.

  8. Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions

    NARCIS (Netherlands)

    Waals, van der Marcelle J.; Pijls, Charles; Sinke, Anja J.C.; Langenhoff, Alette A.M.; Smidt, Hauke; Gerritse, Jan

    2018-01-01

    The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl

  9. Synthesis, stereochemistry, and photochemical and thermal behaviour of bis-tert-butyl substituted overcrowded alkenes

    NARCIS (Netherlands)

    K. J. Ter Wiel, M.; G. Kwit, M.; Meetsma, A.; Feringa, B.L.

    2007-01-01

    In order to study the structural limits in the design of molecular motors, a tert-butyl substituted analogue was prepared. The unexpected photochemical and thermal isomerisation processes and the stereochemistry of new overcrowded alkene 5 are described. The bis tert-butyl substituted alkenes were

  10. NOVEL EMBEDDED CERAMIC ELECTRODE SYSTEM TO ACTIVATE NANOSTRUCTURED TITANIUM DIOXIDE FOR DEGRADATION OF MTBE

    Science.gov (United States)

    A novel reactor combining a flame-deposited nanostructured titanium dioxide film and a set of embedded ceramic electrodes was designed, developed and tested for degradation of methyl tert-butyl ether (MTBE) in water. On applying a voltage to the ceramic electrodes, a surface coro...

  11. 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.

  12. tert-Butyl 2-methyl-2-(4-methylbenzoylpropanoate

    Directory of Open Access Journals (Sweden)

    Graham B. Gould

    2010-02-01

    Full Text Available The title compound, C16H22O3, is bent with a dihedral angle of 75.3 (1° between the mean planes of the benzene ring and a group encompassing the ester functionality (O=C—O—C. In the crystal, the molecules are linked into infinite chains held together by weak C—H...O hydrogen-bonded interactions between an H atom on the benzene ring of one molecule and an O atom on the ketone functionality of an adjacent molecule. The chains are arranged with neighbouring tert-butyl and dimethyl groups on adjacent chains exhibiting hydrophobic stacking, with short C—H...H—C contacts (2.37 Å between adjacent chains

  13. Chirality Sensing of α-Hydroxyphosphonates by N-tert-Butyl Sulfinyl Squaramide.

    Science.gov (United States)

    Li, Yao; Yang, Guo-Hui; He, Cyndi Qixin; Li, Xin; Houk, K N; Cheng, Jin-Pei

    2017-08-18

    N-tert-Butyl sulfinyl squaramides were used for chiral discrimination of α-hydroxyphosphonates using 31 P NMR. A free energy relationship study indicates that both steric and the electronic effects influence the chiral recognition of the donors.

  14. (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.

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

    Indian Academy of Sciences (India)

    TECS

    IV) phenoxides are known to ..... proton resonances may be ascribed to the deshield- ing of these protons due to drainage of electron den- ..... The effects of newly synthesized organotin(IV) 2- tert-butyl-4-methylphenoxides on the thermal deg-.

  16. Di-tert-butyl 1-[2-hydroxy-3-(methylsulfanylpropyl]hydrazine-1,2-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Xiao-Guang Bai

    2014-08-01

    Full Text Available The title compound, C14H28N2O5S, was synthesized by the reaction of 2-[(methylsulfanylmethyl]oxirane with di-tert-butyl oxalate in hydrazine hydrate. In the crystal, molecules are linked by N—H...O and O—H...O hydrogen bonds into supramolecular chains propagating along the b-axis direction.

  17. 2-tert-Butyl-5,6,7,8,9,10-hexahydrocyclohepta[b]indole

    Directory of Open Access Journals (Sweden)

    Janina Wobbe

    2011-09-01

    Full Text Available 2-tert-Butyl-5,6,7,8,9,10-hexahydrocyclohepta[b]indole was synthesized by reaction of cycloheptanone and (4-tert-butylphenylhydrazine hydrochloride in the presence of sodium acetate and sulfuric acid in glacial acetic acid via Fischer indole synthesis.

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

    Indian Academy of Sciences (India)

    TECS

    -2-Me-4) have been synthesized by the reactions of di-n-butyl and dimethyltin dichlorides and tri-n-butyltin(IV) chloride with 2-tert-butyl-4-methylphenol and triethylamine in tetrahydrofuran. The reaction of triphenyltin chloride with trimethylsilyl-2-t-butyl-4- methylphenoxide in the same solvent however, gives a complex of ...

  19. 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...

  20. {2,6-Bis[(di-tert-butyl-phosphino)-methyl]-phenyl}chloridonickel(II).

    Science.gov (United States)

    Boro, Brian J; Dickie, Diane A; Goldberg, Karen I; Kemp, Richard A

    2008-09-20

    In the title compound, [Ni(C(24)H(43)P(2))Cl], the Ni atom adopts a distorted square-planar geometry, with the P atoms of the 2,6-bis-[(di-tert-butyl-phosphino)meth-yl]phenyl ligand trans to one another. The P-Ni-P plane is twisted out of the plane of the aromatic ring by 21.97 (6)°.

  1. 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.

  2. Aerobic radical multifunctionalization of alkenes using tert-butyl nitrite and water

    Directory of Open Access Journals (Sweden)

    Daisuke Hirose

    2013-08-01

    Full Text Available Water induces a change in the product of radical multifunctionalization reactions of aliphatic alkenes involving an sp3 C–H functionalization by an 1,5-hydrogen shift using tert-butyl nitrite and molecular oxygen. The reaction without water, reported previously, gives nitrated γ-lactols, whereas the reaction in the presence of water produces 4-hydroxy-5-nitropentyl nitrate or 4-hydroxy-3-nitropentyl nitrate derivatives.

  3. 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.

  4. Carbonyl{3,3′-di-tert-butyl-5,5′-dimethoxy-2,2′-bis[(4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yloxy]biphenyl-κ2P,P′}hydrido(triphenylphosphane-κPrhodium(I diethyl ether trisolvate

    Directory of Open Access Journals (Sweden)

    Detlef Selent

    2013-01-01

    Full Text Available In the title compound, [RhH(C74H68O8P2(C18H15P(CO]·3C4H10O, the CHP3 coordination set at the RhI ion is arranged in a distorted trigonal–bipyramidal geometry with the P atoms adopting equatorial coordination sites and the C atom of the carbonyl ligand as well as the H atom adopting the axial sites. The asymmetric unit contains two very similar molecules of the rhodium complex, two half-occupied diethyl ether molecules and further diethyl ether solvent molecules which could not be modelled successfully. Therefore contributions of the latter were removed from the diffraction data using the SQUEEZE procedure in PLATON [Spek (2009. Acta Cryst. D65, 148–155].

  5. 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.

  6. 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

  7. 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)

  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. Substituted 2,2'-bipyridines by nickel-catalysis: 4,4'-di-tert-butyl-2,2'-bipyridine.

    Science.gov (United States)

    Buonomo, Joseph A; Everson, Daniel A; Weix, Daniel J

    2013-11-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4'-di- tert -butyl-2,2'-bipyridine is presented. 5,5'-bis(trifluoromethyl)-2,2'-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant.

  10. 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.

  11. Quercetin protects human hepatoma HepG2 against oxidative stress induced by tert-butyl hydroperoxide

    International Nuclear Information System (INIS)

    Alia, Mario; Ramos, Sonia; Mateos, Raquel; Granado-Serrano, Ana Belen; Bravo, Laura; Goya, Luis

    2006-01-01

    Flavonols such as quercetin, have been reported to exhibit a wide range of biological activities related to their antioxidant capacity. The objective of the present study was to investigate the protective effect of quercetin on cell viability and redox status of cultured HepG2 cells submitted to oxidative stress induced by tert-butyl hydroperoxide. Concentrations of reduced glutathione and malondialdehyde, generation of reactive oxygen species and activity and gene expression of antioxidant enzymes were used as markers of cellular oxidative status. Pretreatment of HepG2 with 10 μM quercetin completely prevented lactate dehydrogenase leakage from the cells. Pretreatment for 2 or 20 h with all doses of quercetin (0.1-10 μM) prevented the decrease of reduced glutathione and the increase of malondialdehyde evoked by tert-butyl hydroperoxide in HepG2 cells. Reactive oxygen species generation induced by tert-butyl hydroperoxide was significantly reduced when cells were pretreated for 2 or 20 h with 10 μM and for 20 h with 5 μM quercetin. Finally, some of the quercetin treatments prevented the significant increase of glutathione peroxidase, superoxide dismutase, glutathione reductase and catalase activities induced by tert-butyl hydroperoxide. Gene expression of antioxidant enzymes was also affected by the treatment with the polyphenol. The results of the biomarkers analyzed clearly show that treatment of HepG2 cells in culture with the natural dietary antioxidant quercetin strongly protects the cells against an oxidative insult

  12. Voltammetric Determination of Nitro Derivative of Synthetic Antioxidant 2,6-di-tert-butyl-4-methyl-phenol

    Czech Academy of Sciences Publication Activity Database

    Chýlková, J.; Machalický, O.; Tomášková, M.; Šelešovská, R.; Navrátil, Tomáš

    2016-01-01

    Roč. 49, č. 1 (2016), s. 92-106 ISSN 0003-2719 R&D Projects: GA ČR(CZ) GAP208/12/1645 Institutional support: RVO:61388955 Keywords : 2,6-di-tert-butyl-4-methyl-phenol * handing drop mercury electrode * nitration Subject RIV: CG - Electrochemistry Impact factor: 1.150, year: 2016

  13. Photoelectric conversion and electrochromic properties of lutetium tetrakis(tert-butyl)bisphthalocyaninate

    International Nuclear Information System (INIS)

    Hu, Andrew Teh; Hu Tenyi; Liu Lungchang

    2003-01-01

    Both photoelectric and electrochromic effects on lutetium tetrakis(tert-butyl)bisphthalocyaninate (Lu(TBPc) 2 ) have been carried out in this study. Lu(TBPc) 2 is known for its electrochromic performance, but its photoelectric effect has not mentioned in the literature. The electrochromic properties of Lu(TBPc) 2 have been measured by cyclic voltammetry (CV) and UV-Vis spectrometer at the same time. It takes less than 1.5 s for the color to change from red to green under 0.9 V. Its cycle life is at least over 500 times. Furthermore, we also investigate its photoelectric conversion properties. Its photoelectric cell exhibits a positive photo-electricity conversion effect with a short-circuit photocurrent (46.4 μA/cm 2 ) under illumination of white light (1.201 mW/cm 2 )

  14. 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.

  15. 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...

  16. Effect of Methyl tert-Butyl Ether in Standard Tests for Mutagenicity and Environmental Toxicity

    Czech Academy of Sciences Publication Activity Database

    Vosáhlíková, M.; Cajthaml, Tomáš; Demnerová, K.; Pazlarová, Jarmila

    2006-01-01

    Roč. 21, č. 6 (2006), s. 599-605 ISSN 1520-4081 Institutional research plan: CEZ:AV0Z50200510 Keywords : toxicity * mtbe * ames test Subject RIV: EE - Microbiology, Virology Impact factor: 1.582, year: 2006

  17. Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions.

    Science.gov (United States)

    van der Waals, Marcelle J; Pijls, Charles; Sinke, Anja J C; Langenhoff, Alette A M; Smidt, Hauke; Gerritse, Jan

    2018-04-01

    The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl alcohol (TBA, a possible oxygenate metabolite), was studied at an industrially contaminated site and in the laboratory. Analysis of groundwater samples indicated that in the field MtBE was degraded, yielding TBA as major product. In batch microcosms, MtBE was degraded under different conditions: unamended control, with medium without added electron acceptors, or with ferrihydrite or sulfate (with or without medium) as electron acceptor, respectively. Degradation of EtBE was not observed under any of these conditions tested. TBA was partially depleted in parallel with MtBE. Results of microcosm experiments with MtBE substrate analogues, i.e., syringate, vanillate, or ferulate, were in line with the hypothesis that the observed TBA degradation is a cometabolic process. Microcosms with ferulate, syringate, isopropanol, or diethyl ether showed EtBE depletion up to 86.5% of the initial concentration after 83 days. Benzene was degraded in the unamended controls, with medium without added electron acceptors and with ferrihydrite, sulfate, or chlorate as electron acceptor, respectively. In the presence of nitrate, benzene was only degraded after addition of an anaerobic benzene-degrading community. Nitrate and chlorate hindered MtBE, EtBE, and TBA degradation.

  18. Protective mechanisms of anthocyanins from purple sweet potato against tert-butyl hydroperoxide-induced hepatotoxicity.

    Science.gov (United States)

    Hwang, Yong Pil; Choi, Jae Ho; Choi, Jun Min; Chung, Young Chul; Jeong, Hye Gwang

    2011-09-01

    Anthocyanins have been shown to exert anti-proliferative, anti-inflammatory effects and anti-carcinogenic activity. In the present work, we investigated the protective effects of anthocyanin fraction (AF) from purple sweet potato on tert-butyl hydroperoxide (t-BHP)-induced hepatotoxicity in HepG2 cell line and in rat liver. The result showed that the oral pretreatment of AF before t-BHP treatment significantly lowered the serum levels of the hepatic enzyme markers (ALT and AST) and reduced oxidative stress of the liver by evaluation of malondialdehyde and glutathione. Histopathological evaluation of the livers also revealed that AF reduced the incidence of liver lesions. The in vitro result showed that AF significantly reduced t-BHP-induced oxidative injury, as determined by cell cytotoxicity, intracellular glutathione content, lipid peroxidation, reactive oxygen species (ROS) levels, and caspases activation. Also, AF up-regulated antioxidant enzymes including heme oxygenase-1 (HO-1), NAD(P)H:quinone reductase, and glutathione S-transferase. Moreover, AF induced Nrf2 nuclear translocation and Akt and ERK1/2 activation, pathways that are involved in inducing Nrf2 nuclear translocation. Taken together, these results suggest that the protective effects of AF against t-BHP-induced hepatotoxicity may, at least in part, be due to its ability to scavenge ROS and to regulate the antioxidant enzyme HO-1 via the Akt and ERK1/2/Nrf2 signaling pathways. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine.

    Science.gov (United States)

    Shang, Rong; Saito, Souta; Jimenez-Halla, J Oscar C; Yamamoto, Yohsuke

    2018-04-17

    Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.

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

    Science.gov (United States)

    Zhang, Ying; Han, Seong-Jeong; Park, Iha; Kim, Inyoung; Chay, Kee-Oh; Kim, Seok Mo; Jang, Dong Il; Lee, Tae-Hoon; Lee, Seung-Rock

    2017-05-10

    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.

  2. Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F.

    2005-04-01

    Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

  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(C 21 H 34 BN 6 S 3 )(C 5 H 5 )Cl 2 ]·0.5C 6 H 6 , (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(C 21 H 34 BN 6 S 3 )(C 5 H 5 )Cl 2 ]·0.5C 6 H 6 , (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(C 14 H 24 BN 4 S 2 )(C 5 H 5 )Cl 2 ], (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(C 7 H 11 N 2 S)(C 7 H 12 N 2 S)(C 5 H 5 )Cl 2 ]·C 6 H 6 , (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(C 7 H 7 ) 3 (C 21 H 34 BN 6 S 3 )]·4C 6 H 6 , (V), have been structurally characterized by X-ray diffraction. The [Tm t-Bu ] ligand coordinates to Ti and Zr in Cp[κ 3 S 2 ,H-Tm t-Bu ]MCl 2 [M = Zr, (I), and Ti, (II)] in a κ 3 S 2 ,H mode, while

  4. 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

  5. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrapropynyloxy-2,8,14,20-tetrathiacalix[4]arene

    Directory of Open Access Journals (Sweden)

    Xiang-Gao Meng

    2009-12-01

    Full Text Available The title compound [systematic name: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrapropynyloxy-2,8,14,20-tetrathiacalix[4]arene], C52H56O4S4, is an alkylated product bearing four propyne groups at the lower rim of a 5,11,17,23-tetra-tert-butyl-tetrathiacalix[4]arene. The molecule is located on a crystallographic twofold rotation axis, running through two S atoms and perpendicular to the long axis of the molecule. The four propyne groups, located in an alternate fashion above and below the mean plane of the four S atoms, are almost parallel to the calixarene long axis. The dihedral angle between the two crystallographically independent benzene rings is 86.77 (14°. Two tert-butyl groups are disordered over two positions with site occupancies of 0.59 (2 and 0.41 (2.

  6. 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.

  7. 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

  8. SYNTHESIS OF [C-11] METHYL MAGNESIUM IODIDE AND ITS APPLICATION TO THE INTRODUCTION OF [C-11] N-TERT-BUTYL GROUPS AND [C-11]-SEC-ALCOHOLS

    NARCIS (Netherlands)

    ELSINGA, PH; KELLER, E; DEGROOT, TJ; VISSER, GM; VAALBURG, W

    The C-11 labelled Grignard reagent methyl magnesium iodide was synthesized carrier and non-carrier added from [C-11]methyl iodide and magnesium. This new C-11-synthon was applied in the synthesis of a [C-11]-N-tert-butyl group by reaction with 2,2,3,4-tetramethyl-5-phenyl-oxazolidine and in the

  9. Hydrophobic hydration and anomalous excess partial molar volume of tert-butyl alcohol-water mixture studied by quasielastic neutron scattering

    International Nuclear Information System (INIS)

    Nakada, Masaru; Maruyama, Kenji; Misawa, Masakatsu; Yamamuro, Osamu

    2007-01-01

    Quasielastic neutron scattering has been used to investigate the hydration of alcohol clusters in tert-butyl alcohol-water mixture. The measurements were made in a range of alcohol concentration, x TBA , from 0.0 to 0.17 in mole fraction at 25degC. Fraction, α, of water molecules hydrated to fractal-surface of alcohol clusters in tert-butyl alcohol-water mixture was obtained as a function of alcohol concentration. Average hydration number N WS of tert-butyl alcohol molecule was derived from the value of α as a function of alcohol concentration. The value of N WS for an isolated alcohol molecule in water was 19-21. The anomalous excess partial molar volume of tert-butyl alcohol-water mixture was interpreted successfully by applying the same model with the same values of volume parameter as used for 1-propanol-water mixture, δ 1 (=-0.36 cm 3 ·mol -1 ) and δ 2 (=0.60 cm 3 ·mol -1 ). (author)

  10. 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

  11. Structure of methylene chloride addition product to zirconium tetrachloride complex with 1-tert.-butyl-2,4,4-trimethyl-2-thio-trimethylsilyl-1,3,2,4-diazaphosphasilatedine

    International Nuclear Information System (INIS)

    Brusilovets, A.I.; Rusanov, Eh.B.; Chernega, A.N.

    1995-01-01

    Complex of zirconium tetrachloride with 1-tert.-butyl-2,4,4-trimethyl--2-thio-3-trimethyl-silyl-1,3,2,4-diazaphosphasilatedine interacts with methylene chloride with formation of bis[3-tert.-butyl-2,4,4-trimethyl-1--trimethylsilyl-2-chloremethylthio-1,3,2,4-diazaphosphasilatedinium] decachlorodizirconate. Specific features of crystal and molecular structure of the compound prepared have been studied by X-ray diffraction method. 21 refs.; 2 figs.; 2 tabs

  12. Substituted 2,2′-bipyridines by nickel-catalysis: 4,4′-di-tert-butyl-2,2′-bipyridine

    OpenAIRE

    Buonomo, Joseph A.; Everson, Daniel A.; Weix, Daniel J.

    2013-01-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4′-di-tert-butyl-2,2′-bipyridine is presented. 5,5′-bis(trifluoromethyl)-2,2′-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant.

  13. Substituted 2,2′-bipyridines by nickel-catalysis: 4,4′-di-tert-butyl-2,2′-bipyridine

    Science.gov (United States)

    Buonomo, Joseph A.; Everson, Daniel A.; Weix, Daniel J.

    2014-01-01

    A simple, ligand-free synthesis of the important bipyridyl ligand 4,4′-di-tert-butyl-2,2′-bipyridine is presented. 5,5′-bis(trifluoromethyl)-2,2′-bipyridine is also synthesized by the same protocol. The syntheses efficiently couple the parent 2-chlorpyridies by a nickel-catalyzed dimerization with manganese powder as the terminal reductant. PMID:25221358

  14. 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.

  15. Comparison of the effects of tert-butyl hydroperoxide and peroxynitrite on the oxidative damage to isolated beef heart mitochondria.

    Science.gov (United States)

    Kohutiar, M; Ivica, J; Vytášek, R; Skoumalová, A; Illner, J; Šantorová, P; Wilhelm, J

    2016-11-08

    Isolated beef heart mitochondria have been exposed to tert-butyl hydroperoxide (tBHP) and peroxynitrite (PeN) in order to model the effects of reactive oxygen and nitrogen species on mitochondria in vivo. The formation of malondialdehyde (MDA), protein carbonyls, lipofuscin-like pigments (LFP), and nitrotyrosine was studied during incubations with various concentrations of oxidants for up to 24 h. The oxidants differed in their ability to oxidize particular substrates. Fatty acids were more sensitive to the low concentrations of tBHP, whereas higher concentrations of PeN consumed MDA. Oxidation of proteins producing carbonyls had different kinetics and also a probable mechanism with tBHP or PeN. Diverse proteins were affected by tBHP or PeN. In both cases, prolonged incubation led to the appearance of proteins with molecular weights lower than 29 kDa bearing carbonyl groups that might have been caused by protein fragmentation. PeN induced nitration of protein tyrosines that was more intensive in the soluble proteins than in the insoluble ones. LFP, the end products of lipid peroxidation, were formed more readily by PeN. On the other hand, fluorometric and chromatographic techniques have confirmed destruction of LFP by higher PeN concentrations. This is a unique feature that has not been described so far for any oxidant.

  16. 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.

  17. Synthesis, characterization and gas separation properties of novel polyimides containing cardo and tert-butyl-m-terphenyl moieties

    Directory of Open Access Journals (Sweden)

    L. A. Bermejo

    2018-05-01

    Full Text Available A series of aromatic polyimides has been obtained by the reaction of two dianhydrides, the commercial 2,2′-bis(3,4-dicarboxyphenylhexafluoropropane dianhydride (6FDA and another having a 5′-tert-butyl-m-terphenyl moiety (BTPDA, with several diamines, including two that have a cardo structure (derived from 9H-fluorene, one of them bearing methyl groups ortho to the amino functionalities (TMeCardo. The solubility, and also the thermal, mechanical, and gas separation properties of the corresponding polyimide membranes were evaluated and compared in order to explore the effect of the different groups in the polyimide backbone. The novel polyimides, which were derived from BTPDA and the cardo diamines, showed high thermal stability, excellent solubility in organic solvents and good gas separation properties, especially the polyimide that bore the ortho methyl substituents. The behavior was especially good for the pair O2/N2, where the TMeCardo polymer overpassed the Robeson upper bound.

  18. Electrochemical and Spin-Trapping Properties of para-substituted α-Phenyl-N-tert-butyl Nitrones

    International Nuclear Information System (INIS)

    Rosselin, Marie; Tuccio, Béatrice; Pério, Pierre; Villamena, Frederick A.; Fabre, Paul-Louis; Durand, Grégory

    2016-01-01

    Nitrones are known both as therapeutic antioxidants and efficient spin-traps. In this work, the redox behavior of various para-substituted α-phenyl-N-tert-butyl nitrones (PBN) was studied by cyclic voltammetry. The polar effect of the substituents was found to correlate with the electrochemical properties of the nitronyl function. Compounds bearing an electron-withdrawing group were more easily reduced than those having an electron-donating group and an opposite trend was observed for the oxidation. Ease of oxidation was also computationally rationalized using DFT approach showing increased ease of oxidation with electron donating functionalities. Since electrochemical properties of nitrones are known to correlate with biological properties, this work provides insights in the design of potent nitrone antioxidants. Using cyclic voltammetry the relative rate of superoxide trapping by nitrones was investigated and compared to the classical antioxidant BHT. The determination of the relative rate of phenyl radical trapping was also carried out but showed no clear correlation with the nature of the substituents. This indicates the absence of a polar effect in agreement with previous data and further supports the intermediate nature, that is, non- or weakly nucleophile, of phenyl radical. On the contrary kinetics of hydroxymethyl radical trapping was found to correlate with the nature of the substituents, demonstrating the nucleophilic nature of its addition onto nitrones.

  19. Synthesis, Crystal Growth, Spectroscopic and Electrical Properties of 5-tert-Butyl-1,2,3-trinitrobenzene

    Directory of Open Access Journals (Sweden)

    S. Sahaya Jude Dhas

    2013-01-01

    Full Text Available 5-tert-Butyl-1,2,3-trinitrobenzene (TBTB was synthesized and characterized by NMR so as to confirm the structure. Single crystals were obtained from methanol by solvent evaporation technique at room temperature. Optically transparent single crystals with dimension up to 17×4×3 mm3 have been grown by submerged seed solution method within a period of 30 days. The modes of vibration of different molecular groups present in the title compound were identified by FTIR and FT-Raman spectral analyses, and it was found with the tabulation that both of the spectral vibrations are very close to each other confirming the existence of specific functional groups in the crystal. Optical behaviour of the crystal was analyzed by UV-Vis absorption studies, and the value of the optical band gap energy (Eg of the crystal has been determined using the optical absorption spectrum. The dielectric behaviour and AC conductivity of the grown crystals were also analyzed, and it is shown that both properties vary with respect to frequency and do not vary in accordance with temperature.

  20. 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.

  1. Long term studies on the anaerobic biodegradability of MTBE and other gasoline ethers

    DEFF Research Database (Denmark)

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

    2009-01-01

    to investigate the anaerobic biodegradability of MTBE and other gasoline ethers. Inoculums collected from various environments were used, along with different electron acceptors. Only one set of the batch experiments showed a 30-60% conversion of MTBE to tert-butyl alcohol under Fe(III)-reducing conditions...

  2. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Tingshun, E-mail: tshjiang@mail.ujs.edu.cn; Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-15

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

  3. 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,...

  4. Photoinduced Reactivity of the Soft Hydrotris(6-tert-butyl-3-thiopyridazinyl)borate Scorpionate Ligand in Sodium, Potassium, and Thallium Salts.

    Science.gov (United States)

    Tüchler, Michael; Belaj, Ferdinand; Raber, Georg; Neshchadin, Dmytro; Mösch-Zanetti, Nadia C

    2015-09-08

    The soft scorpionate ligand hydrotris(6-tert-butyl-3-thiopyridazinyl)borate (Tn) was found to exhibit pronounced photoreactivity. Full elucidation of this process revealed the formation of 6-tert-butylpyridazine-3-thione (PnH) and 4,5-dihydro-6-tert-butylpyridazine-3-thione (H2PnH). Under exclusion of light, no solvolytic reactions occur, allowing the development of high-yield preparation protocols for the sodium, potassium, and thallium salts and improving the yield for their derived copper boratrane complex. The photoreactivity is relevant for all future studies with electron-deficient scorpionate ligands.

  5. Photochemical Degradation of Polybrominated Diphenyl Ethers in Microreactor

    Czech Academy of Sciences Publication Activity Database

    Vajglová, Zuzana; Veselý, M.; Hejda, S.; Vondráčková, Magdalena; Křišťál, Jiří; Cajthaml, Tomáš; Křesinová, Zdena; Tříska, Jan; Klusoň, Petr; Jiřičný, Vladimír

    2015-01-01

    Roč. 41, č. 12 (2015), s. 9373-9381 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] R&D Projects: GA ČR(CZ) GAP105/12/0664; GA ČR GA104/09/0880 Institutional support: RVO:67985858 ; RVO:61388971 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * photochemical microreactor * debromination * photo degradation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

  6. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

    International Nuclear Information System (INIS)

    Souane, R.

    2005-03-01

    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO 2 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 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 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 (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO 2 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. (author)

  7. Elevation of the Energy Threshold for Isomerization of 5-Hydroxyindole-(tert-butyl alcohol)1Cluster Cations.

    Science.gov (United States)

    Ikeda, Takamasa; Sakota, Kenji; Sekiya, Hiroshi

    2017-08-10

    Isomerization between two hydrogen-bonded (H-bonded) isomers of 5-hydroxyindole-(tert-butyl alcohol) 1 cluster cations ([5HI-(t-BuOH) 1 ] + ) was investigated in the gas phase. In the S 0 state, jet-cooled 5HI-(t-BuOH) 1 has two structural isomers, 5HI(OH)-(t-BuOH) 1 and 5HI(NH)-(t-BuOH) 1 , in which the t-BuOH molecule is bound to the OH or the NH group of 5HI. The IR photodissociation spectrum of [5HI-(t-BuOH) 1 ] + generated by two-color resonant two-photon ionization (2C-R2PI) via the S 1 -S 0 origin of 5HI(NH)-(t-BuOH) 1 provided evidence of both [5HI(OH)-(t-BuOH) 1 ] + and [5HI(NH)-(t-BuOH) 1 ] + coexisting in the D 0 state, indicating that [5HI(NH)-(t-BuOH) 1 ] + isomerizes to [5HI(OH)-(t-BuOH) 1 ] + after 2C-R2PI of 5HI(NH)-(t-BuOH) 1 . The lower limit of the energy threshold for the isomerization of [5HI(NH)-(t-BuOH) 1 ] + to [5HI(OH)-(t-BuOH) 1 ] + was experimentally determined to be 3362 ± 30 cm -1 , and the corresponding energy threshold for the isomerization of [5HI(NH)-(H 2 O) 1 ] + to [5HI(OH)-(H 2 O) 1 ] + has been reported to be 2127 ± 30 cm -1 . Thus, the energy threshold for the isomerization is elevated by at least 1200 cm -1 when the solvent molecule changes from H 2 O to t-BuOH. The elevation of the energy threshold is explained by the difference in the stabilization energies of [5HI-(t-BuOH) 1 ] + and [5HI-(H 2 O) 1 ] + in the initial and transition states owing to the larger proton affinity of t-BuOH than H 2 O.

  8. Formation of zinc-peptide spherical microparticles during lyophilization from tert-butyl alcohol/water co-solvent system.

    Science.gov (United States)

    Qian, Feng; Ni, Nina; Chen, Jia-Wen; Desikan, Sridhar; Naringrekar, Vijay; Hussain, Munir A; Barbour, Nancy P; Smith, Ronald L

    2008-12-01

    To understand the mechanism of spherical microparticle formation during lyophilizing a tert-Butyl alcohol (TBA)/water solution of a zinc peptide adduct. A small peptide, PC-1, as well as zinc PC-1 at (3:2) and (3:1) ratios, were dissolved in 44% (wt.%) of TBA/water, gradually frozen to -50 degrees C over 2 h ("typical freezing step"), annealed at -20 degrees C for 6 h ("annealing step"), and subsequently lyophilized with primary and secondary drying. Zinc peptide (3:1) lyophile was also prepared with quench cooling instead of the typical freezing step, or without the annealing step. Other TBA concentrations, i.e., 25%, 35%, 54% and 65%, were used to make the zinc peptide (3:1) adduct lyophile with the typical freezing and annealing steps. The obtained lyophile was analyzed by Scanning Electron Microscopy (SEM). The zinc peptide solutions in TBA/water were analyzed by Differential Scanning Calorimeter (DSC). The surface tension of the TBA/water co-solvent system was measured by a pendant drop shape method. With typical freezing and annealing steps, the free peptide lyophile showed porous network-like structure that is commonly seen in lyophilized products. However, with increasing the zinc to peptide ratio, uniform particles were gradually evolved. Zinc peptide (3:1) adduct lyophiles obtained from 25%, 35% and 44% TBA exhibit a distinctive morphology of uniform and spherical microparticles with diameters of approximately 3-4 microm, and the spherical zinc peptide particles are more predominant when the TBA level approaches 20%. Adopting quench cooling in the lyophilization cycle leads to irregular shape fine powders, and eliminating the annealing step causes rough particles surface. When TBA concentration increases above 54%, the lyophiles demonstrate primarily irregular shape particles. A proposed mechanism of spherical particle formation of the 3:1 zinc peptide encompasses the freezing of a TBA/water solution (20-70% TBA) causing the formation of a TBA hydrate

  9. Unexpected complexes from meta-phenylene bis(tert-butyl nitroxides) and gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate

    Science.gov (United States)

    Sekine, Hiroyasu; Ishida, Takayuki

    2018-01-01

    Coordination reaction of the stable ground triplet biradical biphenyl-3,5-diyl bis(tert-butyl nitroxide) and [Gd(hfac)3(H2O)2] unexpectedly gave complexes containing a dimerized diamagnetic ligand via a [3+3] cycloaddition of the benzene rings (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate). To avoid such dimerization, we introduced a bulkier substituent into the ligand; namely, a new ground triplet biradical 5-mesityl-1,3-phenylene bis(tert-butyl nitroxide) was applied to this complexation scheme. However, an unexpected complex was again obtained in a different way, and the magnetic study revealed that the novel ligand involved was diamagnetic. The crystallographic analysis of the product clarified isomerization from the paramagnetic ligand to a diamagnetic N-tert-butylaminoquinone imine N-oxide ligand as a result of disproportionation from two open-shell nitroxide groups to closed-shell groups, an amine and a nitrone. The present paper reports the first structural evidence for a diamagnetic isomer of m-phenylene-bridged bisnitroxde compounds.

  10. Degradation of β-Aryl Ether Bonds in Transgenic Plants

    DEFF Research Database (Denmark)

    Mnich, Ewelina

    of the cell wall. The aim of the study was to alter lignin structure by expression in plants of the enzymes from S. paucimobilis involved in ether bond degradation (LigDFG). Arabidopsis thaliana and Brachypodium distachyon transgenic lines were generated and characterized with respect to lignin structure...... and cell wall polysaccharide extractability. Structural changes in lignin detected by 2D HSQC NMR analysis of transgenic Arabidopsis stems correlated with a slight increase in the saccharification yield. An increase in oxidized guaiacyl and syringyl units resulting from the action of LigDFG was observed...... be degraded by LigDFG, which can presumably cause loosening of the lignin-ferulate-polysaccharide matrix. In a xylanase hydrolysis of Brachypodium transgenic stems, the release of arabinose and xylose was increased compared to wild type. The data presented demonstrate that introduction of lignin degrading...

  11. 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...

  12. Solubility of hyperbranched polymer, Boltorn W-3000, in alcohols, ethers and hydrocarbons

    International Nuclear Information System (INIS)

    Domanska, Urszula; Zolek-Tryznowska, Zuzanna

    2010-01-01

    (Solid/liquid + liquid) phase diagrams at ambient pressure have been determined for the hyperbranched polymer, Boltorn W3000 with alcohols (methanol, ethanol, 1-propanol, 1-hexanol, 1-decanol), or with ethers (tert-butyl methyl ether, tert-butyl ethyl ether), or with hydrocarbons (n-hexane, n-heptane, benzene, toluene) by a dynamic method from T = 240 K to the boiling temperature of the solvent. (Solid + liquid) phase equilibria with immiscibility in the liquid phase were detected for B-W3000 with the alcohols and aliphatic hydrocarbons. The upper critical solution temperatures, UCSTs, were measured for (B-W3000 + 1-hexanol and 1-decanol) systems. The experimental results of (solid + liquid) phase equilibria have been correlated using NRTL equation.

  13. Metabolism of the fungicide Denmert (S-n-butyl S'-p-tert-butyl-benzyl N-3-pyridyldithiocarbonimidate, S-1358) and Denmert sulfoxides in liver enzyme systems

    International Nuclear Information System (INIS)

    Ohkawa, Hideo; Okihara, Yukiko; Miyamoto, Junshi

    1976-01-01

    On incubation with rat liver microsomes plus MADPH, Denmert (S-n-butyl S'-p-tert-butylbenzyl N-3-pyridyldithiocarbonimidate) underwent at least two different types of oxidation; hydroxylation and sulfoxidation. Hydroxylation of Denmert at the tert-butyl group was one of the major metabolic attacks in mammalian metabolism. Sulfoxidation of Denmert gave two isomers of Denmert sulfoxides which were intermediates in the metabolism and readily transformed into 2-(3'-pyridylimino)-4-carboxylthiazolidine (HM) in the presence of L-cysteine without enzymatic mediation. This type of conjugation with cysteine appears to be a new class of metabolic reactions in mammals. Denmert S-oxide showed increased fungicidal activity when assayed in liquid cultures, but not on plant leaves. (auth.)

  14. Microwave-Assisted Synthesis and Crystal Structure of Oxo(diperoxo(4,4'-di-tert-butyl-2,2'-bipyridine-molybdenum(VI

    Directory of Open Access Journals (Sweden)

    Alírio E. Rodrigues

    2009-09-01

    Full Text Available The oxodiperoxo complex MoO(O22(tbbpy (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine was isolated from the reaction of MoO2Cl2(tbbpy in water under microwaveassisted heating at 120 ºC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The MoVI centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O22(tbbpy complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

  15. Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

    Science.gov (United States)

    Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

    2018-05-01

    It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Lessons learned from a case of tert-butyl glucuronide excretion in urine - "New" psychoactive alcohols knocking on the back door?

    Science.gov (United States)

    Arndt, Torsten; Buschmann, Hubert C; Schulz, Katja; Stemmerich, Karsten

    2017-12-01

    Ethyl glucuronide (EtG) in urine is considered a marker of recent ethanol consumption or ethanol exposition. tert-Butanol is primarily used as a solvent and intermediate chemical. Like tert-amyl alcohol, tert-butanol is discussed in Internet forums as ethanol replacement. We discuss false-positive immunological EtG screenings by excretion of different alcohol glucuronides (EtG homologs), mainly tert-butyl glucuronide in urine of a polytoxikomanic in-patient. Three consecutive urine samples from an in-patient with a long history of multiple substance abuse including solvents were analyzed by DRI EtG enzyme immunoassay (ThermoFisher Scientific Microgenics) on a Beckman Coulter AU680 analyzer, an in-house LC-MS/MS for EtG, 1-propyl, 2-propyl, 1-butyl, 2-butyl, and tert-butyl glucuronide, and an in-house headspace GC-FID of free congener substances methanol, 1-propanol, 2-butanone, 2-butanol, isobutanol, 1-butanol, 3-methyl-1-butanol, 2-methyl-1-butanol, and additionally for ethanol, acetone, 2-propanol, tert-butanol and 2-methyl-2-butanol. EtG immunoassay yielded two positive urine samples (0.2 and 0.6mg/L or 0.1 and 0.2mg/g creatinine; cut-off 0.1mg/L) which were tested EtG negative by LC-MS/MS (cut-off 0.1mg/L) but positive for tert-butyl glucuronide (3.7 and 27.1mg/L), 2-butyl glucuronide (1.1 and 3.5mg/L), and 2-propyl glucuronide (0.1 and 0.4mg/L). Headspace GC-FID detected tert-butanol (0.97 and 4.01mg/L), methanol (0.96 and 0.62mg/L), 2-butanone (0.84 and 1.65mg/L), and 2-butanol (0.04 and 0.09mg/L), but no ethanol and no 2-methyl-2-butanol. Cross-reaction of EtG homologs, mainly tert-butyl glucuronide after suspected tert-butanol or isobutane abuse, explains the false-positive EtG immunoassay findings. Future investigations could address the usefulness of alcohol glucuronides (EtG homologs) in urine as (a) biomarkers of an exposition to alkans or their corresponding alcohol metabolites and (b) as markers for using "old"-well known alcohols like tert-butanol or

  1. Isolation and characterization of an ether-type polyurethane-degrading micro-organism and analysis of degradation mechanism by Alternaria sp.

    Science.gov (United States)

    Matsumiya, Y; Murata, N; Tanabe, E; Kubota, K; Kubo, M

    2010-06-01

    To degrade ether-type polyurethane (ether-PUR), ether-PUR-degrading micro-organism was isolated. Moreover, ether-PUR-degrading mechanisms were analysed using model compounds of ether-PUR. A fungus designated as strain PURDK2, capable of changing the configuration of ether-PUR, has been isolated. This isolated fungus was identified as Alternaria sp. Using a scanning electron microscope, the grid structure of ether-PUR was shown to be melted and disrupted by the fungus. The degradation of ether-PUR by the fungus was analysed, and the ether-PUR was degraded by the fungus by about 27.5%. To analyse the urethane-bond degradation by the fungus, a degraded product of ethylphenylcarbamate was analysed using GC/MS. Aniline and ethanol were detected by degradation with the supernatant, indicating that the fungus secreted urethane-bond-degrading enzyme(s). PURDK2 also degraded urea bonds when diphenylmethane-4,4'-dibutylurea was used as a substrate. The enzyme(s) from PURDK2 degraded urethane and urea bonds to convert the high molecular weight structure of ether-PUR to small molecules; and then the fungus seems to use the small molecules as an energy source. Ether-PUR-degrading fungus, strain PURDK2, was isolated, and the urethane- and urea-bonds-degrading enzymes from strain PURDK2 could contribute to the material recycling of ether-PUR.

  2. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

    International Nuclear Information System (INIS)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout

    2017-01-01

    Highlights: • Cu and Au on γ-Al 2 O 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 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 2 O 3 supported copper and gold nanoparticles. Li 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 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 is occurring as a function of

  3. Degradation of the Alternaria mycotoxins alternariol, alternariol monomethyl ether, and altenuene upon bread baking.

    Science.gov (United States)

    Siegel, David; Feist, Michael; Proske, Matthias; Koch, Matthias; Nehls, Irene

    2010-09-08

    The stability of the Alternaria mycotoxins alternariol, alternariol monomethyl ether, and altenuene upon bread baking was investigated by model experiments using a spiked wholemeal wheat flour matrix. For alternariol and alternariol monomethyl ether, but not for altenuene, degradation products, formed through a sequence of hydrolysis and decarboxylation, could be identified in pilot studies. The simultaneous quantification of alternariol, alternariol monomethyl ether, altenuene, and the degradation products was achieved by a newly developed high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) multimethod. The obtained quantitative data indicate that the Alternaria mycotoxins are barely degraded during wet baking, while significant degradation occurs upon dry baking, with the stability decreasing in the order alternariol monomethyl ether>alternariol>altenuene. The novel degradation products could be detected after the wet baking of flour spiked with alternariol and in a sample survey of 24 commercial cereal based baking products.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. Protective effect of black garlic extracts on tert-Butyl hydroperoxide-induced injury in hepatocytes via a c-Jun N-terminal kinase-dependent mechanism.

    Science.gov (United States)

    Lee, Ko-Chao; Teng, Chih-Chuan; Shen, Chien-Heng; Huang, Wen-Shih; Lu, Chien-Chang; Kuo, Hsing-Chun; Tung, Shui-Yi

    2018-03-01

    Black garlic has been reported to show multiple bioactivities against the development of different diseases. In the present study, the hepatoprotective effect of black garlic on injured liver cells was investigated. Rat clone-9 hepatocytes were used for all experiments; tert-Butyl hydroperoxide (tBHP) was used to induce injury of rat clone-9 hepatocytes. The contents of malondialdehyde (MDA) and glutathione (GSH); anti-oxidative enzyme activities of catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPx); and mRNA expression levels of interleukin (IL)-6 and IL-8 in rat clone-9 hepatocytes were determined to evaluate the level of cell damage. Black garlic extracts were demonstrated to significantly attenuate tBHP-induced cell death of rat clone-9 hepatocytes (P<0.05). Pretreatment with black garlic extracts antagonized GSH depletion, tBHP-increased MDA accumulation and the mRNA expression level of IL-6/IL-8, and tBHP-decreased antioxidative enzyme activities (all P<0.05). Moreover, the present study revealed that c-Jun N-terminal kinase signaling regulated black garlic-inhibited tBHP effects in rat clone-9 hepatocytes. Our findings demonstrate that black garlic has the hepatoprotective potential to block tBHP-damaged effects on cell death, lipid peroxidation, oxidative stress, and inflammation in rat clone-9 hepatocytes. Thus, the present study indicates that black garlic may be an excellent natural candidate in the development of adjuvant therapy and healthy foods for liver protection.

  9. Equilibrium surface tension and the interaction energy of DMSO with tert-butyl alcohol or iso-amyl alcohol at various temperatures

    International Nuclear Information System (INIS)

    Bagheri, Ahmad; Moradian, Zohreh

    2014-01-01

    Highlights: • Surface tension of non-ideal binary systems of alcohol/DMSO determined. • The surface tension data of binary mixtures were correlated with five equations. • The interaction energy values were calculated by using LWW model. • The U 12 value shows different behavior for two systems with increasing temperature. - Abstract: Surface tension of binary mixtures of tert-butyl alcohol (TBA) and iso-amyl alcohol (IAA) with DMSO (dimethyl sulfoxide) were measured over the entire concentration range at pressure of 82.5 kPa at temperatures between (298.15 and 328.15) K. Correlating the surface tension and surface tension deviation of the above mentioned binary systems was performed with empirical and thermodynamic based models. The average relative error obtained from the comparison of experimental and calculated surface tension values for the two binary systems with five models at various temperatures is less than 2%. The effect of temperature on the interaction energy values in binary mixtures has been used to obtain information about solute structural effects on DMSO. Also, the experimental data were used to evaluate the nature and type of intermolecular interactions in binary mixtures

  10. Preparation of Langmuir–Blodgett thin films of calix[6]arenes and p-tert butyl group effect on their gas sensing properties

    Energy Technology Data Exchange (ETDEWEB)

    Ozmen, Mustafa, E-mail: musozmen@gmail.com [Department of Chemistry, University of Selcuk, 42075 Konya (Turkey); Ozbek, Zikriye, E-mail: zikriye@comu.edu.tr [Department of Bioengineering, University of Canakkale Onsekiz Mart, 17100 Canakkale (Turkey); Bayrakci, Mevlut [Department of Bioengineering, University of Karamanoglu Mehmetbey, 70200 Karaman (Turkey); Ertul, Seref; Ersoz, Mustafa [Department of Chemistry, University of Selcuk, 42075 Konya (Turkey); Capan, Rifat [Department of Physics, University of Balikesir, 10145 Balikesir (Turkey)

    2015-12-30

    Graphical abstract: - Highlights: • In this work, we prepared Langmuir–Blodgett films of calix[6]arene derivatives. • Then LB films of calixarene compounds were characterized. • Organic vapor sensing properties of prepared LB films were investigated. - Abstract: Organic vapor sensing properties of Langmuir–Blodgett (LB) thin films of p-tert-butyl calix[6]arene and calix[6]arene, and their certain characterization are reported in this work. LB films of these calixarenes have been characterized by contact angle measurement, quartz crystal microbalance (QCM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). QCM system was used for the measurement of sensor response against chloroform, benzene, toluene and ethanol vapors. Forming of stable monolayers was observed at the water surface using surface pressure–area isotherm graph. The results indicate that good quality, uniform LB films can be prepared with a transfer ratio of over 0.95. Due to the adsorption of vapors into the LB film structures; they yield a response to all vapors as of large, fast, and reproducible.

  11. Chlorido(4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridineplatinum(II chloride toluene monosolvate

    Directory of Open Access Journals (Sweden)

    Rami J. Batrice

    2010-12-01

    Full Text Available In the title compound, [PtCl(C27H35N3]Cl·C7H8, the PtII atom is coordinated in a pseudo-square-planar fashion by the N atoms of a 4,4′,4′′-tri-tert-butyl-2,2′:6′,2′′-terpyridine (tbtrpy ligand and a Cl atom. The Pt—N distance of the N atom on the central pyridine is 1.941 (4 Å, while the peripheral N atoms have Pt—N distances of 2.015 (4 and 2.013 (4 Å. The Pt—Cl bond distance is 2.3070 (10 Å. The cations pack as dimers in a head-to-tail orientation with an intermolecular Pt...Pt distance of 3.2774 (3 Å and Pt...N distances of 3.599 (4, 3.791 (4 and 4.115 (4 Å. The solvent molecule is disordered and occupies two positions with a ratio of 0.553 (6:0.447 (6.

  12. 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.

  13. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    Science.gov (United States)

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Solid binary mixtures of neopentanol with tert-Butyl chloride and carbon tetrachloride studied by thermal, X-ray and dielectric techniques

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Girish; Murthy, S.S.N., E-mail: ssnm0700@gmail.com

    2016-05-10

    Highlights: • DSC, dielectric and X-ray measurements have been done on TBC-NPOH and CTC-NPOH. • The results show the formation of solid solution for concentrations 0.7 ≤ x{sub m} ≤ 0.9. • A primary α-process and two sub-T{sub g} processes are found for TBC-NPOH. • For CTC-NPOH only one sub-T{sub g} process is found. • All the three sub-T{sub g} processes are Johari–Goldstein type. - Abstract: The binary mixtures of Neopentanol (NPOH) with tert-Butyl chloride (TBC) and Carbon tetrachloride (CTC), have been studied using Differential Scanning Calorimetry, Dielectric spectroscopy and X-ray diffraction techniques. The results indicate the formation of the solid solutions. The crystalline solid thus formed is found to be orientationally disordered and supercools easily to form glassy crystal for mole fraction of NPOH in the range of 0.7–0.9. The T{sub g} values are in the range of 140–147 K. In the dielectric study, a primary α-process and two sub-T{sub g} processes are found for TBC-NPOH, whereas for CTC-NPOH only one sub-T{sub g} process is found. The dielectric spectra of α- process follows the Havriliak–Negami equation. The sub-T{sub g} processes follow the Cole–Cole equation, and are found to be of Johari–Goldstein type, indicating intermolecular nature.

  15. Dynamics of Back Electron Transfer in Dye-Sensitized Solar Cells Featuring 4-tert-Butyl-Pyridine and Atomic-Layer-Deposited Alumina as Surface Modifiers.

    Science.gov (United States)

    Katz, Michael J; Vermeer, Michael J DeVries; Farha, Omar K; Pellin, Michael J; Hupp, Joseph T

    2015-06-18

    A series of dye-sensitized solar cells (DSCs) was constructed with TiO2 nanoparticles and N719 dye. The standard I3(-)/I(-) redox shuttle and the Co(1,10-phenanthroline)3(3+/2+) shuttle were employed. DSCs were modified with atomic-layered-deposited (ALD) coatings of Al2O3 and/or with the surface-adsorbing additive 4-tert-butyl-pyridine. Current-voltage data were collected to ascertain the influence of each modification upon the back electron transfer (ET) dynamics of the DSCs. The primary effect of the additives alone or in tandem is to increase the open-circuit voltage. A second is to alter the short-circuit current density, JSC. With dependence on the specifics of the system examined, any of a myriad of dynamics-related effects were observed to come into play, in both favorable (efficiency boosting) and unfavorable (efficiency damaging) ways. These effects include modulation of (a) charge-injection yields, (b) rates of interception of injected electrons by redox shuttles, and (c) rates of recombination of injected electrons with holes on surface-bound dyes. In turn, these influence charge-collection lengths, charge-collection yields, and onset potentials for undesired dark current. The microscopic origins of the effects appear to be related mainly to changes in driving force and/or electronic coupling for underlying component redox reactions. Perhaps surprisingly, only a minor role for modifier-induced shifts in conduction-band-edge energy was found. The combination of DSC-efficiency-relevant effects engendered by the modifiers was found to vary substantially as a function of the chemical identity of the redox shuttle employed. While types of modifiers are effective, a challenge going forward will be to construct systems in ways in which the benefits of organic and inorganic modifiers can be exploited in fully additive, or even synergistic, fashion.

  16. 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 groundwater were generally smaller for benzene than for 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.

  17. 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.

  18. Volumetric behaviour of binary liquid systems composed of toluene, isooctane, and methyl tert-butyl ether at temperatures from (298.15 to 328.15) K

    International Nuclear Information System (INIS)

    Moravkova, L.; Wagner, Z.; Linek, J.

    2009-01-01

    The densities and speeds of sound of (toluene + isooctane), (MTBE + toluene), and (MTBE + isooctane) were measured at four temperatures from (298.15 to 328.15) K, and the respective values of excess volumes V m E and adiabatic compressibility κ S were calculated. The V m E and κ S values were fitted to the fourth-order Redlich-Kister equation. The V m E values for (MTBE + toluene) are negative and decreasing with increasing temperature. The other systems show positive V m E with comparatively small temperature dependence

  19. Radiation chemistry of alternative fuel oxygenates - substituted ethers

    International Nuclear Information System (INIS)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-01-01

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

  20. 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.

  1. 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.

  2. Thermal Degradation Study of Decabromodiphenyl Ether. Translating Thermo-Analytical Results into Optimal Chromatographic Conditions

    Directory of Open Access Journals (Sweden)

    Dumitras Mihai

    2016-12-01

    Full Text Available This study aims to investigate the thermal degradation behavior of decabrominated diphenyl ether (BDE 209, a flame retardant (FR which accounts for more than 90% of the total polybrominated diphenyl ethers reported for indoor dust samples collected from Eastern Romania. Simultaneous TG/DTA was applied under various heating rate and atmospheres. The results of this study showed that BDE 209 undergoes thermal degradation in a single step, regardless of the heating rate or atmosphere, with an initial degradation temperature between 297 and 330 °C, depending on the heating rate, and a partial overlapping of melting and thermal degradation in the initial stages which might suggest that the common degradation noticed for the higher brominated FRs analysis might also occur during sample preparation or during injection of the extracts in the GC systems and not necessarily during column elution. The main findings of this research were aimed at designing proper GC analytical methods for the selected halogenated contaminants.

  3. 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

  4. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

    International Nuclear Information System (INIS)

    Serrano V, E. C.

    2011-01-01

    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 3 -3.5 NaNO 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 -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 -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 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

  5. Sodium lauryl ether sulfate (SLES) degradation by nitrate-reducing bacteria

    NARCIS (Netherlands)

    Paulo, Ana M. S.; Aydin, Rozelin; Dimitrov, Mauricio R.; Vreeling, Harm; Cavaleiro, Ana J.; García-Encina, Pedro A.; Stams, Alfons J. M.; Plugge, Caroline M.

    2017-01-01

    The surfactant sodium lauryl ether sulfate (SLES) is widely used in the composition of detergents and frequently ends up in wastewater treatment plants (WWTPs). While aerobic SLES degradation is well studied, little is known about the fate of this compound in anoxic environments, such as

  6. Metabolism of nitrodiphenyl ether herbicides by dioxin-degrading bacterium Sphingomonas wittichii RW1.

    Science.gov (United States)

    Keum, Young Soo; Lee, Young Ju; Kim, Jeong-Han

    2008-10-08

    Nitrodiphenyl ether herbicides, including chlomethoxyfen, nitrofen, and oxyfluorfen are potent herbicides. Some metabolites and parent compounds are considered as possible mutagens and endocrine disruptors. Both properties pose serious hygienic and environmental risks. Sphingomonas wittichii RW1 is a well-known degrader of polychlorinated dibenzo- p-dioxins, dibenzofurans, and diphenyl ethers. However, no detailed research of its metabolic activity has been performed against pesticides with a diphenyl ether scaffold. In this study, we report S. wittichii RW1 as a very potent diphenyl ether herbicide-metabolizing bacterium with broad substrate specificity. The structures of metabolites were determined by instrumental analysis and synthetic standards. Most pesticides were rapidly removed from the culture medium in the order of nitrofen > oxyfluorfen > chlomethoxyfen. In general, herbicides were degraded through the initial reduction and N-acetylation of nitro groups, followed by ether bond cleavage. Relatively low concentrations of phenolic and catecholic metabolites throughout the study suggested that these metabolites were rapidly metabolized and incorporated into primary metabolism. These results indicate that strain RW1 has very versatile metabolic activities over a wide range of environmental contaminants.

  7. Photolytic degradation of polybromodiphenyl ethers under UV-lamp and solar irradiations.

    Science.gov (United States)

    Shih, Yang-hsin; Wang, Chun-Kang

    2009-06-15

    Polybromodiphenyl ethers (PBDEs) are widely used flame retardant additives and have been mainly used in polymers for many plastic and electronic products. PBDEs have been found to bioaccumulate in both aquatic and terrestrial ecosystems and even human bodies. The technical product with the highest use is decabrominated diphenyl ether (BDE-209). Therefore, we chose to examine the solar and UV-lamp degradation of BDE-209. A linear increase of the photodegradation rate constant for BDE-209 was observed with the solar light intensity. The degradation reactions follow the pseudo-first-order kinetics. The photodegradation of BDE-209 produced other less brominated diphenyl ethers under ultraviolet light exposure, suggesting that the photodegradation of BDE-209 is a sequential dehalogenation mechanism. BDE-209 underwent rapid reductive debromination in these photodecomposition experiments. The formation rate constants of three nonabromodiphenyl ethers increase with the order of BDE-206, BDE-207 and BDE-208, indicating debromination mainly occurred at para>meta>ortho positions. These findings of the process properties and reductive debromination mechanism of the photolytic degradation of PBDEs can facilitate the design of remediation processes and also aid in predicting their fate in the environment.

  8. ESI-MSn and LC-ESI-MS studies to characterize forced degradation products of bosentan and a validated stability-indicating LC-UV method.

    Science.gov (United States)

    Bansal, Gulshan; Singh, Ranjit; Saini, Balraj; Bansal, Yogita

    2013-01-01

    The present study reports the characterization of forced degradation products of bosentan and a validated stability-indicating HPLC method for the stability testing of bosentan tablets. The forced degradation was carried out under the conditions of hydrolysis, oxidation, dry heat and photolysis. The drug was found unstable in acid, alkali and oxidative media whereas stable to the hydrolysis in water, to dry heat and to photolysis. In total, six degradation products were formed in all conditions which were resolved in a single run on a C-18 column with gradient elution using ammonium acetate buffer (pH 4.5, 5.0mM), methanol and acetonitrile. Structures of all the degradation products were characterized through +ESI-MS(n) and LC-ESI-MS spectral data of bosentan as well as LC-ESI-MS spectral data of the products. The products II-VI were characterized as 6-amino-[2,2']bipyrimidinyl-4,5-diol, 6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-ol, 2-[6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yloxy]-ethanol, 4-tert-butyl-N-[6-(1-methoxyethoxy)-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yl]-benzenesulfonamide and 4-tert-butyl-N-[6-hydroxy-5-(2-methoxyphenoxy)-[2,2']bipyrimidinyl-4-yl]-benzenesulfonamide, respectively. The peak of the product I was found to be due to two secondary degradation products which co-eluted and were characterized as β-hydroxyethyl p-tert-butylphenylsulfonate (Ia) and 2-[2-(2-hydroxyethoxy)-phenoxy]-ethanol (Ib). These products were formed due to hydrolysis of sulfonamide and alkylaryl ether and the diaryl ether linkages as well as dehydration of the primary alcohol group. The most probable degradation mechanisms were proposed. The HPLC method was found to be stability-indicating, linear (2-100 μg ml(-1)), accurate, precise, sensitive, specific, rugged and robust for quantitation of the drug. The method was applied to the stability testing of the commercially available bosentan tablets successfully. Copyright © 2012 Elsevier B.V. All

  9. Degradation kinetics of poly(ether-urethane) Estane[reg] induced by electron irradiation

    International Nuclear Information System (INIS)

    Dannoux, A.; Esnouf, S.; Begue, J.; Amekraz, B.; Moulin, C.

    2005-01-01

    Radiation effects on a segmented aromatic poly(ether-urethane) induced by electron beam irradiation under oxygen atmosphere were investigated using Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR) in order to determine the degradation mechanisms. Thin films have been irradiated under a dose rate of 1 MGy/h with absorbed doses varying from 25 to 1000 kGy under O 2 . FTIR spectra have shown the formation of hydroperoxides, carboxylic acids, primary amines, alcohols, esters and formates. Moreover, the decrease of urethane and ether absorbances revealed the degradation of both soft and hard segments. Spin-trapping technique was used to monitor the evolution of short-lived peroxy and alkyl radicals at room temperature. Finally, a mechanism of degradation for electron irradiated polyurethane is proposed

  10. Anaerobic degradation of glycol ether-ethanol mixtures using EGSB and hybrid reactors: Performance comparison and ether cleavage pathway.

    Science.gov (United States)

    Ferrero, P; San-Valero, P; Gabaldón, C; Martínez-Soria, V; Penya-Roja, J M

    2018-05-01

    The anaerobic biodegradation of ethanol-glycol ether mixtures as 1-ethoxy-2-propanol (E2P) and 1-methoxy-2-propanol (M2P), widely used in printing facilities, was investigated by means of two laboratory-scale anaerobic bioreactors at 25 o C: an expanded granular sludge bed (EGSB) reactor and an anaerobic hybrid reactor (AHR), which incorporated a packed bed to improve biomass retention. Despite AHR showed almost half of solid leakages compared to EGSB, both reactors obtained practically the same performance for the operating conditions studied with global removal efficiencies (REs) higher than 92% for organic loading rates (OLRs) as high as 54 kg of chemical oxygen demand (COD) m -3 d -1 (REs of 70% and 100% for OLRs of 10.6 and 8.3 kg COD m -3 d -1 for E2P and M2P, respectively). Identified byproducts allowed clarifying the anaerobic degradation pathways of these glycol ethers. Thus, this study shows that anaerobic scrubber can be a feasible treatment for printing emissions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Subacute oral and dermal toxicity of tert-butyl hydroperoxide in Fischer F344/N rats and B6C3F1 mice.

    Science.gov (United States)

    Behl, Mamta; Kadiiska, Maria B; Hejtmancik, Milton R; Vasconcelos, Daphne; Chhabra, Rajendra S

    2012-09-01

    Tert-butyl hydroperoxide (TBHP) is a catalyst frequently used in oxidation and sulfonation reactions in the plastics industry. Since the toxicological evaluation of TBHP remains unknown, the National Toxicology Program (NTP) designed studies to characterize and compare TBHP toxicity by the dermal and oral (gavage) routes in male and female Fischer 344 rats and B6C3F1 mice in 14-day exposures. Rats and mice were administered TBHP at 22, 44, 88, 176 or 352 mg/kg in 0.5% aqueous methylcellulose for the gavage studies. In the dermal studies, mice were administered the same doses as above, while rats were administered four doses (22, 44, 88, 176 mg/kg) in 50% aqueous acetone. Results from the gavage studies revealed treatment-related decreases in survival in male rats and body weights in both male and female rats in the 352 mg/kg group. Clinical signs included post-treatment lethargy, thinness, abnormal breathing, ruffled fur, and/or ataxia which occurred sporadically. The male mice showed a statistically significant decrease in body weight in the 44, 88, 176, and 352 mg/kg groups. The major target organs of toxicity were the forestomach in male and female rats and mice, and the esophagus in male and female rats and in male mice. In addition, there was an increase in the absolute and relative liver weight in female mice with hepatocellular hypertrophy in the top-dose group only. Results from spin trapping experiments revealed the presence of electron paramagnetic resonance signals from radical adducts in the blood and organic extracts of the liver and kidneys of rats treated by gavage with 176 mg/kg TBHP, suggesting the involvement of free- radical generation. The no observed adverse effect level (NOAEL) was considered to be 22 mg/kg in rats and male mice, and 44 mg/kg in female mice. In the dermal studies, there was no effect on survival, body weight, or organ weights in either rats or mice. TBHP administration at the site of application resulted in dermal irritation

  12. 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

    Directory of Open Access Journals (Sweden)

    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.

  13. 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

  14. Degradation of Polybrominated Aiphenyl Ethers in a UV Advanced Reduction Process with Different Reducing Agents

    Science.gov (United States)

    Dong, Xiaoqing; Li, Chaolin; Zheng, Wei; Wang, Guosheng

    2018-02-01

    Polybrominated diphenyl ethers (PBDEs) are toxic and persistent, and their efficient degradation is currently a challenge. In this study, decabromodiphenyl ether (BDE-209) was selected as the target compound and was degraded by a UV photochemical system with different reducing agent. The result showed that the optimal BDE-209 removal in 1 hour by UV/sodium sulphite (Na2SO3) was 86.87%. With the same concentration of BDE-209 and reaction time, the optimal removal rate by UV/sodium borohydride (NaBH4) was 89.25%. Kinetic analysis revealed that the degradation of BDE-209 conformed to the first-order kinetic model. The order of rate constant of different UV photochemical processes is kUVdegradation of BDE-209. As a reducing agent, sodium borohydride showed a better enhanced effect for the removal of bromines.

  15. 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

  16. Protective effect of fucosterol isolated from the edible brown algae, Ecklonia stolonifera and Eisenia bicyclis, on tert-butyl hydroperoxide- and tacrine-induced HepG2 cell injury.

    Science.gov (United States)

    Choi, Jae Sue; Han, Yu Ran; Byeon, Jeong Su; Choung, Se-Young; Sohn, Hee Sook; Jung, Hyun Ah

    2015-08-01

    Fucosterol is the primary sterol found in brown algae. Recently, considerable interest has been generated regarding fucosterol due to its potential antioxidant, anti-inflammatory and antidiabetic effects. The aim of this study was to investigate the protective effects of fucosterol on tert-butyl hydroperoxide (t-BHP)- and tacrine-induced oxidative stress in HepG2 cells. Fucosterol by itself exhibited no cytotoxicity at concentrations below 100 μm by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. The increased intracellular reactive oxygen species (ROS) and decreased glutathione levels observed in t-BHP- and tacrine-treated HepG2 cells were ameliorated by fucosterol pretreatment, indicating that the protective effects of fucosterol are mediated by the induction of cellular defence mechanisms against oxidative stress. Moreover, elevated alanine aminotransferase (ALT) and aspartate aminotransferase (AST) levels in tacrine-treated mice were significantly reduced after oral administration of fucosterol. The hepatoprotective effects of fucosterol may occur via an increase in the hepatic level of glutathione and a decrease in ROS production, thereby preventing hepatic damage and the resultant increases in ALT and AST activity. These results suggest that fucosterol may be an effective hepatoprotective agent that could be useful for preventive therapies against oxidative stress-related hepatotoxicity. © 2015 Royal Pharmaceutical Society.

  17. 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.

  18. Determination of ethers and alcohols in gasolines by gas chromatography/Fourier transform infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Diehl, J.W.; Finkbeiner, J.W.; DiSanzo, F.P. (Mobil Research and Development Corp., Paulsboro, NJ (United States))

    1992-12-15

    In response to clean fuel legislation, research is underway in the petroleum industry to develop fuels which reduce vehicle exhaust emissions. Part of this effort is the addition of certain ethers and alcohols such as methyl tert-butyl ether (MTBE) and ethanol to gasolines. The capability of accurately measuring these compounds is important in maintaining minimum levels prescribed by law as well as optimum levels for engine performance. GC/Fourier transform infrared (FTIR) spectroscopy has already been demonstrated as a good quantitative tool for organic acids and various pollutants. GC/FTIR is definitely a precise and accurate technique for measuring C1-C4 alcohols and C5 and C6 ethers in gasolines. The use of the correct absorbance reconstruction frequencies gives good selectivity over hydrocarbons as well as very linear and stable calibration curves. 8 refs., 5 figs.

  19. Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

    Science.gov (United States)

    Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

    2017-12-01

    With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

  20. Quantum mechanical study and spectroscopic (FT-IR, FT-Raman, UV-Visible) study, potential energy surface scan, Fukui function analysis and HOMO-LUMO analysis of 3-tert-butyl-4-methoxyphenol by DFT methods.

    Science.gov (United States)

    Saravanan, S; Balachandran, V

    2014-09-15

    This study represents an integral approach towards understanding the electronic and structural aspects of 3-tert-butyl-4-methoxyphenol (TBMP). Fourier-transform Infrared (FT-IR) and Fourier-transform Raman (FT-Raman) spectra of TBMP was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structures, vibrational wavenumbers, infrared intensities and Raman activities were calculated using DFT (B3LYP and LSDA) methods using 6-311++G (d,p) basis set. The most stable conformer of TBMP was identified from the computational results. The assignments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability (β0) and related properties (β, α0 and Δα) of TBMP have been discussed. The stability and charge delocalization of the molecule was studied by Natural Bond Orbital (NBO) analysis. UV-Visible spectrum and effects of solvents have been discussed and the electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT approach with B3LYP/6-311++G (d,p) level of theory. The molecule orbital contributions are studied by density of energy states (DOSs). The reactivity sites are identified by mapping the electron density into electrostatic potential surface (MEP). Mulliken analysis of atomic charges is also calculated. The thermodynamic properties at different temperatures were calculated, revealing the correlations between standard heat capacities, standard entropy and standard enthalpy changes with temperatures. Global hardness, global softness, global electrophilicity and ionization potential of the title compound are determined. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. 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.

  2. Synthesis and properties of optically active nanostructured polymers bearing amino acid moieties by direct polycondensation of 4,4'-thiobis(2-tert-butyl-5-methylphenol) with chiral diacids.

    Science.gov (United States)

    Mallakpour, Shadpour; Soltanian, Samaneh

    2012-06-01

    Four derivatives of N-trimellitylimido-L-amino acid (4a-4d) were prepared by the reaction of trimellitic anhydride (1) with the L-amino acids (2a-2d) in acetic acid as diacid monomers and were used with the aim to obtain a new family of amino acid based poly(ester-imide)s (PEI)s. The polymerization was performed by direct polycondensation of chiral diacids (4a-4d) with 4,4'-thiobis(2-tert-butyl-5-methylphenol) (5) in the presence of tosyl chloride (TsCl), pyridine and N,N-dimethyl formamide (DMF). Step-growth polymerization was carried out by varying the time of heating and the molar ratio of TsCl/diacid and the optimum conditions were achieved. The synthesized polymers were characterized by means of specific rotation experiments, FT-IR, 1H-NMR, X-ray diffraction techniques and elemental analysis. The surface morphology of the obtained polymers was studied by field emission scanning electron microscopy. The result showed nanostructure morphology of the resulting polymers. The obtained PEIs were soluble in polar aprotic solvents such as DMF, N,N-dimethyl acetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and protic solvents such as sulfuric acid. Thermal stability and the weight-loss behavior of the PEIs were studied by thermal gravimetric analysis (TGA) techniques. TGA showed that the 10% weight loss temperature in a nitrogen atmosphere was more than 402°C, therefore they had useful levels of thermal stability associated with excellent solubility.

  3. Magnetic Scanometric DNA Microarray Detection of Methyl Tertiary Butyl Ether Degrading Bacteria for Environmental Monitoring

    Science.gov (United States)

    Chan, Mei-Lin; Jaramillo, Gerardo; Hristova, Krassimira R.; Horsley, David A.

    2010-01-01

    A magnetoresistive biosensing platform based on a single magnetic tunnel junction (MTJ) scanning probe and DNA microarrays labeled with magnetic particles has been developed to provide an inexpensive, sensitive and reliable detection of DNA. The biosensing platform was demonstrated on a DNA microarray assay for quantifying bacteria capable of degrading methyl tertiary-butyl ether (MTBE), where concentrations as low as 10 pM were detectable. Synthetic probe bacterial DNA was immobilized on a microarray glass slide surface, hybridized with the 48 base pair long biotinylated target DNA and subsequently incubated with streptavidin-coated 2.8 μm diameter magnetic particles. The biosensing platform then makes use of a micron-sized MTJ sensor that was raster scanned across a 3 mm by 5 mm glass slide area to capture the stray magnetic field from the tagged DNA and extract two dimensional magnetic field images of the microarray. The magnetic field output is then averaged over each 100 μm diameter DNA array spot to extract the magnetic spot intensity, analogous to the fluorescence spot intensity used in conventional optical scanners. The magnetic scanning result is compared with results from a commercial laser scanner and particle coverage optical counting to demonstrate the dynamic range and linear sensitivity of the biosensing platform as a potentially inexpensive, sensitive and portable alternative for DNA microarray detection for field applications. PMID:20889328

  4. IR Laser Ablative Degradation of Poly(phenylene ether sulfone): Deposition of Films Containing Sulfone, Sulfoxide and Sulfide Groups

    Czech Academy of Sciences Publication Activity Database

    Blazevska-Gilev, J.; Bastl, Zdeněk; Šubrt, Jan; Stopka, Pavel; Pola, Josef

    2009-01-01

    Roč. 94, č. 2 (2009), s. 196-200 ISSN 0141-3910 R&D Projects: GA AV ČR IAA400720619 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z40400503; CEZ:AV0Z40320502 Keywords : laser ablation * laser-induced degradation * poly(1,4-phenylene ether-sulfone) Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 2.154, year: 2009

  5. 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).

  6. Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

    Science.gov (United States)

    Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.

    1997-01-01

    The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

  7. The Effect of Antioxidants on Suppression of Thermal Degradation of Insulation Material

    Science.gov (United States)

    Sagae, Masahiro; Sekii, Yasuo; Yoshino, Hiroto; Miyake, Koujirou

    Thermal degradation of EPDM and the effect of antioxidants on the degradation of EPDM was investigated. Using FT-IR (Fourier transform infrared spectrophotometer) micrometer the degree of degradation was analyzed. A new evaluation method of mapping measurement was introduced and showed to be very useful. Among oxidants studied, the phenolic antioxidant 4,4'-tiobis(3-methyl-6-tert.-Butyl phenol was confirmed to be useful. A synergetic effects between phenolic antioxidant 2,2'-methylene- bis (4-methyl-6-tert.buthylphenol) and sulfur type antioxidant, dilauryl thiodipropionate, was also confirmed. The temperature dependence of thermal degradation of EPDM was also analyzed.

  8. Synthesis and X-ray structure determination of highly active Pd(II), Pd(I), and Pd(0) complexes of di(tert-butyl)neopentylphosphine (DTBNpP) in the arylation of amines and ketones.

    Science.gov (United States)

    Hill, Lensey L; Crowell, Jason L; Tutwiler, Strudwick L; Massie, Nicholas L; Hines, C Corey; Griffin, Scott T; Rogers, Robin D; Shaughnessy, Kevin H; Grasa, Gabriela A; Johansson Seechurn, Carin C C; Li, Hongbo; Colacot, Thomas J; Chou, Joe; Woltermann, Christopher J

    2010-10-01

    The air-stable complex Pd(η(3)-allyl)(DTBNpP)Cl (DTBNpP = di(tert-butyl)neopentylphosphine) serves as a highly efficient precatalyst for the arylation of amines and enolates using aryl bromides and chlorides under mild conditions with yields ranging from 74% to 98%. Amination reactions of aryl bromides were carried out using 1-2 mol % Pd(η(3)-allyl)(DTBNpP)Cl at 23-50 °C without the need to exclude oxygen or moisture. The C-N coupling of the aryl chlorides occurred at relatively lower temperature (80-100 °C) and catalyst loading (1 mol %) using the Pd(η(3)-allyl)(DTBNpP)Cl precatalyst than the catalyst generated in situ from DTBNpP and Pd(2)(dba)(3) (100-140 °C, 2-5 mol % Pd). Other Pd(DTBNpP)(2)-based complexes, (Pd(DTBNpP)(2) and Pd(DTBNpP)(2)Cl(2)) were ineffective precatalysts under identical conditions for the amination reactions. Both Pd(DTBNpP)(2) and Pd(DTBNpP)(2)Cl(2) precatalysts gave nearly quantitative conversions to the product in the α-arylation of propiophenone with p-chlorotoluene and p-bromoanisole at a substrate/catalyst loading of 100/1. At lower substrate/catalyst loading (1000/1), the conversions were lower but comparable to that of Pd(t-Bu(3)P)(2). In many cases, the tri-tert-butylphosphine (TTBP) based Pd(I) dimer, [Pd(μ-Br)(TTBP)](2), stood out to be the most reactive catalyst under identical conditions for the enolate arylation. Interestingly, the air-stable Pd(I) dimer, Pd(2)(DTBNpP)(2)(μ-Cl)(μ-allyl), was less active in comparison to [Pd(μ-Br)(TTBP)](2) and Pd(η(3)-allyl)(DTBNpP)Cl. The X-ray crystal structures of Pd(η(3)-allyl)(DTBNpP)Cl, Pd(DTBNpP)(2)Cl(2), Pd(DTBNpP)(2), and Pd(2)(DTBNpP)(2)(μ-Cl)(μ-allyl) are reported in this paper along with initial studies on the catalyst activation of the Pd(η(3)-allyl)(DTBNpP)Cl precatalyst.

  9. 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.

  10. Degradation of industrial waste waters on Fe/C-fabrics. Optimization of the solution parameters during reactor operation.

    Science.gov (United States)

    Bozzi, A; Yuranova, T; Lais, P; Kiwi, J

    2005-04-01

    This study addresses the pre-treatment of toxic and recalcitrant compounds found in the waste waters arriving at a treating station for industrial effluents containing chlorinated aromatics and non-aromatic compounds, anilines, phenols, methyl-tert-butyl-ether (MTBE). By reducing the total organic carbon (TOC) of these waste waters the hydraulic load for the further bacterial processing in the secondary biological treatment is decreased. The TOC decrease and discoloration of the waste waters was observed only under light irradiation in the reactor by immobilized Fenton processes on Fe/C-fabrics but not in the dark. The energy of activation for the degradation of the waste waters was of 4.2 kcal/mol. The degradation of the waste waters was studied in the reactor as a function of (a) the amount of oxidant used (H2O2), (b) the recirculation rate, (c) the solution pH and (d) the applied temperature. With these parameters taken as input factors, statistical modeling allows one to estimate the most economic use of the oxidant and electrical energy to degrade these waste waters. The concentration of the most abundant organic pollutants during waste waters degradation was followed by gas chromatography/mass spectrometry (GC-MS). The ratio of the biological oxygen demand to the total organic carbon BOD5/TOC increased significantly due to the Fe/C-fabric catalyzed treatment from an initial value of 2.03 to 2.71 (2 h). The reactor results show that the recirculation rate has no influence on the TOC decrease of the treated waters but affects the BOD increase of these solutions.

  11. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  12. Volumetric Behaviour of the Ternary Liquid System Composed of Methyl tert-Butyl Ether, Toluene, and Isooctane at Temperatures from (298.15 to 328.15) K. Experimental Data and Correlation

    Czech Academy of Sciences Publication Activity Database

    Morávková, Lenka; Wagner, Zdeněk; Sedláková, Zuzana; Linek, Jan

    2010-01-01

    Roč. 42, č. 7 (2010), s. 920-925 ISSN 0021-9614 R&D Projects: GA ČR GA104/09/0666 Institutional research plan: CEZ:AV0Z40720504 Keywords : isooctane * ternary mixture * adiabatic compressibility Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.794, year: 2010

  13. Photochemical Degradation of Polybrominated Diphenyl Ethers in Micro Photo-Reactor

    Czech Academy of Sciences Publication Activity Database

    Vajglová, Zuzana; Veselý, M.; Křišťál, Jiří; Vychodilová, Hana; Tříska, Jan; Jiřičný, Vladimír

    2012-01-01

    Roč. 42, SI (2012), s. 1378-1382 E-ISSN 1877-7058. [International Congress of Chemical and Process Engineering CHISA 2012 and 15th Conference PRES 2012 /20./. Prague, 25.08.2012-29.08.2012] R&D Projects: GA ČR GA104/09/0880 Institutional support: RVO:67985858 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * micro photo reactor * debromination Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  14. Solvent extraction of Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO22+, Mn2+, Co2+ and Ni2+ into nitrobenzene using strontium dicarbol-lylcobaltate and tetra-tert-butyl p-tert-butylcalix[4]arene tetraacetate

    Directory of Open Access Journals (Sweden)

    E. MAKRLÍK

    2008-12-01

    Full Text Available The exchange extraction constants corresponding to the general equilibrium M2+(aq + SrL2+(nb D ML2+ (nb + Sr2+ (aq occurring in the two-phase water–nitrobenzene system (M2+ = Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO22+, Mn2+, Co2+ or Ni2+; L = tetra-tert-butyl p-tert-butylcalix[4]arene tetraacetate; aq = aqueous phase; nb = nitrobenzene phase were evaluated from extraction experiments and -activity measurements. Furthermore, the stability constants of the ML2+ complexes in water saturated nitrobenzene were calculated; they were found to increase in the cation order Ba2+ < Mn2+ < Pb2+, Co2+ < Cu2+, Zn2+ < Cd2+, Ni2+ < UO22+ < Ca2+.

  15. 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.

  16. 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

  17. Photochemical Degradation of Polybrominated Diphenyl Ethers in Micro Photo-Reactor

    OpenAIRE

    Vajglova, Z.; Vesely, M.; Kristal, J.; Vychodilova, H.; Triska, J.; Jiricny, V.

    2012-01-01

    This work is focused on verification and comparison of the various dehalogenation methods of PBDE. In particular, the photochemical degradation reaction pathways of different selected congeners substituted with 1 to 10 bromines, in solvents are examined. Photochemical reaction is a non-invasive method with a high degradation potential. The photochemical reaction is conducted in batch or continuous reactors. Comparison of experimental results based on determination of individual reaction prod...

  18. A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Gagliardi, M., E-mail: mariacristina.gagliardi@iit.it [Center for Micro Bio-Robotics @SSSA, Istituto Italiano di Tecnologia, Viale Rinaldo Piaggio 34, 56025 Pontedera (Italy); Bertero, A. [Department of Biology, Unit of Cellular and Developmental Biology, University of Pisa, S.S.12 Abetone e Brennero 4, 56127 Pisa (Italy); Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy); Bardi, G. [Center for Bio-Molecular Nanotechnologies @UniLe, Istituto Italiano di Tecnologia, Via Barsanti, 73010 Arnesano (Italy); Bifone, A. [Center for Neuroscience and Cognitive Systems @UNITN, Istituto Italiano di Tecnologia, Corso Bettini 31, 38068 Rovereto (Italy)

    2016-02-01

    This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

  19. A poly(ether-ester) copolymer for the preparation of nanocarriers with improved degradation and drug delivery kinetics

    International Nuclear Information System (INIS)

    Gagliardi, M.; Bertero, A.; Bardi, G.; Bifone, A.

    2016-01-01

    This paper reports the synthesis and the physicochemical, functional and biological characterisations of nanocarriers made of a novel di-block biodegradable poly(ether-ester) copolymer. This material presents tunable, fast biodegradation rates, but its products are less acidic than those of other biosorbable polymers like PLGA, thus presenting a better biocompatibility profile and the possibility to carry pH-sensitive payloads. A method for the production of monodisperse and spherical nanoparticles is proposed; drug delivery kinetics and blood protein adsorption were measured to evaluate the functional properties of these nanoparticles as drug carriers. The copolymer was labelled with a fluorescent dye for internalisation tests, and rhodamine B was used as a model cargo to study transport and release inside cultured cells. Biological tests demonstrated good cytocompatibility, significant cell internalisation and the possibility to vehiculate non-cell penetrating moieties into endothelial cells. Taken together, these results support the potential use of this nanoparticulate system for systemic administration of drugs. - Highlights: • We propose a novel biodegradable nanocarrier for intracellular drug delivery. • Biodegradation rates can be finely tuned by controlling copolymer composition. • Degradation products are less acidic, thus enabling delivery of pH-sensitive cargoes. • We demonstrate intracellular delivery of a non-cell-penetrating model drug. • No significant membrane damage by the polymer nanocarriers is observed.

  20. Synthesis of new poly(ether-urethane-urea)s based on amino acid cyclopeptide and PEG: study of their environmental degradation.

    Science.gov (United States)

    Rafiemanzelat, Fatemeh; Fathollahi Zonouz, Abolfazl; Emtiazi, Giti

    2013-02-01

    Conventional polyurethanes (PUs) are among biomaterials not intended to degrade but are susceptible to hydrolytic, oxidative and enzymatic degradation in vivo. Biodegradable PUs are typically prepared from polyester polyols, aliphatic diisocyanates and chain extenders. In this work we have developed a degradable monomer based on α-amino acid to accelerate hard segment degradation. Thus a new class of degradable poly(ether-urethane-urea)s (PEUUs) was synthesized via direct reaction of 4,4'-methylene-bis(4-phenylisocyanate) (MDI), L-leucine anhydride (LA) and polyethylene glycol with molecular weight of 1,000 (PEG-1000) as polyether soft segment. The resulting polymers are environmentally biodegradable and thermally stable. Decomposition temperatures for 5 % weight loss occurred above 300 °C by TGA in nitrogen atmospheres. Some structural characterization and physical properties of these polymers before and after degradation in soil, river water and sludge are reported. The environmental degradation of the polymer films was investigated by SEM, FTIR, TGA, DSC, GPC and XRD techniques. A significant rate of degradation occurred in PEUU samples under river water and sludge condition. The polymeric films were not toxic to E. coli (Gram negative), Staphylococcus aureus and Micrococcus (Gram positive) bacteria and showed good biofilm formation on polymer surface. Our results show that hard segment degraded selectively as much as soft segment and these polymers are susceptible to degradation in soil and water. Thus our study shows that new environment-friendly polyurethane, which can degrade in soil, river water and sludge, is synthesized.

  1. Study of Biological Degradation of New Poly(Ether-Urethane-Urea)s Containing Cyclopeptide Moiety and PEG by Bacillus amyloliquefaciens Isolated from Soil.

    Science.gov (United States)

    Rafiemanzelat, Fatemeh; Jafari, Mahboobeh; Emtiazi, Giti

    2015-10-01

    The present work for the first time investigates the effect of Bacillus amyloliquefaciens, M3, on a new poly(ether-urethane-urea) (PEUU). PEUU was synthesized via reaction of 4,4'-methylenebis(4-phenylisocyanate) (MDI), L-leucine anhydride cyclopeptide (LACP) as a degradable monomer and polyethylene glycol with molecular weight of 1000 (PEG-1000). Biodegradation of the synthesized PEUU as the only source for carbon and nitrogen for M3 was studied. The co-metabolism biodegradation of the polymer by this organism was also investigated by adding mannitol or nutrient broth to the basic media. Biodegradation of the synthesized polymer was followed by SEM, FT-IR, TGA, and XRD techniques. It was shown that incubation of PEUU with M3 resulted in a 30-44 % reduction in polymer's weight after 1 month. This study indicates that the chemical structure of PEUU significantly changes after exposure to M3 due to hydrolytic and enzymatic degradation of polymer chains. The results of this work supports the idea that this poly(ether-urethane) is used as a sole carbon source by M3 and this bacterium has a good capability for degradation of poly(ether-urethane)s.

  2. 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.

  3. Degradation of lignin β-aryl ether units in Arabidopsis thaliana expressing LigD, LigF and LigG from Sphingomonas paucimobilis SYK-6

    DEFF Research Database (Denmark)

    Mnich, Ewelina; Vanholme, Ruben; Oyarce, Paula

    2017-01-01

    Lignin is a major polymer in the secondary plant cell wall and composed of hydrophobic interlinked hydroxyphenylpropanoid units. The presence of lignin hampers conversion of plant biomass into biofuels; plants with modified lignin are therefore being investigated for increased digestibility....... The bacterium Sphingomonas paucimobilis produces lignin-degrading enzymes including LigD, LigF and LigG involved in cleaving the most abundant lignin inter-unit linkage, the β-aryl ether bond. In this study, we expressed the LigD, LigF and LigG (LigDFG) genes in Arabidopsis thaliana to introduce post......-lignification modifications into the lignin structure. The three enzymes were targeted to the secretory pathway. Phenolic metabolite profiling and 2D HSQC NMR of the transgenic lines showed an increase in oxidized guaiacyl and syringyl units without concomitant increase in oxidized β-aryl-ether units, showing lignin bond...

  4. Levels of polybrominated diphenyl ethers (PBDEs) in dust from personal automobiles in conjunction with studies on the photochemical degradation of decabromodiphenyl ether (BDE-209).

    Science.gov (United States)

    Lagalante, Anthony F; Shedden, Courtney S; Greenbacker, Peter W

    2011-07-01

    The levels of 21 PBDE congeners were detemined in the dust sampled from 66 personal automobiles. The dominant congener in automobile dust was BDE-209 with a median level of 8.12 μg g⁻¹. Personal vehicle dust samples contained the characteristic profile of the PBDE congeners that comprise the PentaBDE and DecaBDE commercial formulations. Levels of PBDEs in personal automobiles are generally reduced in comparison to our previously reported levels in resale vehicles on dealership lots presumably due to a dilution effect introduced by dust or debris that does not originate from the vehicle. Laboratory photochemical studies were conducted on both automobile dust collected from personal vehicles as well as BDE-209 adsorbed to sodium sulfate. No significant degradation occurred in the personal vehicle dust after 56 days of constant UVA irradiation while significant degradation did occur with BDE-209 adsorbed to sodium sulfate. PBDEs from the degradation of BDE-209 were identified and potential degradation pathways elucidated. Human exposure potential to PBDEs from automobile dust ingestion remains a serious concern in the U.S. population. Copyright © 2011 Elsevier Ltd. All rights reserved.

  5. An octanuclear molybdenum(VI) complex containing coordinatively bound 4,4'-di-tert-butyl-2,2'-bipyridine, [Mo8O22(OH)4(di-tBu-bipy)4]: synthesis, structure, and catalytic epoxidation of bio-derived olefins.

    Science.gov (United States)

    Amarante, Tatiana R; Neves, Patrícia; Tomé, Cátia; Abrantes, Marta; Valente, Anabela A; Paz, Filipe A Almeida; Pillinger, Martyn; Gonçalves, Isabel S

    2012-03-19

    The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. © 2012 American Chemical Society

  6. Landfills as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

    Science.gov (United States)

    Weinberg, Ingo; Dreyer, Annekatrin; Ebinghaus, Ralf

    2011-02-01

    In order to investigate landfills as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two landfills (one active and one closed) and two reference sites using high volume air samplers. Contaminants were accumulated on glass fiber filters (particle phase) and PUF/XAD-2/PUF cartridges (gas phase), extracted by methyl-tert butyl ether/acetone (neutral PFCs), methanol (ionic PFCs) or hexane/acetone (PBDEs, musk fragrances), and detected by GC-MS (neutral PFCs, PBDEs, musk fragrances) or HPLC-MS/MS (ionic PFCs). Total concentrations ranged from 84 to 706 pg m -3 (volatile PFCs, gas phase), from MQL to 42 pg m -3 (ionic PFCs, particle phase), from 204 to 1963 pg m -3 (synthetic musk fragrances, gas + particle phase) and from 1 to 11 pg m -3 (PBDEs, gas + particle phase). Observed sum concentrations of PFCs and synthetic musk fragrances and partly PBDE concentrations were elevated at landfill sites compared to corresponding reference sites. Concentrations determined at the active landfill were higher than those of the inactive landfill. Overall, landfills can be regarded as a source of synthetic musk fragrances, several PFCs and potentially of PBDEs to ambient air.

  7. Isolation of bacterial strains able to degrade biphenyl, diphenyl ether and the heat transfer fluid used in thermo-solar plants.

    Science.gov (United States)

    Blanco-Moreno, Rafael; Sáez, Lara P; Luque-Almagro, Víctor M; Roldán, M Dolores; Moreno-Vivián, Conrado

    2017-03-25

    Thermo-solar plants use eutectic mixtures of diphenyl ether (DE) and biphenyl (BP) as heat transfer fluid (HTF). Potential losses of HTF may contaminate soils and bioremediation is an attractive tool for its treatment. DE- or BP-degrading bacteria are known, but up to now bacteria able to degrade HTF mixture have not been described. Here, five bacterial strains which are able to grow with HTF or its separate components DE and BP as sole carbon sources have been isolated, either from soils exposed to HTF or from rhizospheric soils of plants growing near a thermo-solar plant. The organisms were identified by 16S rRNA gene sequencing as Achromobacter piechaudii strain BioC1, Pseudomonas plecoglossicida strain 6.1, Pseudomonas aeruginosa strains HBD1 and HBD3, and Pseudomonas oleovorans strain HBD2. Activity of 2,3-dihydroxybiphenyl dioxygenase (BphC), a key enzyme of the biphenyl upper degradation pathway, was detected in all isolates. Pseudomonas strains almost completely degraded 2000ppm HTF after 5-day culture, and even tolerated and grew in the presence of 150,000ppm HTF, being suitable candidates for in situ soil bioremediation. Degradation of both components of HTF is of particular interest since in the DE-degrader Sphingomonas sp. SS3, growth on DE or benzoate was strongly inhibited by addition of BP. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. An investigation of 2,5-di-tertbutyl-1,4-bis(methoxyethoxy)benzene in ether-based electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Su, Liang; Ferrandon, Magali; Barton, John L.; de la Rosa, Noel Upia; Vaughey, John T.; Brushett, Fikile R.

    2017-08-01

    The identification and development of conductive electrolytes with high concentrations of redox active species is key to realizing energy-dense nonaqueous flow batteries. Herein, we explore the use of ether solvents (1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (DEGDME), and tetraethylene glycol dimethyl ether (TEGDME)) as the basis for redox electrolytes containing a lithium ion supporting salt (LiBF4 or LiTFSI) and 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) as an active material. An automated high-throughput platform is employed to screen various electrolyte compositions by measuring solution conductivity and solute solubility as a function of solvent and salt type, component concentration, and temperature. Subsequently, the electrochemical and transport properties of select redox electrolytes are characterized by cyclic voltammetry using glassy carbon disk electrodes and by linear sweep voltammetry using carbon fiber ultramicroelectrodes. In general, improvements in electrolyte conductivity and solute solubility are observed with ether-based formulations as compared to previously reported propylene carbonate (PC)-based formulations. In particular, the addition of DOL to a DME-based electrolyte increases the conductivity and decreases the temperature for solubilization at high LiTFSI and DBBB concentrations. The redox behavior of DBBB remains consistent across the range of concentrations tested while the diffusion coefficient scales with changes in solution viscosity.

  9. Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

    KAUST Repository

    Kumar, Rajeev Ananda

    2014-03-25

    The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

  10. 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

  11. Removal of technetium from alkaline nuclear-waste media by a solvent-extraction process using crown ethers

    International Nuclear Information System (INIS)

    Bonnesen, P.V.; Presley, D.J.; Haverlock, T.J.; Moyer, B.A.

    1995-01-01

    Crown ethers dissolved in suitably modified aliphatic kerosene diluents can be employed to extract technetium as pertechnetate anion (TcO 4 - ) with good extraction ratios from realistic simulants of radioactive alkaline nitrate waste. The modifiers utilized are non-halogenated and non-volatile, and the technetium can be removed from the solvent by stripping using water. The crown ethers bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 (di-t-BuCH18C6) and dicyclohexano-18-crown-6 (DCH18C6) provide stronger TcO 4 - extraction than dicyclohexano-21-crown-7 and 4-tert-butylcyclohexano 15-crown-5. Whereas DCH18C6 provides somewhat higher TcO 4 - extraction ratios than the more lipophilic di-t-BuCH18C6 derivative, the latter was selected for further study owing to its lower distribution to the aqueous phase. Particularly good extraction and stripping results were obtained with di-t-BuCH 18C6 at 0.02 M in a 2:1 vol/vol blend of tributyl phosphate and Isopar reg-sign M. Using this solvent, 98.9% of the technetium contained (at 6 x 10 -5 M) in a Double-Shell Slurry Feed (DSSF) Hanford tank waste simulant was removed following two cross-current extraction contacts. Two cross-current stripping contacts with deionized water afforded removal of 99.1% of the technetium from the organic solvent

  12. Highly Enhanced Photoreductive Degradation of Polybromodiphenyl Ethers with g-C3N4/TiO2 under Visible Light Irradiation

    Directory of Open Access Journals (Sweden)

    Weidong Ye

    2017-04-01

    Full Text Available A series of high activity photocatalysts g-C3N4-TiO2 were synthesized by simple one-pot thermal transformation method and characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller (BET surface area, and ultraviolet–visible diffuse reflectance spectroscopy (UV-Vis-DRS. The g-C3N4-TiO2 samples show highly improved photoreductive capability for the degradation of polybromodiphenyl ethers compared with g-C3N4 under visible light irradiation. Among all the hybrids, 0.02-C3N4-TiO2 with 2 wt % g-C3N4 loaded shows the highest reaction rate, which is 15 times as high as that in bare g-C3N4. The well-matched band gaps in heterojunction g-C3N4-TiO2 not only strengthen the absorption intensity, but also show more effective charge carrier separation, which results in the highly enhanced photoreductive performance under visible light irradiation. The trapping experiments show that holetrapping agents largely affect the reaction rate. The rate of electron accumulation in the conductive band is the rate-determining step in the degradation reaction. A possible photoreductive mechanism has been proposed.

  13. Highly Enhanced Photoreductive Degradation of Polybromodiphenyl Ethers with g-C3N4/TiO2 under Visible Light Irradiation.

    Science.gov (United States)

    Ye, Weidong; Shao, Yingying; Hu, Xuefeng; Liu, Chulin; Sun, Chunyan

    2017-04-03

    A series of high activity photocatalysts g-C3N4-TiO2 were synthesized by simple one-pot thermal transformation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller (BET) surface area, and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis-DRS). The g-C3N4-TiO2 samples show highly improved photoreductive capability for the degradation of polybromodiphenyl ethers compared with g-C3N4 under visible light irradiation. Among all the hybrids, 0.02-C3N4-TiO2 with 2 wt % g-C3N4 loaded shows the highest reaction rate, which is 15 times as high as that in bare g-C3N4. The well-matched band gaps in heterojunction g-C3N4-TiO2 not only strengthen the absorption intensity, but also show more effective charge carrier separation, which results in the highly enhanced photoreductive performance under visible light irradiation. The trapping experiments show that holetrapping agents largely affect the reaction rate. The rate of electron accumulation in the conductive band is the rate-determining step in the degradation reaction. A possible photoreductive mechanism has been proposed.

  14. Vertical distribution of archaeal communities associated with anaerobic degradation of pentabromodiphenyl ether (BDE-99) in river-based groundwater recharge with reclaimed water.

    Science.gov (United States)

    Yan, Yulin; Ma, Mengsi; Liu, Xiang; Ma, Weifang; Li, Yangyao

    2018-02-01

    When groundwater is recharged with reclaimed water, the presence of trace amounts of biorefractory pentabromodiphenyl ether (PBDE, specifically BDE-99) might cause potential groundwater pollution. A laboratory-scale column was designed to investigate the distribution of the community of archaea in this scenario and the associated anaerobic degradation of BDE-99. The concentration of BDE-99 decreased significantly as soil depth increased, and fluorescence in situ hybridization (FISH) analysis suggested that archaea exerted significant effects on the biodegradation of PBDE. Through 454 pyrosequencing of 16s rRNA genes, we found that the distribution and structure of the archaeal community associated with anaerobic degradation of BDE-99 in the river-based aquifer media changed significantly between different soil depths. The primary debrominated metabolites varied with changes in the vertically distributed archaeal community. The archaea in the surface layer were dominated by Methanomethylovorans, and the middle layer was mainly composed of Nitrososphaera. Nitrosopumilus and Nitrososphaera were equally abundant in the bottom layer. In addition, Methanomethylovorans abundance depended on the depth of soil, and the relative abundance of Nitrosopumilus increased with increasing depth, which was associated with the oxidation-reduction potential and the content of intermediate metabolites. We propose that Nitrososphaera and Nitrosopumilus might be the key archaeal taxa mediating the biodegradation of BDE-99.

  15. Anaerobic degradation of Polychlorinated Biphenyls (PCBs) and Polychlorinated Biphenyls Ethers (PBDEs), and microbial community dynamics of electronic waste-contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Song, Mengke [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100039 (China); Luo, Chunling, E-mail: clluo@gig.ac.cn [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Li, Fangbai [Guangdong Institute of Eco-environmental and Soil Sciences, Guangzhou 510650 (China); Jiang, Longfei [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); College of Life Sciences, Nanjing Agricultural University, Nanjing 210095 (China); Wang, Yan [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhang, Dayi [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Zhang, Gan [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2015-01-01

    Environmental contamination caused by electronic waste (e-waste) recycling is attracting increasing attention worldwide because of the threats posed to ecosystems and human safety. In the present study, we investigated the feasibility of in situ bioremediation of e-waste-contaminated soils. We found that, in the presence of lactate as an electron donor, higher halogenated congeners were converted to lower congeners via anaerobic halorespiration using ferrous ions in contaminated soil. The 16S rRNA gene sequences of terminal restriction fragments indicated that the three dominant strains were closely related to known dissimilatory iron-reducing bacteria (DIRB) and those able to perform dehalogenation upon respiration. The functional species performed the activities of ferrous oxidation to ferric ions and further ferrous reduction for dehalogenation. The present study links iron cycling to degradation of halogenated materials in natural e-waste-contaminated soil, and highlights the synergistic roles of soil bacteria and ferrous/ferric ion cycling in the dehalogenation of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs). - Highlights: • The biodegradation PCBs and PBDEs in e-waste contaminated soils was studied. • DIRB and arylhalorespiring bacteria were responsive to dehalogenation respiration. • Soil bacteria and Fe ion cycling play synergistic roles in dehalogenation.

  16. Anaerobic degradation of polychlorinated biphenyls (PCBs) and polychlorinated biphenyls ethers (PBDEs), and microbial community dynamics of electronic waste-contaminated soil.

    Science.gov (United States)

    Song, Mengke; Luo, Chunling; Li, Fangbai; Jiang, Longfei; Wang, Yan; Zhang, Dayi; Zhang, Gan

    2015-01-01

    Environmental contamination caused by electronic waste (e-waste) recycling is attracting increasing attention worldwide because of the threats posed to ecosystems and human safety. In the present study, we investigated the feasibility of in situ bioremediation of e-waste-contaminated soils. We found that, in the presence of lactate as an electron donor, higher halogenated congeners were converted to lower congeners via anaerobic halorespiration using ferrous ions in contaminated soil. The 16S rRNA gene sequences of terminal restriction fragments indicated that the three dominant strains were closely related to known dissimilatory iron-reducing bacteria (DIRB) and those able to perform dehalogenation upon respiration. The functional species performed the activities of ferrous oxidation to ferric ions and further ferrous reduction for dehalogenation. The present study links iron cycling to degradation of halogenated materials in natural e-waste-contaminated soil, and highlights the synergistic roles of soil bacteria and ferrous/ferric ion cycling in the dehalogenation of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs). Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Occurrence and transport of MTBE in a contaminated groundwater plume from Duesseldorf

    Energy Technology Data Exchange (ETDEWEB)

    Rosell, M.; Lacorte, S.; Barcelo, D. [Dept. of Environmental Chemistry, Barcelona (Spain); Rohns, H.P.; Forner, C. [Stadtwerke Duesseldorf AG (Germany)

    2003-07-01

    In a contaminated site of Duesseldorf (middle-west of Germany), a one-year monitoring program has been carried to determine the presence and evolution of some gasoline additives in groundwater. The origin of contamination was a spill or underground storage tank leakage from a gas station. The target compounds were: methyl tert-butyl ether (MTBE), its main degradation products, tert-butyl alcohol (TBA) and tert-butyl formate (TBF); other gasoline additives, oxygenate dialkyl ethers: ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE); aromatics: benzene, toluene, ethylbenzene and xylenes (BTEX) and other compounds causing odor events in groundwater such as dicyclopentadiene (DCPD) and trichloroethylene (TCE). Purge and trap coupled to gas chromatography - mass spectrometry (P and T-GC/MS) method was used for the simultaneous determination of the above mentioned compounds and permitted to detect concentrations at ng/L (ppt) or sub-ppb concentrations. All samples analysed contained MTBE at levels varied between 0.05 -645 {micro}g/L (ppb). Three contaminated hot spots were identified with levels up to US. Environmental Protection Agency drinking water advisory (20 - 40 {micro}g/L) and one of them doubling Danish suggested toxicity level of 350 {micro}g/L. Samples with high levels of MTBE contained 0.1 - 440 {micro}g/L of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX were at low concentrations or not detected showing less solubility and persistence than MTBE.

  18. Sulfate radical degradation of acetaminophen by novel iron-copper bimetallic oxidation catalyzed by persulfate: Mechanism and degradation pathways

    Science.gov (United States)

    Zhang, Yuanchun; Zhang, Qian; Hong, Junming

    2017-11-01

    A novel iron coupled copper oxidate (Fe2O3@Cu2O) catalyst was synthesized to activate persulfate (PS) for acetaminophen (APAP) degradation. The catalysts were characterized via field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry. The effects of the catalyst, PS concentration, catalyst dosage, initial pH, dissolved oxygen were analyzed for treatment optimization. Results indicated that Fe2O3@Cu2O achieved higher efficiency in APAP degradation than Fe2O3/PS and Cu2O/PS systems. The optimal removal efficiency of APAP (90%) was achieved within 40 min with 0.6 g/L PS and 0.3 g/L catalyst. To clarify the mechanism for APAP degradation, intermediates were analyzed with gas chromatography-mass spectrometry. Three possible degradation pathways were identified. During reaction, Cu(I) was found to react with Fe(III) to generate Fe(II), which is the most active phase for PS activation. Through the use of methanol and tert-butyl alcohol (TBA) as radical trappers, SO4rad - was identified as the main radical species that is generated during oxidation.

  19. Degradation of the fungicide denmert (S-n-butyl S'-p-tert-butylbenzyl N-3-pyridyldithiocarbonimidate, S-1358) by plants, soils and light

    International Nuclear Information System (INIS)

    Ohkawa, Hideo; Shibaike, Reiko; Okihara, Yukiko; Morikawa, Michihide; Miyamoto, Junshi

    1976-01-01

    14 C-Denmert(S-n-butyl S'-p-tert-butylbenzyl N-3-pyridyldithiocarbonimidate, S-1358) labeled at the methylene of the benzyl group was gradually decomposed to yield a number of products, when exposed to sunlight on thin-layer plates or in water solution, applied to plant foliage or nutrient solution, and added to soils under upland conditions. The identified products were almost common to plants, soils and light. The primary reactions occurred: (1), oxidation of the sulfur atoms; (2), cleavage of the dithiocarbonimidate linkage, and (3), oxidation of the methylene of the benzyl group. Also, hydroxylation at the tert-butyl group attached to the benzyl moiety slightly took place in soils. Although radioactivity was absorbed by the plant through leaves or roots, translocation into other parts of the plant occurred to a very small extent. Denmert and its degradation products were hardly leached through the acidic soils tested. (auth.)

  20. 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.

  1. Alkaline-side extraction of technetium from tank waste using crown ethers and other extractants

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.V.; Moyer, B.A.; Presley, D.J.; Armstrong, V.S.; Haverlock, T.J.; Counce, R.M.; Sachleben, R.A.

    1996-06-01

    The chemical development of a new crown-ether-based solvent-extraction process for the separation of (Tc) from alkaline tank-waste supernate is ready for counter-current testing. The process addresses a priority need in the proposed cleanup of Hanford and other tank wastes. This need has arisen from concerns due to the volatility of Tc during vitrification, as well as {sup 99}Tc`s long half-life and environmental mobility. The new process offers several key advantages that direct treatability--no adjustment of the waste composition is needed; economical stripping with water; high efficiency--few stages needed; non-RCRA chemicals--no generation of hazardous or mixed wastes; co-extraction of {sup 90}Sr; and optional concentration on a resin. A key concept advanced in this work entails the use of tandem techniques: solvent extraction offers high selectivity, while a subsequent column sorption process on the aqueous stripping solution serves to greatly concentrate the Tc. Optionally, the stripping solution can be evaporated to a small volume. Batch tests of the solvent-extraction and stripping components of the process have been conducted on actual melton Valley Storage Tank (MVST) waste as well as simulants of MVST and Hanford waste. The tandem process was demonstrated on MVST waste simulants using the three solvents that were selected the final candidates for the process. The solvents are 0.04 M bis-4,4{prime}(5{prime})[(tert-butyl)cyclohexano]-18-crown-6 (abbreviated di-t-BuCH18C6) in a 1:1 vol/vol blend of tributyl phosphate and Isopar{reg_sign} M (an isoparaffinic kerosene); 0.02 M di-t-BuCH18C6 in 2:1 vol/vol TBP/Isopar M and pure TBP. The process is now ready for counter-current testing on actual Hanford tank supernates.

  2. Alkaline-side extraction of technetium from tank waste using crown ethers and other extractants

    International Nuclear Information System (INIS)

    Bonnesen, P.V.; Moyer, B.A.; Presley, D.J.; Armstrong, V.S.; Haverlock, T.J.; Counce, R.M.; Sachleben, R.A.

    1996-06-01

    The chemical development of a new crown-ether-based solvent-extraction process for the separation of (Tc) from alkaline tank-waste supernate is ready for counter-current testing. The process addresses a priority need in the proposed cleanup of Hanford and other tank wastes. This need has arisen from concerns due to the volatility of Tc during vitrification, as well as 99 Tc's long half-life and environmental mobility. The new process offers several key advantages that direct treatability--no adjustment of the waste composition is needed; economical stripping with water; high efficiency--few stages needed; non-RCRA chemicals--no generation of hazardous or mixed wastes; co-extraction of 90 Sr; and optional concentration on a resin. A key concept advanced in this work entails the use of tandem techniques: solvent extraction offers high selectivity, while a subsequent column sorption process on the aqueous stripping solution serves to greatly concentrate the Tc. Optionally, the stripping solution can be evaporated to a small volume. Batch tests of the solvent-extraction and stripping components of the process have been conducted on actual melton Valley Storage Tank (MVST) waste as well as simulants of MVST and Hanford waste. The tandem process was demonstrated on MVST waste simulants using the three solvents that were selected the final candidates for the process. The solvents are 0.04 M bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6 (abbreviated di-t-BuCH18C6) in a 1:1 vol/vol blend of tributyl phosphate and Isopar reg-sign M (an isoparaffinic kerosene); 0.02 M di-t-BuCH18C6 in 2:1 vol/vol TBP/Isopar M and pure TBP. The process is now ready for counter-current testing on actual Hanford tank supernates

  3. 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

    1999-02-01

    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 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

  4. Poly(ethylene oxide monomethyl ether)-block-poly(propylene succinate) nanoparticles. Synthesis and characterization, enzymatic and cellular degradation, micellar solubilization of paclitaxel and in vitro and in vivo evaluation.

    Science.gov (United States)

    Jager, Alessandro; Jäger, Eliézer; Syrová, Zdenka; Mazel, Tomaš; Kováčik, Lubomír; Raška, Ivan; Höcherl, Anita; Kučka, Jan; Konefal, Rafal; Humajova, Jana; Pouckova, Pavla; Stepanek, Petr; Hruby, Martin

    2018-03-30

    Polyester-based nanostructures are widely studied as drug delivery systems due to their biocompatibility and biodegradability. They have already reached the clinical use. In this work we describe a new and simple biodegradable and biocompatible system as alternative to the FDA-approved polyesters (PLGA, PCL and PLA) for the delivery of the anticancer drug paclitaxel (PTX) as a model drug. A hydrophobic polyester, poly(propylene succinate) (PPS) was prepared from a non-toxic alcohol (propylene glycol) and monomer from the Krebs's cycle (succinic acid) in two steps via esterification and melt polycondensation. Further their amphiphilic block copolyester poly(ethylene oxide monomethyl ether)-block-poly(propylene succinate) (mPEO-b-PPS) was prepared by three steps via esterification followed by melt polycondensation and the addition of mPEO to the PPS macromolecules. In vitro cellular behavior of the prepared NPs (enzymatic degradation, uptake, localization and FRET-pair degradation studies) were performed by fluorescence studies from new synthesized Rhodamine B isothiocyanate-poly(propylene succinate) (Rhoda-PPS) and Reactive Blue- poly(propylene succinate) (Blue-PPS) copolymer conjugates. Paclitaxel was loaded to the NPs of variable sizes (30, 70 and 150 nm) and their in vitro release was evaluated in different cell models (Raw 264.7, HeLa, MCF-7 and 4T1 tumor cells) being compared with commercial paclitaxel formulations. The selected 30 nm NPs were chosen for more detailed cytotoxicity in vitro and in vivo tumor efficacy studies. Similarly to the aforementioned copolyesters, the mPEO-b-PPS copolymer present Tg< body temperature degradation products, drug solubilization efficacy, stability against spontaneous hydrolysis during transport in bloodstream and simultaneously enzymatic degradability after uptake into the cells. Detailed cytotoxicity in vitro and in vivo tumor efficacy studies shown the superior efficacy

  5. [Norfloxacin Solution Degradation Under Ultrasound, Potassium Persulfate Collaborative System].

    Science.gov (United States)

    Wei, Hong; Shi, Jing-zhuan; Li, Jia-lin; Li, Ke-bin; Zhao, Lin; Han, Kai

    2015-11-01

    High oxidative sulfate radicals can be produced by potassium persulfate (K2S2O8). The integrated effect of ultrasonic and K2S2O8, on norfloxacin degradation was investigated. The experimental parameters such as K2S2O8 concentration, norfloxacin initial concentration, initial pH value, free radicals quenching agents such as methanol and tert-butyl on norfloxacin degradation were discussed. The results indicated that ultrasonic/K2S2O8, system had an obvious degradation and mineralization effect on norfloxacin. Norfloxacin removal efficiencies were 3.2 and 8.9 times in ultrasonic/K2S2O8 system than those in single K252O8 and ultrasonic oxidation system, respectively. And the reaction followed the first-order kinetics. Norfloxacin removal efficiency varied gently with K2S2O8 concentration. Solution initial pH had a significant effect on norfloxacin degradation, which was attributed to the different oxidizing species under different pH values. The radicals were sulfate radicals under acidic and neutral conditions, and was the combination of sulfate and hydroxyl radicals under alkaline conditions. TOC and agar diffusion test with E. coli showed that 49.12% norfloxacin was mineralized and antibacterial activity was completely removed, with the diameter of E. coli inhibition zone decreased from 45 mm to 14 mm (filter paper diameter). The result implied that ultrasound/K2S2O8 showed promising results as a possible application for treatment of norfloxacin antibiotics wastewater.

  6. ESTCP Cost and Performance Report. In-Situ Bioremediation of MTBE in Ground Water

    National Research Council Canada - National Science Library

    Miller, Karen

    2003-01-01

    ... (methyl-tert-butyl-ether) and other dissolved gasoline components. It was implemented at the Naval Base Ventura County, Port Hueneme, CA to prevent further contamination of ground water by MTBE leaching from gasoline contaminated soils...

  7. Short-term enhancement effect of nitrogen addition on microbial degradation and plant uptake of polybrominated diphenyl ethers (PBDEs) in contaminated mangrove soil.

    Science.gov (United States)

    Chen, Juan; Zhou, Hai Chao; Wang, Chao; Zhu, Chun Quan; Tam, Nora Fung-Yee

    2015-12-30

    Effects of nitrogen (N) addition on the microbial degradation and uptake of a mixture of BDE-47 and -209 by Aegiceras corniculatum, a typical mangrove plant species were investigated. At the end of 3-month experiment, a significant dissipation of BDE-47 was observed in the planted soil, and this dissipation, particularly in rhizosphere soil, was significantly accelerated by the frequent addition of N in the form of ammonium chloride. The removal percentage of BDE-47 in the rhizosphere soil without N addition was 47.3% and increased to 58.2% with N. However, the unplanted soil only removed less than 25% BDE-47, irrespective to N supply. The N addition in planted treatments significantly increased soil N content, urease and dehydrogenase activities, and the abundances of total bacteria and dehalogenating bacteria, leading to more microbial degradation of BDE-47. The N addition also enhanced the root uptake and translocation of PBDEs to above-ground tissues of A. corniculatum. These results suggested that N addition could enhance the phytoremediation of BDE-47-contaminated soil within a short period of time. Different from BDE-47, BDE-209 in all contaminated soils was difficult to be removed due to its persistence and low bioavailability. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. tert-Butyl 3-oxo-2-oxa-5-azabicyclo[2.2.1]heptane-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Claude Didierjean

    2008-10-01

    Full Text Available The title compound, C10H15NO4, also known as N-tert-butyloxycarbonyl-allohydroxy-l-proline lactone, is quite similar to N-acetyl-allohydroxy-l-proline lactone [Lenstra, Petit & Geise (1979. Cryst. Struct. Commun. 8, 1023–1029], whereby both carbonyl groups point roughly in the same direction because of the trans conformation of the peptide bond.

  9. Di-μ-methanolato-bis[(2-tert-butyl-6-methylphenolato-κOmethyltitanium(IV

    Directory of Open Access Journals (Sweden)

    Alastair J. Nielson

    2013-10-01

    Full Text Available The molecule of the title compound, [Ti2(CH32(CH3O2(C11H15O4] or {[Ti(Me(μ-OCH3(OC6H3CMe3-2-Me-6]2}, has a centrosymmetric, dimeric structure with a distorted square pyramidal array about each titanium atom. The methoxide ligands form an asymmetric bridge between the two TiIV atoms [Ti—O bond lengths of 1.9794 (12 and 2.0603 (12 Å] with the two phenolato ligands occupying the remaining basal sites [Ti—O 1.8218 (11 and 1.8135 (11 Å]. The Ti—O—C phenolato bond angles are similar at 161.24 (10 and 160.66 (11°. The methyl ligand attached to the metal atom has a Ti—C bond length of 2.0878 (17 Å.

  10. ``Living polymers'' in organic solvents : stress relaxation in bicopper tetracarboxylate/tert-butyl cyclohexane solutions

    Science.gov (United States)

    Terech, P.; Maldivi, P.; Dammer, C.

    1994-10-01

    Viscoelastic solutions of a bicopper tetracarboxylate complex in tert-butylcyclohexane have been studied by dynamic rheology in a wide range of concentrations (0.5-1.5 % volume fraction). The zero shear viscosity, the elastic modulus, the terminal stress relaxation time and the height of the high-frequency dip, in a Cole-Cole representation of the complex elastic modulus, follow scaling laws. The related exponents are discussed in the context of the physics of “living polymers” : a term used to describe worm-like species undergoing scission/recombination reactions competing mainly with the reptation motions of the chains. The current system, made up of molecular threads (17.5 Å diameter) of Cu2(O2C-CH(C2H5)C4H9)4 in the apolar solvent, is representative of a “living polymer” where, instead of mechanisms involving transient star polymeric crosslinks, a reversible scission mechanism prevails. The dynamics in the high-frequency range evolves from a regime where reptation is the dominant relaxation mechanism to a cross-over regime where “breathing” fluctuations and Rouse motions become important. Large modifications of the stress relaxation function occur for more concentrated systems. The binary system is the first example of a “living polymer” in an organic solvent and exhibits elastic moduli (G ≈ ca. 120 Pa à φ = 1 %) which are at least 20 times larger than those found for the aqueous “living polymer” systems. Les solutions viscoélastiques d'un tétracarboxylate binucléaire de cuivre dans le tert-butylcyclohexane sont étudiées par rhéologie en mode dynamique dans une gamme étendue de concentrations (0,5 %-15,5 %). La viscosité à gradient nul, le module élastique, le temps terminal de relaxation et la hauteur du puits à haute fréquence, dans une représentation Cole-Cole du module élastique complexe, suivent des lois d'échelles. Les exposants correspondants sont discutés dans le contexte de la physique des “polymères vivants" : un terme utilisé pour décrire des espèces vermiformes subissant des réactions de scission/recombinaison en compétition principalement avec les mouvements de reptation des chaînes. Le système constitué de fils moléculaires (17,5 Å de diamètre) de Cu2(O2C-CH(C2H5)C4H9)4 dans le solvant apolaire est typique de “polymères vivants” où le mécanisme de scission réversible prévaut plutôt que les mécanismes impliquant des nœuds transitoires branchés. La dynamique dans le domaine des hautes fréquences évolue d'un régime où la reptation est le mécanisme de relaxation dominant vers un régime intermédiaire où les modes de “respiration” et de Rouse deviennent importants. D'importantes modifications de la relaxation de contrainte se produisent pour les systèmes concentrés. Le système binaire est le premier exemple de “polymère vivant” en milieu organique et présente des modules élastiques (G ≈ ca. 120 Pa à φ = 1 %) qui sont au moins 20 fois plus grands que ceux des homologues aqueux.

  11. 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.

  12. 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.

  13. Absorption, Distribution, and Clearanace o f2,6-Di-tert-Butyl-4-nitrophenol (DBNP)

    National Research Council Canada - National Science Library

    Still, K

    2002-01-01

    .... US sailors may be exposed to OBNP for 24 hr/day for periods up to 6 months. While it is suspected that dermal and respiratory exposure to DBNP provides litte human risk due to its minimal solubility...

  14. Inhibition of Palmityl Carnitine Oxidation in Rat Liver Mitochondria by Tert-Butyl Hydroperoxide

    Czech Academy of Sciences Publication Activity Database

    Červinková, Z.; Rauchová, Hana; Křiváková, P.; Drahota, Zdeněk

    2008-01-01

    Roč. 57, č. 1 (2008), s. 133-136 ISSN 0862-8408 R&D Projects: GA ČR(CZ) GD303/03/H065; GA ČR(CZ) GA305/04/0500; GA MŠk(CZ) 1M0520 Institutional research plan: CEZ:AV0Z50110509 Keywords : liver mitochondria * palmityl carnitine oxidation * tert-butylhydroperoxide Subject RIV: ED - Physiology Impact factor: 1.653, year: 2008

  15. Back-biting termination in methyl methacrylate/tert-butyl acrylate anionic block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Čadová, Eva; Dybal, Jiří; Kříž, Jaroslav; Vlček, Petr; Janata, Miroslav; Toman, Luděk

    2008-01-01

    Roč. 209, č. 16 (2008), s. 1657-1665 ISSN 1022-1352 Institutional research plan: CEZ:AV0Z40500505 Keywords : acrylates * anionic polymerization * spontaneous termination Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.202, year: 2008

  16. Synthesis, structure, and sunlight photolysis of benzyl- and tert-butyl-substituted octamethyltitanocene dihydrosulfides

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal; Císařová, I.; Gyepes, R.; Kubišta, Jiří; Pinkas, Jiří; Lamač, Martin; Mach, Karel

    2014-01-01

    Roč. 755, APR 2014 (2014), s. 141-150 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR GP203/09/P276 Institutional support: RVO:61388955 Keywords : titanium * titanocene * hydrosulphide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.173, year: 2014

  17. 2-tert-Butyl-4-methyl-6-(1,3-oxazinan-1-ylmethylphenol

    Directory of Open Access Journals (Sweden)

    Wen-Jun Lei

    2010-05-01

    Full Text Available The title compound, C16H25NO2, which was synthesized by a Mannich reaction route, is a rare example of an organic compound containing the six-membered oxazine ring. The ring adopts a chair conformation and the N atom is pyramidal. The N atom serves as a hydrogen-bond acceptor to the phenolic OH group.

  18. tert-Butyl 4-carbamoyl-3-methoxyimino-4-methylpiperidine-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Yucheng Wang

    2008-12-01

    Full Text Available The title compound, C13H23N3O4, was prepared starting from ethyl N-benzyl-3-oxopiperidine-4-carboxylate through a nine-step reaction, including hydrogenation, Boc (tert-butoxycarbonyl protection, methylation, oximation, hydrolysis, esterification and ammonolysis. In the crystal structure, molecules are linked by intermolecular N—H...O hydrogen bonds to form a porous three-dimensional network with solvent-free hydrophobic channels extending along the c axis.

  19. Di-tert-butyl N-[2,6-bis(methoxymethoxyphenyl]iminodiacetate

    Directory of Open Access Journals (Sweden)

    Ben Capuano

    2009-04-01

    Full Text Available The title molecule, C20H31NO8, has pseudo-C2 symmetry about the C—N bond, with the bis(tert-butoxycarbonylamino group twisted from the benzene ring plane by ca 60° and the bulky tert-butoxycarbonyl (Boc groups are orientated away from the substituted aniline group. As part of an antibacterial drug discovery programme furnishing analogues of platensimycin, we unexpectedly synthesized the bis-Boc-protected aniline.

  20. ATRP of 2-vinylpyridine and tert-butyl acrylate mixtures giving precursors of polyampholytes

    Czech Academy of Sciences Publication Activity Database

    Čadová, Eva; Konečný, Jiří; Kříž, Jaroslav; Svitáková, Romana; Holler, Petr; Genzer, J.; Vlček, Petr

    2010-01-01

    Roč. 48, č. 3 (2010), s. 735-741 ISSN 0887-624X R&D Projects: GA MŠk 1P05ME753 Institutional research plan: CEZ:AV0Z40500505 Keywords : atom transfer radical polymerization ( ATRP ) * copolymerization * polyelectrolytes Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.894, year: 2010

  1. Preparation and Characterization of Sulfonated Poly (ether ether ...

    African Journals Online (AJOL)

    Proton-conducting membranes of organic–inorganic (sulfonated poly (ether ether ketone)/phosphated zirconia nanoparticles) composite were prepared by incorporating various ratios of phosphated zirconia nanoparticles (ZP) in sulfonated poly (ether ether ketone) (SPEEK). SPEEK/ZP showed an improvement of ...

  2. Functional polyester materials with tunable degradability: Investigations into the use of reductive amination, ketoxime ether, and hydrazone linkages for functionalization, covalent stabilization and crosslinking of poly(epsilon-caprolactone) materials

    Science.gov (United States)

    van Horn, Brooke Angela

    Aliphatic polyesters represent one class of degradable, polymeric materials that is receiving significant attention in the search for, and design of, biocompatible and bioresorbable synthetic substances. Functional and crosslinked polyesters, having potential biomedical value, are the target of many avenues of current research. This dissertation work expands the utility of a specific aliphatic polyester, poly(epsilon-caprolactone-co-2-oxepane-1,5-dione) (P(CL-co-OPD)), which contains backbone ketone units that can be reacted with various functional, nucleophilic agents. Results presented in this dissertation convey both the successes had and the challenges encountered in the employment of different "iminyl" chemistries for the synthesis of functional and crosslinked materials. Specifically, the ketone-functionalized polyester was investigated as a general substrate designed to undergo solution-state intramolecular crosslinking and functionalization upon reductive amination with 1,6-hexanediamine and hexylamine, respectively, in the presence of NaCNBH3. Through detailed analysis of the products from these reactions, and simpler systems including small molecule model compounds, the polymeric gamma-keto ester functionality was determined to be incompatible with the reductive amination chemistry, resulting in chain cleavage via intramolecular lactam formation. Subsequent investigation of ketoxime ether formation using synthetic model hydroxylamines, 1-aminooxydodecane and 1,6-bis(aminooxy)hexane, in solution and in the presence of an acid catalyst, resulted in the targeted graft and crosslinked particulate/gel materials, respectively. With the significant interest in the development of synthetic polymer materials of increasing degrees of complexity, attention has been focused on the efficient and high-yielding conversion of polyesters into multi-functional materials. Facile conjugation of aminooxy- and sulfonyl hydrazide model ligands with P(CL-co-OPD) were also

  3. 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...

  4. Usage of the word 'ether'

    International Nuclear Information System (INIS)

    Duffy, M.C.

    1980-01-01

    Confusion has been caused by scientists using the one word 'ether' to classify models differing from each other in important respects. Major roles assigned to the word are examined, and the nature of modern ether theories surveyed. The part played by the several meanings attached to the word, in the ether concept, is outlined. (author)

  5. Cation permeable membranes from blends of sulfonated poly(ether ether ketone) and poly (ether sulfone)

    NARCIS (Netherlands)

    Wilhelm, F.G.; Punt, Ineke G.M.; van der Vegt, N.F.A.; Strathmann, H.; Wessling, Matthias

    2002-01-01

    Sulfonated poly(aryl ether ether ketone), S-PEEK, is blended with non-sulfonated poly(ether sulfone) (PES) to adjust the properties of ion permeable and ion selective membranes. In this study, membranes are prepared from blends with (i) a S-PEEK content between 10 and 100 wt.% using one S-PEEK batch

  6. Use of liquid chromatography/electrospray ionization tandem mass spectrometry to study the degradation pathways of terbuthylazine (TER) by Typha latifolia in constructed wetlands: identification of a new TER metabolite.

    Science.gov (United States)

    Gikas, Evagelos; Papadopoulos, Nikolaos G; Bazoti, Fotini N; Zalidis, Georgios; Tsarbopoulos, Anthony

    2012-01-30

    S-Triazines are used worldwide as herbicides for agricultural and non-agricultural purposes. Although terbuthylazine (TER) is the second most frequently used S-triazine, there is limited information on its metabolism. For this reason, an analytical method based on liquid chromatography/electrospray ionization tandem mass spectrometry (LC-ESI MS/MS) has been developed aiming at the identification of TER and its five major metabolites (desisopropyl-hydroxy-atrazine, desethyl-hydroxy-terbuthylazine, desisopropyl-atrazine, hydroxy-terbuthylazine and desethyl-terbuthylazine) in constructed wetland water samples. The separation of TER and its major metabolites was performed by reversed-phase high-performance liquid chromatography (HPLC) on a C(8) column using a gradient elution of aqueous acetic acid 1% (solvent A) and acetonitrile (solvent B), followed by MS/MS analysis on a triple quadrupole mass spectrometer. The data-depended analysis (DDA) scan approach has been employed and the main degradation pathways of both hydroxyl and chloro (dealkylated and alkylated) metabolites are elucidated through the tandem mass spectral (MS/MS) interpretation of triazine fragments under CID conditions. In addition, another major metabolite of TER, namely N2-tert-butyl-N4-ethyl-6-methoxy-1,3,5-triazine-2,4-diamine, has been identified. This methodology can be further employed in biodegradation studies of TER, thus assisting the assessment of its environmental impact. Copyright © 2011 John Wiley & Sons, Ltd.

  7. Ether space-time & cosmology

    CERN Document Server

    Levy, Joseph

    2008-01-01

    The aim of this first volume of papers is to examine the different paths by which the modern ether concept has been developed and to highlight the part it plays in major departments of 21st century physics. The evidence for its existence is reviewed, and it is hoped, widespread misconceptions concerning ether are corrected. It is anticipated that the emerging modern concept of ether will play a fundamental part in the development of 21st century physical science.

  8. Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

    Science.gov (United States)

    Kierkegaard, Amelie; Sellström, Ulla; McLachlan, Michael S

    2009-01-16

    Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

  9. Analysis of electron-irradiated poly-ether ether ketone by X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Oyabu, Matashige; Kobayashi, Yoshinori; Seguchi, Tadao; Sasuga, Tsuneo; Kudoh, Hisaaki.

    1995-01-01

    Organic polymers used in atomic power plants or space are damaged by ionizing irradiation. Radicals produced by irradiation cause oxidation, chain scission and crosslinking, all of which lead to degradation of the material. In this paper, the surface of electron-irradiated poly-ether ether ketone (PEEK) was studied by X-ray photoelectron spectroscopy (XPS). The irradiation in air was found to oxidize the PEEK surface producing carboxyl groups, the content of which dependant on the dose. Carboxyl groups were not produced in helium gas. Quantitative spectral analysis indicated that the aromatic structure might be decomposed. Some comparison was made between the semicrystalline and amorphous samples. The oxygen content resulting from irradiation, of semicrystalline PEEK increased more than that of amorphous PEEK. (author)

  10. On the Use of Potential Denaturing Agents for Ethanol in Direct Ethanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    Domnik Bayer

    2011-01-01

    Full Text Available Acidic or alkaline direct ethanol fuel cells (DEFCs can be a sustainable alternative for power generation if they are fuelled with bio-ethanol. However, in order to keep the fuel cheap, ethanol has to be exempted from tax on spirits by denaturing. In this investigation the potential denaturing agents fusel oil, tert-butyl ethyl ether, and Bitrex were tested with regard to their compatibility with fuel cells. Experiments were carried out both in sulphuric acid and potassium hydroxide solution. Beside, basic electrochemical tests, differential electrochemical mass spectrometry (DEMS and fuel cell tests were conducted. It was found that fusel oil is not suitable as denaturing agent for DEFC. However, tert-butyl ethyl ether does not seem to hinder the ethanol conversion as much. Finally, a mixture of tert-butyl ethyl ether and Bitrex can be proposed as promising candidate as denaturing agent for use in acidic and alkaline DEFC.

  11. Exogenous ether lipids predominantly target mitochondria

    DEFF Research Database (Denmark)

    Kuerschner, Lars; Richter, Doris; Hannibal-Bach, Hans Kristian

    2012-01-01

    Ether lipids are ubiquitous constituents of cellular membranes with no discrete cell biological function assigned yet. Using fluorescent polyene-ether lipids we analyzed their intracellular distribution in living cells by microscopy. Mitochondria and the endoplasmic reticulum accumulated high...... amounts of ether-phosphatidylcholine and ether-phosphatidylethanolamine. Both lipids were specifically labeled using the corresponding lyso-ether lipids, which we established as supreme precursors for lipid tagging. Polyfosine, a fluorescent analogue of the anti-neoplastic ether lipid edelfosine...... in ether lipid metabolism and intracellular ether lipid trafficking....

  12. Reproductive toxicity of the glycol ethers.

    Science.gov (United States)

    Hardin, B D

    1983-06-01

    The glycol ethers are an important and widely used class of solvents. Recent studies have demonstrated that ethylene glycol monomethyl ether (EGME), ethylene glycol dimethyl ether (EGdiME), ethylene glycol monoethyl ether (EGEE), and ethylene glycol monoethyl ether acetate (EGEEA) are teratogenic. Other studies have demonstrated that testicular atrophy or infertility follow treatment of males with EGME, ethylene glycol monomethyl ether acetate (EGMEA), EGEE, EGEEA, diethylene glycol dimethyl ether (diEGdiME), and diethylene glycol monoethyl ether (diEGEE). Experimental data are reviewed and structure-activity relationships are speculated upon.

  13. The fate of MtBE during Fenton-like treatments through laboratory scale column tests.

    Science.gov (United States)

    Piscitelli, Daniela; Zingaretti, Daniela; Verginelli, Iason; Gavasci, Renato; Baciocchi, Renato

    2015-12-01

    In Situ Chemical Oxidation (ISCO) based on the Fenton's process is a proven technology for the treatment of groundwater contaminated by organic compounds. Nevertheless, the application of this treatment process to methyl tert-butyl ether (MtBE) is questioned, as there are concerns about its capacity to achieve complete mineralization. Many existing studies have focused on water contaminated by MtBE and are thus not representative of in situ treatments since they do not consider the presence of soil. In this work, the effectiveness of a Fenton-like process for MtBE treatment was proven in soil column tests performed at operating conditions (i.e., oxidant and contaminant concentration and flow rates) resembling those typically used for in situ applications. No MtBE by-products were detected in any of the tested conditions, thus suggesting that the tert-butyl group of MtBE was completely degraded. A mass balance based on the CO2 produced was used as evidence that most of the MtBE removed was actually mineralized. Finally, the obtained results show that preconditioning of soil with a chelating agent (EDTA) significantly enhanced MtBE oxidation. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Understanding the similarities and differences between ozone and peroxone in the degradation of naphthenic acids: Comparative performance for potential treatment.

    Science.gov (United States)

    Meshref, Mohamed N A; Klamerth, Nikolaus; Islam, Md Shahinoor; McPhedran, Kerry N; Gamal El-Din, Mohamed

    2017-08-01

    Ozonation at high doses is a costly treatment for oil sands process-affected water (OSPW) naphthenic acids (NAs) degradation. To decrease costs and limit doses, different peroxone (hydrogen peroxide/ozone; H 2 O 2 :O 3 ) processes using mild-ozone doses of 30 and 50 mg/L were investigated. The degradation efficiency of O x -NAs (classical (O 2 -NAs) + oxidized NAs) improved from 58% at 30 mg/L ozone to 59%, 63% and 76% at peroxone (1:1), 50 mg/L ozone, and peroxone (1:2), respectively. Suppressing the hydroxyl radical (•OH) pathway by adding tert-butyl alcohol did significantly reduce the degradation in all treatments, while molecular ozone contribution was around 50% and 34% for O 2 -NAs and O x -NAs, respectively. Structure reactivity toward degradation was observed with degradation increase for both O 2 -NAs and O x -NAs with increase of both carbon (n) and hydrogen deficiency/or |-Z| numbers in all treatments. However, the combined effect of n and Z showed specific insights and differences between ozone and peroxone treatments. The degradation pathway for |-Z|≥10 isomers in ozone treatments through molecular ozone was significant compared to •OH. Though peroxone (1:2) highly reduced the fluorophore organics and toxicity to Vibrio fischeri, the best oxidant utilization in the degradation of O 2 -NAs (mg/L) per ozone dose (mg/L) was observed in the peroxone (1:1) (0.91) and 30 mg/L ozone treatments (0.92). At n = 9-11, peroxone (1:1) had similar or enhanced effect on the O 2 -NAs degradation compared to 50 mg/L ozone. Enhancing •OH pathway through peroxone versus ozone may be an effective OSPW treatment that will allow its safe release into receiving environments with marginal cost addition. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Preparation and characterization of poly(ether ether ketone) derivatives

    International Nuclear Information System (INIS)

    Conceicao, Thiago F.; Bertolino, Jose R.; Mireski, Sandro L.; Joussef, Antonio C.; Pires, Alfredo T.N.; Barra, Guilherme M.O.

    2008-01-01

    In this study, three derivatives of poly(ether ether ketone) [PEEK] were prepared in suspension by nitration (NO 2 -PEEK), reduction to the amino group (NH 2 -PEEK) and carbonyl reduction (PEEK-OH). These modified polymers were characterized by NMR, IR spectroscopy and thermogravimetric analysis. They showed interesting characteristics, such as, basicity and higher solubility in organic solvents, like DMF, for use as membranes and composites in different applications. (author)

  16. Ether the nothing that connects everything

    CERN Document Server

    Milutis, Joe

    2006-01-01

    In Ether, the histories of the unseen merge with discussions of the technology of electromagnetism. Navigating more than three hundred years of the ether''s cultural and artistic history, Joe Milutis reveals its continuous reinvention and tangible impact without ever losing sight of its ephemeral, elusive nature. The true meaning of ether, Milutis suggests, may be that it can never be fully grasped.

  17. Protective effect of nuclear factor E2-related factor 2 on inflammatory cytokine response to brominated diphenyl ether-47 in the HTR-8/SVneo human first trimester extravillous trophoblast cell line

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hae-Ryung, E-mail: heaven@umich.edu; Loch-Caruso, Rita

    2014-11-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardants, and BDE-47 is a prevalent PBDE congener detected in human tissues. Exposure to PBDEs has been linked to adverse pregnancy outcomes in humans. Although the underlying mechanisms of adverse birth outcomes are poorly understood, critical roles for oxidative stress and inflammation are implicated. The present study investigated antioxidant responses in a human extravillous trophoblast cell line, HTR-8/SVneo, and examined the role of nuclear factor E2-related factor 2 (Nrf2), an antioxidative transcription factor, in BDE-47-induced inflammatory responses in the cells. Treatment of HTR-8/SVneo cells with 5, 10, 15, and 20 μM BDE-47 for 24 h increased intracellular glutathione (GSH) levels compared to solvent control. Treatment of HTR-8/SVneo cells with 20 μM BDE-47 for 24 h induced the antioxidant response element (ARE) activity, indicating Nrf2 transactivation by BDE-47 treatment, and resulted in differential expression of redox-sensitive genes compared to solvent control. Pretreatment with tert-butyl hydroquinone (tBHQ) or sulforaphane, known Nrf2 inducers, reduced BDE-47-stimulated IL-6 release with increased ARE reporter activity, reduced nuclear factor kappa B (NF-κB) reporter activity, increased GSH production, and stimulated expression of antioxidant genes compared to non-Nrf2 inducer pretreated groups, suggesting that Nrf2 may play a protective role against BDE-47-mediated inflammatory responses in HTR-8/SVneo cells. These results suggest that Nrf2 activation significantly attenuated BDE-47-induced IL-6 release by augmentation of cellular antioxidative system via upregulation of Nrf2 signaling pathways, and that Nrf2 induction may be a potential therapeutic target to reduce adverse pregnancy outcomes associated with toxicant-induced oxidative stress and inflammation. - Highlights: • BDE-47 stimulated ARE reporter activity and GSH production. • BDE-47 resulted in differential

  18. Influence of ultrasonic frequency on Swan band sonoluminescence and sonochemical activity in aqueous tert-butyl alcohol solutions.

    Science.gov (United States)

    Pflieger, Rachel; Ndiaye, Abdoul Aziz; Chave, Tony; Nikitenko, Sergey I

    2015-01-08

    The multibubble sonoluminescence (MBSL) spectra of t-BuOH aqueous solutions submitted to power ultrasound at 20, 204, 362, and 613 kHz show emissions for the Δυ = -1 to Δυ = +2 vibrational sequences of C2* Swan system (d(3)Πg → a(3)Πu). The Δυ=+2 emission overlaps with the CH(A-X) emission band. The maximal Swan band emission is observed when the MBSL of water itself is almost completely quenched. In general, MBSL is more intense at high-frequency compared to 20 kHz ultrasound. However, in the presence of Xe, the MBSL of C2* at 20 kHz is so bright that it can be seen by the unaided eye as a blue glow in the close vicinity of the ultrasonic tip. The intensity of the C2* band emission exhibits a maximum vs t-BuOH concentration: 0.1-0.2 M at 20 kHz and (1-8) × 10(-3) M at high-frequency ultrasound. Such a huge difference is attributed to a much smaller bubble size at high ultrasonic frequency or, in other words, to a much higher bubble surface/volume ratio providing more efficient saturation of the bubble interior with t-BuOH vapors and to the fact that high frequency bubbles remain active for many more cycles than 20 kHz ones, thus accumulating more hydrocarbon decomposition products. Simulation of the emission spectra using Specair software demonstrated the absence of thermal equilibrium for C2* radicals (Tv > Tr), where Tv and Tr are the vibrational and the rotational temperature, respectively. In Ar, Tv decreases with increasing t-BuOH concentration reaching a steady value in the concentration domain that corresponds to C2* emission maximum intensity. In the presence of Xe an extremely high Tv is obtained, which is explained by the relatively low ionization potential of Xe providing a higher electron temperature of nonequilibrium plasma generated during bubble collapse. Analysis of the gaseous products of t-BuOH sonolysis reveals a significant sonochemical activity even at high t-BuOH concentration when MBSL is totally quenched, indicating that drastic conditions could be produced also within nonsonoluminescing cavitation bubbles.

  19. Free radical scavenger, N-tert-butyl-alfa-phenylnitrone, affects long-term outcome of status epilepticus in immature rats

    Czech Academy of Sciences Publication Activity Database

    Kubová, Hana; Rejchrtová, Jana; Folbergrová, Jaroslava; Mareš, Pavel

    2005-01-01

    Roč. 46, č. S8 (2005), s. 111-112 [Joint Annual Meeting of the American Epilepsy Society and American Clinical Neurophysiology Society. 02.12.2005-06.12.2005, Washington, DC] R&D Projects: GA ČR(CZ) GA304/05/2582 Institutional research plan: CEZ:AV0Z50110509 Keywords : status epilepticus * PBN * rat Subject RIV: ED - Physiology

  20. The intricate paramagnetic state of [Os(Q)(2)(bpy)](+), Q=4,6-di-tert-butyl-o-iminobenzoquinone

    Czech Academy of Sciences Publication Activity Database

    Das, D.; Scherer, T. M.; Das, A.; Mondal, T. K.; Mobin, S. M.; Fiedler, Jan; Priego, J. L.; Jiménez-Aparicio, R.; Kaim, W.; Lahiri, G. K.

    2012-01-01

    Roč. 41, č. 38 (2012), s. 11675-11683 ISSN 1477-9226 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : DENSITY-FUNCTIONAL THEORY * TRANSITION-METAL-COMPLEXES * NON-INNOCENT LIGANDS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.806, year: 2012

  1. Crystal structure of 2-tert-butyl-2,3-dihydro-1H-benzo[c]pyrrol-1-one

    Czech Academy of Sciences Publication Activity Database

    Donkeng Dazie, Joel; Ludvík, Jiří; Fábry, Jan; Eigner, Václav

    2017-01-01

    Roč. 73, č. 8 (2017), s. 1184-1188 ISSN 2056-9890 R&D Projects: GA ČR GA13-21704S; GA MŠk(CZ) LO1603 EU Projects: European Commission(CZ) CZ.2.16/3.1.00/24510 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : crystal structure * aromaticity * heterocyclic compounds Subject RIV: CF - Physical ; Theoretical Chemistry; BM - Solid Matter Physics ; Magnetism (FZU-D) OBOR OECD: Physical chemistry; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)

  2. Comparison of the effects of tert-butyl hydroperoxide and peroxynitrite on the oxidative damage to isolated beef heart mitochondria

    Czech Academy of Sciences Publication Activity Database

    Kohutiar, Matej; Ivica, Josko; Vytášek, R.; Skoumalová, A.; Illner, Jan; Šantorová, P.; Wilhelm, Jiří

    2016-01-01

    Roč. 65, č. 4 (2016), s. 617-626 ISSN 0862-8408 R&D Projects: GA ČR(CZ) GAP303/11/0298 Institutional support: RVO:67985823 Keywords : oxidative stress * free radicals * lipid peroxidation * lipofuscinlike pigments * nitrotyrosine Subject RIV: ED - Physiology Impact factor: 1.461, year: 2016

  3. Methyl 2-[(3,5-di-tert-butyl-4-hydroxybenzylsulfanyl]pyridine-3-carboxylate n-hexane hemisolvate

    Directory of Open Access Journals (Sweden)

    Azhar Ariffin

    2012-06-01

    Full Text Available The title solvated ester, C22H29NO3S·0.5C6H14, crystallizes with two independent molecules along with a hexane molecule in the asymmetric unit. The two aromatic rings are separated by an –CH2–S– linkage; the rings are aligned at 83.27 (4° in one molecule and 47.66 (7° in the other. The hydroxy group of one molecule forms an O—H...O hydrogen bond to the other molecule.

  4. Interface and properties of inorganic fullerene tungsten sulphide nanoparticle reinforced poly (ether ether ketone) nanocomposites

    Science.gov (United States)

    Wang, Nannan; Yang, Zhuxian; Wang, Yuan; Thummavichai, Kunyapat; Xia, Yongde; Ghita, Oana; Zhu, Yanqiu

    We report a simple and effective method to fabricate PEEK (poly ether ether ketone)/IF-WS2 (Inorganic Fullerene Tungsten Sulphide) nanocomposites with IF-WS2 content up to 8 wt%. We have used electron microscopies to characterise the morphology and structural features of the nancomposites, and FTIR and XPS to show that some chemical interface bondings were formed between the PEEK and IF-WS2. We demonstrate that the resulting PEEK/IF-WS2 nanocomposites showed an extraordinary 190% increase in thermal conductivity, 50 °C higher in degradation temperature, and mild improvements in strength and hardness. The increased degradation activation energy from 64 to 76 kJ/mol for neat PEEK and PEEK/IF-WS2 nanocomposites, respectively, is attributed to the synergistic interface between the PEEK matrix and IF-WS2 nanoparticles. The enhancements in both the mechanical and thermal properties will significantly expand the capacities of PEEK-based nanocomposites towards applications where thermal conductivity and stability are important.

  5. Luminescent Lariat Aza-Crown Ether

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2010-03-01

    Full Text Available Lariat ethers are interesting recognition motifs in supramolecular chemistry. The synthesis of a luminescent lariat ether with triglycol chain by azide–alkyne (Huisgen cycloaddition is presented.

  6. Radiation induced crosslinking of cellulose ethers

    International Nuclear Information System (INIS)

    Wach, A.R.; Mitomo, H.; Yoshii, F.; Kume, T.

    2002-01-01

    The effects of high-energy radiation on four ethers of cellulose: carboxymethyl (CMC); hydroxypropyl (HPC), hydroxyethyl (HEC) and methylcellulose (MC) were investigated. Polymers are irradiated in solid state and in aqueous solutions at various concentrations. Degree of substitution (DS) of the derivatives, the concentration of their aqueous solutions and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid state and in diluted aqueous solutions resulted in their degradation. However, it was found that for concentrated solutions gel formation occurred. Paste-like form of the initial material, when water plasticizes the bulk of polymer as well as the high dose rate, what prevents oxygen penetration of the polymer during irradiation, have been found favourable for hydrogel formation. Up to 95% of gel fraction was obtained from solutions of CMC with concentration over 50% irradiated by γ-rays or electron beam. It was pointed out that the ability to the formation of the three-dimensional network is related to the DS of anhydroglucose units and a type of chemical group introduced to main chain of cellulose. Produced hydrogels swelled markedly in water. Despite of the crosslinked structure they underwent degradation by the action of cellulase enzyme or microorganisms from compost, and can be included into the group of biodegradable materials. (author)

  7. Release of drinking water contaminants and odor impacts caused by green building cross-linked polyethylene (PEX) plumbing systems.

    Science.gov (United States)

    Kelley, Keven M; Stenson, Alexandra C; Dey, Rajarashi; Whelton, Andrew J

    2014-12-15

    Green buildings are increasingly being plumbed with crosslinked polyethylene (PEX) potable water pipe. Tap water quality was investigated at a six month old plumbing system and chemical and odor quality impacts of six PEX pipe brands were examined. Eleven PEX related contaminants were found in the plumbing system; one regulated (toluene) and several unregulated: Antioxidant degradation products, resin solvents, initiator degradation products, or manufacturing aides. Water chemical and odor quality was monitored for new PEX-a, -b and -c pipes with (2 mg/L free chlorine) and without disinfectant over 30 days. Odor and total organic carbon (TOC) levels decreased for all pipes, but odor remained greater than the USA's Environmental Protection Agency's (USEPA) secondary maximum contaminant level. Odors were not attributed to known odorants ethyl-tert-butyl ether (ETBE) or methyl-tert-butyl ether (MTBE). Free chlorine caused odor levels for PEX-a1 pipe to increase from 26 to 75 threshold odor number (TON) on day 3 and affected the rate at which TOC changed for each brand over 30 days. As TOC decreased, the ultraviolet absorbance at 254 nm increased. Pipes consumed as much as 0.5 mg/L as Cl2 during each 3 day stagnation period. Sixteen organic chemicals were identified, including toluene, pyridine, methylene trichloroacetate and 2,4-di-tert-butylphenol. Some were also detected during the plumbing system field investigation. Six brands of PEX pipes sold in the USA and a PEX-a green building plumbing system impacted chemical and drinking water odor quality. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Poly (ether ether ketone) membranes for fuel cells

    International Nuclear Information System (INIS)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D.; Hui, Wang S.; Oliveira, Vivianna S. de

    2015-01-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)

  9. Hydrogen storage by functionalised Poly(ether ether ketone)

    Energy Technology Data Exchange (ETDEWEB)

    Pedicini, R.; Giacoppo, G.; Carbone, A.; Passalacqua, E. [CNR-ITAE, Messina (Italy). Inst. for Advanced Energy Technologies

    2010-07-01

    In this work a functionalised polymer was studied as potential material for hydrogen storage in solid state. A Poly(ether ether ketone) (PEEK) matrix was modified by a manganese oxide in situ formation. Here we report the functionalisation process and the preliminary results on hydrogen storage capability of the synthesised polymer. The polymer was characterized by Scanning Electron Microscopy, X-ray diffraction, Transmission Electron Microscopy and Gravimetric Hydrogen Adsorption measurements. In the functionalised PEEK, morphological changes occur as a function of oxide precursor concentration and reaction time. Promising results by gravimetric measurements were obtained with a hydrogen sorption of 0.24%wt/wt at 50 C and 60 bar, moreover, reversibility hydrogen adsorption and desorption in a wide range of both temperature and pressure was confirmed. (orig.)

  10. 75 FR 70248 - Endocrine Disruptor Screening Program; Second List of Chemicals for Tier 1 Screening

    Science.gov (United States)

    2010-11-17

    ... reasons, it is important to note that these exclusions do not imply that the Agency has no interest in the... 2007 Lindane 58-89-9 X Methanol 67-56-1 X Methoxychlor 72-43-5 X Methyl tert-butyl ether 1634-04-4 X...

  11. 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...

  12. MTBE BIOREMEDIATION WITH BIONETS CONTAINING ISOLITE, PMI, SOS ON AIR

    Science.gov (United States)

    Methyl tert-Butyl Ether (MTBE), a gasoline additive, is a persistent and foul tasting contaminant that is more mobile in ground water than BTEX. It is turning up at many American crossroads. This study's objective was to determine if biologically active in situ Bionets could bior...

  13. MTBE IN SITU BIODEGRADATION IN BIONETS USING ISOLITE, PM1, SLOW RELEASING OXYGEN AND AIR IN INDIAN COUNTRY

    Science.gov (United States)

    Methyl tert-Butyl Ether (MTBE), a gasoline additive, is a persistent, foul tasting chemical and more mobile in ground water than BTEX. Our objective was to determine if biologically active in situ Bionets could bioremediate MTBE. Seven Bionets, most containing 3 fractures each,...

  14. BTEX MTBE BIOREMEDIATION: BIONETS CONTAINING ISOLITE, PM1, SOLID OXYGEN SOURCE

    Science.gov (United States)

    Methyl tert-Butyl Ether (MTBE), a gasoline additive, is a persistent and foul tasting contaminate that is more mobile in ground water than BTEX . It, along with BTEX, is turning up at many American crossroads. This study's objective was to determine if biologically active in sit...

  15. The industrial production of dimethyl carbonate from methanol and carbon dioxide

    NARCIS (Netherlands)

    De Groot, Frank F T; Lammerink, Roy R G J; Heidemann, Casper; Van Der Werff, Michiel P M; Garcia, Taiga Cafiero; Van Der Ham, Louis A G J; Van Den Berg, Henk

    2014-01-01

    This work discusses the design of a dimethyl carbonate (DMC) production plant based on methanol and CO2 as feed materials, which are a cheap and environment-friendly feedstock. DMC is a good alternative for methyl-tert-butyl ether (MTBE) as a fuel oxygenating agent, due to its low toxicity and fast

  16. 2503-IJBCS-Article-Urbain Paul Gnonsoro

    African Journals Online (AJOL)

    hp

    2006.11.001. Chen DZ, Zhang JX, Chen JM. 2010. Adsorption of methyl tert-butyl ether using granular activated carbon: Equilibrium and kinetic analysis. Int. J. Environ. Sci. Tech., 7(2): 235-242. http : www.bioline.org.br/pdf%. 3Fst10023. Danyi S, Brose F, Brasseur C, Schneider YJ,. Larondelle Y, Pussemier L, Robbens J,.

  17. Biosorption of fluoride ion from water using the seeds of the ...

    African Journals Online (AJOL)

    Said

    activated coconut fibre dust . Clean Technol. Environ. Policy. 17:2157-2172. Cengeloglu YE, Gar M, Ersoz M (2002). Removal of fluoride from aqueous solution by using red mud. Sep. Purif. Technol. 28(1):81-86. Chen DZ, Zhang JX, Chen JM (2010). Adsorption of methyl tert-butyl ether using granular activated carbon: ...

  18. Quantifying residues from postharvest fumigation of almonds and walnuts with propylene oxide

    Science.gov (United States)

    A novel analytical approach, involving solvent extraction with methyl tert-butyl ether (MTBE) followed by gas chromatography (GC), was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO,...

  19. CHEMOMETRICS IN BIOANALYTICAL SAMPLE PREPARATION - A FRACTIONATED COMBINED MIXTURE AND FACTORIAL DESIGN FOR THE MODELING OF THE RECOVERY OF 5 TRICYCLIC AMINES FROM PLASMA AFTER LIQUID-LIQUID-EXTRACTION PRIOR TO HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY

    NARCIS (Netherlands)

    WIELING, J; MENSINK, CK; JONKMAN, JHG; COENEGRACHT, PMJ; DUINEVELD, CAA; DOORNBOS, DA

    1993-01-01

    A general systematic approach is described for the chemometric modelling of liquid-liquid extraction data of drugs from biological fluids. Extraction solvents were selected from Snyder's solvent selectivity triangle: methyl tert.-butyl ether, methylene chloride and chloroform. The composition of a

  20. Analysis of Fluorotelomer Alcohols in Soils: Optimization of Extraction and Chromatography

    Science.gov (United States)

    This article describes the development of an analytical method for the determination of fluorotelomer alcohols (FTOHs) in soil. The sensitive and selective determination of the telomer alcohols was performed by extraction with mthyl tert-butyl ether (MTBE) and analysis of the ext...

  1. 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...

  2. An on-line normal-phase high performance liquid chromatography method for the rapid detection of radical scavengers in non-polar food matrixes

    NARCIS (Netherlands)

    Zhang, Q.; Klift, van der E.J.C.; Janssen, H.G.; Beek, van T.A.

    2009-01-01

    An on-line method for the rapid pinpointing of radical scavengers in non-polar mixtures like vegetable oils was developed. To avoid problems with dissolving the sample, normal-phase chromatography on bare silica gel was used with mixtures of hexane and methyl tert-butyl ether as the eluent. The high

  3. Anaerobic biodegradation of gasoline oxygenates. Extrapolation of information to multiple sites and redox conditions

    Energy Technology Data Exchange (ETDEWEB)

    Mormile, M.R.; Liu, S.; Suflita, J.M. (Univ. of Oklahoma, Norman, OK (United States))

    1994-09-01

    A series of alcohol, ketone, ester, and ether oxygenates were tested for their susceptibility to anaerobic decay in samples from four chronically contaminated sedimentary environments. The effect of various electron acceptors on oxygenate biodegradation was also evaluated with a single inoculum source. In addition, two acetogenic bacteria were tested for their ability to metabolize selected oxygenate compounds. The susceptibility of the test oxygenates to anaerobic decay could be related to their chemical structure. That is, compounds other than the ethers that possessed primary or secondary substituted carbon atoms were readily degraded under all conditions tested while compounds that had tertiary substituted carbon atoms resisted biodegradation. The ether oxygenates were generally not degraded when incubated with various inocula, regardless of the electron acceptor status. The exceptions included methyl butyl ether, which was depleted in both sulfate-reducing and methanogenic incubations, and the partial transformation of methyl tert-butyl ether to tert-butanol after a 152-day acclimation period in a single replicate from a river sediment chronically contaminated with fuel. Heat-inactivated control incubations suggested that the latter transformation was biologically catalyzed. 47 refs., 1 fig., 3 tabs.

  4. Sulfonated polyphenyl ether by electropolymerization

    International Nuclear Information System (INIS)

    Hou Hongying; Vacandio, Florence; Di Vona, Maria Luisa; Knauth, Philippe

    2012-01-01

    Highlights: ► Sulfonated polyphenyl ether was for the first time electropolymerized. ► This technique allows the economical preparation of ionomeric membranes for electrochemical energy technologies. ► The mechanism of electropolymerization was discussed in detail. - Abstract: Electropolymerization of sulfonated phenol was for the first time achieved and studied by cyclic voltammetry (CV) and chronoamperometry on stainless steel substrates. The obtained sulfonated polyphenyl ether was characterized in terms of impedance spectroscopy, nuclear magnetic resonance (NMR), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and Fourier-Transform Infrared (FTIR) spectroscopy. Dense films of micrometer thickness can be obtained; the proton conductivity is about 3 mS/cm at room temperature.

  5. Maxwell's ether

    Energy Technology Data Exchange (ETDEWEB)

    Theocharis, T.

    1983-03-12

    A new interpretation of Maxwell's electromagnetic theory of light is proposed, namely that the ambient Coulomb field is the medium (Maxwell's ether) of the electromagnetic radiation fields (Maxwellian waves). This investigation implies an incompleteness of the experimental foundations of the principle of special relativity, and suggests how this principle could be tested more fully. The beginning of an attempt to shape this re-interpretation in the form of an alternative theory is outlined.

  6. Degradation of β-Aryl Ether Bonds in Transgenic Plants

    DEFF Research Database (Denmark)

    Mnich, Ewelina

    Lignin is one of the main building blocks of the plant cell wall. It tethers the cell wall by cross-linking with polysaccharides conferring mechanical strength to plants, aiding water transport and providing a mechanical barrier against pathogens. It is generated by the polymerization of the mono...

  7. Structural and functional roles of ether lipids

    Directory of Open Access Journals (Sweden)

    John M. Dean

    2017-05-01

    Full Text Available ABSTRACT Ether lipids, such as plasmalogens, are peroxisome-derived glycerophospholipids in which the hydrocarbon chain at the sn-1 position of the glycerol backbone is attached by an ether bond, as opposed to an ester bond in the more common diacyl phospholipids. This seemingly simple biochemical change has profound structural and functional implications. Notably, the tendency of ether lipids to form non-lamellar inverted hexagonal structures in model membranes suggests that they have a role in facilitating membrane fusion processes. Ether lipids are also important for the organization and stability of lipid raft microdomains, cholesterol-rich membrane regions involved in cellular signaling. In addition to their structural roles, a subset of ether lipids are thought to function as endogenous antioxidants, and emerging studies suggest that they are involved in cell differentiation and signaling pathways. Here, we review the biology of ether lipids and their potential significance in human disorders, including neurological diseases, cancer, and metabolic disorders.

  8. Application of aluminum-supported Pd, Rh, and Rh-Pd nanoparticles in supercritical carbon dioxide system for hydrodebromination of polybrominated diphenyl ethers.

    Science.gov (United States)

    Wu, Ben-Zen; Sun, Yu-Jie; Chen, Yan-Hua; Yak, Hwa Kwang; Yu, Jya-Jyun; Liao, Weisheng; Chiu, KongHwa; Peng, Shie-Ming

    2016-08-01

    Al-powder-supported Pd, Rh, and Rh-Pd catalysts were synthesized through a spontaneous redox reaction in aqueous solutions. These catalysts hydrodebrominated 4- and 4,4'-bromodiphenyl ethers in supercritical carbon dioxide at 200 atm CO2 containing 10 atm H2 and 80 °C in 1 h. Diphenyl ether was the major product of Pd/Al. Rh/Al and Rh-Pd/Al further hydrogenated two benzene rings of diphenyl ether to form dicyclohexyl ether. The hydrogenolysis of CO bonds on diphenyl ether over Rh/Al and Rh-Pd/Al was observed to generate cyclohexanol and cyclohexane (Rh-Pd/Al among three catalysts is suggested to be used for ex situ degradation of polybrominated diphenyl ethers in supercritical carbon dioxide. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Flow-Induced Crystallization of Poly(ether ether ketone)

    Science.gov (United States)

    Nazari, Behzad; Rhoades, Alicyn; Colby, Ralph

    The effects of an interval of shear above the melting temperature Tm on subsequent isothermal crystallization below Tm is reported for the premier engineering thermoplastic, poly(ether ether ketone) (PEEK). The effect of shear on the crystallization rate of PEEK is investigated by means of rheological techniques and differential scanning calorimetry (DSC) under a protocol of imposing shear in a rotational cone and plate rheometer and monitoring crystallization after quenching. The rate of crystallization at 320 °C was not affected by shear for shear rates <7 s-1 at 350 °C, whereas intervals of adequate shear at higher shear rates prior to the quench to 320 °C accelerated crystallization significantly. As the duration of the interval of shear above 7 s-1 is increased, the crystallization time decreases but at each shear rate eventually saturates once the applied specific work exceeds ~120 MPa. The annealing of the flow-induced precursors was also investigated. The nuclei were fairly persistent at temperatures close to 350 °C, however very unstable at temperatures above 375 °C. This suggests that the nanostructures formed under shear might be akin to crystalline lamellae of greater thickness, compared to quiescently crystallized lamellae.

  10. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

    Directory of Open Access Journals (Sweden)

    Atsushi Morikawa

    2016-02-01

    Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

  11. Atmospheric lifetimes of selected fluorinated ether compounds

    DEFF Research Database (Denmark)

    Heathfield, A.E.; Anastasi, C.; Pagsberg, Palle Bjørn

    1998-01-01

    Atmospheric lifetimes have been estimated for a selection of ethers, the latter representing a class of compounds being considered as replacements for chlorofluorocarbons. The estimates are based on laboratory measurements of rate constants for the reaction of the OH radical with the ethers, and ...

  12. Treatment of N-Nitrosodimethylamine (NDMA) in Groundwater Using a Fluidized Bed Bioreactor

    Science.gov (United States)

    2014-01-01

    for treatment of other contaminants, including nitrate , perchlorate, tert-butyl alcohol and other organics. Systems are currently operating in the...secondary substrate (such as propane, toluene , butane, etc.) and degrades NDMA, may allow threshold limitations to be overcome, and low...degrading NDMA to innocuous products, including formate, nitrate , nitrite, methylamine, and carbon dioxide (Fournier et al., 2009); (2) R. ruber

  13. The mechanism of degradation of bisphenol A using the magnetically separable CuFe{sub 2}O{sub 4}/peroxymonosulfate heterogeneous oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yin; Ai, Jia [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen 518057 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen 518057 (China)

    2016-05-15

    Highlights: • Copper ferrite (CuFe{sub 2}O{sub 4}) was fabricated and utilized in heterogeneous PMS process. • The influence of reaction parameters for the mineralization of BPA were evaluated. • Possible reaction mechanism and the stability of CuFe{sub 2}O{sub 4} were investigated. • Surface bound radicals (mainly ·OH) may be responsible for the BPA degradation. - Abstract: The removal of bisphenol A (BPA) in aqueous solution by an oxidation process involving peroxymonosulfate (PMS) activated by CuFe{sub 2}O{sub 4} magnetic nanoparticles (MNPs) is reported herein. The effects of PMS concentration, CuFe{sub 2}O{sub 4} dosage, initial pH, initial BPA concentration, catalyst addition mode, and anions (Cl{sup −}, F{sup −}, ClO{sub 4}{sup −} and H{sub 2}PO{sub 4}{sup −}) on BPA degradation were investigated. Results indicate that nearly complete removal of BPA (50 mg/L) within 60 min and 84.0% TOC removal in 120 min could be achieved at neutral pH by using 0.6 g/L CuFe{sub 2}O{sub 4} MNPs and 0.3 g/L PMS. The generation of reactive radicals (mainly hydroxyl radicals) was confirmed using electron paramagnetic resonance (EPR). Possible mechanisms on the radical generation from CuFe{sub 2}O{sub 4}/PMS system are proposed based on the results of radical identification tests and XPS analysis. The lack of inhibition of the reaction by free radical scavengers such as methanol and tert-butyl alcohol suggests that these species may not be generated in the bulk solution, and methylene blue probe experiments confirm that this process does not involve free radical generation. Surface-bound, rather than free radicals generated by a surface catalyzed-redox cycle involving both Fe(III) and Cu(II), are postulated to be responsible for the mineralization of bisphenol A.

  14. Clinical comparison of ethyl acetate and diethyl ether in the formalin-ether sedimentation technique.

    OpenAIRE

    Erdman, D D

    1981-01-01

    A substitute for the volatile solvent diethyl ether has been actively sought for the Formalin-ether sedimentation technique. Ethyl acetate has recently been shown to be a comparable substitute. In an effort to verify these findings and evaluate ethyl acetate under clinical conditions, comparison studies with 62 fresh human stool specimens were performed. Parallel concentrates with diethyl ether and ethyl acetate were prepared for each specimen, and the quantity and appearance of recovered par...

  15. Modification of poly(ether ether ketone) by ion irradiation

    Czech Academy of Sciences Publication Activity Database

    Hnatowicz, Vladimír; Havránek, Vladimír; Bočan, Jiří; Macková, Anna; Vacík, Jiří; Švorčík, V.

    2008-01-01

    Roč. 266, č. 2 (2008), s. 283-287 ISSN 0168-583X R&D Projects: GA MŠk(CZ) LC06041 Institutional research plan: CEZ:AV0Z10480505 Keywords : PEEK * ion beam modification * polymer degradation Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 0.999, year: 2008

  16. Activity relationships for aromatic crown ethers

    CERN Document Server

    Wilson, M J

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities...

  17. Ethylene oligomerization promoted by chromium complexes bearing pyrrolide-imine-amine/ether tridentate ligands.

    Science.gov (United States)

    Pinheiro, A C; Roisnel, T; Kirillov, E; Carpentier, J-F; Casagrande, Osvaldo L

    2015-09-28

    Chromium(iii) complexes [CrCl2(L)(THF)] based on monoanionic tridentate ligands [, L = {2-(C4H3N-2'-CH[double bond, length as m-dash]N)C2H4NHPh}; , L = {5-tert-butyl-2-(C4H2N-2'-CH[double bond, length as m-dash]N)C2H3NHPh}; , L = {2-(C4H3N-2'-CH[double bond, length as m-dash]N)C2H4OPh}] have been prepared. Complexes and were converted into the monomeric acetonitrile adducts [CrCl2(L)(NCMe)] [, L = {2-(C4H3N-2'-CH[double bond, length as m-dash]N)C2H4NHPh}; , L = {5-tert-butyl-2-(C4H2N-2'-CH[double bond, length as m-dash]N)C2H3NHPh}] by reaction with acetonitrile at room temperature. All Cr complexes were characterized by IR spectroscopy, elemental analysis, magnetochemistry for , and by X-ray crystallography for and . Upon activation with methylaluminoxane (MAO), chromium precatalysts and showed good activity in ethylene oligomerization (TOF = 47.0-57.0 × 10(3) (mol ethylene)(mol Cr)(-1) h(-1) at 80 °C), producing mostly oligomers (93.0-95.6 wt% of total products). On the other hand, under identical oligomerization conditions, /MAO behaved as a polymerization catalyst generating predominantly polyethylene (73.0 wt%). However, the catalytic behavior of the precatalyst can be adjusted by varying the MAO-to-Cr ratio. Thus, the use of 500 equiv. causes a dramatic shift from polymerization to ethylene oligomerization, eventually producing mainly lighter α-olefin fractions [α-C4 (68.7 wt%) and α-C6 (19.2 wt%)]. A further increase in the amount of MAO (1000 equiv.) leads to a more balanced distribution of oligomers, with a drastic decrease in the α-C4 and increase in the α-C8 fractions.

  18. Skin absorption in vitro of glycol ethers.

    Science.gov (United States)

    Larese Filon, F; Fiorito, A; Adami, G; Barbieri, P; Coceani, N; Bussani, R; Reisenhofer, E

    1999-10-01

    The increased use of glycol ethers (GEs) for water-based paints and cleaning products, combined with a lack of information about many of these products, particularly with regard to the effects of percutaneous exposure, led us to evaluate the skin absorption rates of a group of glycol ethers in vitro. Skin permeation was calculated using the Franz cell method with human skin. A physiological solution was used as the receiving phase. The amount of solvent passing through the skin was analysed with a gas chromatographic technique employing flame ionization detection. A permeation profile was obtained and steady state, lag time and permeation constant flux was calculated for each of the following solvents: ethylene glycol monoethyl ether (EGMEE), propylene glycol mono-methyl ether (PGMME); propylene glycol mono-methyl ether acetate (PGMMEac); 2-propylene glycol 1-butyl ether (2PG1BE), ethylene glycol dimethyl ether (EGDME), ethylene glycol diethyl ether (EGDEE) and diethylene glycol dimethyl ether (DEGDME). All solvents were tested in their pure form and with 70% acetone. For all solvents tested the lag time was less than 2 h, and for the majority of them was about 60 min. Flux at steady state ranged between 0.017 +/- 0.005 and 3.435 +/- 1.897 mg/cm(2)/h and permeation rate was from 0.0192 to 1.02 x 10(-3) cm/h. The presence of acetone in the solution caused a reduction in lag time and an increase in permeation rate, higher for EGMEE, lower for EGDEE, indicating the enhancing effect of this mixture of solvents. Our results confirm the high percutaneous absorption of the GEs tested. The Franz method might be helpful for obtaining a grading of skin notation for hydrophilic substances: in the case of glycol ethers, it can give us precise information about permeation risk, particularly important in the evaluation of exposure. In the case of solvents with high dermal absorption, the air concentration is no longer a sufficient measure of the total exposure to workers, and

  19. Sulfonated poly(ether ether ketone) based composite membranes for nanofiltration of acidic and alkaline media

    NARCIS (Netherlands)

    Dalwani, M.R.; Bargeman, Gerrald; Hosseiny, Seyed Schwan; Schwan Hosseiny, Seyed; Boerrigter, M.E.; Wessling, Matthias; Benes, Nieck Edwin

    2011-01-01

    Several thin film composite nanofiltration membranes have been prepared by spin coating a sulfonated poly(ether ether ketone) solution on a polyethersulfone support, followed by thermal treatment. The most optimal developed nanofiltration membrane shows a clean water permeance of ∼4.5 L m−2 h−1

  20. Optical anisotropy, molecular orientations, and internal stresses in thin sulfonated poly(ether ether ketone) films

    NARCIS (Netherlands)

    Koziara, Beata; Nijmeijer, Dorothea C.; Benes, Nieck Edwin

    2015-01-01

    The thickness, the refractive index, and the optical anisotropy of thin sulfonated poly(ether ether ketone) films, prepared by spin-coating or solvent deposition, have been investigated with spectroscopic ellipsometry. For not too high polymer concentrations (B5 wt%) and not too low spin speeds

  1. Ether modified poly(ether ether ketone) nonwoven membrane with excellent wettability and stability as a lithium ion battery separator

    Science.gov (United States)

    Li, Zhen; Wang, Wenqiang; Han, Yu; Zhang, Lei; Li, Shuangshou; Tang, Bin; Xu, Shengming; Xu, Zhenghe

    2018-02-01

    In this study, poly(ether ether ketone) is first chloromethylated to improve the solubility and is later used for nonwoven membrane fabrication by electrospinning. Finally, the chloromethyl group was converted to the ethyl ether group and dibenzyl ether group in a hot alkaline solution. The abundant polar groups endow the membrane with excellent wettability, reducing the contact angle to 0°. The polymer matrix is crosslinked by dibenzyl ether group, endowing the membrane with excellent stability (insolubility in many solvents, and ultra-low swelling in the electrolyte at 80 °C) and good anti-shrinkage property (0% at 180 °C). The electrospinning-fabricated membrane remains stable until 4.812 V (vs. Li+/Li), meeting the requirement for use in lithium ion batteries. The interwoven structure of the nonwoven membrane effectively gives rise to the high electrolyte uptake of 215.8%. The ionic conductivity of the electrolyte-swelled electrospinning-fabricated membrane is 51% higher than that of the electrolyte-swelled Celgard membrane. As a result, the lithium ion battery with this nonwoven membrane exhibits an enhanced rate performance (up to 42.5% higher than the lithium ion battery with a PP separator) and satisfactory cycling performance.

  2. Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

    Science.gov (United States)

    Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

    2017-05-01

    A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

  3. Methods for degrading lignocellulosic materials

    Science.gov (United States)

    Vlasenko, Elena [Davis, CA; Cherry, Joel [Davis, CA; Xu, Feng [Davis, CA

    2008-04-08

    The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.

  4. Syntheses of Diazadithiacrown Ethers Containing Two 8-Hydroxyquinoline Side Arms

    National Research Council Canada - National Science Library

    Song, H

    2001-01-01

    Ten new diazadithiacrown ethers containing two 8-hydroxyquinoline (HQ) sidearms attached through the HQ 7-positions and four new diazadithiacrown ethers containing two HQ sidearms attached through the HQ 2-positions have been prepared...

  5. Luminescent Lariat Aza-Crown Ether Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Burkhard König

    2010-03-01

    Full Text Available Lariat ethers are interesting recognition motifs in supramolecular chemistry. The synthesis of a luminescent lariat aza-crown ether with a carboxyl group appended by azide-alkyne (Huisgen cycloaddition is presented.

  6. Transformation of 2,2′,4,4′-tetrabromodiphenyl ether under UV irradiation: Potential sources of the secondary pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ji-Zhong [Exposure and Biomonitoring Division, Environmental Health Science and Research Bureau, Environmental and Radiation Health Sciences Directorate, Health Canada, AL: 0800C, EHC, Tunney' s Pasture, Ottawa, Ontario, Canada K1A 0K9 (Canada); Hou, Yuqing [Department of Chemistry and Biochemistry, Southern Illinois University, Mail Code 4405, 1245 Lincoln Drive, Carbondale, IL 62901 (United States); Zhang, Jianshun [Building Energy and Environmental Systems Laboratory, Syracuse University (United States); Zhu, Jiping [Exposure and Biomonitoring Division, Environmental Health Science and Research Bureau, Environmental and Radiation Health Sciences Directorate, Health Canada, AL: 0800C, EHC, Tunney' s Pasture, Ottawa, Ontario, Canada K1A 0K9 (Canada); Feng, Yong-Lai, E-mail: yong-lai.feng@hc-sc.gc.ca [Exposure and Biomonitoring Division, Environmental Health Science and Research Bureau, Environmental and Radiation Health Sciences Directorate, Health Canada, AL: 0800C, EHC, Tunney' s Pasture, Ottawa, Ontario, Canada K1A 0K9 (Canada)

    2013-12-15

    Highlights: • 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47) was found transformed to six less brominated BDE analogs under UV irradiation. • BDE-47 was found degraded faster in liquid phase than in gas phase. • Two brominated phenols were formed in the transformation of BDE-47 in gas phase. • The bromine on the ortho positions of the phenyl rings was found lost first to form 2,4,4′-tribromodiphenyl ether (BDE-28). • The more volatile less brominated BDEs are a source of secondary pollutants in the environment. -- Abstract: A commercial brominated flame retardant 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) was used as the model chemical to investigate the degradation and transformation of polybrominated diphenyl ethers (PBDEs) in gas and liquid phases, respectively, under ultraviolet (UV) irradiation. The results showed that BDE-47 can be transformed to less-brominated BDE analogs. A total of six compounds that are less-brominated BDEs and two brominated phenols were observed as transformation products in the reaction mixtures. Different degradation rates of BDE-47 in n-nonane and in isooctane in the same chamber system were observed. Degradation rate of BDE-47 in n-nonane was faster than in isooctane. Under UV irradiation, the bromine on the ortho positions of the phenyl rings was lost first to form 2,4,4′-tribromodiphenyl ether (BDE-28), which then progressively lead to 4,4′-dibromodiphenyl ether (BDE-15) or 2,4′-dibromodiphenyl ether (BDE-8). An airborne transformation pathway has been proposed according to observed transformation products. The more volatile less-brominated BDEs from transformation of BDE-47 are easily evaporated into air to be a source of secondary pollutants in the environment.

  7. Developmental toxicity of four glycol ethers applied cutaneously to rats.

    OpenAIRE

    Hardin, B D; Goad, P T; Burg, J R

    1984-01-01

    Previous NIOSH studies demonstrated the embryo- and fetotoxicity and teratogenicity of ethylene glycol monoethyl ether (EGEE) applied to the shaved skin of pregnant rats. In the present study ethylene glycol monoethyl ether acetate (EGEEA), ethylene glycol monobutyl ether (EGBE), and diethylene glycol monoethyl ether (diEGEE) were tested in the same experimental model, using distilled water as the negative control and EGEE as a positive control. Water or undiluted glycols were applied four ti...

  8. On new physical reality (on ψ-ether)

    International Nuclear Information System (INIS)

    Isaev, P.S.

    2002-01-01

    It is shown that there exists a new physical reality - the ψ-ether. All the achievements of quantum mechanics and quantum field theory are due to the fact that both the theories include the influence of ψ-ether on the physical processes occurring in the Universe. Physics of the XX century was first of all the physics of ψ-ether

  9. Diaquatetrakis(tert-butyl isocyanide)cobalt(II) bis(perchlorate): an example of cobalt(II) coordinated by only four alkyl isocyanide ligands.

    Science.gov (United States)

    Becker, Clifford A L; Forbes, Roy P; Black, Robert S

    2009-08-01

    The title compound, [Co(C5H9N)4(H2O)2](ClO4)2, crystallizes in the monoclinic space group C2/m. The cation has space-group-imposed 2/m symmetry, while the perchlorate ion is disordered about a mirror plane. The two slightly non-equivalent Co-C bonds [1.900 (3) and 1.911 (3) A] form a rectangular plane, with a C-Co-C bond angle of 86.83 (11) degrees, and the linear O-Co-O C2 axis is perpendicular to this plane. The C[triple-bond]N bond lengths are 1.141 (4) A and the Co-C[triple-bond]N and C[triple-bond]N-C angles average 175.5 (4) degrees. The perchlorate counter-ions are hydrogen bonded to the water molecules. The title compound is the first example of four alkyl isocyanide ligands coordinating Co(II) upon initial reaction of Co(ClO4)(2).6H2O/EtOH with alkyl isocyanide. In all other known examples, five alkyl isocyanide molecules are coordinated, as in [(RNC)5Co-Co(CNR)5](ClO4)4 (R = Me, Et, CHMe2, CH2Ph, C4H9-n or C6H11) or [Co(CNC8H17-t)5](ClO4)2. This complex, therefore, is unique and somewhat unexpected.

  10. 5-tert-Butyl 3-ethyl 1-isopropyl-4,5,6,7-tetrahydro-1H-pyrazolo[4,3-c]pyridine-3,5-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Huan-Mei Guo

    2011-12-01

    Full Text Available In the title compound, C17H27N3O4, the six-membered ring adopts a half-chair conformation with the N atom and the adjacent methylene C atom displaced by −0.391 (2 and 0.358 (2 Å, respectively, from the plane of the other four atoms. In the crystal, molecules are linked by weak C—H...O interactions.

  11. [2,6-Bis(di-tert-butyl-phosphinometh-yl)-phen-yl-κP,C,P'](nitrato-κO)nickel(II).

    Science.gov (United States)

    Boro, Brian J; Dickie, Diane A; Duesler, Eileen N; Goldberg, Karen I; Kemp, Richard A

    2008-10-15

    The Ni(II) atom in the title compound, [Ni(C(24)H(43)P(2))(NO(3))], adopts a distorted square-planar geometry with the P atoms in a trans arrangement. The compound contains a twofold rotational axis with the nitrate group offset from this axis, except for an O atom of the nitrate group, generating two positions of 50% occupancy for the other atoms of the nitrate group.

  12. Effect of free-radical spin trap N-tert-butyl-alpha-phenylnitrone on seizures induced in immature rats by homocysteic acid

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2005-01-01

    Roč. 46, č. S6 (2005), s. 375-375 ISSN 0013-9580. [International Epilepsy Congress /26./. 28.08.2005-01.09.2005, Paris] R&D Projects: GA ČR(CZ) GA309/02/1238; GA ČR(CZ) GA309/05/2015 Keywords : free radical scavenger * epilepsy * immature rats * homocysteic acid Subject RIV: ED - Physiology

  13. C-nitroso compounds. Part XIII: monomeric nitroso compounds by photochemical nitrosation of branched-chain hydrocarbons with tert-butyl nitrite

    NARCIS (Netherlands)

    Mackor, A.; Boer, T.J. de

    1970-01-01

    The photochemical nitrosation with t‐butyl nitrite of some branched‐chain hydrocarbons, containing tertiary hydrogen atoms leads to the formation of monomeric nitroso compounds in yields up to 78%, when a special Soxhlet technique is employed. The use of wavelengths around 400 nm is essential for

  14. 6,6'-Di-tert -butyl-4,4'-dimethoxy-2,2'-[1,3-diazinane-1,3- diylbis(methylene)]diphenol 0.19-hydrate

    Czech Academy of Sciences Publication Activity Database

    Rivera, A.; González, D.M.; Ríos-Motta, J.; Fejfarová, Karla; Dušek, Michal

    2012-01-01

    Roč. 68, Part 1 (2012), "o191"-"o192" ISSN 1600-5368 Grant - others:AVĆR(CZ) Praemium Academiae; AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : crystal structure * X-ray diffraction * Jana2006 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.347, year: 2011

  15. Synthesis of densely grafted copolymers with tert-butyl methacrylate/2-(dimethylamino ethyl) methacrylate side chains as precursors for brush polyelectrolytes and polyampholytes

    Czech Academy of Sciences Publication Activity Database

    Gromadzki, Daniel; Štěpánek, Petr; Makuška, R.

    2013-01-01

    Roč. 137, č. 3 (2013), s. 709-715 ISSN 0254-0584 R&D Projects: GA ČR GA202/09/2078 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymers * fourier transform infrared spectroscopy (FTIR) * nuclear magnetic resonance (NMR) Subject RIV: BO - Biophysics Impact factor: 2.129, year: 2013

  16. Experimental and Theoretical Investigation of the Function of 4- tert-Butyl Pyridine for Interface Energy Level Adjustment in Efficient Solid-State Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Yang, Lei; Lindblad, Rebecka; Gabrielsson, Erik; Boschloo, Gerrit; Rensmo, Håkan; Sun, Licheng; Hagfeldt, Anders; Edvinsson, Tomas; Johansson, Erik M J

    2018-04-11

    4- tert-Butylpyridine ( t-BP) is commonly used in solid state dye-sensitized solar cells (ssDSSCs) to increase the photovoltaic performance. In this report, the mechanism how t-BP functions as a favorable additive is investigated comprehensively. ssDSSCs were prepared with different concentrations of t-BP, and a clear increase in efficiency was observed up to a maximum concentration and for higher concentrations the efficiency thereafter decreases. The energy level alignment in the complete devices was measured using hard X-ray photoelectron spectroscopy (HAXPES). The results show that the energy levels of titanium dioxide are shifted further away from the energy levels of spiro-OMeTAD as the t-BP concentration is increased. This explains the higher photovoltage obtained in the devices with higher t-BP concentration. In addition, the electron lifetime was measured for the devices and the electron lifetime was increased when adding t-BP, which can be explained by the recombination blocking effect at the surface of TiO 2 . The results from the HAXPES measurements agree with those obtained from density functional theory calculations and give an understanding of the mechanism for the improvement, which is an important step for the future development of solar cells including t-BP.

  17. Crystal structure of (1R,4R-tert-butyl 3-oxo-2-oxa-5-azabicyclo[2.2.2]octane-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Suvratha Krishnamurthy

    2015-07-01

    Full Text Available In the title compound, C11H17NO4, commonly known as N-tert-butoxycarbonyl-5-hydroxy-d-pipecolic acid lactone, the absolute configuration is (1R,4R due to the enantiomeric purity of the starting material which remains unchanged during the course of the reaction. In the crystal there no intermolecular hydrogen bonds.

  18. MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Horský, Jiří; Janata, Miroslav

    2015-01-01

    Roč. 72, č. 9 (2015), s. 2227-2239 ISSN 0170-0839 Institutional support: RVO:61389013 Keywords : anionic polymerization * acrylates * block copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.371, year: 2015

  19. Effect of free radical spin trap N-tert-butyl-alpha-phenylnitrone (PBN) on seizures induced in immature rats by homocysteic acid

    Czech Academy of Sciences Publication Activity Database

    Folbergrová, Jaroslava; Druga, Rastislav; Otáhal, Jakub; Haugvicová, Renata; Mareš, Pavel; Kubová, Hana

    2006-01-01

    Roč. 201, č. 1 (2006), s. 105-119 ISSN 0014-4886 R&D Projects: GA ČR(CZ) GA309/05/2015; GA ČR(CZ) GA309/02/1238 Institutional research plan: CEZ:AV0Z50110509; CEZ:AV0Z50200510 Keywords : DL-homocysteic acid induced seizures * neuronal damage * protection Subject RIV: ED - Physiology Impact factor: 4.156, year: 2006

  20. Tert-butyl 3-oxo-2,3,4,5,6,7-hexahydro-1H-pyrazolo[4,3-c]pyridine-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Tara Shahani

    2010-01-01

    Full Text Available In the title compound, C11H17N3O3, the pyrazole ring is approximately planar, with a maximum deviation of 0.005 (2 Å, and forms a dihedral angle of 5.69 (13° with the plane through the six atoms of the piperidine ring. In the crystal, pairs of intermolecular N—H...O hydrogen bonds form dimers with neighbouring molecules, generating R22(8 ring motifs. These dimers are further linked into two-dimensional arrays parallel to the bc plane by intermolecular N—H...O and C—H...O hydrogen bonds.

  1. Electron exchange by hexakis(tert-butyl-isocyanide)- and hexakis(cyclohexyl isocyanide)manganese(I,II). Solvent effect on the rate constant and the volume of activation

    International Nuclear Information System (INIS)

    Stebler, M.; Nielson, R.M.; Siems, W.F.; Hunt, J.P.; Dodgen, H.W.; Wherland, H.W.

    1988-01-01

    The rate of electron self-exchange of Mn(CNC(CH 3 ) 3 ) 6 +/2+ and Mn(CNC 6 H 11 ) 6 +/2+ as the BF 4 - salts has been measured by 55 Mn NMR line broadening as a function of pressure, temperature, and concentration in acetonitrile, bromobenzene, benzonitrile, acetone, diethyl ketone, methanol, ethanol, methylene chloride, and trimethyl phosphate, and various binary mixtures of methylene chloride, bromobenzene, and acetonitrile. The values of ΔV double dagger obtained are negative and cover a range of ca. 12 cm 3 /mol, which is limited by ion pairing in the solvents of lower dielectric constant. The variation of the ambient pressure rate constant with solvent is qualitatively different for Mn(CNC(CH 3 ) 3 ) 6 +/2+ reaction than was observed for the Mn(CNC 6 H 11 ) 6 +/2+ reaction. This is taken as further evidence for a significant influence of rather subtle differences in solvation on the molecular level that are not approximated by dielectric continuum models. 30 references, 3 tables

  2. Biosynthesis of archaeal membrane ether lipids

    NARCIS (Netherlands)

    Jain, Samta; Caforio, Antonella; Driessen, Arnold J. M.

    2014-01-01

    A vital function of the cell membrane in all living organism is to maintain the membrane permeability barrier and fluidity. The composition of the phospholipid bilayer is distinct in archaea when compared to bacteria and eukarya. In archaea, isoprenoid hydrocarbon side chains are linked via an ether

  3. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  4. Microwave sintering of poly-ether-ether-ketone (PEEK) based coatings deposited on metallic substrate

    International Nuclear Information System (INIS)

    Zhang, G.; Leparoux, S.; Liao, H.; Coddet, C.

    2006-01-01

    In this paper, the feasibility of microwave (MW) sintering PEEK (poly-ether-ether-ketone) based coatings was investigated. Three coatings were studied: pure PEEK, micron-SiC and nano-SiC particles filled (wt.10%) PEEK coatings. The results indicate that, for the two composite coatings, the SiC particles distributed in the polymer matrix, as a good MW susceptor, could be heated preferentially by MW radiation. Consequently, the polymer matrix was heated by these particles

  5. Ion-Selective Ionic Polymer Metal Composite (IPMC) Actuator Based on Crown Ether Containing Sulfonated Poly(Arylene Ether Ketone)

    NARCIS (Netherlands)

    Tas, Sinem; Zoetebier, Bram; Sardan Sukas, Ö.; Bayraktar, Muharrem; Hempenius, Mark A.; Vancso, Gyula J.; Nijmeijer, Dorothea C.

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  6. Preparation and characterization of monovalent ion selective cation exchange membranes based on sulphonated poly(ether ether ketone)

    NARCIS (Netherlands)

    Balster, J.H.; Krupenko, O.; Krupenko, O.; Punt, Ineke G.M.; Stamatialis, Dimitrios; Wessling, Matthias

    2005-01-01

    This paper analyses the separation properties of various commercial cation exchange membranes (CEMs) and tailor made membranes based on sulphonated poly(ether ether ketone) and poly(ether sulphone) for binary electrolyte solutions containing protons and calcium ions. All membranes are thoroughly

  7. Evaluation of crystallization kinetics of poly (ether-ketone-ketone) and poly (ether-ether-ketone) by DSC

    OpenAIRE

    Gibran da Cunha Vasconcelos; Rogerio Lago Mazur; Edson Cocchieri Botelho; Mirabel Cerqueira Rezende; Michelle Leali Costa

    2010-01-01

    Abstract: The poly (aryl ether ketones) are used as matrices in advanced composites with high performance due to its high thermal stability, excellent environmental performance and superior mechanical properties. Most of the physical, mechanical and thermodynamic properties of semi-crystalline polymers depend on the degree of crystallinity and morphology of the crystalline regions. Thus, a study on the crystallization process promotes a good prediction of how the manufacturing parameters affe...

  8. Hardness and wear properties of boron-implanted poly(ether-ether-ketone) and poly-ether-imide

    International Nuclear Information System (INIS)

    Lee Youngchul; Lee, E.H.; Mansur, L.K.

    1992-01-01

    The effects of boron beam irradiation on the hardness, friction, and wear of polymer surfaces were investigated. Typical high-performance thermoplastics, poly(ether-ether-ketone) (PEEK) and a poly-ether-imide (Ultem) were studied after 200 keV boron ion beam treatment at ambient temperature to doses of 2.3x10 14 , 6.8x10 14 , and 2.2x10 15 ions cm -2 . The hardnesses of pristine and boron-implanted materials were characterized by a conventional Knoop method and a load-depth sensing nanoindentation technique. Both measurements showed a significant increase in hardness with increasing dose. The increase in hardness was also found to depend on the penetration depth of the diamond indenter. Wear and friction properties were characterized by a reciprocating sliding friction tester with an SAE 52100 high-carbon, chrome steel ball at 0.5 and 1 N normal loads. Wear and frictional properties varied in a complex fashion with polymer type and dose, but not much with normal load. A substantial reduction in friction coefficient was observed for PEEK at the highest dose but no reduction was observed for Ultem. The wear damage was substantially reduced at the highest dose for both Ultem and PEEK. For the system studied, the highest dose, 2.2x10 15 ions cm -2 , appears to be optimum in improving wear resistance for both PEEK and Ultem. (orig.)

  9. Modelling a process for dimerisation of 2-methylpropene

    OpenAIRE

    Ouni, Tuomas

    2005-01-01

    Isooctane can be used to replace methyl-tert-butyl ether (MTBE) as a fuel additive. Isooctane is hydrogenated from isooctene, which is produced by dimerizing 2-methylpropene. In dimerization, two 2-methylpropene molecules react on ion-exchange resin catalyst to produce isooctene isomers (2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene). Presence of 2-methyl-2-propanol (TBA) improves reaction selectivity. Trimers and tetramers are formed as side products. Water and alkenes have reaction e...

  10. Catalytic Oxidative Dehydration of Butanol Isomers: 1-Butanol, 2-Butanol, and Isobutanol

    Science.gov (United States)

    2011-09-01

    methyl tert-butyl ether (MTBE), and isooctane. In addition, synthetic petroleum kerosene (SPK) can be synthesized by oligomerization of 4-carbon...GC gas chromatograph HP-INNOWAX Brand name of a separation column for gas chromatography HPLC High Performance Liquid Chromatography MTBE methyl ...MAIL & RECORDS MGMT ATTN RDRL CIO LL TECHL LIB ATTN RDRL CIO MT TECHL PUB ATTN RDRL SED P A GAMSON ATTN RDRL SED P I LEE ATTN

  11. Poly(aryl-ether-ether-ketone) as a Possible Metalized Film Capacitor Dielectric: Accurate Description of the Band Gap Through Ab Initio Calculation

    Science.gov (United States)

    2014-12-01

    Poly(aryl-ether-ether- ketone ) as a Possible Metalized Film Capacitor Dielectric: Accurate Description of the Band Gap Through Ab Initio...the originator. Army Research Laboratory Adelphi, MD 20783-1138 ARL-TR-7160 December 2014 Poly(aryl-ether-ether- ketone ) as a...REPORT DATE (DD-MM-YYYY) December 2014 2. REPORT TYPE Final 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Poly(aryl-ether-ether- ketone ) as

  12. Model for Photodegradation of Polybrominated Diphenyl Ethers

    Czech Academy of Sciences Publication Activity Database

    Veselý, M.; Vajglová, Zuzana; Kotas, Petr; Křišťál, Jiří; Ponec, Robert; Jiřičný, Vladimír

    2015-01-01

    Roč. 22, č. 7 (2015), s. 4949-4963 ISSN 0944-1344 R&D Projects: GA ČR GA104/09/0880; GA ČR(CZ) GAP105/12/0664 Institutional support: RVO:67985858 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * photodegradation model * quantum chemical calculation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.760, year: 2015

  13. Nikola Tesla, the Ether and his Telautomaton

    Science.gov (United States)

    Milar, Kendall

    2014-03-01

    In the nineteenth century physicists' understanding of the ether changed dramatically. New developments in thermodynamics, energy physics, and electricity and magnetism dictated new properties of the ether. These have traditionally been examined from the perspective of the scientists re-conceptualizing the ether. However Nikola Tesla, a prolific inventor and writer, presents a different picture of nineteenth century physics. Alongside the displays that showcased his inventions he presented alternative interpretations of physical, physiological and even psychical research. This is particularly evident in his telautomaton, a radio remote controlled boat. This invention and Tesla's descriptions of it showcase some of his novel interpretations of physical theories. He offered a perspective on nineteenth century physics that focused on practical application instead of experiment. Sometimes the understanding of physical theories that Tesla reached was counterproductive to his own inventive work; other times he offered new insights. Tesla's utilitarian interpretation of physical theories suggests a more scientifically curious and invested inventor than previously described and a connection between the scientific and inventive communities.

  14. BIODEGRADATION OF MTBE BY A MICROORGANISM CONSORTIUM

    Directory of Open Access Journals (Sweden)

    M. Alimohammadi, A. R. Mesdaghinia, M. Mahmoodi, S. Nasseri, A. H. Mahvi and J. Nouri

    2005-10-01

    Full Text Available Methyl Tert-Butyl Ether (MTBE is one of the ether oxygenates which its use has been increased within the last twenty years. This compound is produced from isobutylene and methanol reaction that is used as octane index enhancer and also increases dissolved oxygen in gasoline and decreases carbon monoxide emission in four phased motors because of better combustion of gasoline. High solubility in water (52 g/L, high vapor pressure (0.54 kg/cm3, low absorption to organic carbon of soil and presence of MTBE in the list of potentially-carcinogens of U.S EPA has made its use of great concern. The culture media used in this study was Mineral Salt Medium (MSM. The study lasted for 236 days and in three different concentrations of MTBE of 200, 5 and 0.8 mg/L. A control sample was also used to compare the results. This research studied the isolation methods of microbial consortium in the MTBE polluted soils in Tehran and Abadan petroleum refinery besides MTBE degradation. The results showed the capability of bacteria in consuming MTBE as carbon source. Final microbial isolation was performed with several microbial passages as well as keeping consortium in a certain amount of MTBE as the carbon source.

  15. APPLICATION OF E-COMMERCE IN LOCAL HOME SHOPPING AND ITS CONSEQUENCES ON ENERGY CONSUMPTION AND AIR POLLUTION REDUCTION

    Directory of Open Access Journals (Sweden)

    S. M. Tehrani and A. R. Karbassi

    2005-10-01

    Full Text Available Methyl Tert-Butyl Ether (MTBE is one of the ether oxygenates which its use has been increased within the last twenty years. This compound is produced from isobutylene and methanol reaction that is used as octane index enhancer and also increases dissolved oxygen in gasoline and decreases carbon monoxide emission in four phased motors because of better combustion of gasoline. High solubility in water (52 g/L, high vapor pressure (0.54 kg/cm3, low absorption to organic carbon of soil and presence of MTBE in the list of potentially-carcinogens of U.S EPA has made its use of great concern. The culture media used in this study was Mineral Salt Medium (MSM. The study lasted for 236 days and in three different concentrations of MTBE of 200, 5 and 0.8 mg/L. A control sample was also used to compare the results. This research studied the isolation methods of microbial consortium in the MTBE polluted soils in Tehran and Abadan petroleum refinery besides MTBE degradation. The results showed the capability of bacteria in consuming MTBE as carbon source. Final microbial isolation was performed with several microbial passages as well as keeping consortium in a certain amount of MTBE as the carbon source.

  16. A physical-chemical screening model for anticipating widespread contamination of community water supply wells by gasoline constituents.

    Science.gov (United States)

    Arey, J Samuel; Gschwend, Philip M

    2005-01-01

    Continuing modifications of fuels like gasoline should include evaluations of the proposed constituents for their potential to damage environmental resources such as subsurface water supplies. Consequently, we developed a screening model to estimate well water concentrations and transport times for gasoline components migrating from underground fuel tank (UFT) releases to typical at-risk community water supply wells. Representative fuel release volumes and hydrogeologic characteristics were used to parameterize the transport calculation. Subsurface degradation processes were neglected in the model in order to make risk-conservative assessments. The model was tailored to individual compounds based on their abundances in gasoline, gasoline-water partition coefficients (Kgw), and organic matter-water partition coefficients (Kom). Transport calculations were conducted for 20 polar and 4 nonpolar compounds found in gasoline, including methyl tert-butyl ether (MTBE) and other ether oxygenates, ethanol, methanol, and some aromatic hydrocarbons. With no calibration, the screening model successfully captured the reported magnitude of MTBE contamination of at-risk community supply wells. Such screening indicates that other oxygenates would cause similar widespread problems unless they were biodegradable. Stochastic analysis of field parameter variability concluded that community supply well contamination estimates had order-of-magnitude reliability. This indicated that such pre-manufacturing analyses may reasonably anticipate widespread environmental problems and/or inspire focused investigations into chemical properties (e.g., biodegradability) before industrial adoption of new fuel formulations.

  17. From ether theory to ether theology: Oliver Lodge and the physics of immortality.

    Science.gov (United States)

    Raia, Courtenay Grean

    2007-01-01

    This article follows the development of physicist Oliver Lodge's religio-scientific worldview, beginning with his reticent attraction to metaphysics in the early 1880s to the full formulation of his "ether theology" in the late 1890s. Lodge undertook the study of psychical phenomena such as telepathy, telekinesis, and "ectoplasm" to further his scientific investigations of the ether, speculating that electrical and psychical manifestations were linked phenomena that described the deeper underlying structures of the universe, beneath and beyond matter. For Lodge, to fully understand the ether was to force from the universe an ultimate Revelation, and psychical research, as the most modern and probatory science, was poised to replace religion as the means of that disclosure. (c) 2007 Wiley Periodicals, Inc.

  18. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketone)s and Linear Poly(ether ketone)s.

    Science.gov (United States)

    Morikawa, Atsushi

    2016-02-16

    Poly(ether ether ketone) dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4'-(4-fluorobenzoyl)diphenyl ether and 3,5-dihydroxy-4'-(4-fluorobenzoyl)diphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy)-3,5-bis(4-fluorobenzoyl)benzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketone)s having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

  19. Preliminary Investigation of Poly-Ether-Ether-Ketone Based on Fused Deposition Modeling for Medical Applications

    Directory of Open Access Journals (Sweden)

    Feng Zhao

    2018-02-01

    Full Text Available Poly-ether-ether-ketone (PEEK fabricated by fused deposition modeling for medical applications was evaluated in terms of mechanical strength and in vitro cytotoxicity in this study. Orthogonal experiments were firstly designed to investigate the significant factors on tensile strength. Nozzle temperature, platform temperature, and the filament diameter were tightly controlled for improved mechanical strength performance. These sensitive parameters affected the interlayer bonding and solid condition in the samples. Fourier transform infrared (FTIR spectrometry analysis was secondly conducted to compare the functional groups in PEEK granules, filaments, and printed parts. In vitro cytotoxicity test was carried out at last, and no toxic substances were introduced during the printing process.

  20. Proton conductivity enhancement by nanostructural control of sulphonated poly (ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuwei; Ge, Junjie; Cui, Zhiming; Liu, Changpeng; Xing, Wei [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Graduate School of the Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, Jilin (China); Zhang, Jiujun [Institute for Fuel Cell Innovation, National Research Council of Canada. 4250 Wesbrook Mall, Vancouver, BC (Canada); Lin, Haidan; Na, Hui [Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012 (China)

    2010-08-15

    A series of sulphonated poly (ether ether ketone) (sPEEK) membranes for direct methanol fuel cells are successfully prepared under different humidity degree conditions. These membranes exhibit enhanced proton conductivity at high humidity degree. It is proved that the different proton conductivity is ascribed to the orientation arrangement of sulphonic acid groups, which is caused by environmental water in the preparing process of membranes. A model is established by analyzing the dynamics of membrane formation and proved by Field emission scanning electron microscopy (ESEM) and X-ray photoelectron spectroscopy (XPS). (author)

  1. Novel Water Treatment Processes Based on Hybrid Membrane-Ozonation Systems: A Novel Ceramic Membrane Contactor for Bubbleless Ozonation of Emerging Micropollutants

    Directory of Open Access Journals (Sweden)

    Stylianos K. Stylianou

    2015-01-01

    Full Text Available The aim of this study is the presentation of novel water treatment systems based on ozonation combined with ceramic membranes for the treatment of refractory organic compounds found in natural water sources such as groundwater. This includes, firstly, a short review of possible membrane based hybrid processes for water treatment from various sources. Several practical and theoretical aspects for the application of hybrid membrane-ozonation systems are discussed, along with theoretical background regarding the transformation of target organic pollutants by ozone. Next, a novel ceramic membrane contactor, bringing into contact the gas phase (ozone and water phase without the creation of bubbles (bubbleless ozonation, is presented. Experimental data showing the membrane contactor efficiency for oxidation of atrazine, endosulfan, and methyl tert-butyl ether (MTBE are shown and discussed. Almost complete endosulfan degradation was achieved with the use of the ceramic contactor, whereas atrazine degradation higher than 50% could not be achieved even after 60 min of reaction time. Single ozonation of water containing MTBE could not result in a significant MTBE degradation. MTBE mineralization by O3/H2O2 combination increased at higher pH values and O3/H2O2 molar ratio of 0.2 reaching a maximum of around 65%.

  2. Ethers as gasoline additives : toxicokinetics and acute effects in humans

    OpenAIRE

    Nihlén, Annsofi

    1999-01-01

    Ethers or other oxygen-containing compounds are used as replacements for lead in gasoline and to ensure complete combustion. Methyl tertiary-butyl ether (MTBE) is already in use world-wide and ethyl tertiary-butyl ether (ETBE) may be used increasingly in the future. The aims of the present thesis were to study the uptake and disposition (toxicokinetics) of MTBE and ETBE in humans, to address the issue of biological monitoring and to measure acute effects (assessed by questio...

  3. Divinyl ether synthase gene and protein, and uses thereof

    Science.gov (United States)

    Howe, Gregg A [East Lansing, MI; Itoh, Aya [Tsuruoka, JP

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  4. Hydrogenolytic cleavage of naphthylmethyl ethers in the presence of sulfides.

    Science.gov (United States)

    Adero, Philip O; Jarois, Dean R; Crich, David

    2017-09-08

    With the aid of a series of model thioether or thioglycoside containing polyols protected with combinations of benzyl ethers and 2-naphthylmethyl ethers it is demonstrated that the latter are readily cleaved selectively under hydrogenolytic conditions in the presence of the frequently catalyst-poisoning sulfides. These results suggest the possibility of employing 2-naphthylmethyl ethers in place of benzyl ethers in synthetic schemes when hydrogenolytic deprotection is anticipated in the presence of thioether type functionality. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

    OpenAIRE

    Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

    2012-01-01

    A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

  6. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    International Nuclear Information System (INIS)

    Chiu, K.-F.; Su, S.-H.

    2013-01-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

  7. Silane Cross-Linked Sulfonted Poly(Ether Ketone/Ether Benzimidazoles for Fuel Cell Applications

    Directory of Open Access Journals (Sweden)

    Zilu Yao

    2017-11-01

    Full Text Available γ-(2,3-epoxypropoxy propyltrimethoxysilane (KH-560 was incorporated in various proportions into side-chain-type sulfonated poly(ether ketone/ether benzimidazole (SPEKEBI as a crosslinker, to make membranes with high ion exchange capacities and excellent performance for direct methanol fuel cells (DMFCs. Systematical measurements including Fourier transform infrared (FT-IR, scanning electron microscopy-energy-dispersive and X-ray photoelectron spectroscopy (XPS proved the complete disappearance of epoxy groups in KH-560 and the existence of Si in the membranes. The resulting membranes showed increased mechanical strength and thermal stability compared to the unmodified sulfonated poly(ether ketone/ether benzimidazole membrane in appropriate doping amount. Meanwhile, the methanol permeability has decreased, leading to the increase of relative selectivities of SPEKEBI-x-SiO2 membranes. Furthermore, the H2/O2 cell performance of SPEKEBI-2.5-SiO2 membrane showed a much higher peak power density compared with the pure SPEKEBI memrbrane.

  8. All solid supercapacitor based on polyaniline and crosslinked sulfonated poly[ether ether ketone

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraman, P.; Kushwaha, R.K.; Shashidhara, K.; Hande, V.R.; Thakur, A.P. [Polymer Department, Naval Materials Research Laboratory (DRDO), Shil-Badlapur Road, Anand Nagar PO, Thane Dist., Ambernath, Maharashtra 421 506 (India); Samui, A.B., E-mail: absamui@rediffmail.co [Polymer Department, Naval Materials Research Laboratory (DRDO), Shil-Badlapur Road, Anand Nagar PO, Thane Dist., Ambernath, Maharashtra 421 506 (India); Khandpekar, M.M. [Materials Research Laboratory, Birla College, Kalyan, Thane Dist, Maharashtra 421 304 (India)

    2010-02-28

    All solid supercapacitor based on polyaniline (PANI) and crosslinked sulfonated poly[ether ether ketone] (XSPEEK,) is reported in this paper. The crosslinker used for sulfonated poly[ether ether ketone] (SPEEK) is 1,4-bis(hydroxymethyl) benzene. The XSPEEK is used as both solid electrolyte and separator membrane. Supercapacitors are fabricated using various PANI/XSPEEK weight ratios. These are characterized by cyclic voltammetry and galvanostatic charge-discharge studies. The supercapacitor with PANI/XSPEEK weight ratio 1:0.5, exhibit a specific capacitance of 480 F g{sup -1} of PANI. To the best of authors' knowledge, the value reported here is the highest for a supercapacitor based on a proton conducting solid polymer electrolyte and PANI. Detailed electrochemical impedance spectroscopy analysis is carried out. The analysis shows that the complex capacitance of the supercapacitor depends on the XSPEEK content. The time constant (t{sub 0}), derived from the imaginary part of complex capacitance decreases with increase in the XSPEEK content in the supercapacitor. Cycle life characteristics of the supercapacitor show a decrease in specific capacitance during initial cycles and get stabilized during later cycles.

  9. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  10. Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

    International Nuclear Information System (INIS)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

    2016-01-01

    A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

  11. Rendimento térmico e emissões de contaminantes atmosféricos de gasolinas formuladas com etanol, MBTE e TAEE Thermal yield and emission of atmospheric contaminants from gasolines formulated with ethanol, MTBE and TAEE

    Directory of Open Access Journals (Sweden)

    Rosângela da Silva

    2008-01-01

    Full Text Available The specific consumption and carbon monoxide (CO and nitrogen oxide (NO emissions from gasolines formulated with ethanol, methyl tert-butyl ether (MTBE and tert-amyl ethyl ether (TAEE were evaluated in the rich, stoichiometric and lean-burn regions during the operation of an Otto-cycle engine. The use of ethanol as an additive presented high specific consumption, while gasoline formulated with TAEE showed low specific consumption with the engine operating under lean-burn conditions. The ethers evaluated here presented a low percentage of CO in the rich-burn region when compared with ethanol.

  12. Cathode degradation

    Energy Technology Data Exchange (ETDEWEB)

    Shores, D.A.; Selman, J.R.; Ong, E.T.

    1989-12-01

    This report describes the results of a three-year study of cathode degradation in molten carbonate fuel cells involving both experimental and theoretical work. A keystone of the study is the development of a mathematical model, which describes cathode degradation in terms of the fundamental processes of a fluxing mechanism, i.e., dissolution, transport and precipitation. New fundamental data have been obtained on the solubility of NiO, especially on the effect of water vapor, and on the kinetics of NiO dissolution in (Li{sub 0.62}K{sub 0.38}){sub 2}CO{sub 3}, and these data have been incorporated in the model. Laboratory cell testing in 3 cm{sup 2} cells has been carried out to obtain experimental data on degradation rates for direct comparison with the calculated results from the model. These comparisons have helped to verify several aspects of the model. For example, the model predicts with fair accuracy the location of the Ni deposit in the tile and the deposition rate. It is also fair to point out that the model is a relatively simple representation of complex processes, and it does not answer all questions about cathode degradation. Further work is needed. Because of its fundamental basis, the model can readily be upgraded and extended when further experimental data become available. The solubility studies, modeling efforts and cell testing have interacted iteratively to optimize progress. 94 figs., 24 tabs.

  13. Experimental studies on toxicity of ethylene glycol alkyl ethers in Japan.

    OpenAIRE

    Nagano, K; Nakayama, E; Oobayashi, H; Nishizawa, T; Okuda, H; Yamazaki, K

    1984-01-01

    Past studies on the toxicological effects of ethylene glycol alkyl ethers as well as the recent data on these chemicals in Japan are reviewed. Only a few researchers have participated in the study of ethylene glycol alkyl ethers in Japan. The effects of ethylene glycol alkyl ethers on testis and embryotoxic effects of ethylene glycol monomethyl ether (EGM) have been studied, as has the teratogenicity of ethylene glycol dimethyl ether (EGdM). Studies on ethylene glycol alkyl ethers and related...

  14. Butylated caffeic acid: An efficient novel antioxidant

    International Nuclear Information System (INIS)

    Shi, G.; Liao, X.; Olajide, T.M.; Liu, J.; Jiang, X.; Weng, X.

    2017-01-01

    A novel antioxidant, butylated caffeic acid (BCA) was rationally designed by adding a tert-butyl group to caffeic acid, which was synthesized at a high yield (36.2%) from 2-methoxy-4-methylphenol (1) by a four-step reaction including Friedel-Crafts alkylation, bromine oxidation, ether bond hydrolysis and Knoevenagel condensation. Its antioxidant capacity was much stronger than common commercial antioxidant tert-butyl hydroquinone (TBHQ) and its mother compound, caffeic acid, in both rancimat and deep frying tests. When investigated via the DPPH method, the antioxidant capacity of BCA was almost equal to TBHQ, but lower than caffeic acid. BCA could be a potentially strong antioxidant, especially for food processing at high temperatures such as deep frying and baking. [es

  15. Synthesis and Antiplasmodial Activity of EG-Artemisinin Ethers and ...

    African Journals Online (AJOL)

    The aim of this study was to synthesize a series of ethylene glycol (EG) ethers and quinoline hybrids of the antimalarial drug artemisinin and to evaluate their antimalarial activity in vitro against Plasmodium falciparum strains. The ethers were synthesized in a ... falciparum, ethylene glycol) (EG), ethylene oxide (EO), hybrid ...

  16. Synthesis and Antiplasmodial Activity of EG-Artemisinin Ethers and ...

    African Journals Online (AJOL)

    NICO

    The aim of this study was to synthesize a series of ethylene glycol (EG) ethers and quinoline hybrids of the antimalarial drug artemisinin and to ... The IC50 values revealed that all the ethers were active against both strains but less potent than ...... Compound 19 was racemate (mixture 3''R and 3''S isomers) isolated as fluffy ...

  17. Chemical Composition and Cytotoxic Activities of Petroleum Ether ...

    African Journals Online (AJOL)

    Chemical Composition and Cytotoxic Activities of Petroleum Ether Fruit Extract of Fruits of Brucea javanica (Simarubaceae) ... Tropical Journal of Pharmaceutical Research ... Purpose: To investigate the chemical composition and antitumor activity of the petroleum ether extract of the dried ripe fruits of Brucea javanica.

  18. Congenital malformations and maternal occupational exposure to glycol ethers

    NARCIS (Netherlands)

    Cordier, S; Bergeret, A; Goujard, J; Ha, MC; Ayme, S; Calzolari, E; DeWalle, HEK; KnillJones, R; Candela, S; Dale, [No Value; Dananche, B; deVigan, C; Fevotte, J; Kiel, G; Mandereau, L

    Glycol ethers are found in a wide range of domestic and industrial products, many of which are used in women's work environments. Motivated by concern about their potential reproductive toxicity, we have evaluated the risk of congenital malformations related to glycol ether exposure during preg

  19. 40 CFR 721.3486 - Polyglycerin mono(4-nonylphenyl) ether.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polyglycerin mono(4-nonylphenyl) ether... Substances § 721.3486 Polyglycerin mono(4-nonylphenyl) ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a polyglycerin mono(4...

  20. Synthesis and bioactivity of rotenone oxime O -ether derivatives ...

    African Journals Online (AJOL)

    A series of rotenone oxime O-ether derivatives were synthesized and characterized. All compounds were tested for their insecticidal, miticidal and fungicidal activities against the selected pests and compared with those of rotenone. The results of biological tests show that the rotenone oxime O-ether derivatives have ...

  1. Analysis of (all-E)-lutein and its (Z)-isomers during illumination in a model system.

    Science.gov (United States)

    Li, Dajing; Xiao, Yadong; Zhang, Zhongyuan; Liu, Chunquan

    2014-11-01

    Light induced-isomerization of (all-E)-lutein in organic solvent and starch model systems was investigated. Lutein and its (Z)-isomers were separated by HPLC using a C30 column and gradient mobile phase based on methanol-methyl-tert-butyl ether-water in 24min. (All-E)-lutein and twelve (Z)-isomers of lutein, in addition a small amount of (all-E)-zeaxanthin and (9Z, 9'Z)-zeaxanthin were identified by HPLC-DAD-APCI-MS. Five di-(Z)-luteins were identified for the first time, namely, (9Z, 9'Z)-, (9Z, 13Z)/(9 Z, 13'Z)-, (13Z, 15Z)- and (9Z, 15Z)-lutein and (9Z, 9'Z)-zeaxanthin. A mixture of (9Z)-lutein and of (9'Z)-lutein was the main product of the iodine-catalyzed photo-isomerization. (9Z, 13Z)/(9Z, 13'Z)-lutein were the major di-(Z)-isomers of lutein formed. The susceptibility of lutein to degradation was much less under dark storage than under lighted storage in starch model system. Isomerization and degradation of lutein and its (Z)-isomers proceeded simultaneously in all the model systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

    Science.gov (United States)

    Höhener, Patrick; Duwig, Céline; Pasteris, Gabriele; Kaufmann, Karin; Dakhel, Nathalie; Harms, Hauke

    2003-10-01

    Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.

  3. Characterization of the Cobalamin and Fep Operons in Methylobium petrolphilum PM1

    Energy Technology Data Exchange (ETDEWEB)

    Ewing, J

    2005-09-06

    The bacterium Methylobium petroleophilum PM1 is economically important due to its ability to degrade methyl tert-butyl ether (MTBE), a fuel additive. Because PM1 is a representative of all MTBE degraders, it is important to understand the transport pathways critical for the organism to survive in its particular environment. In this study, the cobalamin pathway and select iron transport genes will be characterized to help further understand all metabolic pathways in PM1. PM1 contains a total of four cobalamin operons. A single operon is located on the chromosome. Located on the megaplasmid are two tandem repeats of cob operons and a very close representative of the cob operon located on the chromosome. The fep operon, an iron transport mechanism, lies within the multiple copies of the cob operon. The cob operon and the fep operon appear to be unrelated except for a shared need for the T-on-B-dependent energy transduction complex to assist the operons in moving large molecules across the outer membrane of the cell. A genomic study of the cob and the fep operons with that of phylogenetically related organisms helped to confirm the identity of the cob and fep operons and to represent the pathways. More study of the pathways should be done to find the relationship that positions the two seemingly unrelated cob and fep genes together in what appears to be one operon.

  4. Fate of polybrominated diphenyl ethers in the environment of the Pearl River Estuary, South China

    International Nuclear Information System (INIS)

    Guan Yufeng; Sojinu, O.S. Samuel; Li Shaomeng; Zeng, Eddy Y.

    2009-01-01

    Ninety-six riverine runoff samples collected at eight major outlets in the Pearl River Delta (PRD), South China, during 2005-2006 were analyzed for 17 brominated diphenyl ether (BDE) congeners (defined as Σ 17 PBDE). Fourteen and 15 congeners were detected, respectively, in the dissolved and particulate phases. These data were further used to elucidate the partitioning behavior of BDE congeners in riverine runoff. Several related fate processes, i.e. air-water exchange, dry and wet deposition, degradation, and sedimentation, within the Pearl River Estuary (PRE), were examined to estimate the inputs of Σ 10 PBDE (sum of the target BDE congeners, BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, and -183) and BDE-209 from the PRD to the coastal ocean based on mass balance considerations. The results showed that annual outflows of Σ 10 PBDE and BDE-209 were estimated at 126 and 940 kg/year, respectively from the PRE to coastal ocean. Besides sedimentation and degradation, the majority of Σ 10 PBDE and BDE-209 discharged into the PRE via riverine runoff was transported to the coastal ocean. - Fate of polybrominated diphenyl ethers in the environment the Pearl River Estuary, South China.

  5. Remediation of polybrominated diphenyl ethers in soil using Ni/Fe bimetallic nanoparticles: Influencing factors, kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Yingying [School of Chemistry and Environment, South China Normal University, Guangzhou 51006 (China); Guangdong Technology Research Center for Ecological Management and Remediation of Urban Water System, Guangzhou 51006 (China); Fang, Zhanqiang, E-mail: zhqfang@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 51006 (China); Guangdong Technology Research Center for Ecological Management and Remediation of Urban Water System, Guangzhou 51006 (China); Cheng, Wen [School of Chemistry and Environment, South China Normal University, Guangzhou 51006 (China); Guangdong Technology Research Center for Ecological Management and Remediation of Urban Water System, Guangzhou 51006 (China); Tsang, Pokeung Eric [Department of Science and Environmental Studies, The Hong Kong Institute of Education, Hong Kong 00852 (China); Zhao, Dongye [Environmental Engineering Program, Department of Civil Engineering, Auburn University, Auburn, AL 36849 (United States)

    2014-07-01

    Polybrominated diphenyl ethers (PBDEs) are commonly used as additive flame retardants in all kinds of electronic products. PBDEs are now ubiquitous in the environment, with soil as a major sink, especially in e-waste recycling sites. This study investigated the degradation of decabromodiphenyl ether (BDE209) in a spiked soil using Ni/Fe bimetallic nanoparticles. The results indicated that Ni/Fe bimetallic nanoparticles are able to degrade BDE209 in soil at ambient temperature and the removal efficiency can reach 72% when an initial pH of 5.6 and at a Ni/Fe dosage of 0.03 g/g. A declining trend in degradation was noticed with decreasing Ni loading and increasing of initial BDE209 concentration. The degradation products of BDE209 were analyzed by GC-MS, which showed that the degradation of BDE209 was a process of stepwise debromination from nBr to (n − 1)Br. And a possible debromination pathway was proposed. At last, the degradation process was analyzed as two-step mechanism, mass transfer and reaction. This current study shows the potential ability of Ni/Fe nanoparticles to be used for removal of PBDEs in contaminated soil. - Highlights: • Ni/Fe bimetallic nanoparticles could effectively degradate BDE209 in soil. • The effects of various factors on remediation of BDE209 in soil using Ni/Fe were considered. • The degradation of BDE209 was a process of stepwise debromination from nBr to (n − 1)Br. • A possible debromination pathway and mechanism about removal of BDE209 in soil were proposed.

  6. [Recent development of research on the biotribology of carbon fiber reinforced poly ether ether ketone composites].

    Science.gov (United States)

    Chen, Yan; Pan, Yusong

    2014-12-01

    Carbon fiber reinforced poly ether ether ketone (CF/PEEK) composite possesses excellent biocompatible, biomechanical and bioribological properties. It is one of the most promising implant materials for artificial joint. Many factors influence the bioribological properties of CF/PEEK composites. In this paper, the authors reviewed on the biotribology research progress of CF/PEEK composites. The influences of various factors such as lubricant, reinforcement surface modification, functional particles, friction counterpart and friction motion modes on the bio-tribological properties of CF/PEEK composites are discussed. Based on the recent research, the authors suggest that the further research should be focused on the synergistic effect of multiple factors on the wear and lubrication mechanism of CF/PEEK.

  7. Enhanced osteogenic activity of poly ether ether ketone using calcium plasma immersion ion implantation.

    Science.gov (United States)

    Lu, Tao; Qian, Shi; Meng, Fanhao; Ning, Congqin; Liu, Xuanyong

    2016-06-01

    As a promising implantable material, poly ether ether ketone (PEEK) possesses similar elastic modulus to that of cortical bones yet suffers from bio-inertness and poor osteogenic properties, which limits its application as orthopedic implants. In this work, calcium is introduced onto PEEK surface using calcium plasma immersion ion implantation (Ca-PIII). The results obtained from scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) confirm the modified layer with varying contents of calcium are formed on PEEK surfaces. Water contact angle measurements reveal the increasing hydrophobicity of both Ca-PIII treated surfaces. In vitro cell adhesion, viability assay, alkaline phosphatase activity and collagen secretion analyses disclose improved the adhesion, proliferation, and osteo-differentiation of rat bone mesenchymal stem cells (bMSCs) on Ca-PIII treated surfaces. The obtained results indicate that PEEK surface with enhanced osteogenic activity can be produced by calcium incorporation. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Modification of Poly(ether ether ketone Polymer for Fuel Cell Application

    Directory of Open Access Journals (Sweden)

    Devesh Shukla

    2013-01-01

    Full Text Available Polyelectrolyte membrane (PEM is an important part of PEM fuel cell. Nafion is a commercially known membrane which gives the satisfactory result in PEM fuel cell operating at low temperature. Present research paper includes functionalization of Poly(ether ether ketone (PEEK polymer with phosphonic acid group. The functionalization was done with the help of nickel-based catalyst. Further, the polymer was characterized by the FTIR, EDAX, DSC, TGA, and 1H NMR, and it was found that PEEK polymer was functionalized with phosphonic acid group with good thermal stability in comparison to virgin PEEK. Finally, the thin films of functionalized polymer were prepared by solution casting method, and proton conductivity of film samples was measured by impedance spectra whose value was found satisfactory with good thermal stability in comparison to commercially available Nafion membrane.

  9. Dielectric properties of poly (1,4-phenylene ether-ether-sulfone)

    CERN Document Server

    Spasevska, H

    2002-01-01

    Dielectric properties of Poly (1,4-phenylene ether-ether-sulfone) are obtained from dielectric spectroscopy of the polymer pellet. The values of relative dielectric constant epsilon', dielectric losses epsilon sup , dielectric dissipation factor tan delta and complex impedance are obtained at temperature of 75 sup o C. The temperature dependence of these parameters is investigated for three frequencies (8x10 sup 4 Hz; 8x10 sup 5 Hz; 8x10 sup 6 Hz) of applied electric field. The specific conductivity sigma, which depends on temperature, is related to the ohmic resistance R, at temperature in the interval from 66 to 83 sup o C. Fitting the experimental data, the value of the activation energy U is obtained. (Original)

  10. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Tewatia, Arya; Hendrix, Justin [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Dong, Zhizhong [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Taghon, Meredith [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Tse, Stephen [Department of Mechanical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854 (United States); Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States); Lynch, Jennifer, E-mail: jklynch@rci.rutgers.edu [Department of Materials Science and Engineering, Rutgers University, 607 Taylor Road, Piscataway, NJ, 08854 (United States)

    2017-02-15

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  11. Characterization of melt-blended graphene – poly(ether ether ketone) nanocomposite

    International Nuclear Information System (INIS)

    Tewatia, Arya; Hendrix, Justin; Dong, Zhizhong; Taghon, Meredith; Tse, Stephen; Chiu, Gordon; Mayo, William E.; Kear, Bernard; Nosker, Thomas; Lynch, Jennifer

    2017-01-01

    Using a high shear melt-processing method, graphene-reinforced polymer matrix composites (G-PMCs) were produced with good distribution and particle–matrix interaction of bi/trilayer graphene at 2 wt. % and 5 wt. % in poly ether ether ketone (2Gn-PEEK and 5Gn-PEEK). The morphology, structure, thermal properties, and mechanical properties of PEEK, 2Gn-PEEK and 5 Gn-PEEK were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), flexural mechanical testing, and dynamic mechanical analysis (DMA). Addition of graphene to PEEK induces surface crystallization, increased percent crystallinity, offers a composite that is thermally stable until 550 °C and enhances thermomechanical properties. Results show that graphene was successfully melt-blended within PEEK using this method.

  12. Structuring of poly ether ether ketone by ArF excimer laser radiation in different atmospheres

    International Nuclear Information System (INIS)

    Feng, Y.; Gottmann, J.; Kreutz, E.W.

    2003-01-01

    Structuring of poly ether ether ketone (PEEK) by 193 nm ArF excimer laser radiation has been investigated. Experiments were carried out in different atmospheres (air, vacuum, Ar, O 2 ) in order to study its influence on the quality of the structures and the formation of the debris. Repetition rate makes little effect on the ablation rate and roughness of the structure in presence of any kind of atmosphere, indicating for the structuring of PEEK by ArF laser radiation a large window of processing. The roughness at the bottom of the structures and the morphology of the side walls are strongly affected by the properties of the atmosphere. The smallest roughness is achieved at 0.6 J/cm 2 for all kinds of processing gases. Debris around the structures can be diminished by structuring in vacuum. Plasma expansion speed has been measured by using high speed photography

  13. A sulfonated poly (aryl ether ether ketone ketone) isomer: synthesis and DMFC performance

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Liu, Baijun [JILIN UNIV.; Hu, Wei [JILIN UNIV.; Jiang, Zhenhua [JILIN UNIV.; Robertson, Gilles [CANADA NRC; Guiver, Michael [CANADA NRC

    2009-01-01

    A sulfonated poly(aryl ether ether ketone ketone) (PEEKK) having a well-defined rigid homopolymer-like chemical structure was synthesized from a readily-prepared PEEKK post-sulfonation with concentrated sulfuric acid at room temperature within several hours. The polymer electrolyte membrane (PEM) cast from the resulting polymer exhibited an excellent combination of thermal resistance, oxidative and dimensional stability, low methanol fuel permeability and high proton conductivity. Furthermore, membrane electrode assemblies (MEAs) were successfully fabricated and good direct methanol fuel cell (DMFC) performance was observed. At 2 M MeOH feed, the current density at 0.5 V reached 165 mA/cm, which outperformed our reported analogues and eveluated Nafion membranes.

  14. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    Energy Technology Data Exchange (ETDEWEB)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang, E-mail: wolfgang.bacsa@cemes.fr [CEMES-CNRS and University of Toulouse, 29 Jeanne Marvig, 31055 Toulouse (France); Boyer, François; Olivier, Philippe [Université de Toulouse, Institut Clément Ader, I.U.T. Université Paul Sabatier - 133C Avenue de Rangueil - B.P. 67701, 31077 Toulouse CEDEX 4 (France); Sapelkin, Andrei [School of Physics and Astronomy, Queen Mary, University of London, Mile End Road, E1 4NS London (United Kingdom); King, Stephen; Heenan, Richard [ISIS Facility, Rutherford Appleton Laboratory, Chilton, OX11 0QX Didcot (United Kingdom); Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri [AIRBUS FRANCE (B.E. M and P Toulouse), 316 Route de Bayonne, 31060 Toulouse (France)

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  15. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    Energy Technology Data Exchange (ETDEWEB)

    Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

    2011-01-01

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

  16. Molecular structure and transport dynamics in Nafion and sulfonated poly(ether ether ketone ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, P.Y.; Chiu, C.P.; Hong, C.W. [Department of Power Mechanical Engineering, National Tsing Hua University, 101, Sec. 2, Kwang Fu Road, Hsinchu 30013 (China)

    2009-12-01

    An atomistic simulation technique is performed to investigate the molecular structure and transport dynamics inside a hydrated Nafion membrane and a hydrated sulfonated poly(ether ether ketone ketone) (SPEEKK) membrane. The simulation system consists of the representative fragments of the polymer electrolytes, hydronium ions and solvent molecules, such as water plus methanol molecules. Simulation results show that the hydrated SPEEKK has less phase separation among hydrophobic and hydrophilic regions in comparison with the Nafion. Those water channels formed in the SPEEKK are much narrower compared to those in the Nafion. These characteristics lead to a lower mobility of hydronium ions and water molecules and hence relatively lower diffusion coefficient of methanol in the SPEEKK. It results in the reduction of the methanol permeation problem in direct methanol fuel cells. (author)

  17. Preparation and tribological behaviors of poly (ether ether ketone) nanocomposite films containing graphene oxide nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Song Haojie, E-mail: shj6922@163.com; Li Na; Yang Jin; Min Chunying [Jiangsu University, School of Materials Science and Engineering (China); Zhang Zhaozhu [Chinese Academy of Sciences, State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics (China)

    2013-02-15

    The composite films of poly (ether ether ketone) (PEEK) filled with different proportions of graphene oxide (GO) nanosheets were prepared by the cast method. The tribological behaviors of the composite films under boundary lubrication (water and liquid paraffin oil lubrication) were investigated and compared with that under dry sliding on an UMT-2 friction and wear machine, by running a steel sphere against the composite films. The results were as follows: GO nanosheets as the filler greatly improve the wear resistance of PEEK under boundary lubrication, though the composites show a different dependence of wear resistance on the filler content. Scanning electron microscopy and optical microscopy performed to analyze the wear scar surfaces after friction confirmed that the outstanding lubrication performance of GO could be attributed to their small size and extremely thin laminated structure, which allow the GO to easily enter the contact area, thereby preventing the rough surfaces from coming into direct contact.

  18. Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

    2014-02-15

    Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

  19. Polybrominated diphenyl ethers and novel flame retardants

    DEFF Research Database (Denmark)

    Frederiksen, Marie; Vorkamp, Katrin; Nielsen, Jesper Bo

    Besides diet, house dust has been recognized as an important exposure media for polybrominated diphenyl ethers (PBDEs) [1]. Our previous work showed significant associations between levels in dust and in human plasma, for the congeners BDE-28, BDE-47 and BDE-100 as well as for ΣPBDEtri hexa [2......, the objectives were to study whether i) the associations observed for plasma also existed for human milk, ii) the PBDE profiles in dust and milk could provide insights into the bioavailability and bioaccumulation of individual congeners, iii) NFRs were measurable in human milk, and iv) infants were exposed...... of BDE-99 in milk compared with plasma (100% vs. 37%). Hexabromocyclododecane and the NFRs bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), decabromodiphenyl ethane (DBDPE), 2,3-dibromopropyl-2...

  20. Crown ether derivatives of EDTA: Pt. 6

    International Nuclear Information System (INIS)

    Liu Zhongqun; Qin Shengying; Chen Shaojin; Tan Lin

    1988-01-01

    EDTA-diaminodibenzo-18-crown-6 (cis- and trans-) condensation polymer is a new compound of crown ether derivatives of EDTA. In this paper the adsorption behaviors of U(IV) and U(VI) on this polymer from chloride solutions and effects of hydrochloric acid concentrations, salting-out agents and organic solvents on distribution coefficient (K d ) of uranium are investigated. Adsorption mechanism of uranyl ion (UO 2 2+ ) on this polymer was studied with IR spectra and by means of the adsorption behaviors of compounds of similar structure. Experimental results show that both polyether section and carboxyl groups in EDTA-diaminodibenzo-18-crown-6 take part in complexation with uranyl ion and synergistic effect appeared

  1. Cationic Poly(benzyl ether)s as Self-Immolative Antimicrobial Polymers.

    Science.gov (United States)

    Ergene, Cansu; Palermo, Edmund F

    2017-10-09

    Self-immolative polymers (SIMPs) are macromolecules that spontaneously undergo depolymerization into small molecules when triggered by specific external stimuli. We report here the first examples of antimicrobial SIMPs with potent, rapid, and broad-spectrum bactericidal activity. Their antibacterial and hemolytic activities were examined as a function of cationic functionality. Polymers bearing primary ammonium cationic groups showed more potent bactericidal activity against Escherichia coli, relative to tertiary and quaternary ammonium counterparts, whereas the quaternary ammonium polymers showed the lowest hemolytic toxicity. These antibacterial polycations undergo end-to-end depolymerization when triggered by an externally applied stimulus. Specifically, poly(benzyl ether)s end-capped with a silyl ether group and bearing pendant allyl side chains were converted to polycations by photoinitiated thiol-ene radical addition using cysteamine HCl. The intact polycations are stable in solution, but they spontaneously unzip into their component monomers upon exposure to fluoride ions, with excellent sensitivity and selectivity. Upon triggered depolymerization, the antibacterial potency was largely retained but the hemolytic toxicity was substantially reduced. Thus, we reveal the first example of a self-immolative antibacterial polymer platform that will enable antibacterial materials to spontaneously unzip into biologically active small molecules upon the introduction of a specifically designed stimulus.

  2. Thermolysis of phenethyl phenyl ether: A model of ether linkages in low rank coal

    Energy Technology Data Exchange (ETDEWEB)

    Britt, P.F.; Buchanan, A.C. III; Malcolm, E.A.

    1994-09-01

    Currently, an area of interest and frustration for coal chemists has been the direct liquefaction of low rank coal. Although low rank coals are more reactive than bituminous coals, they are more difficult to liquefy and offer lower liquefaction yields under conditions optimized for bituminous coals. Solomon, Serio, and co-workers have shown that: in the pyrolysis and liquefaction of low rank coals, a low temperature cross-linking reaction associated with oxygen functional groups occurs before tar evolution. A variety of pretreatments (demineralization, alkylation, and ion-exchange) have been shown to reduce these retrogressive reactions and increase tar yields, but the actual chemical reactions responsible for these processes have not been defined. In order to gain insight into the thermochemical reactions leading to cross-linking in low rank coal, we have undertaken a study of the pyrolysis of oxygen containing coal model compounds. Solid state NMR studies suggest that the alkyl aryl ether linkage may be present in modest amounts in low rank coal. Therefore, in this paper, we will investigate the thermolysis of phenethyl phenyl ether (PPE) as a model of 0-aryl ether linkages found in low rank coal, lignites, and lignin, an evolutionary precursor of coal. Our results have uncovered a new reaction channel that can account for 25% of the products formed. The impact of reaction conditions, including restricted mass transport, on this new reaction pathway and the role of oxygen functional groups in cross-linking reactions will be investigated.

  3. Effect of ethylene glycol monomethyl ether and diethylene glycol monomethyl ether on hepatic metabolizing enzymes.

    Science.gov (United States)

    Kawamoto, T; Matsuno, K; Kayama, F; Hirai, M; Arashidani, K; Yoshikawa, M; Kodama, Y

    1990-06-01

    Glycol ethers have been extensively used in industry over the past 40-50 years. Numerous studies on the toxicity of glycol ethers have been performed, however, the effects of glycol ethers on the hepatic drug metabolizing enzymes are still unknown. We studied the changes of the putative metabolic enzymes, that is, the hepatic microsomal mixed function oxidase system and cytosolic alcohol dehydrogenase, by the oral administration of diEGME and EGME. Adult male Wistar rats were used. DiEGME was administered orally; 500, 1000, 2000 mg/kg for 1, 2, 5 or 20 days and EGME was 100, 300 mg/kg for 1, 2, 5 or 20 days. Decreases in liver weights were produced by highest doses of diEGME (2000 mg/kg body wt/day for 20 days) and EGME (300 mg/kg body wt/day for 20 days). DiEGME increased hepatic microsomal protein contents and induced cytochrome P-450, but not cytochrome b5 or NADPH-cytochrome c reductase. The activity of cytosolic ADH was not affected by diEGME administration. On the other hand, EGME did not change cytochrome P-450, cytochrome b5 or NADPH-cytochrome c reductase. The activity of cytosolic ADH was increased by repeated EGME treatment. Therefore it is suspected that the enzyme which takes part in the metabolism of diEGME is different from that of EGME, although diEGME is a structural homologue of EGME.

  4. Formulating liquid ethers for microtubular SOFCs

    Science.gov (United States)

    Kendall, Kevin; Slinn, Matthew; Preece, John

    One of the key problems of applying solid oxide fuel cells (SOFCs) in transportation is that conventional fuels like kerosene and diesel do not operate directly in SOFCs without prereforming to hydrogen and carbon monoxide which can be handled by the nickel cermet anode. SOFCs can internally reform certain hydrocarbon molecules such as methanol and methane. However, other liquid fuels usable in petrol or diesel internal combustion engines (ICEs) have not easily been reformable directly on the anode. This paper describes a search for liquid fuels which can be mixed with petrol or diesel and also injected directly into an SOFC without destroying the nickel anode. When fuel molecules such as octane are injected onto the conventional nickel/yttria stabilised zirconia (Ni/YSZ) SOFC fuel electrode, the anode rapidly becomes blocked by carbon deposition and the cell power drops to near zero in minutes. This degeneration of the anode can be inhibited by injection of air or water into the anode or by some upstream reforming just before entry to the SOFC. Some smaller molecules such as methane, methanol and methanoic acid produce a slight tendency to carbon deposition but not sufficient to prevent long term operation. In this project we have investigated a large number of molecules and now found that some liquid ethers do not significantly damage the anode when directly injected. These molecules and formulations with other components have been evaluated in this study. The theory put forward in this paper is that carbon-carbon bonds in the fuel are the main reason for anode damage. By testing a number of fuels without such bonds, particularly liquid ethers such as methyl formate and dimethoxy methane, it has been shown that SOFCs can run without substantial carbon formation. The proposal is that conventional fuels can be doped with these molecules to allow hybrid operation of an ICE/SOFC device.

  5. Evaluation of the impact of fuel hydrocarbons and oxygenates on groundwater resources.

    Science.gov (United States)

    Shih, Tom; Rong, Yue; Harmon, Thomas; Suffet, Mel

    2004-01-01

    The environmental behavior of fuel oxygenates (other than methyl tert-butyl ether [MTBE]) is poorly understood because few data have been systematically collected and analyzed. This study evaluated the potential for groundwater resource contamination by fuel hydrocarbons (FHCs) and oxygenates (e.g., tert-butyl alcohol [TBA], tertamyl methyl ether [TAME], diisopropyl ether [DIPE], ethyl tert-butyl ether [ETBE], and MTBE) by examining their occurrence, distribution, and spatial extent in groundwater beneath leaking underground fuel tank (LUFT) facilities, focusing on data collected from over 7200 monitoring wells in 868 LUFT sites from the greater Los Angeles, CA, region. Excluding the composite measure total petroleum hydrocarbons as gasoline (TPHG), TBA has the greatestsite maximum (geometric mean) groundwater concentration among the study analytes; therefore, its presence needs to be confirmed at LUFT sites so that specific cleanup strategies can be developed. The alternative ether oxygenates (DIPE, TAME, and ETBE) are less likely to be detected in groundwater beneath LUFT facilities in the area of California studied and when detected are present at lower dissolved concentrations than MTBE, benzene, or TBA. Groundwater plume length was used as an initial indicator of the threat of contamination to drinking water resources. Approximately 500 LUFT sites were randomly selected and analyzed. The results demonstrate MTBE to pose the greatest problem, followed by TBA and benzene. The alternative ether oxygenates were relatively localized and indicated lesser potential for groundwater resource contamination. However, all indications suggest the alternative ether oxygenates would pose groundwater contamination threats similar to MTBE if their scale of usage is expanded. Plume length data suggest that in the absence of a completely new design and construction of the underground storage tank (UST) system, an effective management strategy may involve placing greater emphasis

  6. Identification of new chemical structures in poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) irradiated in vacuum at different temperatures

    International Nuclear Information System (INIS)

    Lappan, U.; Geissler, U.; Scheler, U.; Lunkwitz, K.

    2003-01-01

    Electron beam irradiation of perfluorinated copolymer poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) was carried out in vacuum at different temperatures between room temperature and temperature above the melting point of PFA. Changes of chemical structure were studied by 19 F solid-state NMR and IR spectroscopy. Chain scissions and branching reactions occur simultaneously, which are indicated by formation of CF 3 , COF and COOH end groups, CF branching points and CF 3 side groups. Branching density based on concentration of CF groups increases with increasing temperature. Formation of cross-links is concluded for PFA irradiated in molten state. Perfluoropropyl vinyl ether (PPVE) units are found to be more sensitive to radiation than tetrafluoroethylene units. COF and COOH groups are assumed to result from PPVE degradation

  7. Identification of new chemical structures in poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) irradiated in vacuum at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Lappan, U. E-mail: lappan@ipfdd.de; Geissler, U.; Scheler, U.; Lunkwitz, K

    2003-06-01

    Electron beam irradiation of perfluorinated copolymer poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) was carried out in vacuum at different temperatures between room temperature and temperature above the melting point of PFA. Changes of chemical structure were studied by {sup 19}F solid-state NMR and IR spectroscopy. Chain scissions and branching reactions occur simultaneously, which are indicated by formation of CF{sub 3}, COF and COOH end groups, CF branching points and CF{sub 3} side groups. Branching density based on concentration of CF groups increases with increasing temperature. Formation of cross-links is concluded for PFA irradiated in molten state. Perfluoropropyl vinyl ether (PPVE) units are found to be more sensitive to radiation than tetrafluoroethylene units. COF and COOH groups are assumed to result from PPVE degradation.

  8. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  9. Degraded Crater

    Science.gov (United States)

    2004-01-01

    21 October 2004 Near the center of this Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image lies the degraded remnants of an old meteor impact crater. The terrain in which it occurs is a heavily eroded, north middle-latitude surface. The image is located in the fretted terrains north of Arabia Terra near 41.3oN, 305.8oW. The image covers an area about 3 km (1.9 mi) wide and sunlight illuminates the scene from the lower left.

  10. Experimental studies on toxicity of ethylene glycol alkyl ethers in Japan.

    Science.gov (United States)

    Nagano, K; Nakayama, E; Oobayashi, H; Nishizawa, T; Okuda, H; Yamazaki, K

    1984-08-01

    Past studies on the toxicological effects of ethylene glycol alkyl ethers as well as the recent data on these chemicals in Japan are reviewed. Only a few researchers have participated in the study of ethylene glycol alkyl ethers in Japan. The effects of ethylene glycol alkyl ethers on testis and embryotoxic effects of ethylene glycol monomethyl ether (EGM) have been studied, as has the teratogenicity of ethylene glycol dimethyl ether (EGdM). Studies on ethylene glycol alkyl ethers and related compounds administered to mice by oral gavage revealed the occurrence of testicular atrophy and decreased white blood cell count by EGM, EGdM, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate, and the toxicity was related to their chemical structure. On the other hand, ethylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monoacetate or ethylene glycol diacetate showed no such an effect. Studies on EGM using hamsters or guinea pigs revealed the occurrence of testicular atrophy similar to that observed in mice. In regard to the methyl ethers of other glycols, there is no convincing evidence that propylene glycol monomethyl ether, diethylene glycol monomethyl ether or diethylene glycol dimethyl ether causes testicular atrophy in mice. Teratological studies of EGM and EGdM revealed embryotoxic effects in mice.

  11. Evaluation of crystallization kinetics of poly (ether-ketone-ketone and poly (ether-ether-ketone by DSC

    Directory of Open Access Journals (Sweden)

    Gibran da Cunha Vasconcelos

    2010-08-01

    Full Text Available The poly (aryl ether ketones are used as matrices in advanced composites with high performance due to its high thermal stability, excellent environmental performance and superior mechanical properties. Most of the physical, mechanical and thermodynamic properties of semi-crystalline polymers depend on the degree of crystallinity and morphology of the crystalline regions. Thus, a study on the crystallization process promotes a good prediction of how the manufacturing parameters affect the developed structure, and the properties of the final product. The objective of this work was to evaluate the thermoplastics polymers PEKK e PEEK by DSC, aiming to obtain the relationship between kinetics, content, nucleation and geometry of the crystalline phases, according to the parameters of the Avrami and Kissinger models. The analysis of the Avrami exponents obtained for the studied polymers indicates that both showed the formation of crystalline phases with heterogeneous nucleation and growth geometry of the type sticks or discs, depending on the cooling conditions. It was also found that the PEEK has a higher crystallinity than PEKK.

  12. Aquatic Life Criteria - Methyl Tertiary-Butyl Ether (MTBE)

    Science.gov (United States)

    Information pertaining to the 1999 Acute and Chronic Ambient Aquatic Life Water Quality Criteria for Methyl Tertiary-Butyl Ether (MTBE) for freshwater and salt water. Information includes the safe levels of MTBE that should protect the majority of species.

  13. The zeolite mediated isomerization of allyl phenyl ether

    Science.gov (United States)

    Pebriana, R.; Mujahidin, D.; Syah, Y. M.

    2017-04-01

    Allyl phenyl ether is an important starting material in organic synthesis that has several applications in agrochemical industry. The green transformation of allyl phenyl ether assisted by heterogeneous catalyst is an attractive topic for an industrial process. In this report, we investigated the isomerization of allyl phenyl ether by heating it in zeolite H-ZSM-5 and Na-ZSM-5. The conversion of allyl phenyl ether (neat) in H-ZSM-5 was 67% which produced 40% of 2-allylphenol, 17% of 2-methyldihydrobenzofuran, and other product (4:1.7:1), while in Na-ZSM-5 produced exclusively 2-allylphenol with 52% conversion. These results showed that zeolite properties can be tuned to give a selective transformation by substitution of metal ion into the zeolite interior.

  14. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    oxymethylene ethers) from alcohols and paraformaldehyde in the presence of commercially available nickel(II) salt is described. The reaction proceeds readily under neutral, solvent-free conditions using paraformaldehyde as a C1 source.

  15. Nickel-catalyzed direct synthesis of dialkoxymethane ethers

    Indian Academy of Sciences (India)

    MURUGAN SUBARAMANIAN

    free condition. 1. Introduction. Ethers constitute the most diverse family of organic compounds and are ubiquitous in many natural prod- ucts and pharmaceuticals.1 The extent to which they can be utilized as an organic intermediate in contempo-.

  16. SYNTHESIS AND BIOACTIVITY OF ROTENONE OXIME O-ETHER ...

    African Journals Online (AJOL)

    Admin

    mail: g.cao@mail.scut.edu.cn. SYNTHESIS AND BIOACTIVITY OF ROTENONE OXIME O-ETHER DERIVATIVES. Gao Cao*, Zhen Zhou and Ying Wang. School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University,.

  17. Spatial trends of polybrominated diphenyl ether (PBDE) congeners

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Spatial trends of polybrominated diphenyl ether (PBDE) congeners were analyzed in young of the year bluefish collected along the U.S. Atlantic coastline from...

  18. Fluorinated Alkyl Ether Epoxy Resin Compositions and Applications Thereof

    Science.gov (United States)

    Wohl, Christopher J. (Inventor); Connell, John W. (Inventor); Smith, Joseph G. (Inventor); Siochi, Emilie J. (Inventor); Gardner, John M. (Inventor); Palmieri, Frank M. (Inventor)

    2017-01-01

    Epoxy resin compositions prepared using amino terminated fluoro alkyl ethers. The epoxy resin compositions exhibit low surface adhesion properties making them useful as coatings, paints, moldings, adhesives, and fiber reinforced composites.

  19. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

    2018-03-06

    Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

  20. Synthesis and Characterisation of Macrocyclic Diamino Chiral Crown Ethers

    Directory of Open Access Journals (Sweden)

    Janet L. Scott

    2004-05-01

    Full Text Available A benign and efficient synthesis of chiral macrocyclic ‘aza-crown’ ethers of varying ring size is reported. The synthesis involves a Schiff base condensation of ether linked dialdehydes of varying chain length and (1R,2R-(–-1,2-diaminocyclohexane under mild conditions to yield the macrocycles, which are subsequently reduced to yield the diamino analogues.

  1. Marine Sponge Dysidea herbacea revisited: Another Brominated Diphenyl Ether

    Directory of Open Access Journals (Sweden)

    Bruce F. Bowden

    2005-03-01

    Full Text Available Abstract: A pentabrominated phenolic diphenyl ether (1 that has not previously been reported from marine sources has been isolated from Dysidea herbacea collected at Pelorus Island, Great Barrier Reef, Australia. The structure was determined by comparison of NMR data with those of known structurally-related metabolites. NMR spectral assignments for (1 are discussed in context with those of three previously reported isomeric pentabrominated phenolic diphenyl ethers.

  2. Novel electrochemical route to cleaner fuel dimethyl ether.

    Science.gov (United States)

    Cassone, Giuseppe; Pietrucci, Fabio; Saija, Franz; Guyot, François; Sponer, Jiri; Sponer, Judit E; Saitta, A Marco

    2017-07-31

    Methanol, the simplest alcohol, and dimethyl ether, the simplest ether, are central compounds in the search for alternative "green" combustion fuels. In fact, they are generally considered as the cornerstones of the envisaged "Methanol Economy" scenario, as they are able to efficiently produce energy in an environmentally friendly manner. However, despite a massive amount of research in this field, the synthesis of dimethyl ether from liquid methanol has never so far been reported. Here we present a computational study, based on ab initio Molecular Dynamics, which suggests a novel synthesis route to methanol dehydration - leading thus to the dimethyl ether synthesis - through the application of strong electric fields. Besides proving the impressive catalytic effects afforded by the field, our calculations indicate that the obtained dimethyl ether is stable and that it can be progressively accumulated thanks to the peculiar chemical pathways characterising the methanol reaction network under electric field. These results suggest that the experimental synthesis of dimethyl ether from liquid methanol could be achieved, possibly in the proximity of field emitter tips.

  3. Effects of the ether phospholipid AMG-PC on mast cells are similar to that of the ether lipid AMG but different from that of the analogue hexadecylphosphocholine

    DEFF Research Database (Denmark)

    Grosman, Nina

    1991-01-01

    Farmakologi, ether phospholipid, hexacylphosphocholine, miltefosine, protein kinase C, AMG-PC(alkyl-methyl-glycero-phosphocholine), Histamine release, mast cell......Farmakologi, ether phospholipid, hexacylphosphocholine, miltefosine, protein kinase C, AMG-PC(alkyl-methyl-glycero-phosphocholine), Histamine release, mast cell...

  4. Review on Modification of Sulfonated Poly (-ether-ether-ketone Membranes Used as Proton Exchange Membranes

    Directory of Open Access Journals (Sweden)

    Xiaomin GAO

    2015-11-01

    Full Text Available The proton exchange membrane fuel cell (PEMFC is a type of modern power, but the traditional proton exchange membranes (PEM of PEMFC are limited by high methanol permeability and water uptake. Poly-ether-ether-ketone (PEEK is a widely used thermoplastic with good cost-effective property. Sulfonated poly (-ether-ether-ketone (SPEEK has high electric conductivity and low methanol permeability, as well as comprehensive property, which is expected to be used as PEMs. However, the proton exchange ability, methanol resistance, mechanical property and thermal stability of SPEEK are closely related to the degree of sulfonation (DS of SPEEK membranes. Additionally, the proton conductivity, methanol permeability, and stability of SPEEK membranes applied in various conditions need to be further improved. In this paper, the research into modification of SPEEK membranes made by SPEEK and other polymers, inorganic materials are introduced. The properties and modification situation of the SPEEK and the composite membranes, as well as the advantages and disadvantages of membranes prepared by different materials are summarized. From the results we know that, the methanol permeability of SPEEK/PES-C membranes is within the order of magnitude, 10-7cm2/s. The proton conductivity of the SPPESK/SPEEK blend membrane reaches 0.212 S cm-1 at 80 °C. The cross-linked SPEEK membranes have raised thermal and dimensional stability. The non-solvent caused aggregation of the SPEEK ionomers. The proton conductivity of SPEEK/50%BMIMPF6/4.6PA membrane maintains stable as 2.0 x 10-2S cm-1 after 600 h at 160 °C. Incorporation of aligned CNT into SPEEK increases the proton conductivity and reduces the methanol permeability of the composite membranes. The PANI improves the hydrothermal stability. More proton transfer sites lead to a more compact structure in the composite membranes. According to the results, the proton exchange capacity, water uptake, and conductivity of

  5. Aromatic polymers obtained by precipitation polycondensation, 2a) Synthesis of poly(ether ketone ether ketone ketone) (PEKEKK)

    OpenAIRE

    Zolotukhin, Mikhail K.; Rueda, Daniel R.; Baltá Calleja, Francisco José; Bruix, M.; Cagiao, M. E.; Bulai, Anna; Gileva, Natalia G.

    1997-01-01

    A high molecular weight, linear aromatic poly(ether ketone ether ketone ketone) (PEKEKK) has been synthesized by electrophilic Friedel-Crafts acylation condensation of 1,4-diphenoxybenzophenone with terephthaloyl chloride. The syntheses were performed as precipitation polycondensations, and the polyketones were obtained in particle form. The viscosity (molecular weight), shape and size of these particles were found to be strongly dependent on the reaction conditions. For low monomer concen...

  6. Alkali-ion-crown ether in art and conservation: the applied bioinorganic chemistry approach.

    Science.gov (United States)

    Hilfrich, Uwe; Taylor, Harold; Weser, Ulrich

    2004-01-01

    Dried varnish is rich in many ester moieties, which may be broken down into small, soluble compounds by esterase activity or alkaline hydrolysis. Two methods for varnish removal have been developed, including the treatment of either lipase or RbOH / PEG-400 crown ether which allow aged oil varnishes or paint coverings to be removed or thinned. These techniques are designed to proceed in a controlled manner without damaging lower paint or base layers. Unfortunately, lipase did not react with the aged ester groups of dried linseed oil varnish. Surprisingly, the varnish came off in the presence of Tris buffer alone which, in addition, formed reactive metal complexes. A better choice was the use of high M(r) alkali ion polyethylene glycol-400 (PEG-400) crown ether type chelates. PEG-400 complexes alkali ions including rubidium and other alkaliions impeding the diffusion of their basic counter ions into lower varnish or paint layers. Possible migration of alkali metal ions into the paint layer during alkaline varnish removal was determined by labelling the cleansing solutions with (86)Rb. Fortunately, varnish is degraded on the surface only. Lower paint or varnish layers are not attacked even if chemically similar to the varnish or over painting to be removed as virtually no (86)Rb was detected on the paint surface.

  7. Experimental and Predicted Viscosities of Binary Mixtures Containing Chlorinated and Oxygenated Compounds

    Science.gov (United States)

    Montaño, D.; Artigas, H.; Royo, F. M.; Lafuente, Carlos

    2013-01-01

    This study presents the viscosities, both kinematic and dynamic, of binary mixtures of 1-chlorobutane, 2-chlorobutane, or 1-chloro-2-methylpropane with butyl ethyl ether or methyl tert-butyl ether from T = 283.15 K to T = 313.15 K at atmospheric pressure as a function of composition. Kinematics viscosities were measured using an Ubbelohde viscometer. The dynamic viscosities were obtained from experimental kinematic viscosities and previously reported density data. The viscosity results have been employed to check the reliability of the Wu-UNIFAC method.

  8. 40 CFR 712.30 - Chemical lists and reporting periods.

    Science.gov (United States)

    2010-07-01

    ... n-Amyl acetate 1/26/94 3/28/94 768-52-5 N-Isopropylaniline 3/11/94 5/10/94 1300-73-8 Xylidine 3/11...-3 Ethyl tert-butyl ether 12/28/94 2/27/95 994-05-8 Tert-amyl methyl ether 12/28/94 2/27/95 1163-19-5...)phenoxy]-, acetate 04/12/93 06/10/93 50789-44-1 Benzenemethanol, 3-phenoxy-, acetate 04/12/93 06/10/93...

  9. Field Method for Detection of Metal Deactivator Additive in Jet Fuel

    Science.gov (United States)

    2009-04-01

    silica gel. The open column tubes were 1.5 ml polypropylene solid phase extraction reservoirs with frits to contain the silica at top and bottom of the...tube, Figure 7. The polypropylene tubes were not completely transparent. The alternating bands were used to assist with observing the colour formation...is evident when a common phenolic antioxidant such as 2,6 -di-tert-butyl -4- methyl phenol oxidises. Degradation products of phenolic antioxidants

  10. Enhanced osteoblast responses to poly ether ether ketone surface modified by water plasma immersion ion implantation.

    Science.gov (United States)

    Wang, Heying; Lu, Tao; Meng, Fanhao; Zhu, Hongqin; Liu, Xuanyong

    2014-05-01

    Poly ether ether ketone (PEEK) offers a set of characteristics superior for human implants; however, its application is limited by the bio-inert surface property. In this work, PEEK surface was modified using single step plasma immersion ion implantation (PIII) treatment with a gas mixture of water vapor as a plasma resource and argon as an ionization assistant. Field emission scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy were used to investigate the microstructure and composition of the modified PEEK surface. The water contact angle and zeta-potential of the surfaces were also measured. Osteoblast precursor cells MC3T3-E1 and rat bone mesenchymal stem cells were cultured on the PEEK samples to evaluate their cytocompatibility. The obtained results show that the hydroxyl groups as well as a "ravined structure" are constructed on water PIII modified PEEK. Compared with pristine PEEK, the water PIII treated PEEK is more favorable for osteoblast adhesion, spreading and proliferation, besides, early osteogenic differentiation indicated by the alkaline phosphatase activity is also up-regulated. Our study illustrates enhanced osteoblast responses to the PEEK surface modified by water PIII, which gives positive information in terms of future biomedical applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Development and characterization of poli composites (ether ether ketone)(PEEK)(Hydroxyapatite(HA)

    International Nuclear Information System (INIS)

    Ferreira, V.P.; Santos, F.S.F.; Sa, M.D. de; Fook, M.V.L.

    2016-01-01

    The objective of this work was to develop PEEK / HA composites, combining the biological activity of the ceramic phase with the properties of the polymer phase, the materials used in this research were Poly (ether-ether-ketone) (PEEK) and Hydroxyapatite (HA) (50, 60, 70 and 80% m / v HA), this material was subjected to a load of two tons followed by a thermal treatment at 390 ° for a period of 30 minutes. Then they were characterized by FTIR, DRX and MO. In the physical-chemical characterization of FTIR and XRD, it was not possible to identify significant alterations. In the FTIR spectra of the composites, there is no formation of new identifiable chemical bonds. In the composites XRD diffractograms a profile similar to the ceramic phase was observed, with peaks increasing in intensity and narrowing proportional to the increase of the hydroxyapatite concentration in the composites. In optical microscopy it is possible to observe surfaces with heterogeneous morphology, with signs of roughness and in the cross section we observe a heterogeneous aspect, rich in regions with large agglomerates and lighter particles. Considering the processing aspects, the technique proved to be effective for the development of PEEK /HA composites. (author)

  12. Rheological, mechanical and tribological properties of carbon-nanofibre reinforced poly (ether ether ketone composites

    Directory of Open Access Journals (Sweden)

    Volker Altstaedt

    2003-12-01

    Full Text Available Poly(ether ether ketone nanocomposites containing vapour-grown carbon nanofibres (CNF were produced using standard polymer processing techniques. At high shear rates no significant increase in resin viscosity was observed. Nevertheless, the addition of the CNFs results in a higher melt strength at 360°C. Electron microscopy confirmed the homogeneous dispersion and alignment of nanofibres in the polymer matrix. Evaluation of the mechanical composite properties revealed a linear increase in tensile stiffness and strength with nanofibre loading fractions up to 15 wt% whilst matrix ductility was maintained up to 10 wt%. An interpretation of the composite performance by short-fibre theory resulted in rather low intrinsic stiffness properties of the vapour-grown CNF. Differential scanning calorimetry was used to investigate crystallization kinetics and degree of crystallinity. The CNFs were found not to act as nucleating sites. Furthermore, unidirectional sliding tests against two different counterpart materials (100Cr6 martensitic bearing steel, X5CrNi18-10 austenitic stainless steel were performed. The carbon nanofibres were found to reduce the wear rate of PEEK significantly.

  13. Evaluation of workers exposed to ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate.

    Science.gov (United States)

    Park, Jiyoung; Yoon, Chungsik; Byun, Hyaejeong; Kim, Yangho; Park, Donguk; Ha, Kwonchul; Lee, Sang man; Park, Sungki; Chung, Eunkyo

    2012-01-01

    Ethylene glycol monomethyl ether (EGME) and ethylene glycol monomethyl ether acetate (EGMEA) are widely used in industries as solvents for coatings, paint and ink, but exposure data are limited because they are minor components out of mixed solvents, as well as because of inconsistency in desorption solvent use. The objective of this study was to investigate the worker exposure profile of EGME and EGMEA. Our study investigated 27 workplaces from June to September 2008 and detected EGME and EGMEA in 20 and 13, respectively. Both personal and area sampling were conducted using a charcoal tube to collect EGME and EGMEA. Gas chromatography with a flame ionization detector was used to analyze these compounds after desorption using a mixture of methylene chloride and methanol. The arithmetic mean concentrations of EGME and EGMEA during periods of full work shifts were 2.59 ppm and 0.33 ppm, respectively. The exposure levels were lower than the Korean Ministry of Labor (MOL) OEL (5 ppm) but higher than the ACGIH TLV (0.1 ppm). In general, the working environments were poor and required much improvement, including the use of personal protective equipment. Only 50% of the workplaces had local exhaust ventilation systems in operation. The average capture velocity of the operating local exhaust ventilation systems was 0.27 m/s, which did not meet the legal requirement of 0.5 m/s. Educating workers to clearly understand the handling and use of hazardous chemicals and improving working conditions are strongly suggested.

  14. Copoly(arlene ether)s containing pendant sulfonic acid groups as proton exchange membrane

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Kim, Dae Sik [CANADA NRC; Robertson, Gilles [CANADA NRC; Guiver, Michael [CANADA NRC

    2008-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The P AE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sP AE and sP AEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC{sub v}(wet) (volume-based, wet state)) of 1.77 and 2.55 meq./cm{sup 3}, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5-51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the area of outstanding properties in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based). Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  15. The Effects of Sulfonated Poly(ether ether ketone) Ion Exchange Preparation Conditions on Membrane Properties

    Science.gov (United States)

    Yee, Rebecca S. L.; Zhang, Kaisong; Ladewig, Bradley P.

    2013-01-01

    A low cost cation exchange membrane to be used in a specific bioelectrochemical system has been developed using poly(ether ether ketone) (PEEK). This material is presented as an alternative to current commercial ion exchange membranes that have been primarily designed for fuel cell applications. To increase the hydrophilicity and ion transport of the PEEK material, charged groups are introduced through sulfonation. The effect of sulfonation and casting conditions on membrane performance has been systematically determined by producing a series of membranes synthesized over an array of reaction and casting conditions. Optimal reaction and casting conditions for producing SPEEK ion exchange membranes with appropriate performance characteristics have been established by this uniquely systematic experimental series. Membrane materials were characterized by ion exchange capacity, water uptake, swelling, potential difference and NMR analysis. Testing this extensive membranes series established that the most appropriate sulfonation conditions were 60 °C for 6 h. For mechanical stability and ease of handling, SPEEK membranes cast from solvent casting concentrations of 15%–25% with a resulting thickness of 30–50 µm were also found to be most suitable from the series of tested casting conditions. Drying conditions did not have any apparent impact on the measured parameters in this study. The conductivity of SPEEK membranes was found to be in the range of 10−3 S cm−1, which is suitable for use as a low cost membrane in the intended bioelectrochemical systems. PMID:24956945

  16. A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, Jilin (China)

    2010-10-01

    A novel poly(ether ether ketone) (PEEK) containing pendant carboxyl groups has been synthesized by a nucleophilic polycondensation reaction. Sulfonated polymers (SPEEKs) with different ion exchange capacity are then obtained by post-sulfonation process. The structures of PEEK and SPEEKs are characterized by both FT-IR and {sup 1}H NMR. The properties of SPEEKs as candidates for proton exchange membranes are studied. The cross-linking reaction is performed at 140 C using poly(vinyl alcohol) (PVA) as the cross-linker. In comparison with the non-cross-linked membranes, some properties of the cross-linked membranes are significantly improved, such as water uptake, methanol resistance, mechanical and oxidative stabilities, while the proton conductivity decreases. The effect of PVA content on proton conductivity, water uptake, swelling ratio, and methanol permeability is also investigated. Among all the membranes, SPEEK-C-8 shows the highest selectivity of 50.5 x 10{sup 4} S s cm{sup -3}, which indicates that it is a suitable candidate for applications in direct methanol fuel cells. (author)

  17. Nafion {sup registered} /nitrated sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Jie-Cheng; Kuo, Jen-Feng; Chen, Chuh-Yung [Department of Chemical Engineering, National Cheng-Kung University, Tainan, 70148 (China)

    2009-10-20

    Sulfonated poly(ether ether ketone)s (SPEEKs) are substituted on the main chain of the polymer by nitro groups and blended with Nafion {sup registered} to attain composite membranes. The sulfonation, nitration and blending are achieved with a simple, inexpensive process, and the blended membranes containing the nitrated SPEEKs reveal a liquid-liquid phase separation. The blended membranes have a lower water uptake compared to recast Nafion {sup registered}, and the methanol permeability is reduced significantly to 4.29 x 10{sup -7}-5.34 x 10{sup -7} cm{sup 2} s{sup -1} for various contents of nitrated SPEEK for S63N17, and 4.72 x 10{sup -7}-7.11 x 10{sup -7} cm{sup 2} s{sup -1} for S63N38, with a maximum proton conductivity of {proportional_to}0.085 S cm{sup -1}. This study examines the single-cell performance at 80 C of Nafion {sup registered} /nitrated SPEEK membranes with various contents of nitrated SPEEK and a degree of nitration of 23-25 mW cm{sup -2} for S63N17 and 24-29 mW cm{sup -2} for S63N38. Both the power density and open circuit voltage are higher than those of Nafion {sup registered} 115 and recast Nafion {sup registered}. (author)

  18. The Effects of Sulfonated Poly(ether ether ketone Ion Exchange Preparation Conditions on Membrane Properties

    Directory of Open Access Journals (Sweden)

    Rebecca S. L. Yee

    2013-08-01

    Full Text Available A low cost cation exchange membrane to be used in a specific bioelectrochemical system has been developed using poly(ether ether ketone (PEEK. This material is presented as an alternative to current commercial ion exchange membranes that have been primarily designed for fuel cell applications. To increase the hydrophilicity and ion transport of the PEEK material, charged groups are introduced through sulfonation. The effect of sulfonation and casting conditions on membrane performance has been systematically determined by producing a series of membranes synthesized over an array of reaction and casting conditions. Optimal reaction and casting conditions for producing SPEEK ion exchange membranes with appropriate performance characteristics have been established by this uniquely systematic experimental series. Membrane materials were characterized by ion exchange capacity, water uptake, swelling, potential difference and NMR analysis. Testing this extensive membranes series established that the most appropriate sulfonation conditions were 60 °C for 6 h. For mechanical stability and ease of handling, SPEEK membranes cast from solvent casting concentrations of 15%–25% with a resulting thickness of 30–50 µm were also found to be most suitable from the series of tested casting conditions. Drying conditions did not have any apparent impact on the measured parameters in this study. The conductivity of SPEEK membranes was found to be in the range of 10−3 S cm−1, which is suitable for use as a low cost membrane in the intended bioelectrochemical systems.

  19. Sulfonated poly(ether ether ketone) based membranes for direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Roelofs, Kimball S.

    2010-07-01

    The decreasing availability of fossil fuels and the increasing impact of greenhouse gases on the environment lead to an extensive development of more efficient or renewable energy sources. The direct alcohol fuel cell (DAFC) as a portable energy source is a promising and fast growing technology which meets these demands. Up to now, methanol is mostly studied as a fuel for these devices, however, applying ethanol has some evident advantages over methanol. The major challenges in direct ethanol fuel cell (DEFC) research on component level are the catalyst development and the electrolyte membrane development. The focus of this thesis lies on the development and characterization of proton conductive membranes for application in direct ethanol fuel cells (DEFC). Sulfonated poly(ether ether ketone) (sPEEK) based organic-inorganic mixed-matrix membranes are developed and, in addition, the inorganic phase is modified with functional silanes carrying basic groups. The membranes are characterized with respect to fuel crossover, proton conductivity, membrane stability and direct ethanol fuel cell tests. (orig.)

  20. Electrical conductivity of sulfonated poly(ether ether ketone) based composite membranes containing sulfonated polyhedral oligosilsesquioxane

    Science.gov (United States)

    Celso, Fabricio; Mikhailenko, Serguei D.; Rodrigues, Marco A. S.; Mauler, Raquel S.; Kaliaguine, Serge

    2016-02-01

    Composite proton exchange membranes (PEMs) intended for fuel cell applications were prepared by embedding of various amounts of dispersed tri-sulfonic acid ethyl POSS (S-Et-POSS) and tri-sulfonic acid butyl POSS (S-Bu-POSS) in thin films of sulfonated poly ether-ether ketone. The electrical properties of the PEMs were studied by Impedance spectroscopy and it was found that their conductivity σ changes with the filler content following a curve with a maximum. The water uptake of these PEMs showed the same dependence. The investigation of initial isolated S-POSS substances revealed the properties of typical electrolytes, which however in both cases possessed low conductivities of 1. 17 × 10-5 S cm-1 (S-Et-POSS) and 3.52 × 10-5 S cm-1 (S-Bu-POSS). At the same time, the insoluble in water S-POSS was found forming highly conductive interface layer when wetted with liquid water and hence producing a strong positive impact on the conductivity of the composite PEM. Electrical properties of the composites were analysed within the frameworks of effective medium theory and bounding models, allowing to evaluate analytically the range of possible conductivity values. It was found that these approaches produced quite good approximation of the experimental data and constituted a fair basis for interpretation of the observed relationship.

  1. Mutagenicity testing of diethylene glycol monobutyl ether.

    Science.gov (United States)

    Thompson, E D; Coppinger, W J; Valencia, R; Iavicoli, J

    1984-01-01

    The mutagenic potential of diethylene glycol monobutyl ether (diEGBE) was examined with a Tier I battery of in vitro assays followed by a Tier II in vivo Drosophila sex-linked recessive lethal assay. The in vitro battery consisted of: the Salmonella mutagenicity test, the L5178Y mouse lymphoma test, a cytogenetics assay using Chinese hamster ovary cells and the unscheduled DNA synthesis (UDS) assay in rat hepatocytes. Results of the Salmonella mutagenicity test, the cytogenetics test, and the rat hepatocyte assay were negative at concentrations up to 20 microL/plate, 7.92 microL/mL, and 4.4 microL/mL, respectively. Toxicity was clearly demonstrated at all high doses. A weak, but dose-related increase in the mutation frequency (4-fold increase over the solvent control at 5.6 microL/mL with 12% survival) was obtained in the L5178Y lymphoma test in the absence of metabolic activation. Results of the mouse lymphoma assay were negative in the presence of the S-9 activation system. The significance of the mouse lymphoma assay were negative in the presence of the S-9 activation system. The significance of the mouse lymphoma assay results were assessed by performing the Tier II sex-linked recessive lethal assay in Drosophila in which the target tissue is maturing germinal cells. Both feeding (11,000 ppm for 3 days) and injection (0.3 microL of approximately 14,000 ppm solution) routes of administration were employed in the Drosophila assay. Approximately 11,000 individual crosses with an equal number of negative controls were performed for each route of administration. diEGBE produced no increase in recessive lethals under these conditions.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:6389113

  2. Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes

    Science.gov (United States)

    Klose, Carolin; Breitwieser, Matthias; Vierrath, Severin; Klingele, Matthias; Cho, Hyeongrae; Büchler, Andreas; Kerres, Jochen; Thiele, Simon

    2017-09-01

    We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

  3. On the ether-like Lorentz-breaking actions

    International Nuclear Information System (INIS)

    Petrov, A.Yu; Nascimento, J.R.; Gomes, M.; Silva, A. J. da

    2011-01-01

    We demonstrate the generation of the CPT-even, ether-like Lorentz-breaking actions for the scalar and electro-magnetic fields via their appropriate Lorentz-breaking coupling to spinor fields in three, four and five space-time dimensions. Besides, we show that the ether-like terms for the spinor field also can be generated as a consequence of the same couplings. The key result which will be presented here is the finiteness of the ether-like term for the electromagnetic field not only in three and five space-time dimensions where it is natural due to known effects of the dimensional regularization but also in four space-time dimensions. Moreover, we present the calculation of the last result within different calculational schemes and conclude that the result for the four-dimensional ether-like term for the electromagnetic field essentially depending on the calculation scheme, similarly to the result for the Carroll-Field-Jackiw (CFJ) term which probably signalizes a possibility for arising of a new anomaly. Also we discuss the dispersion relations in the theories with ether-like Lorentz-breaking terms which allows to discuss the consistency of the Lorentz-breaking modified theories for different (space-like or time-like) Lorentz-breaking vectors and find the tree-level effective (Breit) potential for fermion scattering and the one-loop effective potential corresponding to the action of the scalar field. (author)

  4. Mechanical Properties Optimization of Poly-Ether-Ether-Ketone via Fused Deposition Modeling

    Directory of Open Access Journals (Sweden)

    Xiaohu Deng

    2018-01-01

    Full Text Available Compared to the common selective laser sintering (SLS manufacturing method, fused deposition modeling (FDM seems to be an economical and efficient three-dimensional (3D printing method for high temperature polymer materials in medical applications. In this work, a customized FDM system was developed for polyether-ether-ketone (PEEK materials printing. The effects of printing speed, layer thickness, printing temperature and filling ratio on tensile properties were analyzed by the orthogonal test of four factors and three levels. Optimal tensile properties of the PEEK specimens were observed at a printing speed of 60 mm/s, layer thickness of 0.2 mm, temperature of 370 °C and filling ratio of 40%. Furthermore, the impact and bending tests were conducted under optimized conditions and the results demonstrated that the printed PEEK specimens have appropriate mechanical properties.

  5. Biofilm behavior on sulfonated poly(ether-ether-ketone) (sPEEK)

    International Nuclear Information System (INIS)

    Montero, Juan F.D.; Tajiri, Henrique A.; Barra, Guilherme M.O.; Fredel, Márcio C.; Benfatti, Cesar A.M.; Magini, Ricardo S.; Pimenta, Andréa L.; Souza, Júlio C.M.

    2017-01-01

    Poly(ether-ether-ketone) (PEEK) has also shown to be very attractive for incorporating therapeutic compounds thanks to a sulfonation process which modifies the material structure resulting in a sulfonated-PEEK (sPEEK). Concerning biomedical applications, the objective of this work was to evaluate the influence of different sulfonation degree of sPEEK on the biofilm growth. PEEK samples were functionalized by using sulphuric acid (98%) and then dissolved into dimethyl-sulfoxide. A dip coating technique was used to synthesize sPEEK thin films. The sulfonation degree of the materials was analyzed by FT-IR, H NMR, TG and IEC. The surfaces were characterized by scanning electron microscopy, profilometry and contact angle analyses. Subsequently, the biofilm formation on sulfonated-PEEK based on Streptococcus mutans and Enterococcus faecalis was measured by spectrophotometry, colony forming units (CFU mL −1 ) and SEM. Results obtained from thermal and chemical analyses showed an intensification in sulfonation degree for sPEEK at 2 and 2.5 h. The E. faecalis or S. mutans biofilm growth revealed statistically significant differences (p < 0.05) between 2 and 3 h sulfonation groups. A significant decrease (p < 0.05) in CFU mL −1 was recorded for S. mutans or E. faecalis biofilm grown on 2.5 or 3 h sPEEK. Regarding the thermal-chemical and microbiologic analyses, the sulfonation degree of sPEEK ranging from 2 up to 3 h was successful capable to decrease the biofilm growth. That revealed an alternative strategy to embed anti-biofilm and therapeutic compounds into PEEK avoiding infections in biomedical applications. - Highlights: • PEEK can be dissolved to incorporate therapeutic compounds. • High sulfonation degree on sPEEK affected the biofilm growth. • The sulfonation degree must be controlled to maintain the properties of sPEEK.

  6. Fuel cell performance of pendent methylphenyl sulfonated poly(ether ether ketone ketone)s

    Science.gov (United States)

    Zhang, Hanyu; Stanis, Ronald J.; Song, Yang; Hu, Wei; Cornelius, Chris J.; Shi, Qiang; Liu, Baijun; Guiver, Michael D.

    2017-11-01

    Meta- and para-linked homopolymers bearing 3-methylphenyl (Me) pendent groups were postsulfonated to create sulfonated poly(ether ether ketone ketone) (SPEEKK) backbone isomers, which are referred to as Me-p-SPEEKK and Me-m-SPEEKK. Their thermal and oxidative stability, mechanical properties, dimensional stability, methanol permeability, and proton conductivity are characterized. Me-p-SPEEKK and Me-m-SPEEKK proton conductivities at 100 °C are 116 and 173 mS cm-1, respectively. Their methanol permeabilities are 3.3-3.9 × 10-7 cm2 s-1, and dimensional swelling at 100 °C is 16.4-17.5%. Me-p-SPEEKK and Me-m-SPEEKK were fabricated into membrane electrode assemblies (MEAs), and electrochemical properties were evaluated within a direct methanol fuel cell (DMFC) and proton-exchange membrane fuel cell (PEMFC). When O2 is used as the oxidant at 80 °C and 100% RH, the maximum power density of Me-m-SPEEKK reaches 657 mW cm-2, which is higher than those of Nafion 115 (552 mW cm-2). DMFC performance is 85 mW cm-2 at 80 °C with 2.0 M methanol using Me-p-SPEEKK due to its low MeOH crossover. In general, these electrochemical results are comparable to Nafion. These ionomer properties, combined with a potentially less expensive and scalable polymer manufacturing process, may broaden their potential for many practical applications.

  7. Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Dae Sik, Kim [Los Alamos National Laboratory; Yu Seung, Kim [Los Alamos National Laboratory; Gilles, Robertson [CANADA-NRC; Guiver, Michael D [CANADA-NRC

    2009-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and P AEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (OS) of 1.0 had high ion exchange capacities (IEC{sub v})(wet) (volume-based, wet state) of 1.77 and 2.55 meq./cm3, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5 -51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  8. Polydopamine-functionalized poly(ether ether ketone) tube for capillary electrophoresis-mass spectrometry.

    Science.gov (United States)

    Zhou, Wei; Zhang, Wenpeng; Liu, Yikun; Yu, Xinhong; Chen, Zilin

    2017-09-22

    Capillary electrophoresis-mass spectrometry (CE-MS) is a hyphenated technique that combines the advantages like low sample consumption, high separation efficiency, short analytical time in CE and high sensitivity, powerful molecular structure elucidation in MS. Polyimide-coated fused silica capillary has become the most dominant capillary for CE, but it suffers from swelling and aminolysis of polyimide coating when treated with organic solvents and alkaline buffer in the CE-MS interface in which the polyimide coating at the end of the capillary is exposed to the solution, and this phenomenon can result in current instability, irregular electrospray and clogging at outlet after prolonged use. In this work, poly(ether ether ketone) (PEEK) capillary was explored as separation capillary for CE-MS. The problems like swelling and aminolysis of polyimide coating were solved due to the high thermal and chemical stability of PEEK material. After modification with polydopamine, PEEK capillary (PD-PEEK) can generate adjustable electroosmotic flow and provide good separation selectivity. The zwitterion polymer of polydopamine can provide cathodic electroosmotic flow (EOF) at high pH value (pH ≥ 5) and anodic EOF at low pH value (pH ≤ 4), and the EOF mobility can also be adjusted by controlling the modification time of polydopamine. Good separation performance was obtained in the analysis for several classes of compounds including amino acids, phenols and plant hormones at rational EOF direction. Repeatability of the PD-PEEK capillary was studied, with relative standard deviations for intra-day, inter-day runs and between tubes less than 4.94%. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Novel sulfonated poly(ether ether ketone)s containing nitrile groups and their composite membranes for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Meimei; Liu, Baijun; Guan, Shaowei; Li, Long; Liu, Chang; Zhang, Yunhe; Jiang, Zhenhua [Alan G. MacDiarmid Institute, Jilin University, 2699 Qianjin Street, Changchun 130012 (China)

    2010-08-01

    A series of novel sulfonated poly(ether ether ketone)s containing a cyanophenyl group (SPEEKCNxx) are prepared based on (4-cyano)phenylhydroquinone via nucleophilic substitution polycondensation reactions. To further improve their properties, novel composite membranes composed of sulfonated poly(ether ether ketone)s containing cyanophenyl group as an acidic component and aminated poly(aryl ether ketone) as a basic component are successfully prepared. Most of the membranes exhibit excellent thermal, oxidative and dimensional stability, low-swelling ratio, high proton conductivity, low methanol permeability and high selectivity. The proton conductivities of the membranes are close to Nafion 117 at room temperature. And especially, the values of SPEEKCN40 and its composite membranes are higher than Nafion 117 at 80 C (0.17 S cm{sup -1} of Nafion, 0.26 S cm{sup -1} of SPEEKCN40, 0.20 S cm{sup -1} of SPEEKCN40-1, and 0.18 S cm{sup -1} of SPEEKCN40-2). Moreover, the methanol permeability is one order magnitude lower than that of Nafion 117. All the data prove that both copolymers and their composite membranes may be potential proton exchange membrane for fuel cells applications. (author)

  10. Synthesis and Biophysical Characterization of Chlorambucil Anticancer Ether Lipid Prodrugs

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob; Christensen, Mikkel Stochkendahl; Ruysschaert, Tristan

    2009-01-01

    The synthesis and biophysical characterization of four prodrug ether phospholipid conjugates are described. The lipids are prepared from the anticancer drug chlorambucil and have C16 and C18 ether chains with phosphatidylcholine or phosphatidylglycerol headgroups. All four prodrugs have the ability...... to form unilamellar liposomes (86-125 nm) and are hydrolyzed by phospholipase A2, resulting in chlorambucil release. Liposomal formulations of prodrug lipids displayed cytotoxicity toward HT-29, MT-3, and ES-2 cancer cell lines in the presence of phospholipase A2, with IC50 values in the 8-36 μM range....

  11. Proton-Ionizable Crown Ethers. A Short Review

    Science.gov (United States)

    1989-05-30

    Triazole’Subcyclic Unit 14. Proton-Ionizable Crown Ethers Containing Sulfonamide Groups 15. Miscellaneous Proton-Ionizable Crown Ethers 1. INTRODUCTION. ""Since...the diaza dinitrile crown. Subsequent hydrolysis produced the diacid 33 (Procedure E). 27 Monoaza-crowns 35-38 (Figure V, Table 5) were obtained by the...followed by hydrolysis of the cetidi to f the acid.3o Complextion by th~eam crownsJ hasJ boon extensively castudieon and transportat es of thos ecaions have

  12. Vertical distribution of dehalogenating bacteria in mangrove sediment and their potential to remove polybrominated diphenyl ether contamination.

    Science.gov (United States)

    Pan, Ying; Chen, Juan; Zhou, Haichao; Farzana, Shazia; Tam, Nora F Y

    2017-11-30

    The removal and degradation of polybrominated diphenyl ethers (PBDEs) in sediments are not clear. The vertical distribution of total and dehalogenating bacteria in sediment cores collected from a typical mangrove swamp in South China and their intrinsic degradation potential were investigated. These bacterial groups had the highest abundances in surface sediments (0-5cm). A 5-months microcosm experiment also showed that surface sediments had the highest rate to remove BDE-47 than deeper sediments (5-30cm) under anaerobic condition. The deeper sediments, being more anaerobic, had lower population of dehalogenating bacteria leading to a weaker BDE-47 removal potential than surface sediments. Stepwise multiple regression analysis indicated that Dehalococcoides spp. were the most important dehalogenating bacteria affecting the anaerobic removal of BDE-47 in mangrove sediments. This is the first study reporting that mangrove sediments harbored diverse groups of dehalogenating bacteria and had intrinsic potential to remove PBDE contamination. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Sulphonated biphenylated poly(aryl ether ketone)s for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Hu, W.; Jiang, Z. [Alan G. MacDiarmid Institute, Jilin University, Changchun 130012 (China); Robertson, G.P.; Guiver, M.D. [Institute for Chemical Process and Environmental Technology, National Research Council, Ottawa, Ontario K1A 0R6 (Canada); Kim, Y.S. [Electronic and Electrochemical Materials and Devices, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Liu, B.

    2010-02-15

    New series of fully aromatic poly(ether ketone)s with a biphenyl pendant groups were synthesised. A direct comparison of sulphonation reaction among monophenylated poly(ether ether ketone) (Ph-PEEK), biphenylated poly(ether ether ketone) (BiPh-PEEK) and PEEK (Victrex) was thoroughly investigated. Several advantages of the pendant-phenyl poly(ether ketone)s compared with commercial PEEK were identified, including ready control over the site of sulphonation and degree of sulphonation (DS), and mild and rapid sulphonation. The basic membrane physical properties comprising of thermal and mechanical properties, dimensional stability and proton conductivity were studied. One new membrane, sulphonated biphenylated poly(ether ether ketone) (BiPh-SPEEKDK) having a good combination of membrane properties was fabricated into a membrane electrode assembly (MEA), and it showed excellent direct methanol fuel cell (DMFC) performance. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  14. Debromination of polybrominated diphenyl ethers by attapulgite-supported Fe/Ni bimetallic nanoparticles: Influencing factors, kinetics and mechanism.

    Science.gov (United States)

    Liu, Zongtang; Gu, Chenggang; Ye, Mao; Bian, Yongrong; Cheng, Yinwen; Wang, Fang; Yang, Xinglun; Song, Yang; Jiang, Xin

    2015-11-15

    To enhance the removal efficiency of 2,2',4,4'-tetrabromodiphenylether (BDE47) in aqueous solutions, novel attapulgite-supported Fe/Ni bimetallic nanoparticles (A-Fe/Ni), which were characterized by a core-shell nanoparticle structure and with an average diameter of 20-40 nm, were synthesized for use in BDE47 degradation. The presence of attapulgite in bimetallic systems could reduce Fe/Ni nanoparticle aggregation and enhance their reactivity. BDE47 was degraded with a significant improvement in removal efficiency of at least 96% by A-Fe/Ni that played a reductive role in the reaction. The degradation kinetics of BDE47 by A-Fe/Ni complied with pseudo-first-order characteristics. To better understand the removal mechanism, detailed analyses were performed for several influential parameters. The improved dosage of A-Fe/Ni was found to be beneficial, and higher values of initial concentration, pH, and methanol/water ratio hindered the degradation rate, which, for example, decreased significantly in mixtures with a methanol proportion higher than 50%. The identification of BDE47 degradation products revealed a stepwise debromination from n-bromo-DE to (n-1)-bromo-DE as a possible pathway, wherein the para-Br was more easily eliminated than ortho-Br. Our findings provide insight into the removal mechanism and evidence for polybrominated diphenyl ether debromination by clay-Fe/Ni bimetallic nanoparticles. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Molecular structure impacts on secondary organic aerosol formation from glycol ethers

    Science.gov (United States)

    Li, Lijie; Cocker, David R.

    2018-05-01

    Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

  16. 40 CFR 721.10017 - Amine terminated bisphenol A diglycidyl ether polymer (generic).

    Science.gov (United States)

    2010-07-01

    ... diglycidyl ether polymer (generic). 721.10017 Section 721.10017 Protection of Environment ENVIRONMENTAL... ether polymer (generic). (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substances identified generically as amine terminated bisphenol A diglycidyl ether polymer (PMNs P...

  17. Fluorescence Sensing Properties of Thiazolobenzo-crown Ether Incorporating Coumarin

    International Nuclear Information System (INIS)

    Lee, Sang Hoon; Helal, Aasif; Kim, Hong Seok

    2010-01-01

    A new coumarin-thiazolobenzo-crown ether based fluorogenic chemosensor BTC (1) was reported. The ion-selective binding properties of 1 with different alkali, alkaline earth metals and transitional metals were investigated in an ethanol- DMSO system. BTC (1) showed the highest binding constant toward Hg 2+ over Ag + , Pb 2+ and Cu 2+

  18. High Resolution Rotational Spectroscopy of a Flexible Cyclic Ether

    Science.gov (United States)

    Gámez, F.; Martínez-Haya, B.; Blanco, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    Crown ethers stand as one cornerstone molecular class inhost-guest Supramolecular Chemistry and constitute building blocks for a broad range of modern materials. We report here the first high resolution rotational study of a crown ether: 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5 ether,15c5). Molecular beam Fourier transform microwave spectroscopy has been employed. The liquid sample of 15c5 has been vaporized using heating methods. The considerable size of 15c5 and the broad range of conformations allowed by the flexibility of its backbone pose important challenges to spectroscopy approaches. In fact, the ab-initio computational study for isolated 15c5, yields at least six stable conformers with relative free energies within 2 kJ Mol-1 (167 Cm-1). Nevertheless, in this investigation it has been possible to identify and characterize in detail one stable rotamer of the 15c5 molecule and to challenge different quantum methods for the accurate description of this system. The results pave the ground for an extensive description of the conformational landscape of 15c5 and related cyclic ethers in the near term. J. L. Alonso, F. J. Lorenzo, J. C. López, A. Lesarri, S. Mata and H. Dreizler, Chem. Phys., 218, 267 (1997) S. Blanco, J.C López, J.L. Alonso, P. Ottaviani, W. Caminati, J. Chem. Phys. 119, 880 (2003) S.E. Hill, D. Feller, Int. J. Mass Spectrom. 201, 41 (2000)

  19. Evaluation of polybrominated diphenyl ethers in sediment of Lagos ...

    African Journals Online (AJOL)

    These highly hazardous organic pollutants of concern are persistent, can bioaccumulate and biomagnify in aquatic organism especially fish, and there appears to be no clear strategy for managing them. In this study, levels of polybrominated diphenyl ethers were determined in sediments collected from Lagos lagoon with ...

  20. Chemical Composition and Cytotoxic Activities of Petroleum Ether ...

    African Journals Online (AJOL)

    Chemical Composition and Cytotoxic Activities of. Petroleum Ether Fruit Extract of Fruits of Brucea javanica. (Simarubaceae). Zhiwei Su1,2, Huijuan Huang3, Jinlian Li1,4, Yuehui Zhu1, Riming Huang1 and. Samuel X Qiu1*. 1Program for Natural Product Medicinal Chemistry and Drug Discovery, Key Laboratory of Plant ...

  1. Why do crown ethers activate enzymes in organic solvents?

    NARCIS (Netherlands)

    van Unen, D.J.; Engbersen, Johannes F.J.; Reinhoudt, David

    2002-01-01

    One of the major drawbacks of enzymes in nonaqueous solvents is that their activity is often dramatically low compared to that in water. This limitation can be largely overcome by crown ether treatment of enzymes. In this paper, we describe a number of carefully designed new experiments that have

  2. Evaluation of polybrominated diphenyl ethers in sediment of Lagos ...

    African Journals Online (AJOL)

    user

    environmental concerns. New organic pollutants especially polybrominated diphenyl ether (PBDEs) employed in electronic equipment and in some household items as flame retardants are now finding their way into the aquatic environment as components of waste discharge into the water body. These highly hazardous ...

  3. Bio-inspired ion selective crown-ether polymer membranes

    NARCIS (Netherlands)

    Tas, Sinem

    2016-01-01

    Development of unctional membranes that are capable of selectively recognizing and transporting ions have key importance for the recovery and separation of specific icons (e.d. K+, Li+, Na+) from multicomponent mixtures. In this thesis, new membrane materials based on crown ether-metal ion

  4. Dimethyl ether in diesel engines - progress and perspectives

    DEFF Research Database (Denmark)

    Sorenson, Spencer C

    2001-01-01

    A review of recent developments related to the use of dimethyl ether (DME) in engines is presented Research work discussed is in the areas of engine performance and emissions, fuel injection systems, spray and ignition delay, and detailed chemical kinetic modeling. DME's properties and safety...

  5. Binary mixtures of carbon dioxide and dimethyl ether as alternative ...

    African Journals Online (AJOL)

    Vapor-liquid equilibrium (VLE) data were predicted for the binary mixture of carbon dioxide (CO2) and dimethyl ether (DME) at ten temperatures ranging from 273.15 to 386.56 K and pressure upto 7.9 MPa to observe this mixture's potential of COP enhancement and capacity modulation as a working fluid in a refrigeration ...

  6. Diethyl Ether Production as a Substitute for Gasoline

    Directory of Open Access Journals (Sweden)

    Alviany Riza

    2018-01-01

    Full Text Available Diethyl ether is one of alternative fuel that could be used as a significant component of a blend or as a complete replacement for transportation fuel. The aim of this research is to produce diethyl ether through dehydration reaction of ethanol with fixed bed reactor using nanocrystalline γ-Al2O3 catalyst. Nanocrystalline γ-Al2O3 catalyst was synthesized by precipitation method using Al(NO33.9H2O as precursors and NH4OH as the precipitating agent. Dehydration reaction was performed at temperature range of 125 to 225°C. The result shows that synthesized γ-Al2O3 catalyst gave higher ethanol conversion and diethyl ether yield than that of commercial Al2O3 catalyst. The use of synthesized γ-Al2O3 catalyst could reach ethanol conversion as high as 94.71% and diethyl ether yield as high as 11,29%.

  7. Synthesis of hydroxytyrosyl alkyl ethers from olive oil waste waters

    OpenAIRE

    Espartero Sánchez, José Luis; Madrona, Andrés; Pereira Cano, Gema; Mateos, Raquel; Rodríguez, Guillermo; Trujillo, Mariana; Fernández Bolaños, Juan

    2009-01-01

    The preparation of a new type of derivatives of the naturally occurring antioxidant hydroxytyrosol is reported. Hydroxytyrosyl alkyl ethers were obtained in high yield by a three-step procedure starting from hydroxytyrosol isolated from olive oil waste waters. Preliminary results obtained by the Rancimat method have shown that these derivatives retain the high protective capacity of free hydroxytyrosol.

  8. Synthesis of Hydroxytyrosyl Alkyl Ethers from Olive Oil Waste Waters

    Directory of Open Access Journals (Sweden)

    Juan Fernández-Bolaños

    2009-05-01

    Full Text Available The preparation of a new type of derivatives of the naturally occurring antioxidant hydroxytyrosol is reported. Hydroxytyrosyl alkyl ethers were obtained in high yield by a three-step procedure starting from hydroxytyrosol isolated from olive oil waste waters. Preliminary results obtained by the Rancimat method have shown that these derivatives retain the high protective capacity of free hydroxytyrosol.

  9. Developmental toxicity of four glycol ethers applied cutaneously to rats

    Energy Technology Data Exchange (ETDEWEB)

    Hardin, B.D.; Goad, P.T.; Burg, J.R.

    1984-08-01

    Previous NIOSH studies demonstrated the embryo- and fetotoxicity and teratogenicity of ethylene glycol monoethyl ether (EGEE) applied to the shaved skin of pregnant rats. In the present study ethylene glycol monoethyl ether acetate (EGEEA), ethylene glycol monobutyl ether (EGBE), and diethylene glycol monoethyl ether (diEGEE) were tested in the same experimental model, using distilled water as the negative control and EGEE as a positive control. Water or undiluted glycols were applied four times daily on days 7 to 16 of gestation to the shaved interscapular skin with an automatic pipetter. Volumes of EGEE (0.25 mL), EGEEA (0.35 mL), and diEGEE (0.35 mL) were approximately equimolar (2.6 mmole per treatment). EGBE at 0.35 mL four times daily (approximately 2.7 mmole per treatment) killed 10 of 11 treated rats, and was subsequently tested at 0.12 mL (0.9 mmole) per treatment. EGEE- and EGEEA-treated rats showed a reduction in body weight relative to water controls that was associated with completely resorbed litters and significantly fewer live fetuses per litter. Fetal body weights were also significantly reduced in those groups. Visceral malformations and skeletal variations were significantly increased in EGEE and EGEEA groups over the negative control group. No embryotoxic, genotoxic, or teratogenic effects were detected in the EGBE- or diEGEE-treated litters. 16 references, 4 tables.

  10. Developmental toxicity of four glycol ethers applied cutaneously to rats.

    Science.gov (United States)

    Hardin, B D; Goad, P T; Burg, J R

    1984-08-01

    Previous NIOSH studies demonstrated the embryo- and fetotoxicity and teratogenicity of ethylene glycol monoethyl ether (EGEE) applied to the shaved skin of pregnant rats. In the present study ethylene glycol monoethyl ether acetate (EGEEA), ethylene glycol monobutyl ether (EGBE), and diethylene glycol monoethyl ether (diEGEE) were tested in the same experimental model, using distilled water as the negative control and EGEE as a positive control. Water or undiluted glycols were applied four times daily on days 7 to 16 of gestation to the shaved interscapular skin with an automatic pipetter. Volumes of EGEE (0.25 mL), EGEEA (0.35 mL), and diEGEE (0.35 mL) were approximately equimolar (2.6 mmole per treatment). EGBE at 0.35 mL four times daily (approximately 2.7 mmole per treatment) killed 10 of 11 treated rats, and was subsequently tested at 0.12 mL (0.9 mmole) per treatment. EGEE- and EGEEA-treated rats showed a reduction in body weight relative to water controls that was associated with completely resorbed litters and significantly fewer live fetuses per litter. Fetal body weights were also significantly reduced in those groups. Visceral malformations and skeletal variations were significantly increased in EGEE and EGEEA groups over the negative control group. No embryotoxic, fetotoxic, or teratogenic effects were detected in the EGBE- or diEGEE-treated litters.

  11. Calix salophen crown ethers as receptors for neutral molecules

    NARCIS (Netherlands)

    Reichwein, A.M.; Reichwein, Arjen M.; Verboom, Willem; Harkema, Sybolt; Spek, Anthony L.; Reinhoudt, David

    1994-01-01

    The calix[4]arene based salophen crown ethers 7 and 8 were synthesized as lipophilic carriers for neutral molecules. The X-ray structures of the H2O, CH3OH and (CH3)2SO complexes of 8a have been determined.

  12. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A.; Spoelma, F.F.; Doren, H.A. van; Gotlieb, K.F.; Bleeker, I.P.; Kellogg, R.M.

    2000-01-01

    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-α-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  13. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A; Spoelma, FF; van Doren, HA; Gotlieb, KF; Bleeker, IP; Kellogg, RM

    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-alpha-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  14. Formation and Structural Analysis of Novel Dibornyl Ethers | Kaye ...

    African Journals Online (AJOL)

    One- and two-dimensional NMR spectroscopy has been used to establish the regio- and stereochemistry of novel dibornyl ethers, obtained by acid-catalysed condensation of camphor-derived a-hydroxybornanones. South African Journal of Chemistry Vol.55 2002: 111-118 ...

  15. Ether and interpretation of some physical phenomena and concepts

    International Nuclear Information System (INIS)

    Rzayev, S.G.

    2008-01-01

    On the basis of the concept of existence of an ether representation about time, space, matters and physical field are profound and also the essence of such phenomena, as corpuscular - wave dualism, change of time, scale and mass at movement body's is opened. The opportunity of transition from probability-statistical interpretation of the quantum phenomena to Laplace's determinism is shown

  16. A novel chlorinated diphenyl ether from Byrsonima microphylla (Malpighiaceae).

    Science.gov (United States)

    Rocha, João H C; Cardoso, Manuela P; David, Juceni P; David, Jorge M

    2006-11-01

    The isolation is described of an unusual chlorinated diphenyl ether named methyl 3,5-dichloro-6-(6-hydroxy-4-methoxy-3-methoxycarbonyl-2-methylphenoxy)-2-hydroxy-4-methylbenzoate that was obtained from the trunk of Byrsonima microphylla (Malpighiaceae). The structure was elucidated by a spectroscopic data analysis, and the presence of this compound in heartwood was confirmed by HPLC and HPTLC analyses.

  17. Comparative evaluation of direct stool smear and Formol-ether ...

    African Journals Online (AJOL)

    Cryptosporidium is a common cause of diarrhoea in patients with Human Immunodeficiency Virus (HIV)/Acquired Immunodeficiency Syndrome (AIDS). Unfortunately this pathogen is not often checked for in Microbiology laboratories because the formol-ether stool concentration method for identification of Cryptosporidium is ...

  18. Determination of bisphenol a diglycidyl ether content in foods from ...

    African Journals Online (AJOL)

    In order to avoid migration issues of chemical compounds from tin cans to foods, covering internal surface of the tin cans with epoxyphenolic and organosol resins is widespread. However, monomers like Bisphenol A Diglycidyl Ether (BADGE), number among the constituents of these resins capable of migrating to foods.

  19. Ether lipids of planktonic archae in the marine water column

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hoefs, M.J.L.; Schouten, S.; King, L.L.; Wakeham, S.G.; Leeuw, J.W. de

    1997-01-01

    Acyclic and cyclic biphytanes derived from the membrane ether lipids of archaea were found in water column particulate and sedimentary organic matter from several oxic and anoxic marine environments. Compound-specific isotope analyses of the carbon skeletons suggest that planktonic archaea utilize

  20. Changes in the molecular structure of a type II-S kerogen (Monterey Formation, USA) during sequential chemical degradation

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hold, I.M.; Brussee, N.J.; Schouten, S.

    1998-01-01

    Flash pyrolysis and sequential chemical degradation were combined to study the molecular composition of an immature Type II-S kerogen from the Miocene Monterey Formation. Firstly, base hydrolysis was performed in order to hydrolyse ester bonds, in the second step aliphatic ethers were cleaved and in

  1. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor

    International Nuclear Information System (INIS)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha

    2014-01-01

    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion ® . • SPEEK exhibited one order lesser oxygen permeability than Nafion ® . • Nafion ® shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion ® . The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion ® , resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria

  2. Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

    Science.gov (United States)

    Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

    2017-09-01

    Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

  3. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha, E-mail: sangeetha@annauniv.edu

    2014-03-01

    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion{sup ®}. • SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}. • Nafion{sup ®} shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion{sup ®}. The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}, resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

  4. Characterization of a novel oxyfluorfen-degrading bacterial strain Chryseobacterium aquifrigidense and its biochemical degradation pathway.

    Science.gov (United States)

    Zhao, Huanhuan; Xu, Jun; Dong, Fengshou; Liu, Xingang; Wu, Yanbing; Wu, Xiaohu; Zheng, Yongquan

    2016-08-01

    Persistent use of the diphenyl ether herbicides oxyfluorfen may seriously increase the health risks and ecological safety problems. A newly bacterium R-21 isolated from active soil was able to degrade and utilize oxyfluorfen as the sole carbon source. R-21 was identified as Chryseobacterium aquifrigidense by morphology, physiobiochemical characteristics, and genetic analysis. Under the optimum cultural conditions (pH 6.9, temperature 33.4 °C, and inoculum size 0.2 g L(-1)), R-21 could degrade 92.1 % of oxyfluorfen at 50 mg L(-1) within 5 days. During oxyfluorfen degradation, six metabolites were detected and identified by atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry and ultra-performance liquid chromatography coupled to quadrupole-time of flight mass spectrometry, and a plausible degradation pathway was deduced. Strain R-21 is a promising potential in bioremediation of oxyfluorfen-contaminated environments.

  5. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  6. RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

    Science.gov (United States)

    Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

  7. Investigation of Volumetric Properties of Some Glycol Ethers Using a Simple Equation of State

    Science.gov (United States)

    Moosavi, M.; Goharshadi, E. K.

    2006-09-01

    In this work, a simple equation of state (EoS) has been used to predict the density and other thermodynamic properties such as the isobaric expansion coefficient, α P , the isothermal compressibility, κ T , and the internal pressure, P i , of six glycol ethers including diethylene glycol monobutyl ether (DEGBE), propylene glycol propyl ether (PGPE), diethylene glycol monomethyl ether (DEGME), diethylene glycol monoethyl ether (DEGEE), triethylene glycol dimethyl ether (TriEGDME), and tetraethylene glycol dimethyl ether (TEGDME) at different temperatures and pressures. A comparison with literature experimental data has been made. Additionally, statistical parameters between experimental and calculated densities for the GMA EoS and four other EoSs (Soave Redlich Kwong, Peng Robinson, Soave Redlich Kwong with volume translation, and Patel Teja) indicate the superiority of the GMA EoS.

  8. Crown ethers as size-selective synergists in solvent extraction systems: a new selectivity parameter

    International Nuclear Information System (INIS)

    Kinard, W.F.; McDowell, W.J.

    1981-01-01

    Mixtures of macrocyclic polyethers (crown ethers) and organic-phase-soluble liquid cation exchangers have been found to produce a synergistic effect in the extraction of metal ions. The synergistic effect is size selective; that is, it tends to be greatest for those ions that best fit the crown ether cavity. The mixtures of a liquid cation exchanger and a crown ether also allow metal ion extraction from common mineral-acid anion systems (NO 3 - , Cl - , SO 4 2- ) that would be impossible with the crown ether alone, because of the difficulty of solubilizing those anions in nonpolar solvents. This cooperation makes the use of crown ethers as size-selective coordinators available for process applications. Size selectivity of compounds such as crown ethers may thus become a useful new parameter in designing selective solvent extraction systems. Results are reported for alkali (including Cs) and alkaline earth (including Sr) extraction by HDEHP mixed with various crown ethers. (author)

  9. A mild and efficient method for the selective deprotection of silyl ethers using KF in the presence of tetraethylene glycol.

    Science.gov (United States)

    Yan, Hailong; Oh, Joong-Suk; Song, Choong Eui

    2011-12-07

    A mild and efficient protocol for the deprotection of silyl ethers using KF in tetraethylene glycol is reported. A wide range of alcoholic silyl ethers can be selectively cleaved in high yield in the presence of certain acid- and base-labile functional groups. Moreover, the phenolic silyl ethers were cleaved exclusively, without affecting the alcoholic silyl ethers, at room temperature.

  10. Behavior of decabromodiphenyl ether (BDE-209) in soil: Effects of rhizosphere and mycorrhizal colonization of ryegrass roots

    Energy Technology Data Exchange (ETDEWEB)

    Wang Sen [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Zhang Shuzhen, E-mail: szzhang@rcees.ac.cn [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Huang, Honglin [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Christie, Peter [Agri-Environment Branch, Agri-Food and Biosciences Institute, Newforge Lane, Belfast BT9 5PX (United Kingdom)

    2011-03-15

    A rhizobox experiment was conducted to investigate degradation of decabromodiphenyl ether (BDE-209) in the rhizosphere of ryegrass and the influence of root colonization with an arbuscular mycorrhizal (AM) fungus. BDE-209 dissipation in soil varied with its proximity to the roots and was enhanced by AM inoculation. A negative correlation (P < 0.001, R{sup 2} = 0.66) was found between the residual BDE-209 concentration in soil and soil microbial biomass estimated as the total phospholipid fatty acids, suggesting a contribution of microbial degradation to BDE-209 dissipation. Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples, respectively, with a higher proportion of di- through hepta-BDE congeners in the plant tissues than in the soils, indicating the occurrence of BDE-209 debromination in the soil-plant system. AM inoculation increased the levels of lower brominated PBDEs in ryegrass. These results provide important information about the behavior of BDE-209 in the soil-plant system. - Research highlights: > BDE-209 dissipation in soil was affected by the proximity to the roots. > Microbial degradation contributes greatly to BDE-209 dissipation in the soil. > Twelve and twenty-four lower brominated PBDEs were detected in soil and plant samples. > AM inoculation increased root uptake and accumulation of BDE-209. - BDE-209 dissipation and degradation in soil were affected by both its proximity to ryegrass roots and inoculation with an AM fungus.

  11. Enhanced debromination of decabrominated diphenyl ether in aqueous solution by attapulgite supported Fe/Ni bimetallic nanoparticles: kinetics and pathways

    Science.gov (United States)

    Liu, Zongtang; Gu, Chenggang; Bian, Yongrong; Jiang, Xin; Sun, Yufeng; Fei, Zhenghao; Dai, Jingtao

    2017-08-01

    In this study, Fe/Ni bimetallic nanoparticles were supported on the attapulgite (A-Fe/Ni) to enhance the degradation reactivity of decabrominated diphenyl ether (BDE209) in aqueous solution. The Fe/Ni nanoparticles were well distributed on the attapulgite surface with an average diameter of 20-40 nm. The removal percentage of BDE209 by A-Fe/Ni was 1.59 times higher than Fe/Ni nanoparticles alone because attapulgite could act as supporting material to disperse Fe/Ni nanoparticles and prevent Fe/Ni nanoparticles from aggregation. The degradation kinetics for BDE209 debromination by A-Fe/Ni could be well described by a pseudo-first-order model, and the debromination rate constant of BDE209 increased with increasing the dosage of A-Fe/Ni, water/THF ratio, and decreasing the initial BDE209 concentration and solution pH. The degradation products were identified using a third-order polynomial regression equation between the experimental and reference gas chromatography relative retention times. Stepwise debromination from n-bromo-DE to (n  -  1)-bromo-DE was a possible pathway with bromines being substituted sequentially by hydrogen. The preferred elimination of bromines of BDE209 by A-Fe/Ni followed the debromination preference of para-Br  >  meta-Br  >  ortho-Br. The results provide evidences for understanding the debromination mechanism of polybrominated diphenyl ether by clay-supported Fe/Ni nanoparticles.

  12. PEM fuel cell degradation

    Energy Technology Data Exchange (ETDEWEB)

    Borup, Rodney L [Los Alamos National Laboratory; Mukundan, Rangachary [Los Alamos National Laboratory

    2010-01-01

    The durability of PEM fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. While significant progress has been made in understanding degradation mechanisms and improving materials, further improvements in durability are required to meet commercialization targets. Catalyst and electrode durability remains a primary degradation mode, with much work reported on understanding how the catalyst and electrode structure degrades. Accelerated Stress Tests (ASTs) are used to rapidly evaluate component degradation, however the results are sometimes easy, and other times difficult to correlate. Tests that were developed to accelerate degradation of single components are shown to also affect other component's degradation modes. Non-ideal examples of this include ASTs examining catalyst degradation performances losses due to catalyst degradation do not always well correlate with catalyst surface area and also lead to losses in mass transport.

  13. Sorption-desorption behavior of polybrominated diphenyl ethers in soils.

    Science.gov (United States)

    Olshansky, Yaniv; Polubesova, Tamara; Vetter, Walter; Chefetz, Benny

    2011-10-01

    Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4'-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K(OC)) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  15. Structural Study of Mismatched Disila-Crown Ether Complexes

    Directory of Open Access Journals (Sweden)

    Kirsten Reuter

    2017-02-01

    Full Text Available Mismatched complexes of the alkali metals cations Li+ and Na+ were synthesized from 1,2-disila[18]crown-6 (1 and 2 and of K+ from 1,2,4,5-tetrasila[18]crown-6 (4. In these alkali metal complexes, not all crown ether O atoms participate in the coordination, which depicts the coordination ability of the C-, Si/C-, and Si-bonded O atoms. Furthermore, the inverse case—the coordination of the large Ba2+ ion by the relatively small ligand 1,2-disila[15]crown-5—was investigated, yielding the dinuclear complex 5. This structure represents a first outlook on sandwich complexes based on hybrid crown ethers.

  16. [Ethylene glycol and propylene glycol ethers - Reproductive and developmental toxicity].

    Science.gov (United States)

    Starek-Świechowicz, Beata; Starek, Andrzej

    2015-01-01

    Both ethylene and propylene glycol alkyl ethers (EGAEs and PGAEs, respectively) are widely used, mainly as solvents, in industrial and household products. Some EGAEs demonstrate gonadotoxic, embriotoxic, fetotoxic and teratogenic effects in both humans and experimental animals. Due to the noxious impact of these ethers on reproduction and development of organisms EGAEs are replaced for considerably less toxic PGAEs. The data on the mechanisms of testicular, embriotoxic, fetotoxic and teratogenic effects of EGAEs are presented in this paper. Our particular attention was focused on the metabolism of some EGAEs and their organ-specific toxicities, apoptosis of spermatocytes associated with changes in the expression of various genes that code for oxidative stress factors, protein kinases and nuclear hormone receptors. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  17. Ether and ester derivatives of the perborate icosahedron

    Science.gov (United States)

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  18. Increasing the thermopower of crown-ether-bridged anthraquinones

    Science.gov (United States)

    Ismael, Ali K.; Grace, Iain; Lambert, Colin J.

    2015-10-01

    We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The thermopowers of both 1 and 2 are negative and at room temperature are optimised by binding with TTF alone, achieving thermpowers of -600 μV K-1 and -285 μV K-1 respectively. At much lower temperatures, which are relevant to cascade coolers, we find that for 1, a combination of TTF and Na+ yields a maximum thermopower of -710 μV K-1 at 70 K, whereas a combination of TTF and Li+ yields a maximum thermopower of -600 μV K-1 at 90 K. For 2, we find that TTF doping yields a maximum thermopower of -800 μV K-1 at 90 K, whereas at 50 K, the largest thermopower (of -600 μV K-1) is obtain by a combination TTF and K+ doping. At room temperature, we obtain power factors of 73 μW m-1 K-2 for 1 (in combination with TTF and Na+) and 90 μW m-1 K-2 for 2 (with TTF). These are higher or comparable with reported power factors of other organic materials.We investigate strategies for increasing the thermopower of crown-ether-bridged anthraquinones. The novel design feature of these molecules is the presence of either (1) crown-ether or (2) diaza-crown-ether bridges attached to the side of the current-carrying anthraquinone wire. The crown-ether side groups selectively bind alkali-metal cations and when combined with TCNE or TTF dopants, provide a large phase-space for optimising thermoelectric properties. We find that the optimum combination of cations and dopants depends on the temperature range of interest. The

  19. Determinação de bussulfano em plasma através de cromatografia líquida de alta eficiência com detector de arranjo de diodos e derivatização com dietilditiocarbamato de sódio

    Directory of Open Access Journals (Sweden)

    Charline Fernanda Backes

    2012-01-01

    Full Text Available A high performance liquid chromatographic-diode array detection method for the determination of busulfan in plasma was developed and validated. Sample preparation consisted of protein precipitation followed by derivatization with sodium diethyldithiocarbamate and liquid-liquid extraction with methyl-tert-butyl ether. Chromatograms were monitored at 277 nm. Separation was carried out on a Lichrospher RP 18 column (5 µm, 250 x 4 mm. The mobile phase consisted of water and acetonitrile (20:80, v/v. The method presented adequate specificity, linearity, precision and accuracy and allowed reliable determination of busulfan in clinical plasma samples, being applied to three patients submitted to bone marrow transplantation.

  20. Electrochemical behaviour of denatured ethanol for use in direct ethanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Bayer, Domnik; Kintzel, Birgit; Joos, Martin; Cremers, Carsten; Tuebke, Jens [Fraunhofer-Institut fuer Chemische Technologie (ICT), Pfinztal (Germany)

    2010-07-01

    In the present study, two denaturing agents, an adjuvant to a denaturing agent and a mixture of a denaturing agend and the adjuvant were tested with regard to their fuel cell compatibility. Therefore, various electrochemical tests including cyclic voltammetry, chronoamperometry and differential electrochemical mass spectroscopy have been conducted at platinum as model catalyst in acidic and alkaline medium. In addition, the most promising denaturing agent, a mixture of tert-butyl ethyl ether (ETBE) with the adjuvant Bitrex {sup registered}, has also been tested at commercial fuel cell catalysts in both acidic and alkaline media. (orig.)

  1. Biodegradation of MTBE in reactors

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin

    2007-01-01

    The fuel oxygenate methyl tert-butyl ether (MTBE) was first introduced in the 1970’s to improve gasoline combustion efficiency and reduce emission of harmful gases. However, it has caused groundwater contamination in Denmark and in many locations worldwide through accidental releases from leaking...... underground gasoline storage tanks and pipelines. Both laboratory experiments and mathematical computer models were used to acquire knowledge on the scientific and engineering aspects related to the use of bioreactors for removal of MTBE from contaminated groundwater. Results from kinetic parameter...

  2. PREPARATIVE ISOLATION AND PURIFICATION OF CHEMICAL CONSTITUENTS OF BELAMCANDA BY MPLC, HSCCC AND PREP-HPLC

    OpenAIRE

    Wang, Xiaohong; Liang, Yong; Peng, Cuilin; Xie, Huichun; Pan, Man; Zhang, Tianyou; Ito, Yoichiro

    2011-01-01

    Combined with medium-pressure liquid chromatography (MPLC) and preparative high-pressure liquid chromatography (Prep-HPLC), high-speed countercurrent chromatography (HSCCC) was successfully applied for separation and purification of isoflavonoids from the extract of belamcanda. HSCCC separation was performed on a two-phase solvent system composed of methyl tert-butyl ether -ethyl acetate - n-butyl alcohol – acetonitrile −0.1% aqueous trifluoroacetic acid at a volume radio of 1:2:1:1:5. Semi-p...

  3. Life cycle analyses applied to first generation bio-fuels consumed in France; Analyses de Cycle de Vie appliquees aux biocarburants de premiere generation consommes en France. Rapport final

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2010-07-01

    This rather voluminous publication reports detailed life cycle analyses for the different present bio-fuels channels also named first-generation bio-fuels: bio-ethanol, bio-diesel, pure vegetal oils, and oil. After a recall of the general principles adopted for this life-cycle analysis, it reports the modelling of the different channels (agricultural steps, bio-fuel production steps, Ethyl tert-butyl ether or ETBE steps, vehicles, animal fats and used vegetal oils, soil assignment change). It gives synthetic descriptions of the different production ways (methyl ester from different plants, ethanol from different plants). It reports and compares the results obtained in terms of performance

  4. Life cycle analyses applied to first generation bio-fuels consumed in France

    International Nuclear Information System (INIS)

    2010-01-01

    This rather voluminous publication reports detailed life cycle analyses for the different present bio-fuels channels also named first-generation bio-fuels: bio-ethanol, bio-diesel, pure vegetal oils, and oil. After a recall of the general principles adopted for this life-cycle analysis, it reports the modelling of the different channels (agricultural steps, bio-fuel production steps, Ethyl tert-butyl ether or ETBE steps, vehicles, animal fats and used vegetal oils, soil assignment change). It gives synthetic descriptions of the different production ways (methyl ester from different plants, ethanol from different plants). It reports and compares the results obtained in terms of performance

  5. Scientific opinion on the evaluation of substances as acceptable previous cargoes for edible fats and oils

    DEFF Research Database (Denmark)

    Petersen, Annette

    Shipping of edible fats and oils into Europe is permitted in bulk tanks, provided that the previous cargo is included in a positive list. The European Commission requested EFSA to evaluate the acceptability as previous cargoes for fats and oils the substances calcium lignosulphonate, methyl acetate......, ethyl tert-butyl ether (ETBE) and ammonium sulphate. The evaluation was based on the same criteria as those used for the evaluation of the substances currently on the list in the Annex to Commission Directive 96/3/EC as acceptable previous cargoes for edible fats and oils. Methyl acetate and ETBE meet...

  6. Detonation characteristics of dimethyl ether and ethanol-air mixtures

    Science.gov (United States)

    Diakow, P.; Cross, M.; Ciccarelli, G.

    2015-05-01

    The detonation cell structure in dimethyl ether vapor and ethanol vapor-air mixtures was measured at atmospheric pressure and initial temperatures in the range of 293-373 K. Tests were carried out in a 6.2-m-long, 10-cm inner diameter tube. For more reactive mixtures, a series of orifice plates were used to promote deflagration-to-detonation transition in the first half of the tube. For less reactive mixtures prompt detonation initiation was achieved with an acetylene-oxygen driver. The soot foil technique was used to capture the detonation cell structure. The measured cell size was compared to the calculated one-dimensional detonation reaction zone length. For fuel-rich dimethyl ether mixtures the calculated reaction zone is highlighted by a temperature gradient profile with two maxima, i.e., double heat release. The detonation cell structure was interpreted as having two characteristic sizes over the full range of mixture compositions. For mixtures at the detonation propagation limits the large cellular structure approached a single-head spin, and the smaller cells approached the size of the tube diameter. There is little evidence to support the idea that the two cell sizes observed on the foils are related to the double heat release predicted for the rich mixtures. There was very little influence of initial temperature on the cell size over the temperature range investigated. A double heat release zone was not predicted for ethanol-air detonations. The detonation cell size for stoichiometric ethanol-air was found to be similar to the size of the small cells for dimethyl ether. The measured cell size for ethanol-air did not vary much with composition in the range of 30-40 mm. For mixtures near stoichiometric it was difficult to discern multiple cell sizes. However, near the detonation limits there was strong evidence of a larger cell structure similar to that observed in dimethyl ether air mixtures.

  7. Ring-opening of cyclic ethers by aluminum hydridotriphenylborate.

    Science.gov (United States)

    Mukherjee, Debabrata; Osseili, Hassan; Truong, Khai-Nghi; Spaniol, Thomas P; Okuda, Jun

    2017-03-25

    Molecular aluminum hydride [(L)AlH 2 ] (L = Me 3 TACD) reacted with 2 equiv. of BPh 3 in THF or THP to give the cationic alkoxides [(L)Al(OR)][HBPh 3 ] (R = nBu, nPent) by facile ring-opening of the cyclic ethers. The C α -O bond cleavage which involves the isolable intermediate [(L)AlH][HBPh 3 ] is a result of hydride transfer to C α from [HBPh 3 ] - .

  8. Extraction separation of lithium isotopes with crown-ethers

    International Nuclear Information System (INIS)

    Tsivadze, A.Yu.; Demin, S.V.; Levkin, A.V.; Zhilov, V.I.; Nikol'skij, S.F.; Knyazev, D.A.

    1990-01-01

    By the method of extraction chromatography lithium isotope separation coefficients are measured during chemical isotope exchange between lithium aquocomplex and its complex in chloroform with crown-ethers: benzo-15-crown-5, 15crown-5, dicyclohexano-18-crown-6 and dibenzo-18-crown-6. Lithium perchlorate and trichloroacetate are the salts extracted. Values of 6 Li/ 7 Li isotope separation are 1.0032-1.020

  9. Numerical investigation on the effect of injection pressure on the internal flow characteristics for diethyl ether, dimethyl ether and diesel fuel injectors using CFD

    Directory of Open Access Journals (Sweden)

    Vijayakumar Thulasi

    2011-01-01

    Full Text Available The spray characteristics of the diesel fuel are greatly affected by the cavitation formed inside the injector due to the high pressure differential across the nozzle. Many researchers across the globe are exploring the potential of using diethyl ether and dimethyl ether as an alternate for diesel fuel to meet the strict emission norms. Due to the variation in the fuel properties the internal flow characteristics in injectors for ether fuels are expected to be different from that of the diesel fuel. In this paper computational technique is used to study and compare the internal flow characteristics of diethyl ether, dimethyl ether and diesel fuel. The two phase flow model considering the fuel as a mixture of liquid and vapor is adopted for the simulation study. The injection pressure is varied from 100 to 400 bar and the flow characteristics of all three fuels are simulated and compared. Results indicate that all three fuels have distinct cavitating patterns owing to different property values. The dimethyl ether is found to be more cavitating than diesel and diethyl ether fuels as expected. The mass of fuel injected are found to be decreasing for the ether fuels when compared with diesel fuel at all injection pressures.

  10. Diethyl Ether Production Process with Various Catalyst Type

    Directory of Open Access Journals (Sweden)

    Widayat

    2013-01-01

    Full Text Available Several H-zeolite and HZSM-5 catalysts was preparated and their characters have also been investigated. H-zeolit Catalyst was preparated from Natural Zeolite that obtained from Malang District and Gunung Kidul District. Diethyl ether was produced by Ethanol with concentration of 95%. This research use fixed bed reactor that 1 gram of catalyst as bed catalyst, atmospheric pressure and temperature 140oC as the operating condition. Ethanol vapor from vaporization tank was driven by 200 ml/min Nitrogen stream. The responds in this research is liquid product concentration; diethyl ether, ethanol, methanol and water concentration. The results showed that the largest ethanol conversion was produced by the use of 56.44% HZSM-5 and the largest yield of diethyl ether diethyl was produced by the use of alumina and H-zeolite catalyst. The larger ratio between natural zeolite with HCl solvent will produce the larger surface area of catalyst and ethanol conversion. The largest ethanol conversion was produced at reactan ratio 1:20.

  11. Thermolysis of surface-immobilized phenethyl phenyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Britt, P.F.; Buchanan, A.C. III; Hitsman, V.M.

    1991-01-01

    Our research has focused on modeling the constraints on free-radical reactions that might be imposed in coal as a consequence of its cross-linked macromolecular structure by covalently bonding diphenylalkanes to an inert silica surface. A surface-immobilized phenethyl phenyl ether ({approx}PhCH{sub 2}CH{sub 2}POh, or {approx}PPE-3) has been prepared as a model for ether linkages in lignin by the condensation of p-HOPhCH{sub 2}CH{sub 2}OPh with the surface hydroxyls of a high purity fumed silica. Thermolysis of {approx}PPE-3 at saturation surface coverage at 375{degree}C produces {approx}PhCH = CH{sub 2} and PhOH as the major products which are consistent with the proposed free-radical chain mechanism for the decomposition of fluid-phase phenethyl phenyl ether. However, significant quantities of {approx}PhCH{sub 3} and PhCHO (ca. 18% of the products) are produced indicating the emergence of a new reaction pathway on the surface. The mechanism for the decomposition of {approx}PPE-3 will be discussed in light of this new information. 18 refs., 1 fig.

  12. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  13. Influence of RANEY Nickel on the Formation of Intermediates in the Degradation of Lignin

    Directory of Open Access Journals (Sweden)

    Daniel Forchheim

    2012-01-01

    Full Text Available Lignin forms an important part of lignocellulosic biomass and is an abundantly available residue. It is a potential renewable source of phenol. Liquefaction of enzymatic hydrolysis lignin as well as catalytical hydrodeoxygenation of the main intermediates in the degradation of lignin, that is, catechol and guaiacol, was studied. The cleavage of the ether bonds, which are abundant in the molecular structure of lignin, can be realised in near-critical water (573 to 673 K, 20 to 30 MPa. Hydrothermal treatment in this context provides high selectivity in respect to hydroxybenzenes, especially catechol. RANEY Nickel was found to be an adequate catalyst for hydrodeoxygenation. Although it does not influence the cleavage of ether bonds, RANEY Nickel favours the production of phenol from both lignin and catechol. The main product from hydrodeoxygenation of guaiacol with RANEY Nickel was cyclohexanol. Reaction mechanism and kinetics of the degradation of guaiacol were explored.

  14. Targeting proteins for degradation.

    Science.gov (United States)

    Schrader, Erin K; Harstad, Kristine G; Matouschek, Andreas

    2009-11-01

    Protein degradation plays a central role in many cellular functions. Misfolded and damaged proteins are removed from the cell to avoid toxicity. The concentrations of regulatory proteins are adjusted by degradation at the appropriate time. Both foreign and native proteins are digested into small peptides as part of the adaptive immune response. In eukaryotic cells, an ATP-dependent protease called the proteasome is responsible for much of this proteolysis. Proteins are targeted for proteasomal degradation by a two-part degron, which consists of a proteasome binding signal and a degradation initiation site. Here we describe how both components contribute to the specificity of degradation.

  15. Microwave spectra of 2-phenylethyl methyl ether and 2-phenylethyl methyl ether-argon: Conformation-dependent tunneling and complexation

    Science.gov (United States)

    Gurusinghe, Ranil M.; Tubergen, Michael J.

    2018-04-01

    High-resolution rotational spectra were recorded for 2-phenylethyl methyl ether and the 2-phenylethyl methyl ether - argon complex using a cavity-based Fourier transform microwave spectrometer. The spectra were assigned to the aao and g-ao monomer conformations and the g-ao - argon complex. Small tunneling splittings arising from more than one internal motion were resolved for eight transitions of the aao conformer; no tunneling splittings were observed in the spectra of the g-ao conformer or the argon complex. The calculated barriers (ωB97XD/6-311++G(d,p)) for methyl and phenyl internal rotations were found to be very similar for both conformers. The observation of tunneling splittings is limited to the aao conformer by relatively large barriers for the internal motions and sensitivity to the rotor axis angles within the two conformers.

  16. Preparation of poly(ether ether ketone)-based polymer electrolytes for fuel cell membranes using grafting technique

    International Nuclear Information System (INIS)

    Hasegawa, Shin; Suzuki, Yasuyuki; Maekawa, Yasunari

    2008-01-01

    Poly(ether ether ketone) (PEEK)-based polymer electrolyte membranes (PEMs) was successfully prepared by radiation grafting of a styrene monomer into PEEK films and the consequent selective sulfonation of the grafting chains in the film state. Using milder sulfonation, the sulfonation reactions proceeded at the grafted chains in preference to the phenylene rings of PEEK main chains; as a result, the grafted films could successfully transform to a PEM with conductivity of more than 0.1 S/cm. The ion exchange capacity (IEC) and conductivity of the grafted PEEK electrolyte membranes were controlled to the ranges of 1.2-2.9 mmol/g and 0.03-0.18 S/cm by changing the grafting degree. It should be noted that this is the first example of directly transforming super-engineering plastic films into a PEM using radiation grafting

  17. Preparation and characterization of poly (methyl methacrylate) and sulfonated poly (ether ether ketone) blend ultrafiltration membranes for protein separation applications

    International Nuclear Information System (INIS)

    Arthanareeswaran, G.; Thanikaivelan, P.; Raajenthiren, M.

    2009-01-01

    Poly (methyl methacrylate) (PMMA) and poly (methyl methacrylate)/sulfonated poly (ether ether ketone) (SPEEK) blend membranes were prepared by phase inversion technique in various composition using N,N'-dimethylformamide as solvent. The prepared membranes were characterized in terms of pure water flux, water content, porosity and thermal stability. The addition of SPEEK to the casting solution resulted in membranes with high pure water flux, water content, porosity and slightly low thermal stability. The cross sectional views of the blend membranes under electron microscope confirm the porosity and water flux results. The effect of the addition of SPEEK into the PMMA matrix on the extent of bovine serum albumin (BSA) separation was studied. It was found that the permeate flux increased significantly while the rejection of BSA from aqueous solution reduced moderately during ultrafiltration (UF) process. The effect was attributed to the increase in porosity and charge of the membrane due to the addition of SPEEK into the PMMA blend solution

  18. Pressure and temperature dependence of excess enthalpies of methanol + tetraethylene glycol dimethyl ether and methanol + polyethylene glycol dimethyl ether 250

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, E.R.; Coxam, J.Y.; Fernandez, J.; Grolier, J.P.E.

    1999-12-01

    The excess molar enthalpies at 323.15 K, 373.15 K, and 423.15 K, at 8 MPa, are reported for the binary mixtures methanol + tetraethylene glycol dimethyl ether (TEGDME) and methanol + poly(ethylene glycol) dimethyl ether 250 (PEGDME 250). Excess molar enthalpies were determined with a Setaram C-80 calorimeter equipped with a flow mixing cell. For both systems, the excess enthalpies are positive over the whole composition range, increasing with temperature. The H{sup E}(x) curves are slightly asymmetrical, and their maxima are skewed toward the methanol-rich region. The excess enthalpies slightly change with the pressure, the sign of this change being composition-dependent. In the case of mixtures with TEGDME, the experimental H{sup E} values have been compared with those predicted with the Gmehling et al. version of UNIFAC (Dortmund) and the Nitta-Chao and DISQUAC group contribution models.

  19. A new catalyst layer based on in situ pore generation of sulfonated poly(ether ether ketone) for PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Wan-Keun; Sung, Kyung A; Oh, Keun-Hwan; Choo, Min-Ju; Park, Jung-Ki [Department of Chemical and Biomolecular Engineering and WCU Energy Science and Engineering, Korea Advanced Institute of Science and Technology, 373-1, Guseong-dong, Yuseong-gu, Daejeon 305-701 (Korea); Cho, Kuk Young [Division of Advanced Materials Engineering, Kongju National University, 275, Budae-dong, Cheonan, Chungnam 303-717 (Korea); Cho, Ki-Yun [Fuel Cell Vehicle Team, Hyundai Motor Company and Kia Motors Corp., 104, Mabuk-Dong, Giheung-Gu, Yongin-Si, Gyunggi-Do 446-912 (Korea)

    2009-08-15

    A new concept of in situ pore generation to reduce water flooding in cathode catalyst layer (CCL) of polymer electrolyte membrane fuel cell (PEMFC) is proposed with the introduction of water soluble poly(ethylene glycol) (PEG) as a porogen to CCL based on sulfonated poly(ether ether ketone) (sPEEK). In this new type of CCL, PEG is directly removed by water produced during the cathode reaction. The new CCL exhibited much higher cell performance especially in mass transport limitation region compared to the pristine sPEEK-CCL. In addition, the presence of PEG in the new CCL lowered the glass transition temperature of the sPEEK binder, and it could improve the transference of catalyst layer onto the polymer electrolyte membrane. (author)

  20. Poly (ether ether ketone) membranes for fuel cells; Membranas de poli (eter eter cetona) sulfonado para celulas a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Marrero, Jacqueline C.; Gomes, Ailton de S.; Filho, Jose C.D., E-mail: jacquecosta@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Hui, Wang S. [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil); Oliveira, Vivianna S. de [Escola Tecnica Rezende-Rammel, Rio de Janeiro, RJ (Brazil)

    2015-07-01

    Polymeric membranes were developed using a SPEEK polymer matrix (sulphonated poly (ether ether ketone)), containing hygroscopic particles of zirconia (Zr) (incorporated by sol-gel method), for use as electrolyte membranes in fuel cells. SPEEK with different sulfonation degrees were used: 63 and 86%. The thermal analysis (TGA and DSC) was carried out to characterize the membranes and electrochemical impedance spectroscopy (EIS) was carried out to evaluating the proton conductivity of the membranes. Additional analysis were underway in order to characterize these membranes, which include: X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to evaluate the influence of zirconia and sulfonation degree on the properties of the membranes. (author)