WorldWideScience

Sample records for halogenated aliphatic compounds

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

    Science.gov (United States)

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

    1983-09-20

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

  2. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    OpenAIRE

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride),...

  3. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    Science.gov (United States)

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride), tetrachloroethylene (perchloroethylene), and trans-dibromoethylene were not degraded. PMID:2339874

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

    Science.gov (United States)

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

    1982-03-31

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

  5. Boiling points of halogenated aliphatic compounds: a quantitative structure-property relationship for prediction and validation.

    Science.gov (United States)

    Oberg, Tomas

    2004-01-01

    Halogenated aliphatic compounds have many technical uses, but substances within this group are also ubiquitous environmental pollutants that can affect the ozone layer and contribute to global warming. The establishment of quantitative structure-property relationships is of interest not only to fill in gaps in the available database but also to validate experimental data already acquired. The three-dimensional structures of 240 compounds were modeled with molecular mechanics prior to the generation of empirical descriptors. Two bilinear projection methods, principal component analysis (PCA) and partial-least-squares regression (PLSR), were used to identify outliers. PLSR was subsequently used to build a multivariate calibration model by extracting the latent variables that describe most of the covariation between the molecular structure and the boiling point. Boiling points were also estimated with an extension of the group contribution method of Stein and Brown.

  6. Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster.

    Science.gov (United States)

    Chroust, Karel; Pavlová, Martina; Prokop, Zbynek; Mendel, Jan; Bozková, Katerina; Kubát, Zdenek; Zajícková, Veronika; Damborský, Jiri

    2007-02-01

    Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.

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

    Science.gov (United States)

    Lim, Seung Joo; Fox, Peter

    2014-02-01

    The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

  8. The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries.

    Science.gov (United States)

    Peijnenburg, W; Eriksson, L; de Groot, A; Sjöström, M; Verboom, H

    1998-01-01

    Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.

  9. Generation of standard gas mixtures of halogenated, aliphatic, and aromatic compounds and prediction of the individual output rates based on molecular formula and boiling point.

    Science.gov (United States)

    Thorenz, Ute R; Kundel, Michael; Müller, Lars; Hoffmann, Thorsten

    2012-11-01

    In this work, we describe a simple diffusion capillary device for the generation of various organic test gases. Using a set of basic equations the output rate of the test gas devices can easily be predicted only based on the molecular formula and the boiling point of the compounds of interest. Since these parameters are easily accessible for a large number of potential analytes, even for those compounds which are typically not listed in physico-chemical handbooks or internet databases, the adjustment of the test gas source to the concentration range required for the individual analytical application is straightforward. The agreement of the predicted and measured values is shown to be valid for different groups of chemicals, such as halocarbons, alkanes, alkenes, and aromatic compounds and for different dimensions of the diffusion capillaries. The limits of the predictability of the output rates are explored and observed to result in an underprediction of the output rates when very thin capillaries are used. It is demonstrated that pressure variations are responsible for the observed deviation of the output rates. To overcome the influence of pressure variations and at the same time to establish a suitable test gas source for highly volatile compounds, also the usability of permeation sources is explored, for example for the generation of molecular bromine test gases.

  10. Organic halogen compounds in the environment

    International Nuclear Information System (INIS)

    1979-07-01

    There are 20 research reports on selected problems concerning the analysis, the occurence, and the behaviour of a wide spectrum of organic halogen compounds. The work was carried out in the framework of the project 'Organic Halogen Compounds in the Environment', financed by the BMFT, between 1975 and 1978. (orig.) [de

  11. Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

    Science.gov (United States)

    Crebelli, R; Carere, A; Leopardi, P; Conti, L; Fassio, F; Raiteri, F; Barone, D; Ciliutti, P; Cinelli, S; Vericat, J A

    1999-03-01

    Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

  12. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

    2002-06-01

    Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

  13. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

    2003-07-01

    Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

  14. Certain Aliphatic Nitramines and Related Compounds

    Science.gov (United States)

    1944-11-29

    compounds are ruite unstable. It has beer , impossible to prepare N-iodcmifcramines by any synthesis thus far attempted and the N-bromonitramines...end of tb’f. tine the solution v;as soured over 1500 g. of crac3:cd ice end neutralised with about GOO z» ot sodium bicarbonate. After extraction

  15. Kinetic isotope effects and aliphatic diazo-compounds

    International Nuclear Information System (INIS)

    Albery, W.J.; Conway, C.W.; Hall, J.A.

    1976-01-01

    Results are reported for the variation of the rate of decomposition of ethyl diazomalonate (EDM) and diazomalonate anions with pH and for the deuterium solvent isotope effect for EDM. The shape of the pH profile is explained by successive protonations of the anions. Ethyl diazoacetate is observed as an intermediate in the decomposition of EDM. The degree of proton transfer in the EDM transition state is deduced from the solvent isotope effect and the results together with those for other aliphatic diazo-compounds are discussed in terms of the Marcus theory. (author)

  16. Allergic contact dermatitis due to highly reactive halogenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, F C; Ive, F A

    1983-11-01

    Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

  17. Estimates of Gibbs free energies of formation of chlorinated aliphatic compounds

    NARCIS (Netherlands)

    Dolfing, Jan; Janssen, Dick B.

    1994-01-01

    The Gibbs free energy of formation of chlorinated aliphatic compounds was estimated with Mavrovouniotis' group contribution method. The group contribution of chlorine was estimated from the scarce data available on chlorinated aliphatics in the literature, and found to vary somewhat according to the

  18. Fate of aliphatic compounds in nitric acid processing solutions

    International Nuclear Information System (INIS)

    Clark, W.E.; Howerton, W.B.

    1975-01-01

    The reaction of hyperazeotropic iodic acid-saturated nitric acid with short chain aliphatic iodides, nitrates, and acids was studied in order to determine the conditions for complete removal of organic materials from nitric acid systems. The aliphatic iodides are converted to the nitrates and the nitrates in strong HNO 3 are extensively converted into CO 2 and acids. The aliphatic acids are rather stable; acetic acid was unattacked by boiling in 20M HNO 3 and n-butyric acid was 80 percent unattacked. The dibasic acids oxalic and malonic are extensively attacked, but succinic acid is relatively stable. A wet oxidation method is successful in destroying acetic acid in 5 to 8M HNO 3 . (U.S.)

  19. PATTERN RECOGNITION STUDIES OF HALOGENATED ORGANIC COMPOUNDS USING CONDUCTING POLYMER SENSOR ARRAYS. (R825323)

    Science.gov (United States)

    Direct measurement of volatile and semivolatile halogenated organic compounds of environmental interest was carried out using arrays of conducting polymer sensors. Mathematical expressions of the sensor arrays using microscopic polymer network model is described. A classical, non...

  20. Halogenated organic compounds in archived whale oil: A pre-industrial record

    International Nuclear Information System (INIS)

    Teuten, Emma L.; Reddy, Christopher M.

    2007-01-01

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s

  1. Halogenated organic compounds in archived whale oil: A pre-industrial record

    Energy Technology Data Exchange (ETDEWEB)

    Teuten, Emma L. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: emma.teuten@plymouth.ac.uk; Reddy, Christopher M. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: creddy@whoi.edu

    2007-02-15

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s.

  2. A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

    Science.gov (United States)

    Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

    1998-01-01

    Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

  3. Six-membered ring aliphatic compounds: A search for regularities in phase transitions

    International Nuclear Information System (INIS)

    Nagrimanov, Ruslan N.; Solomonov, Boris N.; Emel’yanenko, Vladimir N.; Verevkin, Sergey P.

    2016-01-01

    Highlights: • Thermodynamics of sublimation and solution of halogen adamantanes is studied. • Sublimation enthalpies derived from transpiration and solution calorimetry in agreement. • Enthalpies of fusion measured by DSC and used to derive vaporization enthalpies. • Structure-property analysis of vaporization enthalpies was performed. - Abstract: Absolute vapor pressures of 1-Cl-adamantane, 2-Cl-adamantane, 1-Br-adamantane, 2-Br-adamantane, as well as of Br-cyclohexane were measured by using the transpiration method. Standard molar enthalpies of sublimation of halogen substituted adamantanes at 298.15 K were derived from vapor pressure temperature dependences. Standard molar enthalpies of solution of adamantane and halogen adamantanes in cyclohexane were measured with a high-precision solution calorimeter. A theoretical procedure based on the solution calorimetry was applied to derive sublimation enthalpies of halogen adamantanes independently. Molar enthalpies of fusion were measured with help of DSC. The consistent data set of phase transitions for each compound was evaluated and used for discussion of structure-property relations in adamantane and cyclohexane derivatives. A simple way to predict enthalpies of vaporization of compounds containing six-membered rings was suggested for practical thermochemical calculations.

  4. Flue gas corrosion through halogen compounds in fuel gas

    Energy Technology Data Exchange (ETDEWEB)

    Eisenmann, R

    1987-04-01

    The halogens of chlorine and fluorine greatly influence the corrosion speed of metal materials. If small quantities of chlorinated and/or fluorinated hydrocarbons are present in fuel gas like in landfill gas, they must not result in enhanced corrosion of gas appliances. Data from literature and the initial results of tests run by the author indicate that quantities at about 10 mg/cbm (in terms of chlorine) can be assumed not to cause any noticeable acceleration of corrosion speed.

  5. Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

    Energy Technology Data Exchange (ETDEWEB)

    Skinner, G.A.; Parker, L.E.; Marshall, P.J.

    1978-01-01

    Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

  6. Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity.

    Science.gov (United States)

    Zhang, Yimeng; Chu, Wenhai; Yao, Dechang; Yin, Daqiang

    2017-08-01

    The comprehensive control efficiency for the formation potentials (FPs) of a range of regulated and unregulated halogenated disinfection by-products (DBPs) (including carbonaceous DBPs (C-DBPs), nitrogenous DBPs (N-DBPs), and iodinated DBPs (I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment (coagulation-sedimentation, pre-sand filtration), ozone-biological activated carbon (O 3 -BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated. The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide, and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O 3 -BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON. After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles (HANs)≫haloacetamides (HAMs)>haloacetic acids (HAAs)>trihalomethanes (THMs)>halonitromethanes (HNMs)≫I-DBPs (I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored. Copyright © 2017. Published by Elsevier B.V.

  7. Organic halogen compounds and surface water pollution; Composti organoalogenati alifatici e contaminazione delle acque superficiali

    Energy Technology Data Exchange (ETDEWEB)

    Cocchioni, M.; Pellegrini, M. G.; Grappasonni, I.; Nacciarriti, L.; Bernacchia, G. [Camerino, Univ. (Italy). Dipt. di Scienze Igienistiche e Sanitarie-Ambientali

    1997-03-01

    A brief review of the effects of halogenated organic compounds on the fluvial ecosystem is followed by results from a detailed monitoring of these substances in all the Marches Region rivers. The results show generally modest concentrations, except for sporadic peaks for chloroform. Sites revealing significant concentrations of halogenated organic compounds also manifested a worsening of the biological quality of the waters with lessening of E.B.I. Attention is drawn to the negative effects of indiscriminate chlorination of purification plant outputs, as this practice often fails to resolve infective problems and in itself adds toxicity to the watercourse.

  8. Chiral halogenated Schiff base compounds: green synthesis, anticancer activity and DNA-binding study

    Science.gov (United States)

    Ariyaeifar, Mahnaz; Amiri Rudbari, Hadi; Sahihi, Mehdi; Kazemi, Zahra; Kajani, Abolghasem Abbasi; Zali-Boeini, Hassan; Kordestani, Nazanin; Bruno, Giuseppe; Gharaghani, Sajjad

    2018-06-01

    Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV-vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (Rsbnd ClBr) > (Rsbnd Cl2) > (Rsbnd Br2) > (Rsbnd I2) and (Ssbnd ClBr) > (Ssbnd Cl2) > (Ssbnd Br2) > (Ssbnd I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the Ssbnd and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (Hsbnd and X-bond and hX-bond) between synthesized compounds and base pairs of DNA.

  9. Changes in patterns of persistent halogenated compounds through a pelagic food web in the Baltic Sea

    DEFF Research Database (Denmark)

    Stephansen, Diana Agnete; Svendsen, Tore Christian; Vorkamp, Katrin

    2012-01-01

    The concentrations and patterns of persistent halogenated compounds (PHCs), including polychlorinated biphenyls (PCBs), DDT, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs) were examined in a pelagic food web from the southern Baltic Sea consisting...... for the assessment of PHC patterns, e.g. for tracing migratory fish....

  10. A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES USING MOLECULAR DESCRIPTORS

    Directory of Open Access Journals (Sweden)

    B. Souyei

    2013-12-01

    Full Text Available A quantitative structure–property relationship (QSPR study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes to their normal boiling point (NBP and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in remarkable correlations with the descriptors of blokes constitutionals (CON, and connectivity indices (CI (R2 = 0.950, δ = 0.766 (R2 = 0.969, δ = 0.782 respectively.

  11. A method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Fakhriev, A.M.; Galiautdinov, N.G.; Kashevarov, L.A.; Mazgarov, A.M.

    1982-01-01

    The method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons, which involves extracting hydrocarbons using a dimethylsulfoxide extractant, is improved by using a dimethylsulfoxide blend and 10-60 percent (by volume) diethylenetriamine or polyethylenepolyamine which contains diethylenetriamine, triethylenetetramine and tetraethylenepentamine, in order to eliminate the above compounds. Polyethylenepolyamine is produced as a by-product during the production of ethylenediamine. Elimination is performed at 0-50 degrees and 1-60 atmospheres of pressure. Here, the extractant may contain up to 10 percent water. The use of the proposed method, rather than the existing method, will make it possible to increase hydrocarbon elimination from mercaptans by 40 percent and from H/sub 2/S by 10 percent when the same amount is eliminated from dialkylsulfides.

  12. Radiocarbon content of synthetic and natural semi-volatile halogenated organic compounds

    International Nuclear Information System (INIS)

    Reddy, C.M.; Xu Li; Eglinton, T.I.; Boon, J.P.; Faulkner, D.J.

    2002-01-01

    New developments in molecular-level 14 C analysis techniques enable clues about natural versus commercial synthesis of trace organic contaminants. - Some halogenated organic compounds, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polybrominated diphenyl ethers (PBDEs), have been suggested to have natural sources but separating these compounds from their commercially synthesized counterparts is difficult. Molecular-level 14 C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals ( 14 C-free) and natural compounds should have 'modern' or 'contemporary' 14 C levels. As a baseline study, we measured, for the first time, the 14 C abundance in commercial PCB and PBDE mixtures, a number of organochlorine pesticides, as well as one natural product 2-(3', 5'-dibromo-2'-methoxyphenoxy)-3,5-dibromoanisole. The latter compound was isolated from a marine sponge and is similar in structure to a PBDE. All of the synthetic compounds were 14 C-free except for the pesticide toxaphene, which had a modern 14 C abundance, as did the brominated natural compound. The result for toxaphene was not surprising since it was commercially synthesized by the chlorination of camphene derived from pine trees. These results suggest that measuring the 14 C content of halogenated organic compounds may be quite useful in establishing whether organic compounds encountered in the environment have natural or synthetic origins (or both) provided that any synthetic counterparts derive from petrochemical feedstock

  13. Identifying bioaccumulative halogenated organic compounds using a nontargeted analytical approach: seabirds as sentinels.

    Directory of Open Access Journals (Sweden)

    Christopher J Millow

    Full Text Available Persistent organic pollutants (POPs are typically monitored via targeted mass spectrometry, which potentially identifies only a fraction of the contaminants actually present in environmental samples. With new anthropogenic compounds continuously introduced to the environment, novel and proactive approaches that provide a comprehensive alternative to targeted methods are needed in order to more completely characterize the diversity of known and unknown compounds likely to cause adverse effects. Nontargeted mass spectrometry attempts to extensively screen for compounds, providing a feasible approach for identifying contaminants that warrant future monitoring. We employed a nontargeted analytical method using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS to characterize halogenated organic compounds (HOCs in California Black skimmer (Rynchops niger eggs. Our study identified 111 HOCs; 84 of these compounds were regularly detected via targeted approaches, while 27 were classified as typically unmonitored or unknown. Typically unmonitored compounds of note in bird eggs included tris(4-chlorophenylmethane (TCPM, tris(4-chlorophenylmethanol (TCPMOH, triclosan, permethrin, heptachloro-1'-methyl-1,2'-bipyrrole (MBP, as well as four halogenated unknown compounds that could not be identified through database searching or the literature. The presence of these compounds in Black skimmer eggs suggests they are persistent, bioaccumulative, potentially biomagnifying, and maternally transferring. Our results highlight the utility and importance of employing nontargeted analytical tools to assess true contaminant burdens in organisms, as well as to demonstrate the value in using environmental sentinels to proactively identify novel contaminants.

  14. Possibilities of analyzing dump and sewage gas, and determination of halogen and sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Eisenmann, R

    1985-01-01

    In connection with the utilization of refuse and sewage gas efficacions analytical methods are gaining increasing importance especially with regard to halogen and sulfur compounds. The paper describes various possibilities to determine those substances. Besides gas chromatography it takes into account classic analytical methods which can be superior in biogas analytics to modern physical processes. The advantages and disadvantages of each method are discussed and practical experiences obtained by their application reported.

  15. Separation of halogens from uranium compounds by means of pyrohydrolysis and their determination by ion chromatography

    International Nuclear Information System (INIS)

    Pires, M.A.F.; Brandao Filho, D.; Abrao, A.

    1987-07-01

    This paper describs the determination of fluorine in nuclear grade uranium compounds by means of phyrohydrolysis. A stream of wet oxygem at a temperature of 900 to 1000 0 C is passed through a quartz tube where the powdered samples is put. The halogens are volatilized as their respective acids that are absorbed in a buffer solution or water. The measurements are made with ion-seletive eletrodes or by ion chromatography. The sensitivity is of 1μg F - /g and 5μg Cl - /g. The separation of fluorine from uranium compounds by diferent methods is discussed. (Author) [pt

  16. Gas-liquid partitioning of halogenated volatile organic compounds in aqueous cyclodextrin solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ondo, Daniel; Barankova, Eva [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Dohnal, Vladimir, E-mail: dohnalv@vscht.cz [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)

    2011-08-15

    Highlights: > Binding of halogenated VOCs with cyclodextrins examined through g-l partitioning. > Complex stabilities reflect host-guest size matching and hydrophobic interaction. > Presence of halogens in the guest molecule stabilizes the binding. > Thermodynamic origin of the binding varies greatly among the systems studied. > Results obey the guest-CD global enthalpy-entropy compensation relationship. - Abstract: Gas-liquid partitioning coefficients (K{sub GL}) were measured for halogenated volatile organic compounds (VOCs), namely 1-chlorobutane, methoxyflurane, pentafluoropropan-1-ol, heptafluorobutan-1-ol, {alpha},{alpha},{alpha}-trifluorotoluene, and toluene in aqueous solutions of natural {alpha}-, {beta}-, and {gamma}-cyclodextrins (CDs) at temperatures from (273.35 to 326.35) K employing the techniques of headspace gas chromatography and inert gas stripping. The binding constants of the 1:1 inclusion complex formation between the VOCs and CDs were evaluated from the depression of the VOCs volatility as a function of CD concentration. The host-guest size matching and the hydrophobic interaction concept were used to rationalize the observed widely different affinity of the VOC-CD pairs to form the inclusion complex. The enthalpic and entropic component of the standard Gibbs free energy of complex formation as derived from the temperature dependence of the binding constant indicate the thermodynamic origin of the binding to vary greatly among the systems studied, but follow the global enthalpy-entropy compensation relationships reported previously in the literature.

  17. Removal of halogenated organic compounds in landfill gas by top covers containing zero-valent iron

    DEFF Research Database (Denmark)

    Scheutz, Charlotte; Winther, K.; Kjeldsen, Peter

    2000-01-01

    Transformation of gaseous CCl3F and CCl4 by zero-valent iron was studied in systems unsaturated with water under anaerobic conditionssin an N2 gas and in a landfill gas atmosphere. The transformation was studied in batch as well as flow-through column tests. In both systems, the transformation....... During continuous aerobic conditions, the transformation of CCl3F decreased toward zero. Model calculations show that use of zero-valent iron in landfill top covers is a potential treatment technology for emission reduction of halogenated trace compounds from landfills....

  18. Anaerobic biodegradation of halogenated and nonhalogenated N-, s-, and o-heterocyclic compounds in aquifer slurries

    Science.gov (United States)

    Adrian, Neal R.; Suflita, Joseph M.

    1994-01-01

    The fate of several halogenated and nonhalogenated heterocyclic compounds in anoxic aquifer slurries was investigated Substrate depletion and methane formation were monitored in serum bottle incubations by HPLC and GC, respectively Pyridine, pyrimidine, thiophene, and furan were not mineralized following an 11-month incubation, but the corresponding carboxylated or oxygenated compounds were That is, >74% of the theoretically expected amount of methane was recovered from nicotinic acid, uracil, or 2-furoic acid Chlorinated derivatives, like 2 chloro- or 6-chloronicotinic acid, as well as 4 chloro- and 5-chlorouracil resisted mineralization However, 5-bromouracil was reductively dehalogenated to stoichiometric amounts of uracil, whereas 2-chloropyrimidine was metabolized to a more polar unidentified compound that resisted further anaerobic biodegradation Microorganisms acclimated to 5-bromouracil were unable to transform 4 chloro or 5 chlorouracil These findings illustrate how the structure of heterocyclic contaminants influences their susceptibility to anaerobic decay

  19. Liquid chromatographic separation and indirect detection of non-absorbing aliphatic compounds using m-nitrophenol as a detection agent

    International Nuclear Information System (INIS)

    Lee, Seung Seok; Kang, Sam Woo; Moon, Young Ja

    1991-01-01

    m-Nitrophenol(m-NP) was a detection agent for the use of the detection and separation of non-absorbing compounds such as aliphatic acids, alcohols, amines and tetraalkylammonium salts by indirect photometric detection in reversed-phase liquid chromatography. Response of samples was investigated to the several factors such as pH, temperature, and concentration of MeOH as well as concentration of detection reagent in mobile phase. The separation of several mixtures were attempted under optimum condition. (Author)

  20. Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

    International Nuclear Information System (INIS)

    Guo Gaimei; Chen Xiaodong

    2009-01-01

    The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl - ) and aqueous bromine (HOBr/OBr - ) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation

  1. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Sundin, Peter; Wesén, Clas

    1997-01-01

    Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation......), atomic emission spectrometry, and mass spectrometry. For most environmental samples, chlorinated FAMEs must be enriched prior to GC. ELCD is a useful detection method for indicating halogenated FAMEs in the chromatograms, and tentative identification of the halogenated species can be obtained...

  2. Labelling of some iodinated organic compounds by halogen exchange in organic media

    International Nuclear Information System (INIS)

    Hallaba, E.; Suhybani, A.Al-; Khowaiter, S.Al-; Abdel-Wahid, M.

    1983-01-01

    Describes a general method for labelling Rose Bengal in an organic medium. An isotopic exchange technique with interactive iodine as carrier for radioiodine is used. The effect of temperature, carrier, pH of the solvent and solvent are investigated. The optimum conditions for maximum yield of exchange are: .0.2 micro mole carrier inactive iodine per one micro mole of Rose Bengal, reaction mixture is 10ml ethyl alcohol 96% as a solvent for Rose Bengal and 3ml of ether or carbon tetrachloride containing the inactive and radioiodine. In case of ether, the reaction is slow and is completed in two hours with maximum yield of 90% at boiling temperature. Addition of 175 λ of 1 M acetate buffer with carbon tetrachloride gave a yield of 90% in one hour. This method can be applied successfully to label any iodinated organic compound, such as hypuran, thyroxine, tyrosine or aliphatic fatty acids, for application in nuclear medicine. 10 Ref

  3. Evaluation of modulators and electron-capture detectors for comprehensive two-dimensional GC of halogenated organic compounds

    NARCIS (Netherlands)

    Kristenson, E.M.; Korytar, P.; Danielsson, C.; Kallio, M.; Brandt, M.; Makela, J.; Vreuls, R.J.J.; Beens, J.; Brinkman, U.A.T.

    2003-01-01

    Different cryogenic and a heated GC×GC modulator(s) were evaluated and compared for the analysis of high-boiling halogenated compounds. The cryogenic modulators investigated were: (i) the longitudinally modulated cryogenic system; (ii) the liquid-nitrogen-cooled jet modulator (KT2001); (iii) a

  4. A survey of indoor pollution by volatile organo halogen compounds in Katsushika, Tokyo, Japan

    Energy Technology Data Exchange (ETDEWEB)

    Amagai, T.; Olansandan; Matsushita, H. [University of Shizuoka, Shizuoka (Japan); Ono, M. [National Institute for Environmental Studies, Ibaraki (Japan); Nakai, S. [Yokohama National University, Yokohama (Japan); Tamura, K. [National Institute for Minamata Disease, Kumamoto (Japan); Maeda, K. [Tokyo Kasel University, Tokyo (Japan)

    1999-07-01

    A survey of indoor and outdoor pollution by 10 volatile organo halogen compounds (VOHCs) was performed in Katsushika Ward, Tokyo, Japan. Thirteen houses in February and 30 houses in July were sampled. Four consecutive 24-hour samples were collected by passive sampling from living room, kitchen, bedroom, bathroom and outdoors in February and July 1995. Indoor concentrations of carbon tetrachloride and trichloroethylene were at nearly the same as outdoor concentrations; therefore, it was concluded that indoor pollution by these compounds was primarily due to penetration of outdoor pollutants. Indoor concentrations of some VOHCs were considerably higher than outdoor concentrations and they varied widely between households. The list included: p-dichlorobenzene, tetrachloroethylene and tri halomethanes, for which emission sources were insect repellents, dry-cleaned clothes, and tap water, showers and bathtub water, respectively. Indoor concentrations of these compounds were higher in reinforced concrete houses than in wooden houses or wooden houses with mortar walls. This suggests that airtightness of the rooms is responsible for high indoor VOHC concentrations. (author)

  5. Aliphatic alkenes and alkynes

    International Nuclear Information System (INIS)

    Cserep, Gy.

    1981-01-01

    This chapter describes the decomposition of aliphatic alkenes and alkynes by radiolysis, concentrating on results published after 1968. The radiolysis of individual compounds, product yields and possible mechanisms of radiation chemical reactions are discussed in detail. The radiolysis of mixtures of aliphatic alkenes is also investigated. General information on decomposition and some condensation reactions is also presented. (Auth./C.F.)

  6. The gas-chromatographic and gas-chromatographic-mass-spectrometric identification of halogen-containing organic compounds

    Science.gov (United States)

    Gidaspov, B. V.; Zenkevich, I. G.; Rodin, A. A.

    1989-09-01

    The problem of identifying halogen-containing organic compounds in their gas-chromatographic and gas-chromatographic-mass-spectrometric (GC-MS) determination in different materials has been examined. Particular attention has been paid not to the complete characterisation of methods for carrying out this analysis but to the most important problem of increasing the selectivity at the stages of sampling, separation, and interpretation of the gas-chromatographic and GC-MS information. The bibliography contains 292 references.

  7. Modified solution calorimetry approach for determination of vaporization and sublimation enthalpies of branched-chain aliphatic and alkyl aromatic compounds at T = 298.15 K

    International Nuclear Information System (INIS)

    Varfolomeev, Mikhail A.; Novikov, Vladimir B.; Nagrimanov, Ruslan N.; Solomonov, Boris N.

    2015-01-01

    Highlights: • Solution enthalpies of 18 branching-chain alkyl aromatic and aliphatic compounds in cyclohexane were measured. • Group contributions to the enthalpy of solvation due to branching and substitution in carbon chain were evaluated. • Modified solution calorimetry based approach for determination of vaporization/sublimation enthalpies was proposed. • This approach provides vaporization/sublimation enthalpies directly at T = 298.15 K. • Vaporization/sublimation enthalpies of 35 branched-chain alkyl aromatic and aliphatic compounds were determined. - Abstract: The enthalpies of solution, solvation and vaporization/sublimation are interrelated values combined in the simplest thermodynamic circle. Hence, experimental determination of vaporization/sublimation enthalpy can be substituted by experimentally simpler determination of solution enthalpy when solvation enthalpy is known. Previously it was found that solvation enthalpies of a wide range of unbranched aliphatic and aromatic solutes in saturated hydrocarbons are in good linear correlation with their molar refraction values. This allows to estimate the vaporization/sublimation enthalpy of any unbranched organic compound from its solution enthalpy in saturated hydrocarbon and molar refraction. In the present work this approach was modified for determination of vaporization/sublimation enthalpy of branched-chain alkyl aromatic and aliphatic compounds. Group contributions to the enthalpy of solvation due to the branching of carbon chain were evaluated. Enthalpies of solution at infinite dilution of 18 branched-chain aliphatic and alkyl aromatic compounds were measured at T = 298.15 K. Vaporization/sublimation enthalpies for 35 branched aliphatic and alkyl aromatic compounds were determined by using modified solution calorimetry approach. These values are in good agreement with available literature data on vaporization/sublimation enthalpies obtained by conventional methods.

  8. Exhaled human breath measurement method for assessing exposure to halogenated volatile organic compounds.

    Science.gov (United States)

    Pleil, J D; Lindstrom, A B

    1997-05-01

    The organic constituents of exhaled human breath are representative of blood-borne concentrations through gas exchange in the blood/breath interface in the lungs. The presence of specific compounds can be an indicator of recent exposure or represent a biological response of the subject. For volatile organic compounds (VOCs), sampling and analysis of breath is preferred to direct measurement from blood samples because breath collection is noninvasive, potentially infectious waste is avoided, and the measurement of gas-phase analytes is much simpler in a gas matrix rather than in a complex biological tissue such as blood. To exploit these advantages, we have developed the "single breath canister" (SBC) technique, a simple direct collection method for individual alveolar breath samples, and adapted conventional gas chromatography-mass spectrometry analytical methods for trace-concentration VOC analysis. The focus of this paper is to describe briefly the techniques for making VOC measurements in breath, to present some specific applications for which these methods are relevant, and to demonstrate how to estimate exposure to example VOCs on the basis of breath elimination. We present data from three different exposure scenarios: (a) vinyl chloride and cis-1,2-dichloroethene from showering with contaminated water from a private well, (b) chloroform and bromodichloromethane from high-intensity swimming in chlorinated pool water, and (c) trichloroethene from a controlled exposure chamber experiment. In all cases, for all subjects, the experiment is the same: preexposure breath measurement, exposure to halogenated VOC, and a postexposure time-dependent series of breath measurements. Data are presented only to demonstrate the use of the method and how to interpret the analytical results.

  9. Gamma radiolysis of aliphatic sulfur compounds in aqueous solutions. A study to contribute to the analysis of the end products of the OH radical-induced oxidation of aliphatic mercaptanes, sulfides, and disulfides

    International Nuclear Information System (INIS)

    Weiss, J.

    1982-01-01

    By identifying and determining numerous hitherto unknown end products, the study in hand contributes to a better insight into the radiation chemical processes occurring in OH radical-induced oxidation of aliphatic sulfur compounds. An extraction method has been developed for the qualitative and quantitative analysis of end products in aqueous solution in order to determine these compounds down to the level of trace amounts. Separation of endproducts is achieved by means of gas chromatography and high-pressure liquid chromatography, subsequent identification by GC-MS analysis. Aliphatic mercaptanes are oxidized by OH radicals to thiyl radicals which after combination can be detected as disulfide. At high radiation doses, secondary reactions will lead to polysulfides of which the homologues could first be prepared as the pure substance. The end products of the γ-radiolysis of aliphatic thioethers are determined to be dithia compounds, symmetrical or asymmetrical disulfides, or polysulfides, depending on the thioethers. With some end products, the radiation chemical yield is found to be a function of the absorbed dose so that material balances are impossible. Intermediate thiyl, α-alkyl mercaptoalkyl or alkyl radicals can be captured by tetramethyl ethylene, cyclohexene or p-benzoquinone, and can then be identified as the relevant adducts. (orig./RB) [de

  10. Quantitative structure–activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: Wing spot test of Drosophila melanogaster

    Czech Academy of Sciences Publication Activity Database

    Chroust, K.; Pavlová, M.; Prokop, Z.; Mendel, Jan; Božková, K.; Kubát, Z.; Zajíčková, V.; Damborský, J.

    2007-01-01

    Roč. 67, č. 1 (2007), s. 152-159 ISSN 0045-6535 Institutional research plan: CEZ:AV0Z60930519 Keywords : toxicity * wing spot test * QSAR Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.739, year: 2007

  11. Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

    International Nuclear Information System (INIS)

    Poleshchuk, O. K.; Branchadell, V.; Ritter, R. A.; Fateev, A. V.

    2008-01-01

    We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

  12. Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. K., E-mail: poleshch@tspu.edu.ru [Tomsk State Pedagogical University (Russian Federation); Branchadell, V. [Universitat Autonoma de Barcelona, Departament de Quimica (Spain); Ritter, R. A.; Fateev, A. V. [Tomsk State Pedagogical University (Russian Federation)

    2008-01-15

    We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

  13. Generation and alteration of the defects induced by particle irradiation and electromagnetic radiation in alkali halogen compounds

    International Nuclear Information System (INIS)

    Nistor, L.C.

    1979-01-01

    Interactions between electron beams, CO 2 - laser radiation and alkali halogen compound have led to interesting results: 1. The development of two types of F-centre respectively in normal lattice or near the dislocations. 2. The beginning of metal colloids development process at low temperature when a thermal treatment is applied. 3. An experimental confirmation of the Pooley-Hersh model for crystal defects has been brought up. 4. The surface penetration is an explosive process. 5. Surface polygonizations were also investigated. A model has been proposed to describe the destructive channels development within alkali halogen crystals with molecular anions impurities of less than 10 ppm. KCl monocrystals of advanced purity level was prepared for building up passive optical components of strong CO 2 lasers. (author)

  14. Computing sextic centrifugal distortion constants by DFT: A benchmark analysis on halogenated compounds

    Science.gov (United States)

    Pietropolli Charmet, Andrea; Stoppa, Paolo; Tasinato, Nicola; Giorgianni, Santi

    2017-05-01

    This work presents a benchmark study on the calculation of the sextic centrifugal distortion constants employing cubic force fields computed by means of density functional theory (DFT). For a set of semi-rigid halogenated organic compounds several functionals (B2PLYP, B3LYP, B3PW91, M06, M06-2X, O3LYP, X3LYP, ωB97XD, CAM-B3LYP, LC-ωPBE, PBE0, B97-1 and B97-D) were used for computing the sextic centrifugal distortion constants. The effects related to the size of basis sets and the performances of hybrid approaches, where the harmonic data obtained at higher level of electronic correlation are coupled with cubic force constants yielded by DFT functionals, are presented and discussed. The predicted values were compared to both the available data published in the literature and those obtained by calculations carried out at increasing level of electronic correlation: Hartree-Fock Self Consistent Field (HF-SCF), second order Møller-Plesset perturbation theory (MP2), and coupled-cluster single and double (CCSD) level of theory. Different hybrid approaches, having the cubic force field computed at DFT level of theory coupled to harmonic data computed at increasing level of electronic correlation (up to CCSD level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T)) were considered. The obtained results demonstrate that they can represent reliable and computationally affordable methods to predict sextic centrifugal terms with an accuracy almost comparable to that yielded by the more expensive anharmonic force fields fully computed at MP2 and CCSD levels of theory. In view of their reduced computational cost, these hybrid approaches pave the route to the study of more complex systems.

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

    NARCIS (Netherlands)

    Favre-Bulle, Olivier

    1992-01-01

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

  16. Apparatus for washing out halogens

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M; Hahn, J; Kroenig, W

    1941-03-26

    An apparatus is described for washing out of halogens and the like or liquid halogen compounds from the products, which are formed on pressure hydrogenation or splitting of carbon-containing material in the presence of halogens or halogen compounds, consisting of a washing apparatus installed between the reaction vessel and the hot separator, which is inclined in relatively small space for steam regulation and contains, with the steam, arranged baffles, especially spirals.

  17. Estimating the octanol/water partition coefficient for aliphatic organic compounds using semi-empirical electrotopological index.

    Science.gov (United States)

    Souza, Erica Silva; Zaramello, Laize; Kuhnen, Carlos Alberto; Junkes, Berenice da Silva; Yunes, Rosendo Augusto; Heinzen, Vilma Edite Fonseca

    2011-01-01

    A new possibility for estimating the octanol/water coefficient (log P) was investigated using only one descriptor, the semi-empirical electrotopological index (I(SET)). The predictability of four octanol/water partition coefficient (log P) calculation models was compared using a set of 131 aliphatic organic compounds from five different classes. Log P values were calculated employing atomic-contribution methods, as in the Ghose/Crippen approach and its later refinement, AlogP; using fragmental methods through the ClogP method; and employing an approach considering the whole molecule using topological indices with the MlogP method. The efficiency and the applicability of the I(SET) in terms of calculating log P were demonstrated through good statistical quality (r > 0.99; s < 0.18), high internal stability and good predictive ability for an external group of compounds in the same order as the widely used models based on the fragmental method, ClogP, and the atomic contribution method, AlogP, which are among the most used methods of predicting log P.

  18. Investigations on organogermanium compounds; III. N-tributylgermyl-substituted aliphatic and heterocyclic amines

    NARCIS (Netherlands)

    Rijkens, F.; Janssen, M.J.; Kerk, G.J.M. van der

    1965-01-01

    A series of new organogermanium compounds containing a germanium‐nitrogen bond, in many of which the nitrogen atom forms part of an heterocyclic ring, are prepared, in some cases by new methods: transamination reactions and reactions of germoxanes with heterocyclic amines. Striking differences in

  19. Aliphatic alkenes and alkynes

    International Nuclear Information System (INIS)

    Serep, D.

    1985-01-01

    Papers on radiolysis of aliphatic alkenes and alkynes published after 1968 are analytically reviewed. Kinetics and mechanisms of radiolytic processes, dependences of yields of intermediate and final products on conditions of their procedure and molecular structure of compounds are considered. Certain attention is paid to problems of dimerization and oligomerization at radiolysis of the considered compounds

  20. Chemistry of aliphatic sulfurpentafluoride derivatives

    International Nuclear Information System (INIS)

    Bissell, E.R.

    1975-01-01

    This report summarizes the literature through 1974 on aliphatic sulfurpentafluoride compounds. Methods of preparation and methods of transforming one pentafluorothio compound into another are briefly discussed. The physical properties of all known derivatives are tabulated

  1. Biotransformation of chlorinated aliphatic solvents in the presence of aromatic compounds under methanogenic conditions

    International Nuclear Information System (INIS)

    Liang, L.N.; Grbic-Galic, D.

    1993-01-01

    Transformation of carbon tetrachloride (CT) and tetrachloroethylene (PCE) was studied under methanogenic conditions, in the presence or absence of toluene, ethylbenzene, phenol, and benzoate. Microbial inoculate for the experiments were derived from three groundwater aquifers contaminated by jet fuel or creosote. CT and PCE were reductively dechlorinated in all the examined castes (CT to chloroform [CF]; PCE to trichloroethylene [TCE], trans-1,2-dichloroethylene [DCE], and vinyl chloride [VC]). In the aquifer microcosms, the electron donors used for the reductive transformations were most likely the unidentified organic compounds present on aquifer solids, or storage materials in microorganisms. Alternatively, molecular hydrogen from the anaerobic incubator atmosphere could have been used. The addition of benzoate caused a decrease in rates of dechlorination if benzoate was transformed. Phenol and ethylbenzene were not degraded and did not influence the transformation of CT or PCE. Toluene, in most of the studied cases, had no influence on reductive dechlorination of either CT or PCE. Only in microcosms derived from a JP-4 jet fuel-contaminated aquifer did the anaerobic degradation of toluene occur simultaneously with reductive dechlorination of PCE, suggesting that toluene might possibly have been used as an electron donor for reductive transformation of chlorinated solvents

  2. Compound deterioration properties of non-halogen flame-resisting cables

    International Nuclear Information System (INIS)

    Yamamoto, Yasuaki; Yagyu, Hideki; Onishi, Takao; Kamiharako, Shinji

    1984-01-01

    Conventional flame-resisting cables release harmful gas such as hydrogen chloride and smoke on burning. To improve this disadvantage, the cables for nuclear power plants using new non-halogen flame-resisting insulating material have been developed. In this experiment, the non-halogen flame-resisting cables were subjected to the environmental test with varying test conditions. The test conditions included the order of exposure (heat treatment, γ-ray irradiation and steam exposure) and dose rate. After the environmental test, the mechanical and electrical properties of the samples were measured. In all test conditions, the samples did not crack in bending, and withstood the bending and withstand-voltage in-water test. The tensile strength and a.c. breakdown voltage did not change, and were stable. The elongation decreased greatly, but maintained the value of about 100 %, and the volumetric resistivity decreased by only one figure. It was confirmed that these cables were able to withstand various environmental tests. (Yoshitake, I.)

  3. Aliphatic isocyanurates and polyisocyanurate networks

    NARCIS (Netherlands)

    Driest, Pieter Job; Lenzi, V.; Marques, L.S.A.; Ramos, M.M.D; Dijkstra, D.J.; Richter, F.U.; Stamatialis, Dimitrios; Grijpma, Dirk W.

    2016-01-01

    The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking

  4. Aliphatic isocyanurates and polyisocyanurate networks

    NARCIS (Netherlands)

    Driest, P. J.; Lenzi, V.; Marques, L. S. A.; Ramos, M. M. D.; Dijkstra, D. J.; Richter, F. U.; Stamatialis, D.; Grijpma, D. W.

    2017-01-01

    The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking

  5. The effect of halogen hetero-atoms on the vapor pressures and thermodynamics of polycyclic aromatic compounds measured via the Knudsen effusion technique

    International Nuclear Information System (INIS)

    Goldfarb, Jillian L.; Suuberg, Eric M.

    2008-01-01

    Knowledge of vapor pressures of high molar mass organics is essential to predicting their behavior in combustion systems as well as their fate and transport within the environment. This study involved polycyclic aromatic compounds (PACs) containing halogen hetero-atoms, including bromine and chlorine. The vapor pressures of eight PACs, ranging in molar mass from (212 to 336) g . mol -1 , were measured using the isothermal Knudsen effusion technique over the temperature range of (296 to 408) K. These compounds included those with few or no data available in the literature, namely: 1,4-dibromonaphthalene, 5-bromoacenaphthene, 9-bromoanthracene, 1,5-dibromoanthracene, 9,10-dibromoanthracene, 2-chloroanthracene, 9,10-dichloroanthracene, and 1-bromopyrene. Enthalpies of sublimation of these compounds were determined via application of the Clausius-Clapeyron equation. An analysis is presented on the effects of the addition of halogen hetero-atoms to pure polycyclic aromatic hydrocarbons using these data as well as available literature data. As expected, the addition of halogens onto these PACs increases their enthalpies of sublimation and decreases their vapor pressures as compared to the parent compounds

  6. Determination of tetrachloroethylene and other volatile halogenated organic compounds in oil wastes by headspace SPME GC-MS

    Energy Technology Data Exchange (ETDEWEB)

    Fabbri, D.; Bezzi, R.; Torri, C.; Galletti, P.; Tagliavini, E. [Bologna Univ., Ravenna (Italy). Lab. of Chemistry, C.I.R.S.A

    2007-09-15

    Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC-MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg{sup -1}, and linearity was established up to 25 mg kg{sup -1}. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.

  7. Aliphatic isocyanurates and polyisocyanurate networks

    OpenAIRE

    Driest, P. J.; Lenzi, V.; Marques, L.; Ramos, M. M. D.; Dijkstra, D. J.; Richter, F. U.; Stamatialis, D.; Grijpma, D. W.

    2017-01-01

    The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking additives for network formation. However, the mechanism by which these high viscosities are caused is not yet understood. In this work, model aliphatic isocyanurates were synthesized and isolated in hi...

  8. Investigating the Impact of Ecological Succession on Fluxes of Halogenated Volatile Organic Compounds (HVOCs) from Retreating Glacier Forefields

    Science.gov (United States)

    Macdonald, M.; Young, D.; O'Doherty, S.; Wadham, J.

    2017-12-01

    The Arctic is one of the fastest warming regions of the Earth, with temperature increases of +7oC projected by 2100 under a mitigation emission scenario. These climate perturbations are forecast to cause the retreat of extensive glacial systems across Canada, Greenland, Svalbard and the Russian Arctic. This will reveal new proglacial land surfaces for microbial colonisation, ultimately succeeding to tundra over decades to centuries. A relatively unexplored dimension to these changes is their impact upon the emission and consumption of halogenated volatile organic compounds (HVOCs) from proglacial land surfaces. HVOCs are involved in several important atmospheric processes such as ozone destruction and aerosol formation and despite considerable research, uncertainties remain in the natural cycles of some of these compounds. Here, we investigated the influence of biological process on the fluxes of HVOCs from recently (chambers on surfaces spanning recently-exposed sediments, to approx. 100 yr old tundra in front of Midtre Lovenbreen glacier, Svalbard. In-field analysis of a suite of HVOCs was conducted using a GCMS (gas chromatograph mass spectrometer) with a custom-built pre-concentration system. HVOC concentrations were evaluated with reference to biological (e.g. cell numbers) and physio-chemical (e.g. water content) parameters of the land surface, in order to assess the importance of the microbial community on the net flux. Significant rates of consumption of some HVOC species and production of others was detected. Further laboratory incubations supported the findings in the field. Proglacial surfaces are, therefore, a previously unrecognised sink and source of various HVOCs that have the potential to increase in importance with projected future climate change.

  9. Solar driven production of toxic halogenated and nitroaromatic compounds in natural seawater

    Energy Technology Data Exchange (ETDEWEB)

    Calza, Paola [Dipartimento di Chimica Analitica, Universita di Torino, via P. Giuria 5, 10125 Torino (Italy)], E-mail: paola.calza@unito.it; Massolino, Cristina; Pelizzetti, Ezio; Minero, Claudio [Dipartimento di Chimica Analitica, Universita di Torino, via P. Giuria 5, 10125 Torino (Italy)

    2008-07-15

    Natural seawater (NSW) sampled in March and June 2007 in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated in a device simulating solar light spectrum and intensity. Opposite to the case of artificial seawater, for which phenol is slightly degraded by direct photolysis, in NSW the phenol degradation mediated by natural photosensitizers occurs, forming several secondary pollutants, including hydroxyderivatives (1,4-benzoquinone, resorcinol), three chlorophenol isomers, 2,3-dichlorophenol, 2- and 4-bromophenol, 2- and 4-nitrophenol, and several condensed products (2 and 4-phenoxyphenol, 2,2'-, 4,4'- and 2,4-bisphenol). These compounds are toxic to bacteria and other living organisms. Ecotoxicologic effect has been evaluated by using the Vibrio Fischeri luminescent bacteria assay. This technique uses marine organisms, and it is therefore well suited for the study on marine samples. A correlation exists between the intermediates evolution and the toxicity profile, as the largest toxicity is observed when compounds with the lower EC50 (halophenols, phenoxyphenols) are formed at higher concentration.

  10. Solar driven production of toxic halogenated and nitroaromatic compounds in natural seawater

    International Nuclear Information System (INIS)

    Calza, Paola; Massolino, Cristina; Pelizzetti, Ezio; Minero, Claudio

    2008-01-01

    Natural seawater (NSW) sampled in March and June 2007 in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated in a device simulating solar light spectrum and intensity. Opposite to the case of artificial seawater, for which phenol is slightly degraded by direct photolysis, in NSW the phenol degradation mediated by natural photosensitizers occurs, forming several secondary pollutants, including hydroxyderivatives (1,4-benzoquinone, resorcinol), three chlorophenol isomers, 2,3-dichlorophenol, 2- and 4-bromophenol, 2- and 4-nitrophenol, and several condensed products (2 and 4-phenoxyphenol, 2,2'-, 4,4'- and 2,4-bisphenol). These compounds are toxic to bacteria and other living organisms. Ecotoxicologic effect has been evaluated by using the Vibrio Fischeri luminescent bacteria assay. This technique uses marine organisms, and it is therefore well suited for the study on marine samples. A correlation exists between the intermediates evolution and the toxicity profile, as the largest toxicity is observed when compounds with the lower EC50 (halophenols, phenoxyphenols) are formed at higher concentration

  11. Halogenated arsenenes as Dirac materials

    International Nuclear Information System (INIS)

    Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

    2016-01-01

    Highlights: • We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. • All fully-halogenated arsenene except As_2I_2 would spontaneously form and stable in defending the thermal fluctuation in room temperature. - Abstract: Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155–3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

  12. ESR studies of Bunsen-type methane-air flames. II. The effects of the addition of halogenated compounds to the secondary air on the hydrogen atoms in the flame

    Energy Technology Data Exchange (ETDEWEB)

    Noda, S; Fujimoto, S; Claesson, O; Yoshida, H

    1983-09-01

    Hydrogen atoms in a methane-air Bunsen-type flame were detected by the flame-in-cavity ESR method. The addition of a halogenated compound to the secondary air reduced the H-atom concentration linearly with an increase in additive concentration. These 8 halogenated compounds examined showed increased effectiveness in scavenging H atoms in this order: hydrochloric acid < dichlorodifluoromethane < chloroform < methyl chloride < methylene chloride < trichlorofluoromethane < carbon tetrachlorie < methyl bromide. The chemical effects of these additives on the combustion reactions agree well with the inhibitor indices for these compounds. 14 references, 3 figures.

  13. Estimating the physicochemical properties of polyhalogenated aromatic and aliphatic compounds using UPPER: part 1. Boiling point and melting point.

    Science.gov (United States)

    Admire, Brittany; Lian, Bo; Yalkowsky, Samuel H

    2015-01-01

    The UPPER (Unified Physicochemical Property Estimation Relationships) model uses enthalpic and entropic parameters to estimate 20 biologically relevant properties of organic compounds. The model has been validated by Lian and Yalkowsky on a data set of 700 hydrocarbons. The aim of this work is to expand the UPPER model to estimate the boiling and melting points of polyhalogenated compounds. In this work, 19 new group descriptors are defined and used to predict the transition temperatures of an additional 1288 compounds. The boiling points of 808 and the melting points of 742 polyhalogenated compounds are predicted with average absolute errors of 13.56 K and 25.85 K, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Biogeochemistry of Halogenated Hydrocarbons

    Science.gov (United States)

    Adriaens, P.; Gruden, C.; McCormick, M. L.

    2003-12-01

    Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

  15. Extraction of toluene from aliphatic compounds using an ionic liquid as solvent: Influence of the alkane on the (liquid + liquid) equilibrium

    International Nuclear Information System (INIS)

    Gonzalez, Emilio J.; Calvar, Noelia; Dominguez, Irene; Dominguez, Angeles

    2011-01-01

    Research highlights: → An ionic liquid was analyzed as solvent for extraction of toluene from alkanes. → Liquid-liquid equilibrium data were measured at 298.15 K and atmospheric pressure. → Selectivity and solute distribution ratio were obtained and compared with literature. → The Othmer-Tobias equation was used to ascertain the experimental LLE data. → Experimental data were correlated using NRTL and UNIQUAC models. - Abstract: In this paper, the feasibility of using 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, [EMim][ESO 4 ], as solvent for the extraction of toluene from aliphatic compounds (hexane, heptane, octane, or nonane) was analyzed. (Liquid + liquid) equilibrium (LLE) data for the ternary systems {alkane (1) + toluene (2) + [EMim][ESO 4 ] (3)} were measured at T = 298.15 K and atmospheric pressure. Selectivity and solute distribution ratio were calculated from the experimental LLE data, and the obtained values were compared to those previously reported using other ionic liquids and sulfolane. The degree of consistency of the experimental LLE data was ascertained using the Othmer-Tobias equation. Finally, the experimental LLE data were satisfactorily correlated with NRTL and UNIQUAC models.

  16. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

    Science.gov (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

    2018-01-26

    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

  18. Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

    Science.gov (United States)

    Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

    2011-05-01

    This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry

    DEFF Research Database (Denmark)

    Sloth, Jens Jørgen; Larsen, Erik Huusfeldt; Julshamn, K.

    2005-01-01

    for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at mug kg(-1) concentrations, were detected in 25, 23 and 17......Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid...

  20. Non-coding RNA/microRNA-modulatory dietary factors and natural products for improved cancer therapy and prevention: Alkaloids, organosulfur compounds, aliphatic carboxylic acids and water-soluble vitamins

    Directory of Open Access Journals (Sweden)

    Bernhard Biersack

    2016-10-01

    Full Text Available Non-coding small RNA molecules, the microRNAs (miRNAs, contribute decisively to the epigenetic regulation processes in cancer cells. Problematic pathogenic properties of cancer cells and the response of cancers towards anticancer drugs are highly influenced by miRNAs. Both increased drug activity and formation of tumor resistance are regulated by miRNAs. Further to this, the survival and proliferation of cancer cells and the formation of metastases is based on the modulated expression of certain miRNAs. In particular, drug-resistant cancer stem-like cells (CSCs depend on the presence and absence of specific miRNAs. Fortunately, several small molecule natural compounds were discovered that target miRNAs involved in the modulation of tumor aggressiveness and drug resistance. This review gives an overview of the effects of a selection of naturally occurring small molecules (alkaloids, organosulfur compounds, aliphatic carboxylic acids and water-soluble vitamins on miRNAs that are closely tangled with cancer diseases. Keywords: MiRNA, Alkaloids, Organosulfur compounds, Aliphatic carboxylic acids, Water-soluble vitamins, Anticancer drugs

  1. In vivo evaluation of an antibacterial coating containing halogenated furanone compound-loaded poly(l-lactic acid) nanoparticles on microarc-oxidized titanium implants.

    Science.gov (United States)

    Cheng, Yicheng; Gao, Bo; Liu, Xianghui; Zhao, Xianghui; Sun, Weige; Ren, Huifang; Wu, Jiang

    2016-01-01

    To prevent peri-implant infection, a new antibacterial coating containing a halogenated furanone compound, (Z-)-4-bromo-5-(bromomethylene)-2(5H)-furanone-loaded poly(l-lactic acid) nanoparticles, has been fabricated. The current study was designed to evaluate the preventive effect of the antibacterial coating under a simulated environment of peri-implant infection in vivo. Microarc-oxidized titanium implants treated with minocycline hydrochloride ointment were used as positive control group, and microarc-oxidized titanium implants without any treatment were used as blank control group. Three kinds of implants were implanted in dogs' mandibles, and the peri-implant infection was simulated by silk ligation and feeding high sugar diet. After 2-month implantation, the results showed that no significant differences were detected between the experimental and positive control groups (P>0.05), but the data of clinical measurements of the blank control group were significantly higher than those of the other two groups (Pmicroscope observation and histological examination showed that more new bone was formed on the surface of the experimental and positive control groups. It can be concluded that the antibacterial coating fabricated on implants has remarkable preventive effect on peri-implant infection at the early stage.

  2. Bioaccumulation and biomagnification of classical flame retardants, related halogenated natural compounds and alternative flame retardants in three delphinids from Southern European waters

    International Nuclear Information System (INIS)

    Barón, E.; Giménez, J.; Verborgh, P.; Gauffier, P.; De Stephanis, R.; Eljarrat, E.; 2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain))" data-affiliation=" (Institute of Environmental Assessment and Water Research Studies (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain))" >Barceló, D.

    2015-01-01

    Occurrence and behaviour of classical (PBDEs) and alternative (HNs, HBB, PBEB, DBDPE and HBCD) flame retardants, together with naturally produced MeO-PBDEs, were studied in short-beaked common dolphin (Delphinus delphis), bottlenose dolphin (Tursiops truncatus) and long-finned pilot whale (Globicephala melas) in two sampling locations from Southern European waters. PBDEs, Dec 602, Dec 603, DP, α-HBCD and two MeO-PBDEs were detected in all three species. ∑PBDEs were between 17 and 2680 ng/g lw; ∑HNs were between 1.1 and 59 ng/g lw; α-HBCD levels ranged between 3.2 and 641 ng/g lw; ∑MeO-PBDEs were between 34 and 1966 ng/g lw. Bottlenose dolphins were the most contaminated species and some individuals could present health risk for endocrine disruption since levels found were above the reported threshold (1500 ng/g lw). Stable isotope analysis was used to evaluate the biomagnification capacity of these compounds. PBDEs, MeO-PBDEs and Dec 602 showed a significant positive correlation with trophic position. - Highlights: • Several FRs were detected in three dolphin species from Southern European waters. • Concentrations of classical FRs were higher than concentrations of alternative FRs. • MeO-PBDE concentrations were generally similar to PBDE concentrations. • Evidence of biomagnification capacity of some FRs was observed. • Some individuals were above the threshold level associated to endocrine disruption. - Bioaccumulation and biomagnification of halogenated compounds in dolphins

  3. Development of an enzymatic fiber-optic biosensor for detection of halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Bidmanova, Sarka; Chaloupkova, Radka; Damborsky, Jiri; Prokop, Zbynek [Masaryk University, Loschmidt Laboratories, Department of Experimental Biology and Research Centre for Toxic Compounds in the Environment, Faculty of Science, Brno (Czech Republic)

    2010-11-15

    An enzyme-based biosensor was developed by co-immobilization of purified enzyme haloalkane dehalogenase (EC 3.8.1.5) and a fluorescence pH indicator on the tip of an optical fiber. Haloalkane dehalogenase catalyzes hydrolytic dehalogenation of halogenated aliphatic hydrocarbons, which is accompanied by a pH change influencing the fluorescence of the indicator. The pH sensitivity of several fluorescent dyes was evaluated. The selected indicator 5(6)-carboxyfluorescein was conjugated with bovine serum albumin and its reaction was tested under different immobilization conditions. The biosensor was prepared by cross-linking of the conjugate in tandem with haloalkane dehalogenase using glutaraldehyde vapor. The biosensor, stored for 24 h in 50 mM phosphate buffer (pH 7.5) prior to measurement, was used after 15 min of equilibration, the halogenated compound was added, and the response was monitored for 30 min. Calibration of the biosensor with 1,2-dibromoethane and 3-chloro-2-(chloromethyl)-1-propene showed an excellent linear dependence, with detection limits of 0.133 and 0.014 mM, respectively. This biosensor provides a new tool for continuous in situ monitoring of halogenated environmental pollutants. (orig.)

  4. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    International Nuclear Information System (INIS)

    Goodman, D.W.; Haw, J.F.; Lunsford, J.

    1998-01-01

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  5. Marine mammal blubber reference and control materials for use in the determination of halogenated organic compounds and fatty acids

    Energy Technology Data Exchange (ETDEWEB)

    Kucklick, John R.; Pugh, Rebecca S.; Becker, Paul R. [Hollings Marine Laboratory, National Institute of Standards and Technology (NIST), Charleston, SC (United States); Schantz, Michele M.; Porter, Barbara J.; Poster, Dianne L.; Leigh, Stefan; Wise, Stephen A. [NIST, Analytical Chemistry Division, Gaithersburg, MD (United States); Rowles, Teri K. [National Marine Fisheries Service, National Oceanic and Atmospheric Administration, Silver Spring, MD (United States)

    2010-05-15

    The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners, coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale blubber (Homogenates III and IV), Blainville's beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V). (orig.)

  6. Release of chlorinated, brominated and mixed halogenated dioxin-related compounds to soils from open burning of e-waste in Agbogbloshie (Accra, Ghana).

    Science.gov (United States)

    Tue, Nguyen Minh; Goto, Akitoshi; Takahashi, Shin; Itai, Takaaki; Asante, Kwadwo Ansong; Kunisue, Tatsuya; Tanabe, Shinsuke

    2016-01-25

    Although complex mixtures of dioxin-related compounds (DRCs) can be released from informal e-waste recycling, DRC contamination in African e-waste recycling sites has not been investigated. This study examined the concentrations of DRCs including chlorinated, brominated, mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in surface soil samples from the Agbogbloshie e-waste recycling site in Ghana. PCDD/F and PBDD/F concentrations in open burning areas (18-520 and 83-3800 ng/g dry, respectively) were among the highest reported in soils from informal e-waste sites. The concentrations of PCDFs and PBDFs were higher than those of the respective dibenzo-p-dioxins, suggesting combustion and PBDE-containing plastics as principal sources. PXDFs were found as more abundant than PCDFs, and higher brominated analogues occurred at higher concentrations. The median total WHO toxic equivalent (TEQ) concentration in open burning soils was 7 times higher than the U.S. action level (1000 pg/g), with TEQ contributors in the order of PBDFs>PCDD/Fs>PXDFs. DRC emission to soils over the e-waste site as of 2010 was estimated, from surface soil lightness based on the correlations between concentrations and lightness, at 200mg (95% confidence interval 93-540 mg) WHO-TEQ over three years. People living in Agbogbloshie are potentially exposed to high levels of not only chlorinated but also brominated DRCs, and human health implications need to be assessed in future studies. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Rigid particle toughening of aliphatic polyketone

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Huetink, Han; Gaymans, R.J.

    2006-01-01

    The influence of precipitated calcium carbonate particles on the toughening behaviour of aliphatic polyketone has been studied. The calcium carbonate particles had a particle size of 0.7 mm and a stearic acid coating (1%). Composites of 0e31.5 vol% CaCO3 content have been compounded and injection

  8. Development and application of bacterial cultures for the removal of chlorinated aliphatics

    NARCIS (Netherlands)

    Janssen, Dick B.; de Koning, Wim

    1995-01-01

    The possibility of obtaining microbial cultures for the degradation of halogenated aliphatic hydrocarbons is mainly determined by the diversity and activity of catabolic enzymes that exist in nature. If a suitable organism is available, applications for the treatment of different waste streams can

  9. Halogen bond: a long overlooked interaction.

    Science.gov (United States)

    Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

    2015-01-01

    Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

  10. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer-chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS).

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A; Schimmelmann, Arndt

    2017-03-30

    Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and

  11. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.

    2015-06-16

    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  12. Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

    Science.gov (United States)

    Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

    2016-11-23

    The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

  13. Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

    Science.gov (United States)

    Shapiro, S.D.; Busenberg, E.; Focazio, M.J.; Plummer, Niel

    2004-01-01

    Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl4), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl4, chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6

  14. Molecular activation analysis for organo-halogen contaminants in yogurt

    International Nuclear Information System (INIS)

    Zhang Hong; Chai Zhifang

    2004-01-01

    The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

  15. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  16. SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

    Directory of Open Access Journals (Sweden)

    Eugenio Torres

    2013-12-01

    Full Text Available In this work a novel procedure of synthesis of compounds analogues to curcumin with halogens atoms in its structure is described, which can increase its solubility and biological activity. Four halogenated curcuminoids were obtained with great pharmacological interest, none of them reported in literature before. Synthesis was carried out by means of the aldol condensation assisted by microwaves of halogenated aromatic aldehydes and acetylacetona, using morpholine as basic catalyst, in absence of solvent, and the reaction just needed 1 min. The products were purified by treatment of the reaction mixture with methanol under ultrasound irradiation, followed by chromatographic column. All obtained compounds were characterized by infrared spectroscopy, nuclear magnetic resonance, quantitative elementary analysis and high resolution mass spectrometry. The RMN-1H data demonstrate in all structures of synthesized curcuminoids the enol form is the most favored.

  17. Direct or photostimulated luminescence after X-Ray irradiation of divalent europium in alkaline earth compounds containing some halides; Luminescence directe ou photostimulee apres irradiation X de l'europium divalent dans des familles de composes alcalino-terreux comportant un halogene

    Energy Technology Data Exchange (ETDEWEB)

    Merigou, C

    1990-10-15

    With a view for digitizing of radiological images, the luminescent properties of divalent europium in diverse halogen compounds involving strontium or barium have been studied. In halogen-rich compounds (MCl{sub 2}, M{sub 4}OCl{sub 6}, M{sub 5}SiO{sub 4}Cl{sub 6},... where M is Sr or Ba), the thermal extinction of the emission begins only above 300 K. High densities of coloured spots have been produced with X-ray irradiation. The combining of these 2 features has led to the obtention of high yields for argon laser stimulated luminescence in the case of Sr{sub 5}SiO{sub 4}Cl{sub 5}Br:Eu halogen silicate. Although these yields are high they stay below that of BaXF:Eu which is usually used in photon-stimulated screens.

  18. Aliphatic long chain quaternary ammonium compounds analysis by ion-pair chromatography coupled with suppressed conductivity and UV detection in lysing reagents for blood cell analysers.

    Science.gov (United States)

    Giovannelli, D; Abballe, F

    2005-08-26

    A method has been developed which allows simultaneous determination of three linear alkyl trimethylammonium salts. Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride are widely used as main active ingredients of lysing reagents for blood cell analyzers which perform white blood cells differential determination into two or more sub-populations by impedance analysis. The ion-pair on styrene-divinyl benzene chromatographic phase looks like a suitable, reliable and long term stable tool for separation of such quaternary compounds. The detection based on suppressed conductivity was chosen because of the lack of significance chromophores. A micromembrane suppressor device compatible with high solvent concentration (up to 80%) was used in order to minimize the conductivity background before the detection. In the present work we show how the chemical post column derivatization makes the alkyl chain detectable also by UV direct detection at 210 nm.

  19. Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

    International Nuclear Information System (INIS)

    Serrano, Antonio; Gallego, Mercedes; Gonzalez, Jose Luis; Tejada, Manuel

    2008-01-01

    A diesel fuel spill at a concentration of 1 L m -2 soil was simulated on a 12 m 2 plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill. - The effect of aliphatic hydrocarbons contamination on soil quality was monitored over a period of 400 days after a Diesel fuel spill

  20. Substrate specific hydrolysis of aromatic and aromatic-aliphatic esters in orchid tissue cultures

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available We found that tissue cultures of higher plants were able, similarly as microorganisms, to transform low-molecular-weight chemical compounds. In tissue cultures of orchids (Cymbidium 'Saint Pierre' and Dendrobium phalaenopsis acetates of phenols and aromatic-aliphatic alcohols were hydrolyzed, whereas methyl esters of aromatic and aromatic-aliphatic acids did not undergo this reaction. Acetates of racemic aromatic-aliphatic alcohols were hydrolyzed with distinct enantiospecificity.

  1. Organic halogens in landfill leachates

    DEFF Research Database (Denmark)

    Grøn, C.; Christensen, J. B.; Jensen, Dorthe Lærke

    2000-01-01

    Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organi...

  2. Interaction between t-butyl hydroperoxide (I) and positive halogen compounds. part I. Intermediates in the reaction between I and CI2O

    NARCIS (Netherlands)

    Ham, J. van; Schors, A.; Kooyman, E.C.

    1973-01-01

    “positive halogen” compounds were found to induce the decomposition of t-butyl hydroperoxide (I) in the dark. In this Cl2O proved to be particularly effective, liberating oxygen from I instantaneously at 0°. At temperature between −80° and −30°, two oxygen-rich intermediates could be observed with

  3. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    Science.gov (United States)

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-04-26

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  4. Experimental and computational evidence of halogen bonds involving astatine

    Science.gov (United States)

    Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

    2018-03-01

    The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

  5. Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

    Science.gov (United States)

    Miura, Michiko; Wu, Haitao

    2013-05-21

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  6. Tropospheric Halogen Chemistry

    Science.gov (United States)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

  7. Infrared Absorption Spectra, Radiative Efficiencies, and Global Warming Potentials of Newly-Detected Halogenated Compounds: CFC-113a, CFC-112 and HCFC-133a

    Directory of Open Access Journals (Sweden)

    Maryam Etminan

    2014-07-01

    Full Text Available CFC-113a (CF3CCl3, CFC-112 (CFCl2CFCl2 and HCFC-133a (CF3CH2Cl are three newly detected molecules in the atmosphere that are almost certainly emitted as a result of human activity. It is important to characterise the possible contribution of these gases to radiative forcing of climate change and also to provide information on the CO2-equivalence of their emissions. We report new laboratory measurements of absorption cross-sections of these three compounds at a resolution of 0.01 cm−1 for two temperatures 250 K and 295 K in the spectral range of 600–1730 cm−1. These spectra are then used to calculate the radiative efficiencies and global warming potentials (GWP. The radiative efficiencies are found to be between 0.15 and 0.3 W∙m−2∙ppbv−1. The GWP for a 100 year time horizon, relative to carbon dioxide, ranges from 340 for the relatively short-lived HCFC-133a to 3840 for the longer-lived CFC-112. At current (2012 concentrations, these gases make a trivial contribution to total radiative forcing; however, the concentrations of CFC-113a and HCFC-133a are continuing to increase. The 2012 CO2-equivalent emissions, using the GWP (100, are estimated to be about 4% of the current global CO2-equivalent emissions of HFC-134a.

  8. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    Science.gov (United States)

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    Directory of Open Access Journals (Sweden)

    J. Ofner

    2012-07-01

    Full Text Available Reactive halogen species (RHS, such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

    Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  10. Critical properties of some aliphatic symmetrical ethers

    International Nuclear Information System (INIS)

    Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

    2014-01-01

    Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

  11. Natural halogenated compounds in forest soils

    DEFF Research Database (Denmark)

    Albers, Christian Nyrop

    Formålet med nærværende afhandling er at undersøge forekomst, dannelse og skæbne af halogenerede organiske stoffer, dannet gennem naturlige processer i jorden. Halogenerede og herunder specielt klorerede stoffer har haft et stærkt fokus inden for miljøkemien i de sidste 40 år, på grund af de mang...

  12. Determination of N-containing halogenated natural products using gas chromatography in combination of a nitrogen-phosphorus-detector

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie

    2004-09-15

    In the last few years several nonpolar halogenated natural products (HNPs) such as Q1, MHC-1, BC-2, BC-3, BC-10 were detected at elevated concentrations in marine biota samples. In addition, there are still some abundant peaks of halogenated compounds frequently found in the gas chromatograms of many marine samples which have not yet been identified. Some of the known halogenated natural products (Q1, HDBPs including BC-10, bromoindoles) contain N-heterocyclic backbones. Since nitrogen is scarcely found in anthropogenic halogenated compounds, the detection of N-containing halogenated substances may be used as a first indicator for the presence of HNPs in a sample extract. In the presented method we studied the suitability of a nitrogen phosphorous detector (NPD) for quantification of Q1 and the detection of Ncontaining compounds in marine biota. Analyses were accompanied with GC/ECD analyses.

  13. Evidence for Interfacial Halogen Bonding.

    Science.gov (United States)

    Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Isostructurality and non-isostructurality in the series of halogenated organic crystal substances. The structure of Hal-aggregates

    International Nuclear Information System (INIS)

    Grineva, O.V.; Zorkij, P.M.

    2001-01-01

    Local characteristics and the type of intermolecular Hal-aggregates (ensembles of contacting halogen atoms of adjacent molecules) present in chemically similar halogenated crystal substances, differing only in the nature of Hal atoms, are compared. 23 series of halogenated hydrocarbons, including 57 crystal structures were considered. A clearly pronounced specificity of Hal-aggregates for compounds with a low and intermediate content of halogen was revealed. It was found that, as a rule, coordination number of Hal atom by Hal adjacent atoms increases in the series F-Cl-Br-I [ru

  15. Low molecular weight halogenated hydrocarbons (LMHHs) in Mediterranean sea water: Preliminary observations

    International Nuclear Information System (INIS)

    Elder, D.L.; Villeneuve, J.P.; Harvey, G.R.

    1976-01-01

    Halogenated organic compounds containing 1-3 carbon atoms are among the most extensively produced synthetic chemicals. Within this group of compounds are solvents such as chloroform, carbon tetrachloride, trichloroethane and the chlorofluoro carbons or freons which are used as refrigerants and aerosol sprays. Once produced many of these compounds are eventually released to the environment

  16. Fiscal 1998 achievement report on regional consortium research and development project. Venture business fostering regional consortium research and development in its 2nd year--Creation of key industries (Development of energy-efficient catalytic decomposition device for persistent halogen compounds for environmental conservation); 1998 nendo kankyo hozen no tame no nanbunkaisei halogen kagobutsu no sho energy shokubai bunkai sochi no kaihatsu seika hokokusho. 2

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    Devices that decompose halogen compounds by use of AlPO{sub 4} are built, and studies are made concerning the collection of basic knowledge and findings, the settlement of problems that accompany scaleup, and the elucidation of mechanism of catalytic function occurrence. Tests are conducted at an intermediate plant, when catalytic performance is observed using a unit accommodating 1 liter of catalyst and chlorofluorocarbon (CFC) 12 is subjected to decomposition for the selection of proper operating conditions. Results similar to those from micro-reactor operation are attained when the reaction tube temperature is controlled. On the basis of the results, a real reactor and reaction system are designed and constructed, and CFC12 containing some CFC115 and CFC22 is made to undergo a decomposition reaction in this real reactor. It is then clarified that CFC catalytic decomposition proceeds at a low cost without generating dioxins and that therefore the process is commercially viable. In the study of catalytic adjustment, it is found that adjustment may be sufficiently effected when baking is conducted at 1,000 degrees C even when the extrusion process which demands low manufacturing cost is employed. Studies are also conducted about the mechanism of co-catalytic function occurrence. (NEDO)

  17. The unique role of halogen substituents in the design of modern agrochemicals.

    Science.gov (United States)

    Jeschke, Peter

    2010-01-01

    The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

  18. Aliphatic Nucleophilic Radio-fluorination

    International Nuclear Information System (INIS)

    Roeda, D.; Dolle, F.

    2010-01-01

    In this review we are looking at some aspects of nucleophilic aliphatic radio-fluorination, notably the labelled fluoride source, design aspects, the leaving group and the solvent. It should be clear that there is more to this branch of radiolabelling than one would suspect from the frequently used standard tosylate replacement with kryptofix/[ 18 F]fluoride in acetonitrile or DMSO. Competitive elimination can be a serious problem that can affect both yield and purification. De-protection of sensitive groups after radiolabelling and its possible side reactions can complicate purification. The right choice of leaving group and protecting groups may be crucial. Newer developments such as the use of tertiary alcohols or ionic liquids as solvents, long-chain poly-fluorinated sulphonate leaving groups facilitating fluorous solid phase extraction, or immobilisation of the precursor on a solid phase support may help to solve these problems, for example the longstanding problems with [ 18 F]FLT, whereas older concepts such as certain cyclic reactive entities for ring opening or even an abandoned reagent as [ 18 F]DAST should not be forgotten. (authors)

  19. SYNTHESIS AND STUDY OF HALOGENATED BENZYLAMIDES OF SOME ISOCYCLIC AND HETEROCYCLIC ACIDS AS POTENTIAL ANTICONVULSANTS.

    Science.gov (United States)

    Strupińska, Marzanna; Rostafińska-Suchar, Grażyna; Pirianowicz-Chaber, Elżbieta; Grabczuk, Mateusz; Józwenko, Magdalena; Kowalczyk, Hubert; Szuba, Joanna; Wójcicka, Monika; Chen, Tracy; Mazurek, Aleksander P

    2015-01-01

    A series of potential anticonvulsants have been synthesized. There are eight fluorobenzylamides and three chlorobenzylamides of isocyclic or heterocyclic acids. Two not halogenated benzylamides were also synthesized to compare the effect of halogenation. The aim of the research performed was to evaluate whether halogenation of the mother structure is able to improve its anticonvulsant activity. The compounds were tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Compound 1 showed MES ED50 = 80.32 mg/kg, PI = 3.16. Compound 7 showed CKM ED50 = 56.72 mg/kg. Compound 8 showed MES ED50 = 34.23 mg/kg and scPTZ ED50 > 300 mg/kg, PI = 8.53.Compound 13 showed 6Hz ED50 = 78.96, PI = 3.37. The results indicate that fluorination does not improve activity, whereas chlorination in our experiment even reduces it.

  20. Process for reducing halogen impurities in oil products

    Energy Technology Data Exchange (ETDEWEB)

    Basler, F.

    1990-08-14

    Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

  1. Risk assessment for halogenated solvents

    International Nuclear Information System (INIS)

    Travis, C.C.

    1988-01-01

    A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

  2. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  3. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Wesén, Clas; Sundin, Peter

    1997-01-01

    Chlorinated fatty acids have been found to be major contributors to organohalogen compounds in fish, bivalves, jellyfish, and lobster, and they have been indicated to contribute considerably to organohalogens in marine mammals. Brominated fatty acids have been found in marine sponges. Also...

  4. Halogen-Mediated Conversion of Hydrocarbons to Commodities.

    Science.gov (United States)

    Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

    2017-03-08

    Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

  5. Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2017-10-01

    Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

  6. Aliphatic amine oxides as ligands

    International Nuclear Information System (INIS)

    Garla, L.C.; Betarello, V.H.; Chiericato Junior, G.; De Giovani, W.F.

    1984-01-01

    The reaction between some hydrated lanthanide perchlorates with trimethylamine oxide (TMAO) was studied. Compounds of general formula Ln(Cl 4 ) 3 : . 5,5 TMAO (Ln = La, Pr, Er and Y) were isolated. (Author) [pt

  7. Aliphatic-aromatic separation using deep eutectic solvents as extracting agents

    NARCIS (Netherlands)

    Rodriguez Rodriguez, Nerea; Fernandez Requejo, Patricia; Kroon, Maaike

    2015-01-01

    The separation of aliphatic and aromatic compounds is a great challenge for chemical engineers. There is no efficient separation process for mixtures with compositions lower than 20 wt % in aromatics. In this work, the feasibility of two different deep eutectic solvents (DESs) as novel extracting

  8. VOC contamination in hospital, from stationary sampling of a large panel of compounds, in view of healthcare workers and patients exposure assessment.

    Directory of Open Access Journals (Sweden)

    Vincent Bessonneau

    Full Text Available BACKGROUND: We aimed to assess, for the first time, the nature of the indoor air contamination of hospitals. METHODS AND FINDINGS: More than 40 volatile organic compounds (VOCs including aliphatic, aromatic and halogenated hydrocarbons, aldehydes, alcohols, ketones, ethers and terpenes were measured in a teaching hospital in France, from sampling in six sampling sites--reception hall, patient room, nursing care, post-anesthesia care unit, parasitology-mycology laboratory and flexible endoscope disinfection unit--in the morning and in the afternoon, during three consecutive days. Our results showed that the main compounds found in indoor air were alcohols (arithmetic means ± SD: 928±958 µg/m³ and 47.9±52.2 µg/m³ for ethanol and isopropanol, respectively, ethers (75.6±157 µg/m³ for ether and ketones (22.6±20.6 µg/m³ for acetone. Concentrations levels of aromatic and halogenated hydrocarbons, ketones, aldehydes and limonene were widely variable between sampling sites, due to building age and type of products used according to health activities conducted in each site. A high temporal variability was observed in concentrations of alcohols, probably due to the intensive use of alcohol-based hand rubs in all sites. Qualitative analysis of air samples led to the identification of other compounds, including siloxanes (hexamethyldisiloxane, octamethyltrisiloxane, decamethylcyclopentasiloxane, anesthetic gases (sevoflurane, desflurane, aliphatic hydrocarbons (butane, esters (ethylacetate, terpenes (camphor, α-bisabolol, aldehydes (benzaldehyde and organic acids (benzoic acid depending on sites. CONCLUSION: For all compounds, concentrations measured were lower than concentrations known to be harmful in humans. However, results showed that indoor air of sampling locations contains a complex mixture of VOCs. Further multicenter studies are required to compare these results. A full understanding of the exposure of healthcare workers and patients

  9. Exploring the C-X…π Halogen Bonding Motif: An Infrared and Raman Study of the Complexes of CF3X (X = Cl, Br and I with the Aromatic Model Compounds Benzene and Toluene

    Directory of Open Access Journals (Sweden)

    Wouter A. Herrebout

    2013-06-01

    Full Text Available The formation of halogen bonded complexes formed between the trifluorohalomethanes CF3Cl, CF3Br and CF3I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF3Br and CF3I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF3I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF3Br.benzene, CF3I.benzene and (CF3I2.benzene are −6.5(3, −7.6(2 and −14.5(9 kJ mol−1. The values for CF3Br.toluene and CF3I.toluene are −6.2(5 and −7.4(5 kJ mol−1. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2/aug-cc-pVDZ(-PP and MP2/aug-cc-pVTZ(-PP ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X···π halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne.

  10. Formation and evolution of point defects created in alkali halogen compounds irradiated by heavy ions; Formation et evolution des defauts ponctuels crees dans certains halogenures alcalins irradies par des ions lourds

    Energy Technology Data Exchange (ETDEWEB)

    Hourdequin, E [Nantes Univ., 44 (France)

    1993-07-16

    The goal of this study was to achieve a better understanding of the heavy-ion material interaction. Alkali halogen crystals were chosen since the color centers produced by heavy ions can be distinguished easier from those generated by X rays. Measurements on KI irradiated at low temperature showed that the usual process of non radiative de-excitation of self-captured exciton is not prevailing. As the main objective of this work was the exact determination of the defects created by accelerated heavy ions, an important effort was dedicated to the spectrum deconvolution. Due to the high quality of the obtained spectra the V band analyse was possible. The defect stability was found to have the same nature in all the cubical alkali halogens and depend essentially on the crystal type. The defect evolution after irradiation is related to the diffusion coefficients corresponding to each mobile species and to the crystal lattice in which they move. Based on measurements made at different temperatures a simple modeling of the recombination kinetics was proposed. This effect was found to be specific to irradiation by heavy ions. It is difficult to determine the initial processes from the fossil defects, so, the defect history must be known as the described investigation methods do not permit to establish the transient aspect of defect creation. The important role of impurities should be stressed as the third intruder in the ion/crystal configuration; it can modify significantly the final state of the irradiated crystal, as it was found in KI, for instance. The open problems underlined in this study will probably be solved by using the atomic force microscopy and diffraction or on-line Raman measurements in ISOC chamber to avoid the passage to ambient conditions of the crystals irradiated at low temperatures 60 refs.

  11. Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

    Science.gov (United States)

    Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

    2017-05-01

    Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

  12. Microbial degradation of aliphatic and aliphatic-aromatic co-polyesters.

    Science.gov (United States)

    Shah, Aamer Ali; Kato, Satoshi; Shintani, Noboru; Kamini, Numbi Ramudu; Nakajima-Kambe, Toshiaki

    2014-04-01

    Biodegradable plastics (BPs) have attracted much attention since more than a decade because they can easily be degraded by microorganisms in the environment. The development of aliphatic-aromatic co-polyesters has combined excellent mechanical properties with biodegradability and an ideal replacement for the conventional nondegradable thermoplastics. The microorganisms degrading these polyesters are widely distributed in various environments. Although various aliphatic, aromatic, and aliphatic-aromatic co-polyester-degrading microorganisms and their enzymes have been studied and characterized, there are still many groups of microorganisms and enzymes with varying properties awaiting various applications. In this review, we have reported some new microorganisms and their enzymes which could degrade various aliphatic, aromatic, as well as aliphatic-aromatic co-polyesters like poly(butylene succinate) (PBS), poly(butylene succinate)-co-(butylene adipate) (PBSA), poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), poly(L-lactic acid) (PLA), poly(3-hydroxybutyrate) and poly(3-hydoxybutyrate-co-3-hydroxyvalterate) (PHB/PHBV), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(butylene adipate-co-terephthalate (PBAT), poly(butylene succinate-co-terephthalate) (PBST), and poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL). The mechanism of degradation of aliphatic as well as aliphatic-aromatic co-polyesters has also been discussed. The degradation ability of microorganisms against various polyesters might be useful for the treatment and recycling of biodegradable wastes or bioremediation of the polyester-contaminated environments.

  13. Experiments on the VERONA test facility on formation and decomposition of polyhalogenated dioxins and furans and other organic halogen compounds in the combustion process; Untersuchungen an der Technikumsanlage VERONA zur Bildung und zum Abbau von polyhalogenierten Dioxinen und Furanen und anderen Organohalogenverbindungen in Verbrennungsprozessen

    Energy Technology Data Exchange (ETDEWEB)

    Schueler, D.

    2002-09-01

    The study examines measures to reduce dioxin formation in thermal waste treatment. The VERONA pilot plant (VErbrennungsanlage mit feststehendem ROst und getrennter NAchbrennkammer - incineration plant with stationary grate and separate post-combustion chamber) was developed to carry out practical experiments. The experiments were conducted using wood and propane as basic combustible materials and with controlled dosage of various bromine-, chlorine- and copper-containing compounds. The behaviour of the following compounds was studied in the combustion chamber, after the post-combustion chamber and after the heat exchanger: PCPh, PBrPh, PCBz, PBrBz, PCDD/F and PBDD/F. Experiments involving the variation of various primary measures (moisture content of combustible material, air supply, temperature in the combustion chamber, quality of post-combustion, quantities and structures of halogen compounds) have shown that the quality of post-combustion plays a much greater role than the other measures. For this reason, a search was launched for indicators which can be measured readily and by means of which the quality of post-combustion in terms of organohalide decomposition can be evaluated, and which correlate closely with the dioxin concentrations after the heat exchanger. It became apparent that the congeners of the chlorophenols and of the chlorobenzenes, measured in various incineration stages, are not suited, nor is the CO content. (orig.)

  14. Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

    Science.gov (United States)

    Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

    2018-03-01

    The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

  15. METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

    Science.gov (United States)

    Frazer, J.W.

    1959-08-18

    A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

  16. Notch sensitivity of aliphatic polyketone terpolymers

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Huetink, Han; Gaymans, R.J.

    2004-01-01

    The notch sensitivity of aliphatic polyketone (PK) terpolymers was investigated in this article. The notch-tip radius was varied between the size of an actual propagating crack tip of 1-2 m and the largest notch tip of 1000 m radius. The larger notch-tip radii (1000-15 m) were milled into the

  17. Comparative study in vitro of contraction percentage by polymerization of the compound resins: FiltekTMZ350 XT, BRILLIANTTMNG, Vit-l-escence®, when subjected to halogen light, applying the Archimedes' principle

    International Nuclear Information System (INIS)

    Castro Brenes, Maria Jose; Duran Leon, Luis Edgardo

    2013-01-01

    The contraction by polymerization in vitro is determined in three resins (Filtek TM Z350 XT, BRILLIANT TM NG, Vit-l-escence®), when exposed to halogen light during 60 seconds and applying the Archimedes' principle. This method has provided to professional the criteria to consider for the selection of the material according to the therapeutic requirements. Archimedes' principle is applied like a tool to determine the contraction by polymerization of the resins; however, human errors may be present due to manipulation, omission or losses of the product during processing. The contraction by polymerization of the resins is estimated, where Filtek TM Z350 XT has been the that least volumetric contraction has experienced, followed by BRILLIANT TM NG and lastly Vit-l-escence®, has been the most is contracted of the three. Differences found between the resins studied are established according to contraction by polymerization and compared with the 'literature' and properties that are offered by fabricators. The characteristics of the resins Filtek TM Z350 XT, BRILLIANT TM NG, Vit-l-escence® are evaluated with respect to properties that have had higher or lower contraction by polymerization, to establish patterns of behavior according to their characteristics [es

  18. Halogenated hydrocarbons - an environmental problem

    Energy Technology Data Exchange (ETDEWEB)

    Schoeler, H F; Thofern, E

    1984-01-01

    The paper provides a survey of the incidence of highly volatile halogenated hydrocarbons in ground, surface and drinking water as well as in the snows of Western Germany. Almost the entire production of chlorinated solvents is released into the environment. The absorption media are mostly soil, water and atmosphere. Whereas in the atmosphere elimination reactions take place, solvents that have passed the soil get into the ground water owing to their persistence and can cause considerable pollutions of drinking water. Moreover haloforms may occur in drinking water, which are produced during chlorine disinfection of pre-treated water.

  19. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

    Science.gov (United States)

    Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

    2014-12-01

    Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

  20. ANTHOCYANINS ALIPHATIC ALCOHOLS EXTRACTION FEATURES

    Directory of Open Access Journals (Sweden)

    P. N. Savvin

    2015-01-01

    Full Text Available Anthocyanins red pigments that give color a wide range of fruits, berries and flowers. In the food industry it is widely known as a dye a food additive E163. To extract from natural vegetable raw materials traditionally used ethanol or acidified water, but in same technologies it’s unacceptable. In order to expand the use of anthocyanins as colorants and antioxidants were explored extracting pigments alcohols with different structures of the carbon skeleton, and the position and number of hydroxyl groups. For the isolation anthocyanins raw materials were extracted sequentially twice with t = 60 C for 1.5 hours. The evaluation was performed using extracts of classical spectrophotometric methods and modern express chromaticity. Color black currant extracts depends on the length of the carbon skeleton and position of the hydroxyl group, with the alcohols of normal structure have higher alcohols compared to the isomeric structure of the optical density and index of the red color component. This is due to the different ability to form hydrogen bonds when allocating anthocyanins and other intermolecular interactions. During storage blackcurrant extracts are significant structural changes recoverable pigments, which leads to a significant change in color. In this variation, the stronger the higher the length of the carbon skeleton and branched molecules extractant. Extraction polyols (ethyleneglycol, glycerol are less effective than the corresponding monohydric alcohols. However these extracts saved significantly higher because of their reducing ability at interacting with polyphenolic compounds.

  1. Localized aliphatic organic material on the surface of Ceres

    Science.gov (United States)

    De Sanctis, M. C.; Ammannito, E.; McSween, H. Y.; Raponi, A.; Marchi, S.; Capaccioni, F.; Capria, M. T.; Carrozzo, F. G.; Ciarniello, M.; Fonte, S.; Formisano, M.; Frigeri, A.; Giardino, M.; Longobardo, A.; Magni, G.; McFadden, L. A.; Palomba, E.; Pieters, C. M.; Tosi, F.; Zambon, F.; Raymond, C. A.; Russell, C. T.

    2017-02-01

    Organic compounds occur in some chondritic meteorites, and their signatures on solar system bodies have been sought for decades. Spectral signatures of organics have not been unambiguously identified on the surfaces of asteroids, whereas they have been detected on cometary nuclei. Data returned by the Visible and InfraRed Mapping Spectrometer on board the Dawn spacecraft show a clear detection of an organic absorption feature at 3.4 micrometers on dwarf planet Ceres. This signature is characteristic of aliphatic organic matter and is mainly localized on a broad region of ~1000 square kilometers close to the ~50-kilometer Ernutet crater. The combined presence on Ceres of ammonia-bearing hydrated minerals, water ice, carbonates, salts, and organic material indicates a very complex chemical environment, suggesting favorable environments to prebiotic chemistry.

  2. CYP79F1 and CYP79F2 have distinct functions in the biosynthesis of aliphatic glucosinolates in Arabidopsis.

    Science.gov (United States)

    Chen, Sixue; Glawischnig, Erich; Jørgensen, Kirsten; Naur, Peter; Jørgensen, Bodil; Olsen, Carl-Erik; Hansen, Carsten H; Rasmussen, Hasse; Pickett, John A; Halkier, Barbara A

    2003-03-01

    Cytochromes P450 of the CYP79 family catalyze the conversion of amino acids to oximes in the biosynthesis of glucosinolates, a group of natural plant products known to be involved in plant defense and as a source of flavor compounds, cancer-preventing agents and bioherbicides. We report a detailed biochemical analysis of the substrate specificity and kinetics of CYP79F1 and CYP79F2, two cytochromes P450 involved in the biosynthesis of aliphatic glucosinolates in Arabidopsis thaliana. Using recombinant CYP79F1 and CYP79F2 expressed in Escherichia coli and Saccharomyces cerevisiae, respectively, we show that CYP79F1 metabolizes mono- to hexahomomethionine, resulting in both short- and long-chain aliphatic glucosinolates. In contrast, CYP79F2 exclusively metabolizes long-chain elongated penta- and hexahomomethionines. CYP79F1 and CYP79F2 are spatially and developmentally regulated, with different gene expression patterns. CYP79F2 is highly expressed in hypocotyl and roots, whereas CYP79F1 is strongly expressed in cotyledons, rosette leaves, stems, and siliques. A transposon-tagged CYP79F1 knockout mutant completely lacks short-chain aliphatic glucosinolates, but has an increased level of long-chain aliphatic glucosinolates, especially in leaves and seeds. The level of long-chain aliphatic glucosinolates in a transposon-tagged CYP79F2 knockout mutant is substantially reduced, whereas the level of short-chain aliphatic glucosinolates is not affected. Biochemical characterization of CYP79F1 and CYP79F2, and gene expression analysis, combined with glucosinolate profiling of knockout mutants demonstrate the functional role of these enzymes. This provides valuable insights into the metabolic network leading to the biosynthesis of aliphatic glucosinolates, and into metabolic engineering of altered aliphatic glucosinolate profiles to improve nutritional value and pest resistance.

  3. Combinations of Aromatic and Aliphatic Radiolysis.

    Science.gov (United States)

    LaVerne, Jay A; Dowling-Medley, Jennifer

    2015-10-08

    The production of H(2) in the radiolysis of benzene, methylbenzene (toluene), ethylbenzene, butylbenzene, and hexylbenzene with γ-rays, 2-10 MeV protons, 5-20 MeV helium ions, and 10-30 MeV carbon ions is used as a probe of the overall radiation sensitivity and to determine the relative contributions of aromatic and aliphatic entities in mixed hydrocarbons. The addition of an aliphatic side chain with progressively from one to six carbon lengths to benzene increases the H(2) yield with γ-rays, but the yield seems to reach a plateau far below that found from a simple aliphatic such as cyclohexane. There is a large increase in H(2) with LET (linear energy transfer) for all of the substituted benzenes, which indicates that the main process for H(2) formation is a second-order process and dominated by the aromatic entity. The addition of a small amount of benzene to cyclohexane can lower the H(2) yield from the value expected from a simple mixture law. A 50:50% volume mixture of benzene-cyclohexane has essentially the same H(2) yield as cyclohexylbenzene at a wide variation in LET, suggesting that intermolecular energy transfer is as efficient as intramolecular energy transfer.

  4. Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

    International Nuclear Information System (INIS)

    Rey, M.D.; Font, R.; Aracil, I.

    2013-01-01

    An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm 3 which is below the limit of 150 mg/Nm 3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines

  5. Non-hazardous organic solvents in the paraffin-embedding technique: a rational approach. Aliphatic monoesters for clearing and dewaxing: butyldecanoate

    DEFF Research Database (Denmark)

    Lyon, H; Holm, I; Prentø, P

    1995-01-01

    The aim of this study was to substitute hazardous compounds, used in tissue processing and dewaxing, with compounds having lowest possible toxicity and inflammability without impairing the morphology, staining characteristics, or diagnostic value of the tissue sections. All aromatic compounds...... and aliphatic hydrocarbons (e.g. alkanes, isoparaffins, petroleum distillates, etc.) were rejected, primarily due to their high vapour pressure. Based on a theoretical study of compounds used for clearing, a number of non-hazardous potential substitutes were chosen. The following experimental study narrowed...... the group to three unbranched, saturated, aliphatic monoesters containing 12-14 carbon atoms. On large-scale testing of these compounds, we found butyldecanoate to be the closest to an ideal substitute for aromatic and aliphatic hydrocarbons in the histology department: the section quality is at least equal...

  6. Vapour pressures and enthalpies of vapourization of a series of the linear aliphatic nitriles

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Koutek, Bohumir; Doubsky, Jan

    2005-01-01

    Vapour pressures and the molar enthalpies of vapourization ΔlgHm-bar of the linear aliphatic nitriles C 7 -C 17 have been determined by the transpiration method. Kovat's indices of these compounds were measured by capillary gas-chromatography. A linear correlation of enthalpies of vapourization ΔlgHm-bar at T=298.15 K of the nitriles studied with the Kovats indices has been found

  7. Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

    International Nuclear Information System (INIS)

    Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue; Jin Weijun

    2012-01-01

    Highlights: ► Halogen bonding (XB) is firstly utilised in solid phase extraction. ► The perfluorinated iodine alkanes can be extracted by C-I⋯Cl − halogen bonding. ► The C-I⋯Cl − halogen bond is well characterised by spectroscopy methods. ► The analytes with strong halogen-bonding abilities can be selectively extracted. - Abstract: For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19 F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the C-I⋯Cl − halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL −1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl − . The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g −1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g −1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

  8. Organic halogens in spruce forest throughfall

    DEFF Research Database (Denmark)

    Öberg, G.; Johansen, C.; Grøn, C.

    1998-01-01

    . No relationship between the position of the collectors and the forest edge or dominating wind-direction was found, suggesting that dry deposition was not a major source. The concentration of organic halogens was related to that of organic carbon and decreased from the tree-trunk and outwards. In addition......, the concentrations were higher during the growing season than during the dormant season. This indicates that the major part of the organic carbon and organic halogens in spruce forest throughfall originates from canopy leachates or other internal sources. (C) 1998 Elsevier Science Ltd.......Deposition of dissolved organic halogens by throughfall was determined in a small spruce forest site in Denmark (56 degrees 28'N, 8 degrees 24'E). The mean annual deposition of dissolved organic halogens was 377 g ha(-1)yr(-1), and larger than the general deposition by precipitation...

  9. The halogen bond: Nature and applications

    Science.gov (United States)

    Costa, Paulo J.

    2017-10-01

    The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

  10. Synthesis and evaluation of antimicrobial activity of halogenated furans and analogue compounds to nostoclides; Sintese e avaliacao da atividade antimicrobiana de furanonas halogenadas e de compostos analogos aos nostoclideos

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, Luiz C.A.; Maltha, Celia R.A.; Demuner, Antonio J.; Pinheiro, Patricia F.; Varejao, Jodieh O.S.; Montanari, Ricardo M., E-mail: lcab@ufv.b [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Quimica; Andrade, Nelio J. [Universidade Federal de Vicosa (UFV), MG (Brazil). Dept. de Ciencia e Tecnologia de Alimentos

    2010-07-01

    Considering the broad spectrum of biological activity of gamma-butyrolactone derivatives, we presented the synthesis of 3,4-dihalo-5-arylidenefuran-2(5H)-ones (17-21) and analogues (24-28) of the natural product nostoclide (7,8). Furanones 17-21 were synthesized from the condensation of aromatic aldehydes with lactones 14 and 15, that were obtained from mucobromic and mucochloric acids. Lactone 15 was converted into the intermediate 23 in 36% overall yield. Compound 23 was then transformed into the nostoclide analogues 24-28. Some of the compounds prepared showed antimicrobial activities against Escherichia coli, Staphylococcus aureus and Bacillus cereus comparable to commercial antibiotics. (author)

  11. Structural characterisation of aliphatic, non-hydrolyzable biopolymers in freshwater algae and a leaf cuticle by ruthenium tetroxide degradation

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Moerkerken, P.; Gelin, F.; Baas, M.; Leeuw, J.W. de

    1998-01-01

    Aliphatic, non-hydrolyzable biopolymers were subjected to RuO4-oxidation in order to examine the potential of this method in revealing details on their structures. The method was tested on model compounds first and found to cleave alkyl chains of aromatic moieties, double bonds and ether bonds.

  12. Metal-free synthesis of novel biobased dihydroxyl-terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes

    NARCIS (Netherlands)

    Tang, D.; Noordover, B.A.J.; Sablong, R.J.; Koning, C.E.

    2011-01-01

    Using the organic compound 1,5,7-triazabicyclo[ 4.4.0]dec-5-ene (TBD) as a catalyst for step-growth polymerization, a series of well-defined hydroxyl-telechelic renewable aliphatic polyesters (including poly(1,3-propylene adipate); poly(1,4-butylene adipate); poly(1,12-dodecylene sebacate); and

  13. Sodium hypochlorite oxidation of petroleum aliphatic contaminants in calcareous soils.

    Science.gov (United States)

    Picard, François; Chaouki, Jamal

    2016-02-01

    This research project investigated the sodium hypochlorite (NaClO) oxidation of aliphatic petroleum contaminants (C10-C50) in a calcareous soil (average 5473 ppm C10-C50, 15 wt% Ca), which had been excavated from a contaminated industrial site. The decontamination objective was to lower the C10-C50 concentration to 700 ppm. CO2 acidity was used in the project to boost the NaClO oxidation yield and seems to have played a role in desorbing the natural organic matter. The experimental conditions were a 2- to 16-h reaction time, at room temperature, with a 1 to 12.5 wt% NaClO oxidative solution and a fixed 2:1 solution-to-soil ratio. With a 3 wt% NaClO solution and with a CO2 overhead, the NaClO dosage requirement was maintained below 60 g NaClO/g of oxidized C10-C50 over the entire decontamination range. The strong chlorine smell remaining after the reaction was completed suggests that part of the NaClO requirement can be recycled. Except traces of chloroform, there were no regulation-listed organochloride contaminants detected on either the treated soil samples or leachates and the total count of chlorinated compounds in treated soil samples was below the detection limit of 250 mg/kg. The NaClO oxidation mechanism on aliphatic substrates might be triggered by transition metals, such as manganese, but no attempt has been made to investigate the oxidation mechanism. Further investigations would include a constant-fed NaClO system and other techniques to lower the required NaClO dosage. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

    Science.gov (United States)

    Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

    2017-09-01

    Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

  15. Corrosion inhibition of brass by aliphatic amines

    International Nuclear Information System (INIS)

    Taha, K. K.; Sheshadri, B. S; Ahmed, M. F.

    2005-01-01

    Aliphatic amines hexylamine (HCA), octylamine (OCA) and decylamine (DCA) have been used as corrosion inhibitors for (70/30) brass in 0.I M HCIO 4 . The inhibitor efficiency (%P) calculated using weight loss, Tafel extrapolation, linear polarization and impedance methods was found to be in the order DCA> OCA> HCA. These adsorb on brass surface following bockris-swinkels' isotherm. DCA, OCA and HCA displaced 4, 3 and 2 molecules of water from interface respectively. Displacement of water molecules brought a great reorganization of double layer at the interface. These amines during corrosion form complexes with dissolved zinc and copper ions.(Author)

  16. Structure and isotopic ratios of aliphatic side chains in the insoluble organic matter of the Murchison carbonaceous chondrite

    Science.gov (United States)

    Huang, Yongsong; Alexandre, Marcelo R.; Wang, Yi

    2007-07-01

    We report in this paper the first molecular and isotopic characterization of individual aliphatic side chains from the insoluble organic matter (IOM) in the Murchison carbonaceous chondrite using a novel combined approach of RuO 4 oxidation and solid phase microextraction (SPME). The aliphatic side chains in the IOM of Murchison were first released by oxidizing aromatic structures using RuO 4. Because the IOM of carbonaceous chondrites contains predominantly short (C 1 to C 9) aliphatic substitutions, the resulting low molecular weight monocarboxylic acids (MCAs) are highly volatile and water-soluble. The conventional aqueous extraction and derivatization procedures following RuO 4 oxidation are unable to recover MCAs for subsequent analyses. We overcame this problem by employing SPME to directly capture the MCAs from the aqueous solution. We selected a SPME fiber with greater affinity for longer chain monoacids to compensate for the exponential decline of monoacid concentrations with increasing carbon numbers in meteorite IOM, allowing more accurate identification and quantification for the less abundant monoacids. We also determined the carbon and hydrogen isotopic ratios of individual MCAs derived from Murchinson IOM. Our results reveal significant similarity in both molecular structures and hydrogen isotopic ratios between the IOM aliphatic side chains and water-soluble MCAs in Murchison, suggesting that these compounds had common precursors. Our combined new approach of RuO 4 oxidation-SPME provides a new way to probe the molecular and isotopic characteristics of aliphatic side chains in carbonaceous chondrites.

  17. Radiolysis of other organic compounds

    International Nuclear Information System (INIS)

    Pikaev, A.K.

    1986-01-01

    Peculiarities of radiolysis of organic halogen, phosphorus, sulfur and nitrogen (including amines, amides, nitriles et al.) compounds in liquid phase are discussed. Intermediate and stable finish products of radiolysis of the given compounds, properties and radiochemical yields of these products are considered

  18. Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

    Science.gov (United States)

    Sumner, A. J.; Plata, D.

    2017-12-01

    Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

  19. Studies on halogen quenching through the Stern-Volmer plot

    International Nuclear Information System (INIS)

    Takiue, Makoto; Ishikawa, Hiroaki.

    1978-01-01

    The quenching effect for halogenated benzenes, methanes and ethanes have been investigated. The halogen quenching was accurately measured using the internal conversion electrons emitted from 113 Sn-sup(113m)In. From the quenching constants determined by the Stern-Volmer plots with respect to various halogen quenchers, the following results have been obtained. (1) The quenching constants increase with the number of halogen substituents, so as linearly in halogenated benzenes and exponentially in halogenated methanes and ethanes. Even the isomers of halogenides have different quenching constants. (2) There is a linearity between logarithm of the quenching constant and a polarographic half-wave reduction potential. (3) Electron excitation provides larger quenching constants than UV excitation for halogenated methanes. Based on these results, the mechanism of halogen quenching have been discussed in connection with the exciplex formation. (auth.)

  20. Halogens in chondritic meteorites and terrestrial accretion

    Science.gov (United States)

    Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

    2017-11-01

    Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

  1. Thermal behavior of halogenated imidebismaleimide resins

    International Nuclear Information System (INIS)

    Mohammad, A.; Al-Halim, N.Z.

    1995-01-01

    Several new poly-halogenated malecimides, bismaleimides and therir copoly resins were synthessised thermally from their corresponding amic acids. The synthesis was accomplished by two way method (amic acid-polimide) instead of the well-known three way method (amic acid-imide-polyimide). Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The effect of halogen substituent, especially in the ortho postion, is clear in the imidization proces, while polymerization proceeds almost equally in all systems. Thermal properties of homo and copolymers were correlated with their chemical structures. (author). 15 refs., 4

  2. Passivation of quartz for halogen-containing light sources

    Science.gov (United States)

    Falkenstein, Zoran

    1999-01-01

    Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

  3. N-Chloro and N-bromosaccharins: valuable reagents for halogenation of electron rich aromatics and cohalogenation of alkenes

    Directory of Open Access Journals (Sweden)

    Souza Soraia P. L. de

    2003-01-01

    Full Text Available N-Chloro- and N-bromosaccharins react with electron rich aromatic compounds (anisole, acetanilide, N,N-dimethylaniline producing halogenated compounds. The reaction with N-bromosaccharin gives para- substituted compounds only, whereas N-chlorosaccharin produces orto and para mixtures (para isomer predominantly, ca. 4-5 : 1. The reactions of the N-halosaccharins with alkenes (cyclohexene, styrene, a-methylstyrene, and 1-hexene give the corresponding halohydrins.

  4. Retention efficiencies of halogenated and non-halogenated hydrocarbons in selected wetland ecosystem in Lake Victoria Basin

    Directory of Open Access Journals (Sweden)

    Shadrack Mule

    2015-06-01

    Full Text Available The determination of retention efficiencies of halogenated and non-halogenated hydrocarbon in selected wetland ecosystems in Lake Victoria basin was carried out. Qualitative and quantitative determination of the presence of residual hydrocarbons in Kigwal/Kimondi, Nyando and Nzoia wetland ecosystems using Gas Chromatography - Mass Spectrometer (GC-MS instrument indicated the presence of residual organochlorines, organophosphorus, carbamates and synthetic pyrethroid hydrocarbons in water, sediment and plant materials. In order to compare the retention efficiencies of the wetlands, the wetland ecosystems were divided into three different sections, namely: inlet, mid and outlet. Calculations of mass balances of residual halogenated and non-halogenated hydrocarbons at the respective sections was done taking into account the partition of the studied compounds in samples of water, sediments and papyrus reed plant materials and analyzed using validated Gas Chromatography - Mass Spectrometer (GC-MS method. From the analysis, several residual hydrocarbons namely: bendiocarb, benzene hexachloride (BHC, carbaryl, cypermethrin, decis, deltamethrin, diazinon, dieldrin, DDT, DDD, DDE, malathion, propoxur, sumithion, 5-phenylrhodanine, 1,3,5-trichlorobenzene, 1-(2-phenoxybenzylhydrazine were detected and quantified. The levels of the selected residual hydrocarbons in water samples were used to calculate the retention efficiencies of a specific hydrocarbon and the values recorded. Generally, River Nyando wetland recorded mean percentage retention efficiencies of 76 and 94% for dry and rainy seasons respectively; Kigwal/Kimondi wetland had seasonal mean percentage retention efficiencies of 63 to 78%. River Nzoia also had calculated seasonal mean percentage retention efficiencies of between 56 to 88%. Dry season had lower mean percentages retention efficiencies as compared to rainy season in the three wetlands of interest during the period of study. The study

  5. Aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil: a review.

    Science.gov (United States)

    Vranova, Valerie; Rejsek, Klement; Formanek, Pavel

    2013-11-10

    Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic) and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research.

  6. Aliphatic, Cyclic, and Aromatic Organic Acids, Vitamins, and Carbohydrates in Soil: A Review

    Directory of Open Access Journals (Sweden)

    Valerie Vranova

    2013-01-01

    Full Text Available Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research.

  7. Enzymatic degradation of aliphatic nitriles by Rhodococcus rhodochrous BX2, a versatile nitrile-degrading bacterium.

    Science.gov (United States)

    Fang, Shumei; An, Xuejiao; Liu, Hongyuan; Cheng, Yi; Hou, Ning; Feng, Lu; Huang, Xinning; Li, Chunyan

    2015-06-01

    Nitriles are common environmental pollutants, and their removal has attracted increasing attention. Microbial degradation is considered to be the most acceptable method for removal. In this work, we investigated the biodegradation of three aliphatic nitriles (acetonitrile, acrylonitrile and crotononitrile) by Rhodococcus rhodochrous BX2 and the expression of their corresponding metabolic enzymes. This organism can utilize all three aliphatic nitriles as sole carbon and nitrogen sources, resulting in the complete degradation of these compounds. The degradation kinetics were described using a first-order model. The degradation efficiency was ranked according to t1/2 as follows: acetonitrile>trans-crotononitrile>acrylonitrile>cis-crotononitrile. Only ammonia accumulated following the three nitriles degradation, while amides and carboxylic acids were transient and disappeared by the end of the assay. mRNA expression and enzyme activity indicated that the tested aliphatic nitriles were degraded via both the inducible NHase/amidase and the constitutive nitrilase pathways, with the former most likely preferred. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Hydrodeoxygenation of aliphatic and aromatic oxygenates on sulphided catalysts for production of second generation biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Senol, O.I.

    2007-07-01

    Environmental concerns and diminishing petroleum reserves have increased the importance of biofuels for traffic fuel applications. Second generation biofuels produced from wood, vegetable oils and animal fats have been considered promising for delivering biofuels in large amount with low production cost. The abundance of oxygen in the form of various aliphatic and aromatic oxygenates decreases the quality of biofuels, however, and therefore the oxygen content of biofuels must be reduced. Upgrading of biofuels can be achieved by hydrodeoxygenation (HDO), which is similar to hydrodesulphurisation in oil refining. In HDO, oxygen-containing compounds are converted to hydrocarbons by eliminating oxygen in the form of water in the presence of hydrogen and a sulphided catalyst. Due to the low sulphur content of biofuels, a sulphiding agent is typically added to the HDO feed to maintain activity and stability of the catalyst. The aim of this work was to investigate HDO using aliphatic and aromatic oxygenates as model compounds on sulphided NiMo/gamma-Al{sub 2}O3 and CoMo/gamma-Al{sub 2}O3 catalysts. The effects of side product, water, and of sulphiding agents, H{sub 2}S and CS{sub 2}, on HDO were determined. The primary focus was on the HDO of aliphatic oxygenates, because a reasonable amount of data regarding the HDO of aromatic oxygenates already exists. The HDO of aliphatic esters produced hydrocarbons from intermediate alcohol, carboxylic acid, aldehyde and ether compounds. A few sulphur-containing compounds were also detected in trace amounts, and their formation caused desulphurisation of the catalysts. Hydrogenation reactions and acid-catalysed reactions (dehydration, hydrolysis, esterification, E{sub 2} elimination and SN{sub 2} nucleophilic substitution) played a major role in the HDO of aliphatic oxygenates. The NiMo catalyst showed a higher activity for HDO and hydrogenation reactions than the CoMo catalyst, but both catalysts became deactivated because of

  9. Aliphatic, Cyclic, and Aromatic Organic Acids, Vitamins, and Carbohydrates in Soil: A Review

    Science.gov (United States)

    Vranova, Valerie; Rejsek, Klement; Formanek, Pavel

    2013-01-01

    Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic) and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research. PMID:24319374

  10. Chlorinated aliphatic and aromatic VOC decomposition in air mixture by using electron beam irradiation

    International Nuclear Information System (INIS)

    Chmielewski, A.G.; Sun Yongxia; Bulka, S.; Zimek, Z.

    2004-01-01

    Chlorinated aliphatic and aromatic hydrocarbons, which are emitted from coal power station and waste incinerators, are very harmful to the environment and human health. Recent studies show that chlorinated aliphatic and aromatic hydrocarbons are suspected to be the precursors of dioxin's formation. Dioxin's emission into atmosphere will cause severe environmental problems by ecology contamination. l,4-dichlorobenzene(l,4-DCB) and cis-dichloroethylene(cis-DCE) were chosen as representative chlorinated aromatic and aliphatic compounds, respectively. Their decomposition was investigated by electron beam irradiation. The experiments were carried out 'in batch' system. It is found that over 97% cis-DCE is decomposed having an initial concentration of 661 ppm. G-values of cis-DCE decomposition vary from 10 to 28 (molecules/100 eV) for initial concentration of 270-1530 ppm cis-DCE. The decomposition is mainly caused by secondary electron attachment and Cl addition reactions. Comparing with cis-DCE, 1,4-DCB decomposition needs higher absorbed dose. G-value of 1,4-DCB is below 4 molecules/100 eV

  11. Combined electrochemical degradation and activated carbon adsorption treatments for wastewater containing mixed phenolic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Rajkumar, D.; Palanivelu, K.; Balasubramanian, N. [Anna University, Madras (India). Center for Environmental Studies

    2005-01-01

    Electrochemical degradation of mixed phenolic compounds present in coal conversion wastewater was investigated in the presence of chloride as supporting electrolyte. Initially, the degradation experiments were conducted separately with 300 mg/L of individual phenolic compound in the presence of 2500 mg/L chloride using Ti/TiO{sub 2}-RuO{sub 2}-IrO{sub 2} anode at 5.4 A/dm{sup 2} current density. Comparison of the experimental results of the chemical oxygen demand (COD) removal versus charge indicated that the order of decreasing COD removal for various phenolic compounds as catechol {gt} resorcinol {gt} m-cresol {gt} o-cresol {gt} phenol {gt} p-cresol. Degradation of the mixture of phenolic compounds and high-pressure liquid chromatography (HPLC) determinations at various stages of electrolysis showed that phenolic compounds were initially converted into benzoquinone and then to lower molecular weight aliphatic compounds. The COD and the total organic carbon (TOC) removal were 83 and 58.9% after passing 32 Ah/L with energy consumption of 191.6 kWh/kg of COD removal. Experiments were also conducted to remove adsorbable organic halogens (AOX) content in the treated solution using granular activated carbon. The optimum conditions for the removal of AOX was at pH 3.0, 5 mL/min flow rate and 31.2 cm bed height. Based on the investigation, a general scheme of treatment of mixed phenolic compounds by combined electrochemical and activated carbon adsorption treatment is proposed.

  12. Retention of Halogens in Waste Glass

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R.

    2010-05-01

    In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

  13. Aryl Polyphosphonates: Useful Halogen-Free Flame Retardants for Polymers

    Directory of Open Access Journals (Sweden)

    Li Chen

    2010-10-01

    Full Text Available Aryl polyphosphonates (ArPPN have been demonstrated to function in wide applications as flame retardants for different polymer materials, including thermosets, polycarbonate, polyesters and polyamides, particularly due to their satisfactory thermal stability compared to aliphatic flame retardants, and to their desirable flow behavior observed during the processing of polymeric materials. This paper provides a brief overview of the main developments in ArPPN and their derivatives for flame-retarding polymeric materials, primarily based on the authors’ research work and the literature published over the last two decades. The synthetic chemistry of these compounds is discussed along with their thermal stabilities and flame-retardant properties. The possible mechanisms of ArPPN and their derivatives containing hetero elements, which exhibit a synergistic effect with phosphorus, are also discussed.

  14. Microwave assisted pyrolysis of halogenated plastics recovered from waste computers.

    Science.gov (United States)

    Rosi, Luca; Bartoli, Mattia; Frediani, Marco

    2018-03-01

    Microwave Assisted Pyrolysis (MAP) of the plastic fraction of Waste from Electric and Electronic Equipment (WEEE) from end-life computers was run with different absorbers and set-ups in a multimode batch reactor. A large amount of various different liquid fractions (up to 76.6wt%) were formed together with a remarkable reduction of the solid residue (up to 14.2wt%). The liquid fractions were characterized using the following different techniques: FT-IR ATR, 1 H NMR and a quantitative GC-MS analysis. The liquid fractions showed low density and viscosity, together with a high concentration of useful chemicals such as styrene (up to 117.7mg/mL), xylenes (up to 25.6mg/mL for p-xylene) whereas halogenated compounds were absent or present in a very low amounts. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay

    CSIR Research Space (South Africa)

    Ojijo, Vincent O

    2014-05-01

    Full Text Available This article gives an overview of the recent developments in the preparation, characterisation, properties, crystallisation behaviour, and melt rheology of clay-containing composites of biodegradable synthetic aliphatic polyesters such as poly...

  16. Attachment of inorganic moieties onto aliphatic polyurethanes

    Directory of Open Access Journals (Sweden)

    Eliane Ayres

    2007-06-01

    Full Text Available Polyurethanes have been used in a series of applications due basically to their versatility in terms of controlling the behavior by altering basically the type of reagents used. However, for more specific and advanced applications, such as in membranes, biomaterials and sensors, well-organized and defined chemical functionalities are necessary. In this work, inorganic functionalities were incorporated into aliphatic polyurethanes (PU having different macromolecular architectures. Polyurethanes were synthesized using a polyether diol and dicyclohexylmethane 4,4' diisocyanate (H12-MDI. Polyurethanes having carboxylic acid groups were also produced by introducing 2,2- bis (hydroxymethyl propionic acid in the polymerization process. Inorganic functionalities were inserted into polyurethanes by reacting isocyanate end capped chains with aminopropyltriethoxysilane followed by tetraethoxysilane. PU having carboxylic acid groups yielded transparent samples after the incorporation of inorganic entities, as an evidence of smaller and better dispersed inorganic entities in the polymer network. FTIR and swelling measurements showed that polyurethanes having carboxylic acid groups had inorganic domains less packed, condensed and cross-linked when compared to polyurethanes with no carboxylic acid groups. Results also suggested that the progressive incorporation of inorganic moieties in both types of polyurethanes occurred in regions previously activated with inorganic functionalities, instead of by the creation of new domains. The temperatures of thermal decomposition and glass transition were also shifted to higher temperatures when inorganic functionalities were incorporated into polyurethanes.

  17. Synthesis of 4-Halogenated 3-Fluoro-6-methoxyquinolines: Key Building Blocks for the Synthesis of Antibiotics

    DEFF Research Database (Denmark)

    Flagstad, Thomas; Petersen, Mette Terp; Hinnerfeldt, Daniel Michael

    2014-01-01

    A practical and scalable 4-step route is presented for the synthesis of 4-bromo-3-fluoro-6-methoxyoquinoline and 3-fluoro-4-iodo-6-methoxyoquinoline from readily available 2,4-dichloro-3-fluoroquinoline with an overall yield of 81-85%. Halogenated quinoline building blocks have found much use in ...... in antimicrobial drug discovery, and the method reported here would be useful for the synthesis of these compounds. © Georg Thieme Verlag....

  18. Selective Halogen-Lithium Exchange of 1,2-Dihaloarenes for Successive [2+4] Cycloadditions of Arynes and Isobenzofurans

    Directory of Open Access Journals (Sweden)

    Shohei Eda

    2015-10-01

    Full Text Available Successive [2+4] cycloadditions of arynes and isobenzofurans by site-selective halogen-lithium exchange of 1,2-dihaloarenes were developed, allowing the rapid construction of polycyclic compounds which serve as a useful synthetic intermediates for the preparation of various polyacene derivatives.

  19. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu; Al-Misba'a, Zahra; Huang, Kuo-Wei

    2014-01-01

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  20. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  1. Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions.

    Science.gov (United States)

    Han, Jiarui; Zhang, Xiangru; Liu, Jiaqi; Zhu, Xiaohu; Gong, Tingting

    2017-08-01

    Chlorine dioxide (ClO 2 ) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen (TOX), a collective parameter for all halogenated DBPs, formed in ClO 2 -treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid-liquid extraction (LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO 2 -treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE. With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols, were detected in the drinking water sample pretreated with multiple extractions; two of them, trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO 2 disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water. Copyright © 2017. Published by Elsevier B.V.

  2. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    Science.gov (United States)

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

  3. The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

    Science.gov (United States)

    Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

    2017-10-13

    Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

  4. Sonogashira–Hagihara reactions of halogenated glycals

    Directory of Open Access Journals (Sweden)

    Dennis C. Koester

    2012-05-01

    Full Text Available Herein, we report on our findings of the Sonogashira–Hagihara reaction with 1-iodinated and 2-brominated glycals using several aromatic and aliphatic alkynes. This Pd-catalyzed cross-coupling reaction presents a facile access to alkynyl C-glycosides and sets the stage for a reductive/oxidative refunctionalization of the enyne moiety to regenerate either C-glycosidic structures or pyran derivatives with a substituent in position 2.

  5. Process for removal of hydrogen halides or halogens from incinerator gas

    Science.gov (United States)

    Huang, H.S.; Sather, N.F.

    1987-08-21

    A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

  6. New Type of Halogen Bond: Multivalent Halogen Interacting with π- and σ-Electrons

    Directory of Open Access Journals (Sweden)

    Sławomir J. Grabowski

    2017-12-01

    Full Text Available MP2/aug-cc-pVTZ calculations were performed for complexes of BrF3 and BrF5 acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its σ-bond, while in remaining moieties—in complexes of hydrocarbons; such an electron transfer follows from π-electrons. The complexes are linked by a kind of the halogen bond that is analyzed for the first time in this study, i.e., it is the link between the multivalent halogen and π or σ-electrons. The nature of such a halogen bond is discussed, as well as various dependencies and correlations are presented. Different approaches are applied here, the Quantum Theory of Atoms in Molecules, Natural Bond Orbital method, the decomposition of the energy of interaction, the analysis of electrostatic potentials, etc.

  7. Unravelling Protein-Protein Interaction Networks Linked to Aliphatic and Indole Glucosinolate Biosynthetic Pathways in Arabidopsis

    Directory of Open Access Journals (Sweden)

    Sebastian J. Nintemann

    2017-11-01

    Full Text Available Within the cell, biosynthetic pathways are embedded in protein-protein interaction networks. In Arabidopsis, the biosynthetic pathways of aliphatic and indole glucosinolate defense compounds are well-characterized. However, little is known about the spatial orchestration of these enzymes and their interplay with the cellular environment. To address these aspects, we applied two complementary, untargeted approaches—split-ubiquitin yeast 2-hybrid and co-immunoprecipitation screens—to identify proteins interacting with CYP83A1 and CYP83B1, two homologous enzymes specific for aliphatic and indole glucosinolate biosynthesis, respectively. Our analyses reveal distinct functional networks with substantial interconnection among the identified interactors for both pathway-specific markers, and add to our knowledge about how biochemical pathways are connected to cellular processes. Specifically, a group of protein interactors involved in cell death and the hypersensitive response provides a potential link between the glucosinolate defense compounds and defense against biotrophic pathogens, mediated by protein-protein interactions.

  8. Aliphatic alcohols in spirits inhibit phagocytosis by human monocytes.

    Science.gov (United States)

    Pál, László; Árnyas, Ervin M; Bujdosó, Orsolya; Baranyi, Gergő; Rácz, Gábor; Ádány, Róza; McKee, Martin; Szűcs, Sándor

    2015-04-01

    A large volume of alcoholic beverages containing aliphatic alcohols is consumed worldwide. Previous studies have confirmed the presence of ethanol-induced immunosuppression in heavy drinkers, thereby increasing susceptibility to infectious diseases. However, the aliphatic alcohols contained in alcoholic beverages might also impair immune cell function, thereby contributing to a further decrease in microbicidal activity. Previous research has shown that aliphatic alcohols inhibit phagocytosis by granulocytes but their effect on human monocytes has not been studied. This is important as they play a crucial role in engulfment and killing of pathogenic microorganisms and a decrease in their phagocytic activity could lead to impaired antimicrobial defence in heavy drinkers. The aim of this study was to measure monocyte phagocytosis following their treatment with those aliphatic alcohols detected in alcoholic beverages. Monocytes were separated from human peripheral blood and phagocytosis of opsonized zymosan particles by monocytes treated with ethanol and aliphatic alcohols individually and in combination was determined. It was shown that these alcohols could suppress the phagocytic activity of monocytes in a concentration-dependent manner and when combined with ethanol, they caused a further decrease in phagocytosis. Due to their additive effects, it is possible that they may inhibit phagocytosis in a clinically meaningful way in alcoholics and episodic heavy drinkers thereby contribute to their increased susceptibility to infectious diseases. However, further research is needed to address this question.

  9. Study on the dynamics of halogen elements in the agro-environment and these element`s deficiency, toxicity and environmental hazards by the application of the neutron activation analysis method

    Energy Technology Data Exchange (ETDEWEB)

    Yuita, Kouichi [National Inst. of Agro-Environmental Sciences, Tsukuba, Ibaraki (Japan)

    1998-03-01

    A neutron activation analysis method is an accurate and highly sensitive method for analyzing halogen elements (iodine, bromine and chlorine) except fluorine. It is unsubstitutable and valuable method especially for iodine (including radioactive {sup 129}I) and bromine which are present at lower levels. Halogen elements have high chemical and physiological activities and move widely in the environment. As a result, deficiency and an excess of halogen elements in plants and animals have occurred and artificial halogen compounds have caused environmental pollution in wide areas. We efficiently utilized the neutron activation analysis method and an activable tracer method to obtain valuable findings which contribute to the clarification of and measures against these actual problems and which are also concerned with the occurrence, distribution and migration of halogen elements in the environment, especially agricultural and forestry ecosystems in space and in time. (author)

  10. Pharmacological evaluation of halogenated and non-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles as D(2) and 5-HT(2A) receptor ligands.

    Science.gov (United States)

    Tomić, Mirko; Vasković, Djurdjica; Tovilović, Gordana; Andrić, Deana; Penjišević, Jelena; Kostić-Rajačić, Sladjana

    2011-05-01

    Five groups of previously synthesized and initially screened non-substituted and 4-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles were estimated for their in-vitro binding affinities at the rat D(2) , 5-HT(2A) , and α(1) -adrenergic receptors. Among all these compounds, 2-methoxyphenyl and 2-chlorophenyl piperazines demonstrate the highest affinities for the tested receptors. The effects of 4-halogenation of benzimidazoles reveal that substitution with bromine may greatly increase the affinity of the compounds for the studied receptors, while the effect of substitution with chlorine is less remarkable. Most of the tested components show 5-HT(2A)/D(2) pK(i) binding ratios slightly above or less than 1, while only 4-chloro-6-(2-{4-[3-(trifluoromethyl)phenyl]piperazin-1-yl}ethyl)-1H-benzimidazole expresses an appropriate higher binding ratio (1.14), which was indicated for atypical neuroleptics. This compound exhibits a non-cataleptic action in rats and prevents d-amphetamine-induced hyperlocomotion in mice, which suggest its atypical antipsychotic potency. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Design, Synthesis and Cytotoxic Activities of Novel Aliphatic Amino-Substituted Flavonoids

    Directory of Open Access Journals (Sweden)

    Guannan Liu

    2013-11-01

    Full Text Available A series of flavonoids 9a–f, 13b, 13d, 13e and 14a–f bearing diverse aliphatic amino moieties were designed, synthesized and evaluated for their cytotoxic activities against the ECA-109, A-549, HL-60, and PC-3 cancer cell lines. Most of the compounds exhibited moderate to good activities. The structure-activity relationships were studied, revealing that the chalcone skeleton is the most preferable for cytotoxic activities. Chalcone 9d was the most promising compound due to its high potency against the examined cancer cell lines (its IC50 values against ECA-109, A549, HL-60 and PC-3 cells were 1.0, 1.5, 0.96 and 3.9 μM, respectively.

  12. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    International Nuclear Information System (INIS)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F.

    2013-01-01

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  13. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    Energy Technology Data Exchange (ETDEWEB)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

    2013-09-15

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  14. Oxidation of the persistent compounds in the oxygen-hydrogen plasma

    International Nuclear Information System (INIS)

    Brozek, V.; Novak, M.; Vonka, P.; Kopecky, V.; Hrabovsky, M.

    1995-01-01

    The effectiveness of plasma-chemical decomposition of the persistent halogenated aliphatic hydrocarbons (CCl 4 , CF 2 Cl 2 , CF 3 Cl 3 and C 6 Cl 6 ) was examined by the analysis of emergent products in the dependence on the next parameters of the plasma-chemical reactor: power of the plasmatron; geometry of the plasmatic cone; velocity of flow of the gases by reaction chamber; stoichiometry of the ratio of the oxygen-air-water

  15. Mercury and halogens in coal: Chapter 2

    Science.gov (United States)

    Kolker, Allan; Quick, Jeffrey C.; Granite, Evan J.; Pennline, Henry W.; Senior, Constance L.

    2014-01-01

    Apart from mercury itself, coal rank and halogen content are among the most important factors inherent in coal that determine the proportion of mercury captured by conventional controls during coal combustion. This chapter reviews how mercury in coal occurs, gives available concentration data for mercury in U.S. and international commercial coals, and provides an overview of the natural variation in halogens that influence mercury capture. Three databases, the U.S. Geological Survey coal quality (USGS COALQUAL) database for in-ground coals, and the 1999 and 2010 U.S. Environmental Protection Agency (EPA) Information Collection Request (ICR) databases for coals delivered to power stations, provide extensive results for mercury and other parameters that are compared in this chapter. In addition to the United States, detailed characterization of mercury is available on a nationwide basis for China, whose mean values in recent compilations are very similar to the United States in-ground mean of 0.17 ppm mercury. Available data for the next five largest producers (India, Australia, South Africa, the Russian Federation, and Indonesia) are more limited and with the possible exceptions of Australia and the Russian Federation, do not allow nationwide means for mercury in coal to be calculated. Chlorine in coal varies as a function of rank and correspondingly, depth of burial. As discussed elsewhere in this volume, on a proportional basis, bromine is more effective than chlorine in promoting mercury oxidation in flue gas and capture by conventional controls. The ratio of bromine to chlorine in coal is indicative of the proportion of halogens present in formation waters within a coal basin. This ratio is relatively constant except in coals that have interacted with deep-basin brines that have reached halite saturation, enriching residual fluids in bromine. Results presented here help optimize mercury capture by conventional controls and provide a starting point for

  16. Laboratory Investigations of Stratospheric Halogen Chemistry

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  17. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    Science.gov (United States)

    Yoshida, Suguru; Fujita, Yasunobu

    The current state of knowledge on heat transfer to boiling refrigerants (halogenated hydrocarbons) in a pool and flowing inside a horizontal tube is reviewed with an emphasis on information relevant to the design of refrigerant evaporators, and some recommendations are made for future research. The review covers two-phase flow pattern, heat transfer characteristics, correlation of heat transfer coefficient, influence of oil, heat transfer augmentation, boiling from tube-bundle, influence of return bend, burnout heat flux, film boiling, dryout and post-dryout heat transfer.

  18. Scientific conferences: A big hello to halogen bonding

    Science.gov (United States)

    Erdelyi, Mate

    2014-09-01

    Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

  19. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Science.gov (United States)

    2010-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

  20. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujing; Li, Jing, E-mail: jingli@rutgers.edu

    2015-04-15

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  1. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    International Nuclear Information System (INIS)

    Wang, Sujing; Li, Jing

    2015-01-01

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn 2 S 2 (bza) (1), Zn 2 S 2 (mbza) (2), Zn 2 S 2 (fbza) (3), Zn 2 S 2 (pca) (4), and Zn 2 S 2 (thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn 2 S 2 (L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy

  2. Applicability of the theory of thermodynamic similarity to predict the enthalpies of vaporization of aliphatic aldehydes

    Science.gov (United States)

    Esina, Z. N.; Korchuganova, M. R.

    2015-06-01

    The theory of thermodynamic similarity is used to predict the enthalpies of vaporization of aliphatic aldehydes. The predicted data allow us to calculate the phase diagrams of liquid-vapor equilibrium in a binary water-aliphatic aldehyde system.

  3. Prediction of anticancer activity of aliphatic nitrosoureas using ...

    African Journals Online (AJOL)

    Design and development of new anticancer drugs with low toxicity is a very challenging task and computer aided methods are being increasingly used to solve this problem. In this study, we investigated the anticancer activity of aliphatic nitrosoureas using quantum chemical quantitative structure activity relation (QSAR) ...

  4. In vitro evaluation of aliphatic fatty alcohol metabolites of ...

    African Journals Online (AJOL)

    From the seeds of P. americana, five known 1, 2, 4-dihydroxy derivatives aliphatic alcohols, called avocadenols were isolated and identified by spectroscopic methodsincluding 1D- and 2D NMR, and comparison with reported data in literature. Antifungal activity for 1, 2, 4-Trihydroxyheptadec-6-en-16-yne (5)(IC50< 8 μg/mL) ...

  5. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  6. Vapor Pressure of Selected Aliphatic Alcohols by Ebulliometry. Part 1

    Czech Academy of Sciences Publication Activity Database

    Čenský, M.; Roháč, V.; Růžička, K.; Fulem, M.; Aim, Karel

    2010-01-01

    Roč. 298, č. 2 (2010), s. 192-198 ISSN 0378-3812 R&D Projects: GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : vapor pressure * ebulliometry * aliphatic alcohols Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.253, year: 2010

  7. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Science.gov (United States)

    2010-07-01

    ... methods for protecting against such risk, into an MSDS as described in § 721.72(c) within 90 days from the..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... manner or method of manufacture, import, or processing associated with any use of this substance without...

  8. Kinetics and mechanism of oxidation of aliphatic primary alcohols by ...

    Indian Academy of Sciences (India)

    Unknown

    Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate. SONU SARASWAT, VINITA SHARMA and K K BANERJI*. Department of Chemistry, JNV University, Jodhpur 342 005, India e-mail: banerjikk@rediffmail.com. MS received 4 December 2001; revised 2 November 2002.

  9. Kinetics of Oxidation of Aliphatic Alcohols by Potassium Dichromate ...

    African Journals Online (AJOL)

    The kinetics of oxidation of four aliphatic alcohols in acidic aqueous and micellar media were investigated. The reaction was found to be first-order with respect to both alcohol and oxidant. Pseudo-first-order kinetics were found to be perfectly applicable with ethanol, 1-propanol and 2-propanol while deviation was observed ...

  10. Occurrence and Sources of Aliphatic Hydrocarbons in Soils within ...

    African Journals Online (AJOL)

    ADOWIE PERE

    Keywords: Asphalt Plants; Soil; Aliphatic hydrocarbons; Pristane; Phytane. Hot mix asphalt (HMA) plant is an assemblage of mechanical equipment where aggregates or inert mineral materials such as sand, gravel, crushed stones, Slag, rock dust or powder are blended, heated, dried and mixed with bitumen in measured ...

  11. Chemical modifications and applications of alternating aliphatic polyketones

    NARCIS (Netherlands)

    Zhang, Youchun

    2008-01-01

    Alternating aliphatic polyketones, produced by co- and terpolymerization of carbon monoxide and olefins (mixtures of ethylene and propylene) using palladium-based homogeneous catalysis represent a very promising class of polymers for a wide range of applications. Besides many interesting chemical

  12. Direct electrochemical imidation of aliphatic amines via anodic oxidation.

    Science.gov (United States)

    Zhang, Li; Su, Ji-Hu; Wang, Sujing; Wan, Changfeng; Zha, Zhenggen; Du, Jiangfeng; Wang, Zhiyong

    2011-05-21

    Direct electrochemical synthesis of sulfonyl amidines from aliphatic amines and sulfonyl azides was realized with good to excellent yields. Traditional tertiary amine substrates were broadened to secondary and primary amines. The reaction intermediates were observed and a reaction mechanism was proposed and discussed. © The Royal Society of Chemistry 2011

  13. Inhibition of Tetrahymena pyriformis growth by Aliphatic Alcohols ...

    African Journals Online (AJOL)

    A Quantitative Structure- Activity Relationship (QSAR) study was undertaken to evaluate the relative toxicity of a mixed series of 21 (linear and branched-chain) alcohols and 9 normal aliphatic amines in term of the 50% inhibitory growth concentration (IGC50) of Tetrahymena pyriformis. The applied simple linear regression ...

  14. [Near infrared light irradiator using halogen lamp].

    Science.gov (United States)

    Ide, Yasuo

    2012-07-01

    The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

  15. Synthesis and improved photochromic properties of pyrazolones in the solid state by incorporation of halogen

    Science.gov (United States)

    Guo, Jixi; Yuan, Hui; Jia, Dianzeng; Guo, Mingxi; Li, Yinhua

    2017-01-01

    Four novel photochromic pyrazolones have been prepared by introducing halogen atoms as substituents on the benzene ring. All as-synthesized compounds exhibited excellent reversible photochromic performances in the solid state. Upon UV light irradiation, the as-synthesized compounds can change their structures from E-form to K-form with yellow coloration. Further processed by heating, they rapidly reverted to their initial states at 120 °С. Their photo-response and thermal bleaching kinetics were detailed investigated by UV absorption spectra. The results showed that the time constants were higher than that of our previously reported compounds at least one order of magnitude and the rate constants of the as-synthesized compounds were significantly influenced by the size and electronegativity of different halogen atoms. The fluorescence emission were modulated in a high degree via photoisomerization of pyrazolones, which might be due to the efficient energy transfer from E-form to K-form isomers for their partly overlaps between their E-form absorption spectra and K-form fluorescence spectra.

  16. Tannins and Tannin-Related Derivatives Enhance the (Pseudo-)Halogenating Activity of Lactoperoxidase.

    Science.gov (United States)

    Gau, Jana; Prévost, Martine; Van Antwerpen, Pierre; Sarosi, Menyhárt-Botond; Rodewald, Steffen; Arnhold, Jürgen; Flemmig, Jörg

    2017-05-26

    Several hydrolyzable tannins, proanthocyanidins, tannin derivatives, and a tannin-rich plant extract of tormentil rhizome were tested for their potential to regenerate the (pseudo-)halogenating activity, i.e., the oxidation of SCN - to hypothiocyanite - OSCN, of lactoperoxidase (LPO) after hydrogen peroxide-mediated enzyme inactivation. Measurements were performed using 5-thio-2-nitrobenzoic acid in the presence of tannins and related substances in order to determine kinetic parameters and to trace the LPO-mediated - OSCN formation. The results were combined with docking studies and molecular orbital analysis. The - OSCN-regenerating effect of tannin derivatives relates well with their binding properties toward LPO as well as their occupied molecular orbitals. Especially simple compounds like ellagic acid or methyl gallate and the complex plant extract were found as potent enzyme-regenerating compounds. As the (pseudo-)halogenating activity of LPO contributes to the maintenance of oral bacterial homeostasis, the results provide new insights into the antibacterial mode of action of tannins and related compounds. Furthermore, chemical properties of the tested compounds that are important for efficient enzyme-substrate interaction and regeneration of the - OSCN formation by LPO were identified.

  17. Organohalide respiration in pristine environments: implications for the natural halogen cycle.

    Science.gov (United States)

    Atashgahi, Siavash; Häggblom, Max M; Smidt, Hauke

    2018-03-01

    Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens could have primed development of metabolic machineries for their degradation, especially in microorganisms. Among these, a special group of anaerobic microorganisms was discovered that could conserve energy by reducing organohalogens as terminal electron acceptor in a process termed organohalide respiration. Originally discovered in a quest for biodegradation of anthropogenic organohalogens, these organohalide-respiring bacteria (OHRB) were soon found to reside in pristine environments, such as the deep subseafloor and Arctic tundra soil with limited/no connections to anthropogenic activities. As such, accumulating evidence suggests an important role of OHRB in local natural halogen cycles, presumably taking advantage of natural organohalogens. In this minireview, we integrate current knowledge regarding the natural origin and occurrence of industrially important organohalogens and the evolution and spread of OHRB, and describe potential implications for natural halogen and carbon cycles. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  18. Photofragmentation spectra of halogenated methanes in the VUV photon energy range

    Energy Technology Data Exchange (ETDEWEB)

    Cartoni, Antonella, E-mail: antonella.cartoni@uniroma1.it [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185 (Italy); Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo [CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015 (Italy)

    2014-05-14

    In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

  19. Environmental levels and toxicological potencies of a novel mixed halogenated carbazole

    Directory of Open Access Journals (Sweden)

    Miren Pena-Abaurrea

    2016-09-01

    Full Text Available The present work involves an extensive analytical and toxicological description of a recently identified mixed halogenated carbazole found in sediment samples, 1,8-dibromo-3,6-dichloro-9H-carbazole (BCCZ. Concentrations and the relative effect potency (REP were calculated for the target BCCZ in a set of stream sediments collected in 2008 in Ontario, Canada. The levels calculated for BCCZ as compared to those previously assessed for legacy persistent organic pollutants (POPs in the same samples revealed a significant contribution of BCCZ to the total organic chemical contamination (<1%–95%; average 37%. The corresponding dioxin toxic equivalencies (TEQs of BCCZ in the sediment extracts were estimated from experimental REP data. The experimental data presented supports the classification of this emerging halogenated chemical as a contaminant of emerging environmental concern. Although potential emission sources could not be identified, this study highlights the importance of on-going research for complete characterization of halogenated carbazoles and related compounds.

  20. Aliphatic and aromatic hydrocarbons in tropical recent sediments of Campos dos Goytacazes, RJ, Brazil

    Directory of Open Access Journals (Sweden)

    Gomes Alexandre de O.

    2003-01-01

    Full Text Available Sediment samples from the Imbé, the Urubu and the Ururaí rivers and from Lake de Cima were studied. These sites are located in the county of Campos dos Goytacazes, Rio de Janeiro, Brazil. Aliphatic and aromatic fractions were analyzed by GC-FID and GC-MS in order to gather information on the degree of contamination by anthropogenic activities and other biogenic contributions. Concentrations of total aliphatic and aromatic hydrocarbons were 1.2, 2.8, 5.8 and 4.3 mug g-1 and 74, 30, 722 and 340 ng g-1 in the Imbé, Ururaí, Urubu rivers and Lake de Cima, respectively. The C20 highly branched isoprenoid alkane was identified in the Urubu sediment. There were no hopanes or steranes in any sample. Anthropogenic aromatic compounds, detected at trace levels, were observed only in the Imbé and in Lake de Cima (227 ng g-1. The fluoranthene/pyrene rate for Lake de Cima was 4.2, suggesting a combustion origin for the PAH. This data is consistent with the frequently sugar cane burning practice that occurs in this region. A greater input from higher plants was observed in the Urubu, Imbé and Lake de Cima sediments; on the other hand, the aquatic input predominates for Ururaí. In summary, Lake de Cima sediment is considered very slightly polluted, while the others are unpolluted.

  1. Occurrence and sources of aliphatic hydrocarbons in surface soils from Riyadh city, Saudi Arabia

    Directory of Open Access Journals (Sweden)

    Ahmed I. Rushdi

    2013-01-01

    Full Text Available Soil particles contain a variety of anthropogenic and natural organic components derived from many sources such as industrial and traffic fossil fuel emissions and terrestrial biota. The organic contents of soil and sand from the Arabian region have not fully characterized. Thus, samples of fine soil particles (sieved to <125 μM were collected from the Riyadh area in November 2006 (late summer and February 2007 (late winter. The samples were extracted with a mixture of dichloromethane/hexane and analyzed by gas chromatography–mass spectroscopy (GCMS in order to characterize the chemical composition and sources of aliphatic hydrocarbons. The results showed that both anthropogenic and natural biogenic inputs were the major sources of the aliphatic hydrocarbons in these extracts. Vehicular emission products and discarded plastics were the major anthropogenic sources in the fine particles of the soils and ranged from 64% to 96% in November 2006 and from 70% to 92% in February 2007. Their tracers were n-alkanes, hopanes, sterane, plasticizers and UCM. Vegetation was also a major natural source of hydrocarbon compounds in samples ranging from ∼0% to18% in November 2006 and from 1% to 13% in February 2007 and included n-alkanes and triterpenoids.

  2. A comprehensive evaluation of the toxicology of cigarette ingredients: aliphatic and aromatic carboxylic acids.

    Science.gov (United States)

    Coggins, Christopher R E; Liu, Jianmin; Merski, Jerome A; Werley, Michael S; Oldham, Michael J

    2011-06-01

    Aromatic and aliphatic carboxylic acids are present in tobacco and tobacco smoke. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing eight aromatic and aliphatic carboxylic acids and the salt of one acid that were added individually at three different levels (lowest and highest target inclusions were 100 and 90,000 ppm, respectively). Mainstream smoke from cigarettes containing each of the test ingredients was evaluated using analytical chemistry and assays to measure in vitro cytotoxicity (neutral red uptake) and Salmonella (five strains) mutagenicity. For four of the compounds (citric, lactic, benzoic acids, and sodium benzoate), 90-day rodent inhalation studies were also performed. Although sporadic statistically significant differences in some experimental cigarette smoke constituents occurred, none resulted in significant changes in mutagenicity or cytotoxicity responses, nor in responses measured in the inhalation studies, except for lactic acid (LA). Inclusion of LA resulted in dose-dependent increase in water and caused a dose-dependent decrease in cytotoxicity. Incorporation of LA into cigarettes resulted in several dose-related reductions in histopathology, which were largely restricted to the nasal passages. Incorporation of LA also ameliorated some of the typical decrease in body weight gain seen in cigarette smoke-exposed rats. Inclusion of these ingredients at exaggerated use levels resulted in sporadic dose-related and treatment effects for some smoke constituents, but no toxicological response was noted in the in vitro and in vivo tests performed.

  3. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polycarboxylic acid metal... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under this...

  4. Chromatographic methods of the measurements of the chloride compounds in troposphere and stratosphere

    International Nuclear Information System (INIS)

    Lasa, J.; Rosiek, J.

    1992-01-01

    The paper contains a description of various chromatographic techniques used for the analysis of the tropospheric techniques used for the analysis of the tropospheric and stratospheric halogenated compounds. The types of the column packings used for separation of halogenated compounds are described. Model chromatograms illustrating the separation of halogenated compounds are presented. The methods of the air sampling and injection for the packed and capillary columns were described. The methods of the preparation of gas calibration mixtures are presented. Operational conditions for electron capture detector used by the authors of quoted paper are also given. (author). 66 refs, 29 figs, 13 tabs

  5. Aliphatic and polycyclic aromatic hydrocarbons characterisation of Coimbra and Oporto PM2.5 urban aerosol

    Science.gov (United States)

    Rocha, A. C.; Mirante, F.; Gonçalves, C.; Nunes, T.; Alves, C.; Evtyugina, M.; Kowacz, M.; Pio, C.; Rocha, C.; Vasconcelos, T.

    2009-04-01

    The concentration of organic pollutants in urban areas is mostly due to incomplete combustion from vehicles, industries and domestic heating. Some of these compounds, principally the aliphatic (ALIPH) and polycyclic aromatic hydrocarbons (PAHs) promote harmful effects in human health. The determination of the ALIPH and PAHs concentration levels and their possible emission sources are useful for air quality management and source apportionment studies. In order to estimate and compare the ambient concentrations and establish the main sources of these compounds, the fine fraction of the atmospheric particulate matter (PM2.5) was collected simultaneously in Oporto and Coimbra during summer and winter seasons using a high volume sampler. The organic compounds were extracted from the particulate matter, under reflux with dichloromethane and the total organic extract (TOE) was fractionated by flash chromatography using five different eluents with increasing polarity. The hydrocarbon fractions were analysed by gas chromatography/mass spectrometry (GC/MS). Here we present and discuss the qualitative and quantitative composition of the aliphatic and aromatic fractions present in PM2.5 samples from both cities. The homologous series of C14 to C34 n-alkanes, isoprenoid hydrocarbons (pristane and phytane), PAHs and some petroleum markers have been identified and quantified. With the purpose of identifying the possible sources, various molecular diagnostic ratios were calculated. The global carbon preference index (CPI) closer to the unity, the large concentration of the unresolved complex mixture (UCM) and the presence of PAHs indicate that motor vehicle exhaust was the main emission source of the aliphatic and polycyclic aromatic fractions of Oporto and Coimbra aerosol, especially in the first city. Also, the remarkable presence of petroleum biomarkers such, as hopanes, confirms the previous results. Concentration ratios between PAHs were calculated and used to assign emission

  6. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    Energy Technology Data Exchange (ETDEWEB)

    Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

    1981-02-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

  7. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    International Nuclear Information System (INIS)

    Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

    1981-01-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

  8. Protection of aliphatic alcohols by thiols

    International Nuclear Information System (INIS)

    Nanobashivili, E.M.; Chirakadze, G.G.; Panchvidze, M.V.; Gvilava, S.E.; Khidesheli, G.I.

    1973-01-01

    Study was made of methyl, ethyl, propyl, butyl and penthyl alcohols. The aqueous solutions of the alcohols were X-irradiated. Results are presented of the action of high-energy particles on the solutions of ethyl, propyl and butyl alcohols in the presence and absence of the minor amounts of ethanthiol. Protective effect of the -SH group was established. Addition of 1.10 -6 mol/1 of ethanthiol to butyl alcohol protects it completely against radiation conversions up to a dose of 8.10 19 eV/ml. Consideration is given to the effect of thioalcohol additives on the formation of some products of alcohol radiation oxidation. Introduction of mercaptans to the system or that of the -SH group to the organic compound molecule enhances its radiation resistance [ru

  9. Spectrographic determination of traces of halogens; Dosage de traces d'halogenes par la methode spectrographique

    Energy Technology Data Exchange (ETDEWEB)

    Melamed, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    Hollow cathode source is employed for determining traces of halogens (fluorine - chlorine) in the uranium oxide U{sub 3}O{sub 8} qualitatively, detection of at least 40 ppm of fluorine, as alkali fluoride and 125 ppm of chlorine, is possible. (author) [French] Un tube a decharge a cathode creuse a ete utilise pour la determination spectrographique des halogenes (fluor - chlore) presentes a l'etat de traces dans un oxyde d'uranium U{sub 3}O{sub 8}. On a pu deceler qualitativement des teneurs de 40 ppm de fluor sous forme de fluorures alcalins. En ce qui concerne le chlore, la plus faible teneur decelee a ete de 125 ppm. (auteur)

  10. Independent Evolution of Six Families of Halogenating Enzymes.

    Science.gov (United States)

    Xu, Gangming; Wang, Bin-Gui

    2016-01-01

    Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

  11. Identification and quantification of the halogenated natural product BC-3

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Olbrich, D.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie; Marsh, G. [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry; Gaus, C.; Mueller, J.F. [National Research Centre for Environmental Toxicology, Coopers Plains (Australia)

    2004-09-15

    Halogenated natural products (HNPs) of marine origin are increasingly recognized as critical residues in foodstuff (e. g. fish) and environmental samples (e. g. marine mammals and birds). Some of these HNPs (Q1, MHC-1, BC-2, and HDBPs including BC-10) were detected in diverse fish and marine mammal samples at concentrations sometimes exceeding those of PCBs, DDT, and other anthropogenic pollutants. Recent studies with marine mammal samples from Australia led to the detection of six abundant HNPs (Q1, BC-1, BC-2, BC-3, BC-10, and BC-11). In the meantime, Q1 was identified as heptachloro-1{sup '}-methyl-1,2{sup '}-bipyrrole, BC-2 as 4,6-dibromo-2-(2{sup '},4{sup '}-dibromo)phenoxyanisole, BC- 10 as 1,1{sup '}-dimethyl-3,3{sup '},4,4{sup '}-tetrabromo-5,5{sup '}-dichloro-2,2{sup '}-bipyrrole, and BC-11 as 3,5-dibromo- 2-(3{sup '},5{sup '}-dibromo,2{sup '}-methoxy)phenoxyanisole. However the identity of BC-1 and BC-3 remained unclear. The goal of the present study was the identification of BC-3. The tetrabromo compound BC-3 has previously been detected in marine mammals from four continents. Furthermore, we attempted establishing quantitative concentrations in diverse marine biota samples.

  12. Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

    Directory of Open Access Journals (Sweden)

    Tjarda J. Roberts

    2018-02-01

    Full Text Available Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA, a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2. Measurements in grounding plume (at 5 ppmv SO2 about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere.

  13. Segregation and Alteration of Phenolic and Aliphatic Components of Root and Leaf Litter by Detritivores and Microbes

    Science.gov (United States)

    Filley, T. R.; Altmann, J.; Szlavecz, K. A.; Kalbitz, K.; Gamblin, D.; Nierop, K.

    2012-12-01

    The physical and microbial transformation of plant detritus in the litter layer and soil is accompanied by chemical separation of progressively soluble fractions and their movement into the rhizosphere driving subsequent soil processes. We investigated the combined action of specific detritivores, microbial decay, and leaching on the chemical separation of plant aromatic and aliphatic components from root, wood, and leaf tissue using 13C-TMAH thermochemolysis. This method enabled the simultaneous analysis of hydrolyzable tannin and lignin fragments, substituted fatty acids, and condensed tannin composition and revealed process-specific chemical transformations to plant secondary compounds. Long-term incubation and field sampling demonstrated how plant residues are progressively leached of the water soluble, oxidized fragments generated through decay. The residues appeared only slightly altered, in the case of brown rot wood, or enriched in aliphatic fragments, in the case of leaf and root tissue. Water extractable fractions were always selectively dominated by polyphenolics, either as demethylated lignin or tannins, and nearly devoid of aliphatic materials, despite high concentrations in the starting materials. Additionally, for plant materials with high tannin contents, such as pine needles, consumption and passage through some arthropod guts revealed what appeared to be microbially-mediated methylation of phenols, and a loss of tannins in leachates. These findings are indications for an in-situ phenol detoxification mechanism. This research provides important information regarding the links between biochemical decay and the chemical nature of organic matter removed and remaining in the soil profile.

  14. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    K. Toyota

    2004-01-01

    Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

  15. Antibacterial Compounds from Red Seaweeds (Rhodophyta)

    OpenAIRE

    Noer Kasanah; Triyanto Triyanto; Drajad Sarwo Seto; Windi Amelia; Alim Isnansetyo

    2015-01-01

    Seaweeds produce great variety of metabolites benefit for human. Red seaweeds (Rhodophyta) are well known as producer of phycocolloids such agar, agarose, carragenan and great variety of secondary metabolites. This review discusses the red algal secondary metabolites with antibacterial activity. The chemical constituents of red algae are steroid, terpenoid, acetogenin and dominated by halogenated compounds mainly brominated compounds. Novel compounds with intriguing skeleton are also reported...

  16. Structural study of some halogen oxyfluorides

    International Nuclear Information System (INIS)

    Tantot, Georges.

    1976-12-01

    Some halogen oxyfluorides are studied from a structural point of view by vibrational spectroscopy and nuclear magnetic resonance. Force constant and molecular orbital calculations are added to the experimental data. The pyramidal shape of ClO 2 F under its three physical states is confirmed. In the gas and liquid phases an intermolecular association is observed. A similar interaction takes place in ClOF 3 . ClO 3 F has only a solid state transition above 10K. The structures of ClO 2 F and KBrO 2 F 2 are partly determined. The theoretical calculations are well correlated with the experimental data. They suggest a major influence of the ligands [fr

  17. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Science.gov (United States)

    Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

    2009-03-01

    Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  18. Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

    International Nuclear Information System (INIS)

    Efimova, Anastasia A.; Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Chernyak, Yury

    2010-01-01

    Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.

  19. Supercritical fluid extraction of triterpenes and aliphatic hydrocarbons from olive tree derivatives

    Directory of Open Access Journals (Sweden)

    Aimen Issaoui

    2017-05-01

    Full Text Available Olive leaves and tree bark were extracted through supercritical fluid extraction (SFE and the chemical composition of the extracted mixture was determined by Gas Chromatography–Mass Spectrometry (GC–MS. Both samples contain a great number of triterpenes as squalene, which were used since 1997 as a main constituent of the flu vaccine (FLUAD, and the alpha-tocopherol the most biologically active form of vitamin E. We also underline the presence of many aliphatic compounds such nonacosane and heptacosane in low concentrations. The extractions were carried out at 313 and 333 K, at a pressure varying from 90 to 250 bars and using pure carbon dioxide in its supercritical phase. Therefore, their solubilities at equilibrium were numerically optimized via two assumptions and compared with the experimental values. Indeed, a good agreement between several results was shown.

  20. Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

    Energy Technology Data Exchange (ETDEWEB)

    D' Ambrosio, Steven M. [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Comprehensive Cancer Center, The Ohio State University, Columbus, OH 43210 (United States); Han, Chunhua [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Pan, Li; Douglas Kinghorn, A. [Division of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, The Ohio State University, Columbus, OH 43210 (United States); Ding, Haiming, E-mail: ding.29@osu.edu [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States)

    2011-06-10

    Highlights: {yields} The aliphatic acetogenins [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] (1) and [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate] (2) isolated from avocado fruit inhibit phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). {yields} Aliphatic acetogenin 2, but not 1, prevents EGF-induced activation of EGFR (Tyr1173). {yields} Combination of both aliphatic acetogenins synergistically inhibits c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation and human oral cancer cell proliferation. {yields} The potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins targeting two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. {yields} Providing a double hit on a critical cancer pathway such as EGFR/RAS/RAF/MEK/ERK1/2 by phytochemicals like those found in avocado fruit could lead to more effective approach toward cancer prevention. -- Abstract: Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003) was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compounds 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not

  1. Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

    International Nuclear Information System (INIS)

    D'Ambrosio, Steven M.; Han, Chunhua; Pan, Li; Douglas Kinghorn, A.; Ding, Haiming

    2011-01-01

    Highlights: → The aliphatic acetogenins [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] (1) and [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate] (2) isolated from avocado fruit inhibit phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). → Aliphatic acetogenin 2, but not 1, prevents EGF-induced activation of EGFR (Tyr1173). → Combination of both aliphatic acetogenins synergistically inhibits c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation and human oral cancer cell proliferation. → The potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins targeting two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. → Providing a double hit on a critical cancer pathway such as EGFR/RAS/RAF/MEK/ERK1/2 by phytochemicals like those found in avocado fruit could lead to more effective approach toward cancer prevention. -- Abstract: Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003) was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compounds 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not compound 1, prevented EGF

  2. Swift Heavy Ion Induced Modification of Aliphatic Polymers

    OpenAIRE

    Hossain, Umme Habiba

    2015-01-01

    In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy I...

  3. Modification of Aliphatic Petroleum Resin by Peracetic Acid

    OpenAIRE

    Bondaletov, Vladimir Grigoryevich; Bondaletova, Lyudmila Ivanovna; Hamlenko, A.; Bondaletov, Oleg Vladimirovich; Starovoit, M.

    2014-01-01

    This work demonstrates the possibility of obtaining modified aliphatic resin (PRC5) by means of petroleum resin oxidation by peracetic acid. We have experimentally determined oxidation conditions that lead to producing resin with maximum epoxy and acid numbers. Ratio of "oxidative system: PRC5" is 0.5:1, process duration is 2 hours. The modified resin structure is determined by IR and NMR spectroscopy.

  4. Molecular Connectivity Predefines Polypharmacology: Aliphatic Rings, Chirality, and sp3 Centers Enhance Target Selectivity

    Directory of Open Access Journals (Sweden)

    Stefania Monteleone

    2017-08-01

    Full Text Available Dark chemical matter compounds are small molecules that have been recently identified as highly potent and selective hits. For this reason, they constitute a promising class of possible candidates in the process of drug discovery and raise the interest of the scientific community. To this purpose, Wassermann et al. (2015 have described the application of 2D descriptors to characterize dark chemical matter. However, their definition was based on the number of reported positive assays rather than the number of known targets. As there might be multiple assays for one single target, the number of assays does not fully describe target selectivity. Here, we propose an alternative classification of active molecules that is based on the number of known targets. We cluster molecules in four classes: black, gray, and white compounds are active on one, two to four, and more than four targets respectively, whilst inactive compounds are found to be inactive in the considered assays. In this study, black and inactive compounds are found to have not only higher solubility, but also a higher number of chiral centers, sp3 carbon atoms and aliphatic rings. On the contrary, white compounds contain a higher number of double bonds and fused aromatic rings. Therefore, the design of a screening compound library should consider these molecular properties in order to achieve target selectivity or polypharmacology. Furthermore, analysis of four main target classes (GPCRs, kinases, proteases, and ion channels shows that GPCR ligands are more selective than the other classes, as the number of black compounds is higher in this target superfamily. On the other side, ligands that hit kinases, proteases, and ion channels bind to GPCRs more likely than to other target classes. Consequently, depending on the target protein family, appropriate screening libraries can be designed in order to minimize the likelihood of unwanted side effects early in the drug discovery process

  5. Vapor pressure and enthalpy of vaporization of aliphatic propanediamines

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Chernyak, Yury

    2012-01-01

    Highlights: ► We measured vapor pressure of four aliphatic 1,3-diamines. ► Vaporization enthalpies at 298 K were derived. ► We examined consistency of new and available data in the literature. ► A group-contribution method for prediction was developed. - Abstract: Vapor pressures of four aliphatic propanediamines including N-methyl-1,3-propanediamine (MPDA), N,N-dimethyl-1,3-propanediamine (DMPDA), N,N-diethyl-1,3-propanediamine (DEPDA) and N,N,N′,N′-tetramethyl-1,3-propanediamine (4MPDA) were measured using the transpiration method. The vapor pressures developed in this work and reported in the literature were used to derive molar enthalpy of vaporization values at the reference temperature 298.15 K. An internal consistency check of the enthalpy of vaporization was performed for the aliphatic propanediamines studied in this work. A group-contribution method was developed for the validation and prediction vaporization enthalpies of amines and diamines.

  6. Biodegradation of aliphatic vs. aromatic hydrocarbons in fertilized arctic soils

    Science.gov (United States)

    Braddock, J.F.

    1999-01-01

    A study was carried out to test a simple bioremediation treatment strategy in the Arctic and analyze the influence of fertilization the degradation of aliphatic and aromatic hydrocarbons, e.g., pristine, n-tetradecane, n-pentadecane, 2-methylnaphthalene, naphthalene, and acenaphthalene. The site was a coarse sand pad that once supported fuel storage tanks. Diesel-range organics concentrations were 250-860 mg/kg soil at the beginning of the study. Replicate field plots treated with fertilizer yielded final concentrations of 0, 50, 100, or 200 mg N/kg soil. Soil pH and soil-water potentials decreased due to fertilizer application. The addition of fertilizer considerably increased soil respiration potentials, but not the populations of microorganisms measured. Fertilizer addition also led to ??? 50% loss of measured aliphatic and aromatic hydrocarbons in surface and subsurface soils. For fertilized plots, hydrocarbon loss was not associated with the quantity of fertilizer added. Losses of aliphatic hydrocarbons were ascribed to biotic processes, while losses of aromatic hydrocarbons were due to biotic and abiotic processes.

  7. Occurrence and Distribution of Pharmaceutical Organic Compounds in the Groundwater Downgradient of a Landfill (Grindsted, Denmark)

    DEFF Research Database (Denmark)

    Holm, John V.; Rügge, Kirsten; Bjerg, Poul Løgstrup

    1995-01-01

    Usually landfill leachates contain specific organic compounds as BTEXs (benzene, toluene, ethylbenzene, and xylenes), chlorinated aliphatic hydrocarbons and chlorobenzenes originating from household chemicals and waste from small businesses (I). However, where industrial waste has been landfilled...

  8. UARS Halogen Occultation Experiment (HALOE) Level 2 V001

    Data.gov (United States)

    National Aeronautics and Space Administration — The HALOE home page on the WWW is http://haloe.gats-inc.com/home/index.php The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

  9. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

    Directory of Open Access Journals (Sweden)

    Bonaventure Gustavo

    2009-11-01

    Full Text Available Abstract Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA and small polar molecules (e.g., jasmonic acid (JA, salicylic acid (SA containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the

  10. Halogenation dictates the architecture of amyloid peptide nanostructures.

    Science.gov (United States)

    Pizzi, Andrea; Pigliacelli, Claudia; Gori, Alessandro; Nonappa; Ikkala, Olli; Demitri, Nicola; Terraneo, Giancarlo; Castelletto, Valeria; Hamley, Ian W; Baldelli Bombelli, Francesca; Metrangolo, Pierangelo

    2017-07-20

    Amyloid peptides yield a plethora of interesting nanostructures though difficult to control. Here we report that depending on the number, position, and nature of the halogen atoms introduced into either one or both phenylalanine benzene rings of the amyloid β peptide-derived core-sequence KLVFF, four different architectures were obtained in a controlled manner. Our findings demonstrate that halogenation may develop as a general strategy to engineer amyloidal peptide self-assembly and obtain new amyloidal nanostructures.

  11. Halogenated flame retardants in the Great Lakes environment.

    Science.gov (United States)

    Venier, Marta; Salamova, Amina; Hites, Ronald A

    2015-07-21

    Flame retardants are widely used industrial chemicals that are added to polymers, such as polyurethane foam, to prevent them from rapidly burning if exposed to a small flame or a smoldering cigarette. Flame retardants, especially brominated flame retardants, are added to many polymeric products at percent levels and are present in most upholstered furniture and mattresses. Most of these chemicals are so-called "additive" flame retardants and are not chemically bound to the polymer; thus, they migrate from the polymeric materials into the environment and into people. As a result, some of these chemicals have become widespread pollutants, which is a concern given their possible adverse health effects. Perhaps because of their environmental ubiquity, the most heavily used group of brominated flame retardants, the polybrominated diphenyl ethers (PBDEs), was withdrawn from production and use during the 2004-2013 period. This led to an increasing demand for other flame retardants, including other brominated aromatics and organophosphate esters. Although little is known about the use or production volumes of these newer flame retardants, it is evident that some of these chemicals are also becoming pervasive in the environment and in humans. In this Account, we describe our research on the occurrence of halogenated and organophosphate flame retardants in the environment, with a specific focus on the Great Lakes region. This Account starts with a short introduction to the first generation of brominated flame retardants, the polybrominated biphenyls, and then presents our measurements of their replacement, the PBDEs. We summarize our data on PBDE levels in babies, bald eagles, and in air. Once these compounds came off the market, we began to measure several of the newer flame retardants in air collected on the shores of the Great Lakes once every 12 days. These new measurements focus on a tetrabrominated benzoate, a tetrabrominated phthalate, a hexabrominated diphenoxyethane

  12. Impact of bromide on halogen incorporation into organic moieties in chlorinated drinking water treatment and distribution systems.

    Science.gov (United States)

    Tan, J; Allard, S; Gruchlik, Y; McDonald, S; Joll, C A; Heitz, A

    2016-01-15

    The impact of elevated bromide concentrations (399 to 750 μg/L) on the formation of halogenated disinfection by-products (DBPs), namely trihalomethanes, haloacetic acids, haloacetonitriles, and adsorbable organic halogen (AOX), in two drinking water systems was investigated. Bromine was the main halogen incorporated into all of the DBP classes and into organic carbon, even though chlorine was present in large excess to maintain a disinfectant residual. Due to the higher reactivity of bromine compared to chlorine, brominated DBPs were rapidly formed, followed by a slower increase in chlorinated DBPs. Higher bromine substitution and incorporation factors for individual DBP classes were observed for the chlorinated water from the groundwater source (lower concentration of dissolved organic carbon (DOC)), which contained a higher concentration of bromide, than for the surface water source (higher DOC). The molar distribution of adsorbable organic bromine to chlorine (AOBr/AOCl) for AOX in the groundwater distribution system was 1.5:1 and almost 1:1 for the surface water system. The measured (regulated) DBPs only accounted for 16 to 33% of the total organic halogen, demonstrating that AOX measurements are essential to provide a full understanding of the formation of halogenated DBPs in drinking waters. In addition, the study demonstrated that a significant proportion (up to 94%) of the bromide in source waters can be converted AOBr. An evaluation of AOBr and AOCl through a second groundwater treatment plant that uses conventional treatment processes for DOC removal produced 70% of AOX as AOBr, with 69% of the initial source water bromide converted to AOBr. Exposure to organobromine compounds is suspected to result in greater adverse health consequences than their chlorinated analogues. Therefore, this study highlights the need for improved methods to selectively reduce the bromide content in source waters. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. GC-MS Study of Mono- and Bishaloethylphosphonates Related to Schedule 2.B.04 of the Chemical Weapons Convention: The Discovery of a New Intramolecular Halogen Transfer

    Science.gov (United States)

    Picazas-Márquez, Nerea; Sierra, María; Nova, Clara; Moreno, Juan Manuel; Aboitiz, Nuria; de Rivas, Gema; Sierra, Miguel A.; Martínez-Álvarez, Roberto; Gómez-Caballero, Esther

    2016-09-01

    A new class of compounds, mono- and bis-haloethylphosphonates (HAPs and bisHAPs, respectively), listed in Schedule 2.B.04 of the Chemical Weapons Convention (CWC), has been synthesized and studied by GC-MS with two aims. First, to improve the identification of this type of chemicals by the Organization for the Prohibition of Chemical Weapons, (OPCW). Second, to study the synergistic effect of halogen and silicon atoms in molecules undergoing mass spectrometry. Fragmentation patterns of trimethylsilyl derivatives of HAPs were found to depend on the nature of the halogen atom; this was in agreement with DFT-calculations. The data suggest that a novel intramolecular halogen transfer takes place during the fragmentation process.

  14. A Quantitative Structure-Property Relationship (QSPR Study of Aliphatic Alcohols by the Method of Dividing the Molecular Structure into Substructure

    Directory of Open Access Journals (Sweden)

    Bin Cheng

    2011-04-01

    Full Text Available A quantitative structure–property relationship (QSPR analysis of aliphatic alcohols is presented. Four physicochemical properties were studied: boiling point (BP, n-octanol–water partition coefficient (lg POW, water solubility (lg W and the chromatographic retention indices (RI on different polar stationary phases. In order to investigate the quantitative structure–property relationship of aliphatic alcohols, the molecular structure ROH is divided into two parts, R and OH to generate structural parameter. It was proposed that the property is affected by three main factors for aliphatic alcohols, alkyl group R, substituted group OH, and interaction between R and OH. On the basis of the polarizability effect index (PEI, previously developed by Cao, the novel molecular polarizability effect index (MPEI combined with odd-even index (OEI, the sum eigenvalues of bond-connecting matrix (SX1CH previously developed in our team, were used to predict the property of aliphatic alcohols. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. QSPR models were generated using only calculated descriptors and multiple linear regression techniques. These QSPR models showed high values of multiple correlation coefficient (R > 0.99 and Fisher-ratio statistics. The leave-one-out cross-validation demonstrated the final models to be statistically significant and reliable.

  15. Is free halogen necessary for disinfection?

    Science.gov (United States)

    Williams, D E; Elder, E D; Worley, S D

    1988-10-01

    The principle of Le Chatelier was used in demonstrating that 3-chloro-4,4-dimethyl-2-oxazolidinone (compound 1) itself kills Staphylococcus aureus rather than the very small amount of free chlorine in hydrolysis equilibrium with compound 1. On the other hand, when the N-bromo analog of compound 1 (compound 1B) was used as the disinfectant, the mixture of combined compound 1B and free bromine formed in the hydrolysis equilibrium provided disinfection. When the hydrolysis equilibrium for 1B was suppressed to the level at which a negligible amount of free bromine remained in solution, combined compound 1B was much more efficacious than combined compound 1 at killing S. aureus.

  16. Fluorine-18 labelled compounds

    International Nuclear Information System (INIS)

    Kleijn, J.P. de

    1978-01-01

    The work presented in this thesis deals with the problems involved in the adaption of reactor-produced fluorine-18 to the synthesis of 18 F-labelled organic fluorine compounds. Several 18 F-labelling reagents were prepared and successfully applied. The limitations to the synthetic possibilities of reactor-produced fluoride- 18 become manifest in the last part of the thesis. An application to the synthesis of labelled aliphatic fluoro amino acids has appeared to be unsuccessful as yet, although some other synthetic approaches can be indicated. Seven journal articles (for which see the availability note) are used to compose the four chapters and three appendices. The connecting text gives a survey of known 18 F-compounds and methods for preparing such compounds. (Auth.)

  17. Mortality of Bemisia tabaci biotype B (sternorrhyncha: aleyrodidae adults by aliphatic and aromatic synthetic sucrose esters

    Directory of Open Access Journals (Sweden)

    Mariangela Alves

    2008-12-01

    Full Text Available The B-strain of Bemisia tabaci Gennadius is a key pest of several crops and chemical control is the main control method used by growers, although reduction in efficacy due to insecticide resistance has already been reported. The aim of this work was to investigate the insecticidal effect of an array of synthetic sucrose esters with the aliphatic and aromatic groups on whitefly adults. Sucrose butyrate, caprate, octanoate, palmitate, oleate, octaacetate, phthalate, benzoate, and sucrose diacetate hexaisobutyrate were tested. The solutions were prepared and applied on the adults caught on yellow sticky traps using the Potter spray tower. Long-chains sucrose aliphatic esters were more effective against the silverleaf whiteflies and the highest mortality was obtained with sucrose oleate and sucrose octanoate. Since these compounds were tensoactive, sodium dodecylsulphate was also tested for the comparison but no effect was observed. Sucrose butyrate and other aliphatic and aromatic sucrose polyesters showed negligible effect on the silverleaf whiteflies.O biótipo B de B. tabaci Gennadius tem se destacado como uma praga-chave de diversas culturas. O controle químico tem sido a principal tática de controle utilizada, embora já se tenha observado redução na eficiência dos produtos devido ao desenvolvimento de resistência. Assim, o objetivo do presente trabalho foi avaliar o efeito de diversos ésteres de sacarose com grupos alifáticos ou aromáticos sobre adultos de mosca-branca. Butirato de sacarose, caprato, octanoato, palmitato, oleato, actaacetato, ftlato, benzoato e diacetato hexaisobutirato de sacarose foram testados. Soluções de éster de sacarose foram preparadas e aplicadas sobre adultos capturados em armadilhas adesivas utilizando Torre de Potter. Ésteres alifáticos de sacarose com longas cadeias foram mais efetivos contra mosca-branca e as maiores taxas de mortalidade foram obtidas com oleato e octanoato de sacarose. Uma vez que

  18. Characterization of aliphatic and polycyclic aromatic hydrocarbons in environmental tobacco smokes

    International Nuclear Information System (INIS)

    Mohammad Fais Fadzil; Norhayati Mohd Tahir

    2007-01-01

    A study has been conducted to investigate the distribution of aliphatic and polycyclic aromatic hydrocarbons in Environmental Tobacco Smoke (ETS). ETS is the smoke that is present in the ambient air due to smoking of tobacco. Types of cigarettes (C1R1 and C6R1) were chosen based on a result of a simple survey carried out to determine the consumer choice of cigarette brand. In analyzing the ETS, volunteers were asked to smoke each brand of cigarette in a closed room and the ETS was then collected using the high Volume Air Sampler fitted with a glass fiber filter. Smoke samples from the glass fiber filter were then extracted using Ultrasonic Agitation and fractionated into aliphatic and aromatic fraction using silica-alumina column. Identification and quantification was done using gas chromatography with flame ionization detector. Results indicated the presence of n-alkanes in ETS, ranging from C 13 to C 36 with an odd to even carbon number predominance with Carbon Preference Index(CPI) values ranging from 3.34 to 4.90. Total identified resolved aliphatic hydrocarbons (TIRAH) concentration found in ETS ranged from 590 μg m -3 to 591 μg m -3 with the percentage of plant wax n-alkanes ranging from 61% to 64% of the TIRAH found in ETS samples. In source apportionment, CPI > 1 and high percentage of plant wax n-alkanes has generally been associated with the contribution of terrestrial plant source, thus this result indicates that even after curing process and smoking of tobacco, the overall signature of the source of n-alkanes is still preserved. Amount of PAHs detected in all ETS samples ranged from 11.7 ng m -3 to 56.1 ng m -3 . Results also indicated the presence of medium to high molecular weight PAHs with dominant presence of benzo(g, h, i)perylene compound. This result seems to support the contention that smoking process involves a high temperature burning with an oxygen deficient zone in the cigarette itself. Although the concentrations were low, the

  19. Negative Halogen Ions for Fusion Applications

    International Nuclear Information System (INIS)

    Grisham, L.R.; Kwan, J.W.; Hahto, S.K.; Hahto, S.T.; Leung, K.N.; Westenskow, G.

    2006-01-01

    Over the past quarter century, advances in hydrogen negative ion sources have extended the usable range of hydrogen isotope neutral beams to energies suitable for large magnetically confined fusion devices. Recently, drawing upon this experience, negative halogen ions have been proposed as an alternative to positive ions for heavy ion fusion drivers in inertial confinement fusion, because electron accumulation would be prevented in negative ion beams, and if desired, the beams could be photo-detached to neutrals. This paper reports the results of an experiment comparing the current density and beam emittance of Cl+ and Cl- extracted from substantially ion-ion plasmas with that of Ar+ extracted from an ordinary electron-ion plasma, all using the same source, extractor, and emittance scanner. At similar discharge conditions, the Cl- current was typically 85-90% of the positive chlorine current, with an e-/ Cl- ratio as low as seven without grid magnets. The Cl- was as much as 76% of the Ar+ current from a discharge with the same RF drive. The minimum normalized beam emittance and inferred ion temperatures of Cl+, Cl-, and Ar+ were all similar, so the current density and optical quality of Cl- appear as suitable for heavy ion fusion driver applications as a positive noble gas ion of similar mass. Since F, I, and Br should all behave similarly in an ion source, they should also be suitable as driver beams

  20. The interaction of mercury with halogenated graphene

    Science.gov (United States)

    Kirchofer, Abigail; Sasmaz, Erdem; Wilcox, Jennifer

    2011-03-01

    The interaction of mercury with halogenated graphene was studied using plane-wave density functional theory. Various configurations of H, Hg, O and Br or Cl on the zigzag edge sites of graphene were investigated. Although Hg-Br (or -Cl) complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The surface atoms Hg, O, and Br tend to repel each other during geometric optimization, moving towards an H atom nearest-neighbor where possible. The strength of the Hg-graphene interaction is very sensitive to the local environment. The Hg-graphene binding energy is strongest when the Hg is located next to a surface O but not immediately next to a bound Br. DOS analysis revealed that Hg adsorption involves a gain in Hg 6 p-states and a loss in Hg 5 s electron density, resulting in an oxidized surface-bound Hg complex. DOS analysis suggests that Br strengthens the Hg-graphene interaction by modifying the surface carbon electron density; however, when Br is adjacent to Hg, a direct Hg-Br interaction weakens the Hg-C bond. These investigations provide insight into the mechanism associated with enhanced Hg adsorption on Br-functionalized carbon materials for Hg emissions reductions from coal-fired power plant applications. The authors acknowledge the financial support by Electric Power Research Institute (EPRI).

  1. Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sang-Won, E-mail: spark3@uncc.edu; Kim, Sung-Kuk; Kim, Jeong-Bae; Choi, Sung-Woo [Keimyung University, Department of Environmental Science and Engineering (Korea, Republic of); Inyang, Hilary I. [University of North Carolina at Charlotte, Global Institute for Energy and Environmental Systems (United States); Tokunaga, Shuzo [National Institute of Advanced Industrial Science and Technology (Japan)

    2006-02-15

    Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl{sub 4} and C{sub 2}Cl{sub 6} reduction by FeS and FeS{sub 2}, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS{sub 2} were found to be 0.11 sites/nm{sup 2} and 0.21 sites/nm{sup 2}, respectively. During the dehalogenation reaction process, CCl{sub 4} was found to decrease to its first intermediate product CHCl{sub 3} within the first 20 hours followed by a slower process of conversion to CH{sub 2}Cl{sub 2}. The results also show that FeS is less hydrated (more hydrophobic) than FeS{sub 2}. For CCl{sub 4} and C{sub 2}Cl{sub 6}, FeS is a better dehalogenator than FeS{sub 2}. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.

  2. Formation of organobromine and organoiodine compounds by engineered TiO2 nanoparticle-induced photohalogenation of dissolved organic matter in environmental waters.

    Science.gov (United States)

    Hao, Zhineng; Yin, Yongguang; Wang, Juan; Cao, Dong; Liu, Jingfu

    2018-08-01

    There are increasing concerns about the adverse effects of released engineered nanoparticles and photochemically formed organohalogen compounds (OHCs) on human health and the environment. Herein, we report that titanium dioxide nanoparticles (TiO 2 NPs) can photocatalytically halogenate dissolved organic matter (DOM) to form a large number of organobromine compounds (OBCs) and organoiodine compounds (OICs), as characterized by negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry. Compared with no OHCs produced in control samples in darkness and/or without TiO 2 NPs under sunlight irradiation, various OBCs and OICs were detected in freshwater and seawater under sunlight irradiation for 12h and 24h even in the presence of 1mgL -1 TiO 2 NPs, indicating the photocatalytic roles TiO 2 NPs played in DOM halogenation. Furthermore, TiO 2 NPs could result in the photodegradation of newly formed OHCs, as evidenced by the intensity and the number of some OHCs decreased with reaction time. In addition, many TiO 2 NP-induced OBCs contained two or three bromine atoms, and/or nitrogen and sulfur elements, belonging to lignin-like, tannin-like, unsaturated hydrocarbon and aliphatic compounds. While the OICs were primarily contained one iodine, and very few consisted of nitrogen and sulfur elements, most were lignin-like and tannin-like compounds. Finally, the OBCs in freshwater were found to be formed mainly via a substitution reaction or addition reaction and were accompanied by other reactions such as photooxidation, while the OBCs in seawater and OICs were formed primarily via substitution reactions. Given the abundance of produced OHCs and their toxicity, our findings call for further studies on the exact structure and toxicity of the formed OHCs, taking account the TiO 2 NP-induced DOM photohalogenation in aquatic environments during the evaluation of the environmental effects of engineered TiO 2 NPs. Copyright © 2018

  3. Reactivity of polyester aliphatic amine surfactants as corrosion inhibitors for carbon steel in formation water (deep well water)

    International Nuclear Information System (INIS)

    Alsabagh, A.M.; Migahed, M.A.; Awad, Hayam S.

    2006-01-01

    Effect of different concentrations, 40-200 ppm, of various polyester aliphatic amine surfactants on inhibition of the corrosion of carbon steel in the formation water (deep well water) was investigated. These surfactants exhibit different levels of inhibition particularly at high concentration (200 ppm). Inhibition efficiencies in the range 86-96% were determined by weight loss method. Comparable results were obtained from electrochemical measurements using Tafel extrapolation and polarisation resistance methods. It was shown that all the investigated surfactants act primarily as anodic inhibitors; however, they also affect the rate and mechanism of the cathodic reaction. These compounds function via adsorption on reactive sites on the corroding surface reducing the corrosion rate of the metal. It was revealed that the adsorption of these surfactants obey Langmuir adsorption isotherm. The inhibition effectiveness increases with the length of the aliphatic hydrocarbon chain, being a maximum in the presence of surfactant IV (∼96% efficiency). The corrosion inhibition feature of this compound is attributed to the presence of a long hydrocarbon chain that ensures large surface coverage as well as the presence of multiple active centers for adsorption. Scanning electron microscopy, SEM, has been applied to identify the surface morphology of carbon steel alloy in the absence and presence of the inhibitor molecules

  4. Reactivity of polyester aliphatic amine surfactants as corrosion inhibitors for carbon steel in formation water (deep well water)

    Energy Technology Data Exchange (ETDEWEB)

    Alsabagh, A.M. [Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Ahmed El-Zomor Street 1, Nasr City, Cairo 11727 (Egypt); Migahed, M.A. [Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Ahmed El-Zomor Street 1, Nasr City, Cairo 11727 (Egypt)]. E-mail: mohamedatiyya707@hotmail.com; Awad, Hayam S. [Chemistry Department, Faculty of Girls for Science, Art and Education, Ain Shams University, Asmaa Fahmi Street, Helliopolis, Cairo (Egypt)

    2006-04-15

    Effect of different concentrations, 40-200 ppm, of various polyester aliphatic amine surfactants on inhibition of the corrosion of carbon steel in the formation water (deep well water) was investigated. These surfactants exhibit different levels of inhibition particularly at high concentration (200 ppm). Inhibition efficiencies in the range 86-96% were determined by weight loss method. Comparable results were obtained from electrochemical measurements using Tafel extrapolation and polarisation resistance methods. It was shown that all the investigated surfactants act primarily as anodic inhibitors; however, they also affect the rate and mechanism of the cathodic reaction. These compounds function via adsorption on reactive sites on the corroding surface reducing the corrosion rate of the metal. It was revealed that the adsorption of these surfactants obey Langmuir adsorption isotherm. The inhibition effectiveness increases with the length of the aliphatic hydrocarbon chain, being a maximum in the presence of surfactant IV ({approx}96% efficiency). The corrosion inhibition feature of this compound is attributed to the presence of a long hydrocarbon chain that ensures large surface coverage as well as the presence of multiple active centers for adsorption. Scanning electron microscopy, SEM, has been applied to identify the surface morphology of carbon steel alloy in the absence and presence of the inhibitor molecules.

  5. Organic astatine compounds, their preparation and properties

    Energy Technology Data Exchange (ETDEWEB)

    Vasaros, L; Berei, K

    1985-01-01

    Aromatic astatine compounds of possible medical application were prepared by high energy substitutions, by astatine-halogen, and by electrophil astatine-hydrogen substitutions at the Joint Institute of Nuclear Researches, Dubna. Physico-chemical properties of organic astatine compounds such as boiling point and evaporation heat, and the refraction and dissociation energy of carbon-astatine bonds were determined experimentally by gas chromatography. The results are compared with extrapolated data. (V.N.). 41 refs.; 7 figs.; 5 tables.

  6. Ozone variability and halogen oxidation within the Arctic and sub-Arctic springtime boundary layer

    Directory of Open Access Journals (Sweden)

    J. B. Gilman

    2010-11-01

    Full Text Available The influence of halogen oxidation on the variabilities of ozone (O3 and volatile organic compounds (VOCs within the Arctic and sub-Arctic atmospheric boundary layer was investigated using field measurements from multiple campaigns conducted in March and April 2008 as part of the POLARCAT project. For the ship-based measurements, a high degree of correlation (r = 0.98 for 544 data points collected north of 68° N was observed between the acetylene to benzene ratio, used as a marker for chlorine and bromine oxidation, and O3 signifying the vast influence of halogen oxidation throughout the ice-free regions of the North Atlantic. Concurrent airborne and ground-based measurements in the Alaskan Arctic substantiated this correlation and were used to demonstrate that halogen oxidation influenced O3 variability throughout the Arctic boundary layer during these springtime studies. Measurements aboard the R/V Knorr in the North Atlantic and Arctic Oceans provided a unique view of the transport of O3-poor air masses from the Arctic Basin to latitudes as far south as 52° N. FLEXPART, a Lagrangian transport model, was used to quantitatively determine the exposure of air masses encountered by the ship to first-year ice (FYI, multi-year ice (MYI, and total ICE (FYI+MYI. O3 anti-correlated with the modeled total ICE tracer (r = −0.86 indicating that up to 73% of the O3 variability measured in the Arctic marine boundary layer could be related to sea ice exposure.

  7. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.; Li, Ruipeng; Obaid, Abdulmalik; Payne, Marcia M.; Smilgies, Detlef Matthias; Anthony, John Edward; Amassian, Aram; Jurchescu, Oana D.

    2014-01-01

    new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting

  8. Determination of halogens by flame emission of metal halogenides

    International Nuclear Information System (INIS)

    Henrion, G.; Marquardt, D.; Stoecker, B.

    1979-01-01

    The A-B systems InF, InCl, InBr, and InI have been excited by laminar H 2 -N 2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10 -4 molar solutions with errors of 2 to 10 per cent. (author)

  9. MORPHOLOGICAL ALTERATIONS OF STAPHYLOCOCCUS AUREUS CAUSED BY ARYL ALIPHATIC AMINOALCOHOL DERIVATIVE

    Directory of Open Access Journals (Sweden)

    Dronova M.

    2015-05-01

    Full Text Available Increasing of antimicrobial resistance has created a critical need of the novel antimicrobial agents. One of the promising chemical classes for its development are aryl aliphatic aminoalcohols. New compounds of this class were synthesized at the Institute of organic chemistry (Kiev, Ukraine, by Y. Korotkiy. After the screening studies compound KVM-194 was selected as the potent antistaphylococcal agent. The aim of the study was to examine ultrastructural changes in the bacterial cells under the influence of the compound KVM-194. Materials and methods. Staphylococcus aureus ATCC 25923 was used in all experiments. The minimum inhibitory concentration was determined by serial macrodilution method in Mueller-Hinton broth. Bacteria were exposed to the 0,5 MIC and 5 MICs of the KVM- 194 for 1 h and 24 h. Ultrastructure of intact and treated Staphylococcus aureus cells was examined by transmission electron microscopy after contrasting by osmium tetraoxide and lead citrate. Results and Discussion. The compound KVM-194 possesses a distinct antibacterial activity against Staphylococcus aureus, the minimum inhibitory concentration is 1.25 μg/ml. We found that exposure to KVM-194 at a subinhibitory concentration resulted in alterations of the cell morphology even after 1 h of treatment. The roughness of the cell surface and emerging of the intracellular particles of different electron density were observed. Increase of the incubation time to 24 h led to detachment of membrane from cytoplasm, multimembrane structures within cells emergence and formation of nonpolar septum. 1 h exposition to suprainhibitory concentration of KVM-194 resulted in nucleoid fragmentation, septum abnormalities and necrosis of some cells. We found that increasing of the incubation period to 24 h led to exacerbation of alterations: cell wall rupture, leakage of cytoplasm and a large number of lysed cells were registered. Conclusion. Observed alterations, suggest the possible

  10. Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

    Science.gov (United States)

    Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

    2012-10-03

    A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

  11. Halogens determination in vegetable NBS standard reference materials

    International Nuclear Information System (INIS)

    Stella, R.; Genova, N.; Di Casa, M.

    1977-01-01

    Levels of all four halogens in Orchard Leaves, Pine Needles and Tomato Leaves NBS reference standards were determined. For fluorine a spiking isotope dilution method was used followed by HF absorption on glass beads. Instrumental nuclear activation analysis was adopted for chlorine and bromine determination. Radiochemical separation by a distillation procedure was necessary for iodine nuclear activation analysis after irradiation. Activation parameters of Cl, Br and I are reported. Results of five determinations for each halogen in Orchard Leaves, Pine Needles and Tomato Leaves NBS Standard Materials and Standard deviations of the mean are reported. (T.I.)

  12. Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

    Directory of Open Access Journals (Sweden)

    Pierre Baillargeon

    2016-04-01

    Full Text Available Isomorphous crystals of two diacetylene derivatives with carbamate functionality (BocNH-CH2-diyne-X, where X = H or Br have been obtained. The main feature of these structures is the original 2D arrangement (as supramolecular sheets or walls in which the H bond and halogen bond have a prominent effect on the whole architecture. The two diacetylene compounds harbor neighboring carbamate (Boc protected amine and conjugated alkyne functionalities. They differ only by the nature of the atom located at the penultimate position of the diyne moiety, either a hydrogen atom or a bromine atom. Both of them adopt very similar 2D wall organizations with antiparallel carbamates (as in antiparallel beta pleated sheets. Additional weak interactions inside the same walls between molecular bricks are H bond interactions (diyne-H···O=C or halogen bond interactions (diyne-Br···O=C, respectively. Based on crystallographic atom coordinates, DFT (B3LYP/6-31++G(d,p and DFT (M06-2X/6-31++G(d,p calculations were performed on these isostructural crystals to gain insight into the intermolecular interactions.

  13. Ab initio study of weakly bound halogen complexes: RX⋯PH3.

    Science.gov (United States)

    Georg, Herbert C; Fileti, Eudes E; Malaspina, Thaciana

    2013-01-01

    Ab initio calculations were employed to study the role of ipso carbon hybridization in halogenated compounds RX (R=methyl, phenyl, acetyl, H and X=F, Cl, Br and I) and its interaction with a phosphorus atom, as occurs in the halogen bonded complex type RX⋯PH3. The analysis was performed using ab initio MP2, MP4 and CCSD(T) methods. Systematic energy analysis found that the interaction energies are in the range -4.14 to -11.92 kJ mol(-1) (at MP2 level without ZPE correction). Effects of electronic correlation levels were evaluated at MP4 and CCSD(T) levels and a reduction of up to 27% in interaction energy obtained in MP2 was observed. Analysis of the electrostatic maps confirms that the PhCl⋯PH3 and all MeX⋯PH3 complexes are unstable. NBO analysis suggested that the charge transfer between the moieties is bigger when using iodine than bromine and chlorine. The electrical properties of these complexes (dipole and polarizability) were determined and the most important observed aspect was the systematic increase at the dipole polarizability, given by the interaction polarizability. This increase is in the range of 0.7-6.7 u.a. (about 3-7%).

  14. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

  15. Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

    DEFF Research Database (Denmark)

    Boas, Ulrik; Andersen, Heidi Gertz; Christensen, Jørn B.

    2004-01-01

    Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formatio...

  16. The influence of aliphatic side chain of anacardic acid on molecular ...

    African Journals Online (AJOL)

    Interestingly, the presence of the aliphatic side chain in AnMcr resulted in more uniform imprinted beads as compared to particle agglomerates obtained from SaMcr in the presence of propranolol template. Therefore, the aliphatic side chain of anacardic acid improves both molecular recognition of imprinted polymers as ...

  17. The use of quantum chemically derived descriptors for QSAR modelling of reductive dehalogenation of aromatic compounds

    NARCIS (Netherlands)

    Rorije E; Richter J; Peijnenburg WJGM; ECO; IHE Delft

    1994-01-01

    In this study, quantum-chemically derived parameters are developed for a limited number of halogenated aromatic compounds to model the anaerobic reductive dehalogenation reaction rate constants of these compounds. It is shown that due to the heterogeneity of the set of compounds used, no single

  18. Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2 H-azirines

    Science.gov (United States)

    Gómez-Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana L.; Pinho e Melo, Teresa M. V. D.; Fausto, Rui

    2007-05-01

    In this study, the UV induced photochemical reactions of two 2 H-azirines - methyl 2-chloro-3-methyl-2 H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2 H-azirine-2-carboxylate (MMAC) - isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) C sbnd C bond cleavage, with production of nitrile ylides (P1-type products), and (b) C sbnd N bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a C dbnd N +dbnd C - group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC. The C sbnd N photochemical cleavage is an unusual process in aliphatic 2 H-azirines. In the studied compounds, its preference over the commonly observed C sbnd C azirine-ring bond photocleavage is attributed to the presence of electron withdrawing substituents (methylcarboxy group in both azirines and also the chlorine atom in MCMAC), which accelerates intersystem crossing towards the triplet state from where the cleavage of the C sbnd N bond takes place. The lack of the chlorine atom in MMAC may be partially compensated by the significantly higher stabilization of the P2-type photoproduct derived from this molecule ( ca. -52 kJ mol -1) relatively to the reactant, when

  19. A statistical approach to the interpretation of aliphatic hydrocarbon distributions in marine sediments

    Science.gov (United States)

    Rapp, J.B.

    1991-01-01

    Q-mode factor analysis was used to quantitate the distribution of the major aliphatic hydrocarbon (n-alkanes, pristane, phytane) systems in sediments from a variety of marine environments. The compositions of the pure end members of the systems were obtained from factor scores and the distribution of the systems within each sample was obtained from factor loadings. All the data, from the diverse environments sampled (estuarine (San Francisco Bay), fresh-water (San Francisco Peninsula), polar-marine (Antarctica) and geothermal-marine (Gorda Ridge) sediments), were reduced to three major systems: a terrestrial system (mostly high molecular weight aliphatics with odd-numbered-carbon predominance), a mature system (mostly low molecular weight aliphatics without predominance) and a system containing mostly high molecular weight aliphatics with even-numbered-carbon predominance. With this statistical approach, it is possible to assign the percentage contribution from various sources to the observed distribution of aliphatic hydrocarbons in each sediment sample. ?? 1991.

  20. Decomposition of halogenated organic chemicals in ionic liquid by ionizing radiation

    International Nuclear Information System (INIS)

    Kimura, A.; Taguchi, M.; Kojima, T.; Nagaishi, R.; Hiratsuka, H.

    2006-01-01

    Introduction: Halogenated organic chemicals such as polychlorodibenzo-p-dioxin, polychlorobiphenyls and hexachlorobenzene are widely spread in water environment. These pollutants are persistent against advanced oxidation treatments such as ozone/UV, ozone/hydrogen peroxide, ionizing radiation and photocatalysts. The ionizing radiation, however, can also produce homogeneously and quantitatively reducing species in water. On the other hand, room temperature ionic liquids (RTILs) have unique properties such as nonflammable, high polarity, low melting point, hydrophobicity and wide electrochemical window. The combined method of reduction by ionizing radiation and RTILs is investigated as a new environmental conservation technology. Experimental: Chlorophenol (CP) is selected as model chemicals having the main frame of halogenated organic chemicals. Each o - , m - and p-CP were irradiated with 60 Co γ-ray in each diethylmethyl(2-methoxy-ethyl)ammonium bis(trifluoromethylsulfonyl)imide (DEMMA- TFSI), diethylmethyl(2-methoxyethyl)-ammonium tetrafluoroborate (DEMMA-BF4), methanol and ethanol as solvent. Decomposition of CP and formation of irradiation products were studied using HPLC, LC-MS and ion chromatography. Results and discussion: Concentration of CP in each solution decreased as a function of dose. G-value was estimated from the slope at the primary stage of the decomposition curve. The G(-CP) and G(Phenol) were shown in Table 1. G(-CP) in the aliphatic alcohols was 0.21 to 0.37, which is lower than G-value of reducing species in the alcohols, e.g. G=1.0 to 1.5 for solvated electron. Since the rate constant for reaction of CP with hydrated electron is 1.3 x 10 9 mol -1 ·dm 3 ·s -1 , the reverse reaction is considered to attribute. G(-CP) in DEMMA-TFSI or DEMMA-BF4 was about 2 to 3 times higher than that in each alcohol. Lifetime of the reducing species in RTILs would be longer than that in each alcohol. G(-CP) in DEMMA-TFSI decreased by adding acetone or oxygen

  1. New halogenated phenylcoumarins as tyrosinase inhibitors.

    Science.gov (United States)

    Matos, Maria João; Santana, Lourdes; Uriarte, Eugenio; Delogu, Giovanna; Corda, Marcella; Fadda, Maria Benedetta; Era, Benedetta; Fais, Antonella

    2011-06-01

    With the aim to find out structural features for the tyrosinase inhibitory activity, in the present communication we report the synthesis and pharmacological evaluation of a new series of phenylcoumarin derivatives with different number of hydroxyl or ether groups and bromo substituent in the scaffold. The synthesized compounds 5-12 were evaluated as mushroom tyrosinase inhibitors showing, two of them, lower IC(50) than the umbelliferone. Compound 12 (IC(50)=215 μM) is the best tyrosinase inhibitor of this series. Copyright © 2011 Elsevier Ltd. All rights reserved.

  2. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

    Science.gov (United States)

    Oliveira, Vytor; Cremer, Dieter

    2017-08-01

    Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

  3. Primary investigation on contamination pattern of legacy and emerging halogenated organic pollutions in freshwater fish from Liaohe River, Northeast China

    Energy Technology Data Exchange (ETDEWEB)

    Ren Guofa, E-mail: rgf2008@shu.edu.cn [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Zhao, Wang [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Zhiqiang, Yu [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Yang, Wang [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Shengtao, Ma [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Minghong, Wu [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); Guoying, Sheng [State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Jiamo, Fu [Institute of Environmental Pollution and Health, School of Environment and Chemical Engineering, Shanghai University, 99 Shangda Road, Baoshan Disrict, Shanghai 200072 (China); State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment Protection and Resource Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2013-01-15

    Legacy halogenated compounds, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and emerging organo-halogen pollutants such as Dechlorane Plus (DP), were detected in fish from an old industrial region in Northeast China. PCBs and PBDEs were detected in all of the samples, with concentrations ranging from 38.15 to 170.51 ng/g lipid weight, and 9.40-39.69 ng/g lipid weight, respectively. DP was detected in more than 90% of the samples with concentrations ranging from not detected (ND) to 470 pg g/g lipid weight. Compared with similar data in other areas of the world, PCBs, PBDEs and DP in fish from Liaohe River were at medium or low level. An unusually high percentage of PCB-209 was first reported in the fish samples collected from China. Other halogenated pollutions, such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, octachlorostyrene, chlorinated anisole, chlorinated thioanisole, triclosan-methyl, and other pesticides, have also been identified in the fish samples. - Highlights: Black-Right-Pointing-Pointer DP was reported in fish samples from river close to an old industrial base in China. Black-Right-Pointing-Pointer The first report on the unusually high fraction of PCB-209 in samples from China. Black-Right-Pointing-Pointer GC Multiplication-Sign GC-TOFMS was used to identify non-targeted halogenated pollutants. - An unusually high percentage of PCB-209 was first reported in the fish samples collected from China, which might indicate that there were distinct sources of pure PCB-209 in the region of Liaohe River.

  4. Primary investigation on contamination pattern of legacy and emerging halogenated organic pollutions in freshwater fish from Liaohe River, Northeast China

    International Nuclear Information System (INIS)

    Ren Guofa; Wang Zhao; Yu Zhiqiang; Wang Yang; Ma Shengtao; Wu Minghong; Sheng Guoying; Fu Jiamo

    2013-01-01

    Legacy halogenated compounds, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and emerging organo-halogen pollutants such as Dechlorane Plus (DP), were detected in fish from an old industrial region in Northeast China. PCBs and PBDEs were detected in all of the samples, with concentrations ranging from 38.15 to 170.51 ng/g lipid weight, and 9.40–39.69 ng/g lipid weight, respectively. DP was detected in more than 90% of the samples with concentrations ranging from not detected (ND) to 470 pg g/g lipid weight. Compared with similar data in other areas of the world, PCBs, PBDEs and DP in fish from Liaohe River were at medium or low level. An unusually high percentage of PCB-209 was first reported in the fish samples collected from China. Other halogenated pollutions, such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, octachlorostyrene, chlorinated anisole, chlorinated thioanisole, triclosan-methyl, and other pesticides, have also been identified in the fish samples. - Highlights: ► DP was reported in fish samples from river close to an old industrial base in China. ► The first report on the unusually high fraction of PCB-209 in samples from China. ► GC × GC–TOFMS was used to identify non-targeted halogenated pollutants. - An unusually high percentage of PCB-209 was first reported in the fish samples collected from China, which might indicate that there were distinct sources of pure PCB-209 in the region of Liaohe River.

  5. Vapor pressure and enthalpy of vaporization of linear aliphatic alkanediamines

    International Nuclear Information System (INIS)

    Pozdeev, Vasiliy A.; Verevkin, Sergey P.

    2011-01-01

    Highlights: → We measured vapor pressure of diamines H 2 N-(CH 2 ) n -NH 2 with n = 3 to 12. → Vaporization enthalpies at 298 K were derived. → We examined consistency of new and available in the literature data. → Enthalpies of vaporization show linear dependence on numbers n. → Enthalpies of vaporization correlate linearly with Kovat's indices. - Abstract: Vapor pressures and the molar enthalpies of vaporization of the linear aliphatic alkanediamines H 2 N-(CH 2 ) n -NH 2 with n = (3 to 12) have been determined using the transpiration method. A linear correlation of enthalpies of vaporization (at T = 298.15 K) of the alkanediamines with the number n and with the Kovat's indices has been found, proving the internal consistency of the measured data.

  6. Hydrolytic And Enzymatic Degradation Characteristics Of Biodegradable Aliphatic Polysters

    Institute of Scientific and Technical Information of China (English)

    LI Suming

    2004-01-01

    Aliphatic polyesters, especially those derived from lactide (PLA), glycolide (PGA) and ε-caprolactone (PCL), are being investigated worldwide for applications in the field of surgery (suture material, devices for internal bone fracture fixation), pharmacology (sustained drug delivery systems), and tissue engineering (scaffold for tissue regeneration) [1,2]. This is mainly due to their good biocompatibility and variable degradability. These polymers present also a growing interest for environmental applications in agriculture (mulch films) and in our everyday life (packaging material)as the development of biodegradable materials is now considered as one of the potential solutions to the problem of plastic waste management.For both biomedical and environmental applications, it is of major importance to understand the degradation characteristics of the polymers. The hydrolytic degradation of aliphatic polyesters has been investigated by many research groups. Our group has shown that degradation of PLAGA large size devices is faster inside than at the surface. This heterogeneous degradation is due to the autocatalytic effect of carboxylic endgroups formed by ester bond cleavage. Moreover,degradation-induced morphological and compositional changes were also elucidated. In the case of PCL, the hydrolytic degradation is very slow due to its hydrophobicity and crystallinity.The enzymatic degradation of these polymers has been investigated by a number of authors. A specific enzyme, proteinase K, has been shown to have significant effects on PLA degradation. This enzyme preferentially degrade L-lactate units as opposed to D-lactate ones, amorphous zones as opposed to crystalline ones [3]. The enzymatic degradation of PCL polymers has also been investigated. A number of lipase-type enzymes were found to significantly accelerate the degradation of PCL despite its high crystallinity. In the case of PLA/PCL blends, the two components exhibited well separated crystalline domains

  7. Development of halogen-free cables for nuclear power plants

    International Nuclear Information System (INIS)

    Yamamoto, Mitsuo; Ito, Kazumi; Yaji, Takeo; Yoshida, Shin; Sakurai, Takako; Matsushita, Shigetoshi.

    1990-01-01

    On the occasion where serious fire accidents were experienced in the past, the need for making flame-retardant wire and cable incombustible took place and has since been generalizing. Various sorts of flame-retardant cables have already been developed and been actually used. From the viewpoint of avoiding the interference with the evacuation and fire-fighting activity in case of fire or the secondary accidents such as corrosion of the distributing panel, etc., the demand for non-halogen flame-retardant cable has rapidly been increasing in recent years in some fields of general industries, because this specific cable would generate the least amount of toxic smoke or corrosive gas even when it should burn. Similar demand has been increasing also for the cable used for nuclear power plants. In this field, earnest desire has been made for the development of non-halogen flame-retardant cable having specific environmental resistance specially required at nuclear power plants in addition to the properties and capacities required in general industries. The authors have continued examinations on the anti-environmental properties of the materials for cable such as long heat resistance, radiation resistance, steam resistance and succeeded in completing various sorts of non-halogen flame-retardant cable for nuclear power plants. In this report, we will introduce various features of the cable we have developed this time as well as the long-term reliability of non-halogen flame-retardant materials. (author)

  8. Development of non-halogen cables for nuclear power stations

    Energy Technology Data Exchange (ETDEWEB)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao (Hitachi Cable, Ltd., Tokyo (Japan))

    1983-12-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables.

  9. Polar Flattening and the Strength of Halogen Bonding

    Czech Academy of Sciences Publication Activity Database

    Sedlák, Robert; Kolář, Michal H.; Hobza, Pavel

    2015-01-01

    Roč. 11, č. 10 (2015), s. 4727-4732 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * interaction energies * halogen bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

  10. Is there theoretical evidence for mutual influence between halogen

    Indian Academy of Sciences (India)

    Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the ...

  11. Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Riley, Kevin Eugene; Hobza, Pavel

    2012-01-01

    Roč. 8, č. 11 (2012), s. 4285-4292 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : halogenated molecules * noncovalent interactions * benchmark calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

  12. Development of non-halogen cables for nuclear power stations

    International Nuclear Information System (INIS)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao

    1983-01-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables. (Yoshitake, I.)

  13. Synthesis of Scutellarein Derivatives with a Long Aliphatic Chain and Their Biological Evaluation against Human Cancer Cells

    Directory of Open Access Journals (Sweden)

    Guanghui Ni

    2018-02-01

    Full Text Available Scutellarin is the major active flavonoid extracted from the traditional Chinese herbal medicine Erigeron breviscapus (Vant. Hand-Mazz., which is widely used in China. Recently, accumulating evidence has highlighted the potential role of scutellarin and its main metabolite scutellarein in the treatment of cancer. To explore novel anticancer agents with high efficiency, a series of new scutellarein derivatives with a long aliphatic chain were synthesized, and the antiproliferative activities against Jurkat, HCT-116 and MDA-MB-231 cancer cell lines were assessed. Among them, compound 6a exhibited the strongest antiproliferative effects on Jurkat (IC50 = 1.80 μM, HCT-116 (IC50 = 11.50 μM and MDA-MB-231 (IC50 = 53.91 μM. In particular, 6a even showed stronger antiproliferative effects than the positive control NaAsO2 on Jurkat and HCT-116 cell lines. The results showed that a proper long aliphatic chain enhanced the antiproliferative activity of scutellarein.

  14. Synthesis of Scutellarein Derivatives with a Long Aliphatic Chain and Their Biological Evaluation against Human Cancer Cells.

    Science.gov (United States)

    Ni, Guanghui; Tang, Yanling; Li, Minxin; He, Yuefeng; Rao, Gaoxiong

    2018-02-01

    Scutellarin is the major active flavonoid extracted from the traditional Chinese herbal medicine Erigeron breviscapus (Vant.) Hand-Mazz., which is widely used in China. Recently, accumulating evidence has highlighted the potential role of scutellarin and its main metabolite scutellarein in the treatment of cancer. To explore novel anticancer agents with high efficiency, a series of new scutellarein derivatives with a long aliphatic chain were synthesized, and the antiproliferative activities against Jurkat, HCT-116 and MDA-MB-231 cancer cell lines were assessed. Among them, compound 6a exhibited the strongest antiproliferative effects on Jurkat (IC 50 = 1.80 μM), HCT-116 (IC 50 = 11.50 μM) and MDA-MB-231 (IC 50 = 53.91 μM). In particular, 6a even showed stronger antiproliferative effects than the positive control NaAsO₂ on Jurkat and HCT-116 cell lines. The results showed that a proper long aliphatic chain enhanced the antiproliferative activity of scutellarein.

  15. Deuterium magnetic resonance of some polymorphic liquid crystals: The conformation of the aliphatic end chains

    International Nuclear Information System (INIS)

    Hsi, S.; Zimmermann, H.; Luz, Z.

    1978-01-01

    Deuterium magnetic resonance measurements of four members of the homologous series p-alkoxybenzylidene-p-alkylaniline (noxm), perdeuterated in their alkoxy chains, are reported. The compounds studied were 40x7, 50x7, 60x7, and 70x7. For 50x7 various isotopic species specifically deuterated in the alkoxy chains, as well as in the benzylidine moiety, were prepared and their DMR studied. These measurements allowed a complete assignment of the resonances from the alkoxy chain. The spectrum of all four compounds was studied over their whole mesomorphic regions. In most phases well resolved spectra were obtained yielding the various quadrupole splittings and in many cases also the dipolar interactions within the methylene and methyl groups. Using double quantum spectroscopy dipolar splitting between different methylene deuterons could also be resolved. The methylene quadrupolar splittings and the dipolar interaction within the methylene groups decrease along the chain towards the methyl end in a characteristic stepwise manner. This behavior is attributed to chain reorientational freedom and is quantitatively interpreted in terms of two structural factors: (i) Fast dynamical equilibrium between the all-trans conformation of the alkoxy chains and chain conformations involving one or more kinks, and (ii) a molecular model in which the aliphatic chain axis is inclined with respect to the molecular long axis. The characteristic pattern of the splitting can then be reproduced by assuming a monotonically increasing kink probabilities along the chain towards its methyl end. This interpretation is used to estimate the kink probability distribution in the alkoxy chains in the various compounds and mesophases. No significant effect of the mesophase structure on the kink statistics was found

  16. Long-chain aliphatic beta-diketones from epicuticular wax of Vanilla bean species. Synthesis of nervonoylacetone.

    Science.gov (United States)

    Ramaroson-Raonizafinimanana, B; Gaydou, E M; Bombarda, I

    2000-10-01

    Analysis of the neutral lipids from Vanilla fragrans and Vanilla tahitensis (Orchidaceae) without saponification resulted in the isolation and identification of a new product family in this plant: beta-dicarbonyl compounds. The compound structures are composed of a long aliphatic chain with 2,4-dicarbonyl carbons and a cis double bond at the n-9 position. They represent approximately 28% of the neutral lipids, that is, 1.5%, in immature beans, and approximately 10% of the neutral lipids, that is, 0.9%, in mature beans. Using retention indices, gas chromatography-mass spectrometry, derivatization reactions, and chemical degradation, five beta-dicarbonyl compounds have been identified including 16-pentacosene-2,4-dione, 18-heptacosene-2,4-dione, 20-nonacosene-2, 4-dione, 22-hentriacontene-2,4-dione, and 24-tritriacontene-2, 4-dione. Among them (Z)-18-heptacosene-2,4-dione, or nervonoylacetone, has been synthesized in two steps starting from nervonic acid. The major constituent, nervonoylacetone, represented 74.5% of the beta-dicarbonyl fraction. The range of these compounds has been studied in relation with bean maturity for V. fragrans and V. tahitensis species. This compound family has not been found in the leaves or stems of any of the three vanilla species studied and is markedly absent in the beans of V. madagascariensis.

  17. A basic study on electrodeposition of metal halogen mixture in fluoride/chloride molten salts

    International Nuclear Information System (INIS)

    Shim, Z. H.; Kang, Y. H.; Hwang, S. C.; Woo, M. S.; Yoo, J. H.

    2001-01-01

    The electrodeposition experiments of metal mixture composed of U, Y, Gd, Nd and Ce were carried out in the KCl-LiCl and LiF-NaF-KF (FLINAK) eutectic melts at 500 .deg. C and 600 .deg. C, respectively. Uranium was major component in the cathode deposits, and the separation factors of uranium with respect to the rare earths (REs) are nearly same in both electrolytes. REs content in the cathode deposits increased sharply below -1.9V which is the decomposition voltage of the halogen compounds of REs. The current efficiency for electrodeposition of metals was inversely in proportion to the applied voltage in the range of -1.0 V to -1.9 V(vs. S.S. 304 or Ni)

  18. Nonthmicin, a Polyether Polyketide Bearing a Halogen-Modified Tetronate with Neuroprotective and Antiinvasive Activity from Actinomadura sp.

    Science.gov (United States)

    Igarashi, Yasuhiro; Matsuoka, Noriaki; In, Yasuko; Kataura, Tetsushi; Tashiro, Etsu; Saiki, Ikuo; Sudoh, Yuri; Duangmal, Kannika; Thamchaipenet, Arinthip

    2017-03-17

    Nonthmicin (1), a new polyether polyketide bearing a chlorinated tetronic acid, was isolated from the culture extract of a soil-derived Actinomadura strain. The structure of 1 was elucidated by interpretation of NMR and MS spectroscopic data, and the absolute configuration of 1 was proposed on the basis of the crystal structure of its dechloro congener ecteinamycin (2) also isolated from the same strain. Tetronic acids modified by halogenation have never been reported from natural products. Compounds 1 and 2 were found to have neuroprotective activity and antimetastatic properties at submicromolar concentrations in addition to antibacterial activity.

  19. Halogenated 1-Hydroxynaphthalene-2-Carboxanilides Affecting Photosynthetic Electron Transport in Photosystem II

    Directory of Open Access Journals (Sweden)

    Tomas Gonec

    2017-10-01

    Full Text Available Series of seventeen new multihalogenated 1-hydroxynaphthalene-2-carboxanilides was prepared and characterized. All the compounds were tested for their activity related to the inhibition of photosynthetic electron transport (PET in spinach (Spinacia oleracea L. chloroplasts. 1-Hydroxy-N-phenylnaphthalene-2-carboxamides substituted in the anilide part by 3,5-dichloro-, 4-bromo-3-chloro-, 2,5-dibromo- and 3,4,5-trichloro atoms were the most potent PET inhibitors (IC50 = 5.2, 6.7, 7.6 and 8.0 µM, respectively. The inhibitory activity of these compounds depends on the position and the type of halogen substituents, i.e., on lipophilicity and electronic properties of individual substituents of the anilide part of the molecule. Interactions of the studied compounds with chlorophyll a and aromatic amino acids present in pigment-protein complexes mainly in PS II were documented by fluorescence spectroscopy. The section between P680 and plastoquinone QB in the PET chain occurring on the acceptor side of PS II can be suggested as the site of action of the compounds. The structure-activity relationships are discussed.

  20. E. S. R. studies of halogenated pyrimidines in. gamma. -irradiated alkaline glasses. [Halogenated uracil bases; bromouridine; bromodeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, L D; Zimbrick, J D [Kansas Univ., Lawrence (USA)

    1975-11-01

    The reactions of mobile electrons (e/sup -//sub m/) and oxygen radical anions (O./sup -/) with halogenated bases and nucleosides have been studied in ..gamma..-irradiated alkaline glasses by e.s.r. and specific halogen-ion electrode techniques. It was shown that electrons react with halogenated uracil bases (XUr where X = Cl, Br, I but not F) by dissociative electron attachment to form uracil-5-yl radicals (U.) and halogen anions. The relative rates of reaction of e/sup -//sub m/ with XUr decreased in the sequence BrUr > ClUr > FUr > IUr. Thermal annealing studies carried out on U. in H/sub 2/O and D/sub 2/O matrices supported the hypothesis that U. in H/sub 2/O hydrates across the 5-6 double bond in the temperature region 135/sup 0/ to 155/sup 0/ K, and deuterates to a much smaller extent in D/sub 2/O at temperatures above 155/sup 0/ K. Studies on bromouridine and bromodeoxyuridine suggested that e/sup -/sub(m) reacts with the base moieties to form U. type radicals which abstract H. from the sugar moieties of adjacent nucleosides.

  1. Dynamics of the central phenylene ring torsional motion in halogenated phenylene ethynylene oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Pejov, Ljupco [Institute of Chemistry, Department of Physical Chemistry, SS. Cyril and Methodius University, Arhimedova 5, P.O. Box 162, 1000 Skopje(Macedonia, The Former Yugoslav Republic of)], E-mail: ljupcop@iunona.pmf.ukim.edu.mk; La Rosa, Manuela [PST Group- M6, STMicroelectronics, Stradale Primosole 50, 95121 Catania (Italy); Kocarev, Ljupco [Institute for Nonlinear Science, University of California, San Diego 9500 Gilman, Drive, La Jolla, CA 92093-0402 (United States); Macedonian Academy of Sciences and Arts, bul. Krste Misirkov 2, P.O. Box 428, 1000 Skopje (Macedonia, The Former Yugoslav Republic of)

    2007-11-09

    The dynamics of intramolecular torsional motion of central phenylene ring in a series of phenylene ethynylene oligomer derivatives was investigated. On the basis of calculated hindered rotational potentials corresponding to this motion, the torsional energy levels were obtained by solving the torsional Schroedinger equation. Subsequently, the torsional correlation time and transition probability was computed within the Bloembergen-Purcell-Pound (BPP) formalism, considering both the classical and quantum mechanical tunneling contributions to the intramolecular rotation. The results were interpreted in the context of molecular conductivity switching behavior of the considered series of compounds. Also some other parameters relevant to molecular admittance were calculated, such as the HOMO-LUMO energy difference and the spatial extent of the frontier molecular orbitals. Classical electrostatic arguments were applied to understand the physical basis of the conformational stability differences in the studied compounds. It was found that halogenation of the central phenylene ring may be used for fine-tuning of molecular conduction behavior, in the sense of modulating the HOMO-LUMO energy difference, the spatial extent of frontier MOs, as well as the barrier height to torsional motion of the central phenylene ring. The time scale of the temperature induced stochastic conformational switching between the 'on' and 'off' states, along with the corresponding transition probability could be varied by an order of magnitude upon halogenation of the central phenylene ring. The tunneling contributions to the torsional correlation time were found to be of minor importance in this context, and this quantity may be quite correctly estimated with the classical BPP approach.

  2. Dynamics of the central phenylene ring torsional motion in halogenated phenylene ethynylene oligomers

    International Nuclear Information System (INIS)

    Pejov, Ljupco; La Rosa, Manuela; Kocarev, Ljupco

    2007-01-01

    The dynamics of intramolecular torsional motion of central phenylene ring in a series of phenylene ethynylene oligomer derivatives was investigated. On the basis of calculated hindered rotational potentials corresponding to this motion, the torsional energy levels were obtained by solving the torsional Schroedinger equation. Subsequently, the torsional correlation time and transition probability was computed within the Bloembergen-Purcell-Pound (BPP) formalism, considering both the classical and quantum mechanical tunneling contributions to the intramolecular rotation. The results were interpreted in the context of molecular conductivity switching behavior of the considered series of compounds. Also some other parameters relevant to molecular admittance were calculated, such as the HOMO-LUMO energy difference and the spatial extent of the frontier molecular orbitals. Classical electrostatic arguments were applied to understand the physical basis of the conformational stability differences in the studied compounds. It was found that halogenation of the central phenylene ring may be used for fine-tuning of molecular conduction behavior, in the sense of modulating the HOMO-LUMO energy difference, the spatial extent of frontier MOs, as well as the barrier height to torsional motion of the central phenylene ring. The time scale of the temperature induced stochastic conformational switching between the 'on' and 'off' states, along with the corresponding transition probability could be varied by an order of magnitude upon halogenation of the central phenylene ring. The tunneling contributions to the torsional correlation time were found to be of minor importance in this context, and this quantity may be quite correctly estimated with the classical BPP approach

  3. Hybrid structures formed by homo- and heteroleptic aliphatic dicarboxylates of lead with 2-D inorganic connectivity

    International Nuclear Information System (INIS)

    Thirumurugan, A.; Rao, C.N.R.

    2008-01-01

    Three-dimensional homoleptic (single type of ligand) lead dicarboxylates with hybrid structures involving Pb-O-Pb linkages of the compositions, Pb(C 5 H 6 O 4 ), I, and Pb(C 6 H 8 O 4 ), II and III, have been synthesized and characterized. Three-dimensional heteroleptic (mixed ligands) lead dicarboxylates of the formulae, Pb 2 (C 2 O 4 )(C 4 H 4 O 4 ), IV and Pb 2 (C 2 O 4 )(C 6 H 8 O 4 ), V, with hybrid structures involving Pb-O-Pb linkages have also been prepared and characterized along with a novel two-dimensional lead nitrate-oxalate of the composition, (OPb 2 ) 2 (C 2 O 4 )(NO 3 ) 2 , VI. In all these dicarboxylates, there is two-dimensional inorganic connectivity and the lead (II) cation has hemi- or holo-directed coordination geometry. Depending upon the torsional angle and the coordination mode of the dicarboxylate anions as well as the geometry of the lead (II) cations, these hybrid compounds exhibit two types of two-dimensional inorganic connectivities. - Graphical abstract: Three homoleptic and two heteroleptic three-dimensional lead aliphatic dicarboxylates along with a novel two-dimensional lead nitrate-oxalate with hybrid structures involving Pb-O-Pb linkages have been synthesized and charecterized. In all these dicarboxylates, there is two-dimensional inorganic connectivity. The lead (II) cation has hemi- or holo-directed coordination geometry

  4. Mathematical simulation of the kinetics of radiation induced hydroxyalkylation of aliphatic saturated alcohols

    International Nuclear Information System (INIS)

    Silaev, M.M.; Bugaenko, L.T.

    1992-01-01

    The paper reports on the development of the kinetics of radiation hydroxymethylation and hydroxypropylation chain processes relating to aliphatic saturated alcohols in the γ-radiolysis of the alcohol-unsaturated compound systems to give 1,2- and 1,4-diols respectively. These processes were simulated mathematically. The kinetic curves computed are in good agreement with the experimental dependences. The kinetic parameters of the processes, including the rate constants for the addition of α-hydroxyalkyl radicals from the saturated alcohols to the double bond of the unsaturated component, viz formaldehyde or 2-propene-1-ol in the systems, were estimated. The constants (in dm 3 /mol.s) for the saturated alcohol-formaldehyde systems incorporating ethanol as the saturated alcohol were found to be (1.5±0.3).10 4 at 413 K and (2.1±0.5).10 4 at 443K; incorporating 1-propanol- (6.0±1.3).10 3 at 413 K; for the saturated alcohol-2-propene-1-ol systems incorporating methanol, ethanol, 1- and 2-propanol-(2.5±0.3).10 4 , (6.5±0.9).10 4 , (2.7±0.4).10 4 and (1.0±0.1).10 5 , respectively, at 433 K. (author)

  5. Clustering of comb and propolis waxes based on the distribution of aliphatic constituents

    Directory of Open Access Journals (Sweden)

    Custodio Angela R.

    2003-01-01

    Full Text Available Chemical composition data for 41 samples of propolis waxes and 9 samples of comb waxes of Apis mellifera collected mainly in Brazil were treated using Principal Component Analysis (PCA and Hierarchical Cluster Analysis (HCA. For chemometrical analysis, the distribution of hydrocarbons and residues of alcohols and carboxylic acids of monoesters were considered. The clustering obtained revealed chemical affinities and differences not previously grasped by simple eye-inspection of the data. No consistent differences were detected between comb and propolis waxes. These and previous results suggest that hydrocarbons, carboxylic acids, aliphatic alcohols and esters from both comb and propolis waxes are bee-produced compounds and, hence, the differences detected between one and another region are dependent on genetic factors related to the insects rather than the local flora. The samples analyzed were split into two main clusters, one of them comprising exclusively material collected in the State of São Paulo. The results are discussed with respect to the africanization of honeybees that first took place in that State and therefrom irradiated to other parts of Brazil.

  6. Comparison of decomposition characteristics between aromatic and aliphatic VOCs using electron beam

    International Nuclear Information System (INIS)

    Kim, Jo-Chun

    2011-01-01

    The removal efficiency of n-decane (C 10 H 22 ) by electron beam was the highest among aliphatic VOCs of concern, and that of n-hexane (C 6 H 14 ), n-butane (C 4 H 10 ), and methane (CH 4 ) followed. On the other hand, in terms of aromatic VOC decomposition efficiencies, benzene (C 6 H 6 ) decomposition was the lowest and that of toluene (C 7 H 8 ), ethylbenzene (C 8 H 10 ), and p-xylene (C 8 H 10 ) were similar. It was also found that there was increase in by-product (untreated VOC, CO, CO 2 , O 3 , and other compounds) formation as well as all VOC removal efficiencies. It was demonstrated that the removal efficiency of VOC increased as its concentration decreased and the irradiation dose increased. In addition, low removal efficiency was observed because helium was relatively stable compared to the other gases, and nothing but electrons produced by electron accelerator reacted with VOC. It was also found that relative humidity had some effects on the decomposition rates of VOC. The removal efficiency at the 100% RH condition was slightly higher than that at 7.4% RH (dry condition) due to OH radical formation. (author)

  7. Comparison of decomposition characteristics between aromatic and aliphatic VOCs using electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jo-Chun [Department of Environmental Engineering, Konkuk University, Seoul (Korea, Republic of)

    2011-07-01

    The removal efficiency of n-decane (C{sub 10}H{sub 22}) by electron beam was the highest among aliphatic VOCs of concern, and that of n-hexane (C{sub 6}H{sub 14}), n-butane (C{sub 4}H{sub 10}), and methane (CH{sub 4}) followed. On the other hand, in terms of aromatic VOC decomposition efficiencies, benzene (C{sub 6}H{sub 6}) decomposition was the lowest and that of toluene (C{sub 7}H{sub 8}), ethylbenzene (C{sub 8}H{sub 10}), and p-xylene (C{sub 8}H{sub 10}) were similar. It was also found that there was increase in by-product (untreated VOC, CO, CO{sub 2}, O{sub 3}, and other compounds) formation as well as all VOC removal efficiencies. It was demonstrated that the removal efficiency of VOC increased as its concentration decreased and the irradiation dose increased. In addition, low removal efficiency was observed because helium was relatively stable compared to the other gases, and nothing but electrons produced by electron accelerator reacted with VOC. It was also found that relative humidity had some effects on the decomposition rates of VOC. The removal efficiency at the 100% RH condition was slightly higher than that at 7.4% RH (dry condition) due to OH radical formation. (author)

  8. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Directory of Open Access Journals (Sweden)

    P. J. Silva

    2009-03-01

    Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  9. Integrated analysis of halogenated organic pollutants in sub-millilitre volumes of venous and umbilical cord blood sera

    Energy Technology Data Exchange (ETDEWEB)

    Grimalt, Joan O.; Carrizo, Daniel; Otero, Raquel; Vizcaino, Esther [Institute of Environmental Assessment and Water Research (IDAeA-CSIC), Department of Environmental Chemistry, Barcelona, Catalonia (Spain); Howsam, Mike [Universite de Lille 2, Centre Universitaire de Mesure et d' Analyse, Faculte de Pharmacie, Lille (France); Rodrigues de Marchi, Mary Rosa [Institute of Chemistry UNESP, Department of Analytical Chemistry, Araraquara, SP (Brazil)

    2010-03-15

    A rapid, robust and economical method for the analysis of persistent halogenated organic compounds in small volumes of human serum and umbilical cord blood is described. The pollutants studied cover a broad range of molecules of contemporary epidemiological and legislative concern, including polychlorobiphenyls (PCBs), polychlorobenzenes (CBs), hexachlorocyclohexanes (HCHs), DDTs, polychlorostyrenes (PCSs) and polybromodiphenyl ethers (PBDEs). Extraction and clean-up with n-hexane and concentrated sulphuric acid was followed with analysis by gas chromatography coupled to electron capture (GC-ECD) and GC coupled to negative ion chemical ionisation mass spectrometry (GC-NICI-MS). The advantages of this method rest in the broad range of analytes and its simplicity and robustness, while the use of concentrated sulphuric acid extraction/clean-up destroys viruses that may be present in the samples. Small volumes of reference serum between 50 and 1000{mu}L were extracted and the limits of detection/quantification and repeatability were determined. Recoveries of spiked compounds for the extraction of small volumes ({>=}300 {mu}L) of the spiked reference serum were between 90% and 120%. The coefficients of variation of repeatability ranged from 0.1-14%, depending on the compound. Samples of 4-year-old serum and umbilical cord blood (n=73 and 40, respectively) from a population inhabiting a village near a chloro-alkali plant were screened for the above-mentioned halogenated pollutants using this method and the results are briefly described. (orig.)

  10. Fig volatile compounds--a first comparative study.

    Science.gov (United States)

    Grison-Pigé, Laure; Hossaert-McKey, Martine; Greeff, Jaco M; Bessière, Jean-Marie

    2002-09-01

    We analysed the compounds of volatile blends released by receptive figs of twenty Ficus species to attract their specific pollinating wasps. In all, 99 different compounds were identified. The compounds are mainly terpenoids, aliphatic compounds and products from the shikimic acid pathway. In each species blend, there are few major compounds, which are generally common among floral fragrances. Most species blends also include rare compounds, but generally their proportion in the blend is low. A possible basis for species-specificity of Ficus-wasp interactions is discussed in relation to the patterns of volatiles found in this interspecies comparison. Copyright 2002 Elsevier Science Ltd.

  11. Distribution of trichloroethylene and selected aliphatic and aromatic hydrocarbons between ''weathered'' and ''unweathered'' fuel mixtures and groundwater: Equilibrium and kinetic considerations

    International Nuclear Information System (INIS)

    Doucette, W.J.; Dupont, R.R.

    1995-01-01

    The distribution of trichloroethylene and several aliphatic and aromatic fuel components between 46 weathered and 11 unweathered fuel mixtures and groundwater was investigated using a slow stirring method. The weathered fuel mixtures were obtained from several contaminated field sites. Both unlabeled and 14C-labeled test compounds were used in the distribution experiments. Analyses of the test compound concentrations over time was performed by gas chromatograph or liquid scintillation counting. The time required to reach equilibrium varied from about 24 to 72 hours. Generally, the greater the hydrophobicity of the test compounds the longer time that was required to reach equilibrium. It was also observed that the fuel/water distribution coefficients were generally larger for the weathered fuels than those measured for the unweathered fuels, in some cases by a factor of 100. The weathered fuel mixtures obtained from the field site were depleted of the more water soluble compounds over time and became significantly more enriched in long chain aliphatic hydrocarbons. The ability of several models to describe the observed distribution behavior was examined

  12. Evaluation of Aliphatic and Aromatic Compounds Degradation by Indigenous Bacteria Isolated from Soil Contaminated with Petroleum

    Directory of Open Access Journals (Sweden)

    Farhad Gilavand

    2015-12-01

    Full Text Available Background:  The major of this study was to isolate oil-degrading bacteria from soil contaminated with petroleum and examining the removal of hydrocarbons by these bacteria. Methods: Oil-degrading colonies were purified from the samples obtained of around Ahvaz oil wells. Organic matter degradation was investigated with 1 g of crude oil in basal salt medium (BSM as sole carbon source. The growth rate was determined through total protein assay and hydrocarbon consuming was measured through organic carbon oxidation and titration by dichromate as oxidizing agent. Results: Two potential isolates named S1 and S2 strains were screened and identified as Planococcus and Pseudomonas aeruginosa. As results for S1 and S2 could degrade 80.86 and 65.6% of olive oil, 59.6 and 35.33 of crude oil, while 32 and 26.15 % of coal tar were consumed during 14 days incubation. Conclusion: The results of this investigation showed these indigenous strains high capability to biodegradation at short time and are desirable alternatives for treatment of oil pollutants.

  13. Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

    Directory of Open Access Journals (Sweden)

    H. Herrmann

    2009-12-01

    Full Text Available Monomethylamine (MA, dimethylamine (DMA and diethylamine (DEA were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0–30 pg m−3 for MA, 130–360 pg m−3 for DMA and 5–110 pg m−3 for DEA during the spring bloom in May 2007 and 2–520 pg m−3 for MA, 100–1400 pg m−3 for DMA and 90–760 pg m−3 for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14–0.42 μm indicate that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC content ranged from 0.2–2.5% C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the nitrogen content in the marine atmosphere. The average contribution of the amines to the detected nitrogen species in sub-micrometer particles can be non-negligible, especially in the winter months (0.1% N–1.5% N in the sum of nitrate, ammonium and amines. This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment.

  14. Development of technology for the alkylation of hydroquinone with aliphatic alcohols

    Directory of Open Access Journals (Sweden)

    V. M. Bolotov

    2017-01-01

    Full Text Available The paper presents the results of research of technology of alkylation of hydroquinone, propyl, isopropyl, isobutyl and tert-butyl alcohols in the presence of concentrated phosphoric acid. The temperature of the alkylation reaction was maintained between 70–72 °С. On the basis of literature data and preliminary investigations the reaction was performed for 4 hours. Upon completion of the reaction, we removed the unreacted hydroquinone, aliphatic alcohol and phosphoric acid are added to a solution of distilled water (solvent corresponding connections and sodium bicarbonate to slightly acidic (pH 5–6. For separation from the reaction medium of alkylhydroquinones in the reaction mixture was added benzene in which the original hydroquinone dissolves much less. Concentration of the benzene extract alkylhydroquinones conducted by Stripping the solvent under vacuum at temperatures above 70 °С in air atmosphere. Higher temperature vacuum distillation AIDS in the oxidation of alkylhydroquinones to alkylphenones. Precipitated after crystallization, alkylhydroquinones were dried under vacuum in a drying pistol at 56 °С. Dried products were identified by defining the melting temperature, the study of spectral characteristics and qualitative reactions with FeCl3. We also studied the solubility of alkylhydroquinones in various solvents, which showed low solubility of alkylhydroquinones in water, benzene, toluene and higher solubility in propyl and isopropyl alcohols and in acetone. Analysis of the results shows that the obtained alkylhydroquinones are not chemically pure compounds, and contain in their composition of admixture source of hydroquinone. Qualitative reactions of solutions of alkylhydroquinones with FeCl3 solution differ from the corresponding reaction of a solution of hydroquinone. The results of investigations of electronic absorption spectra of alkylhydroquinones and source of hydroquinone in isopropyl alcohol solution did not

  15. New insight on aliphatic linkages in the macromolecular organic fraction of Orgueil and Murchison meteorites through ruthenium tetroxide oxidation

    Science.gov (United States)

    Remusat, Laurent; Derenne, Sylvie; Robert, François

    2005-09-01

    Ruthenium tetroxide oxidation was used to examine the macromolecular insoluble organic matter (IOM) from the Orgueil and Murchison meteorites and especially to characterize the aliphatic linkages. Already applied to various terrestrial samples, ruthenium tetroxide is a selective oxidant which destroys aromatic units, converting them into CO 2, and yields aliphatic and aromatic acids. In our experiment on chondritic IOM, it produces mainly short aliphatic diacids and polycarboxylic aromatic acids. Some short hydroxyacids are also detected. Aliphatic diacids are interpreted as aliphatic bridges between aromatic units in the chemical structure, and polycarboxylic aromatic acids are the result of the fusion of polyaromatic units. The product distribution shows that aliphatic links are short with numerous substitutions. No indigenous monocarboxylic acid was detected, showing that free aliphatic chains must be very short (less than three carbon atoms). The hydroxyacids are related to the occurrence of ester and ether functional groups within the aliphatic bridges between the aromatic units. This technique thus allows us to characterize in detail the aliphatic linkages of the IOMs, and the derived conclusions are in agreement with spectroscopic, pyrolytic, and degradative results previously reported. Compared to terrestrial samples, the aliphatic part of chondritic IOM is shorter and highly substituted. Aromatic units are smaller and more cross-linked than in coals, as already proposed from NMR data. Orgueil and Murchison IOM exhibit some tiny differences, especially in the length of aliphatic chains.

  16. Emission of Volatile OrganoHalogens by Southern African Solar Salt Works

    Science.gov (United States)

    Kotte, Karsten; Weissflog, Ludwig; Lange, Christian Albert; Huber, Stefan; Pienaar, Jacobus J.

    2010-05-01

    Volatile organic compounds containing halogens - especially chlorine - have been considered for a long time of industrial origin only, and it was assumed that the production and emission of these compounds can easily be controlled by humans in case they will cause a threat for life on Earth. Since the middle of the 80ies of the last century it became clear that the biologically active organohalogens isolated by chemists are purposefully produced by nature as antibiotics or as antifeedant etc. To date more than 3800 organohalogens are known to be naturally produced by bio-geochemical processes. The global budgets of many such species are poorly understood and only now with the emergence of better analytical techniques being discovered. For example the compound chloromethane nature's production (5 GT) outdates the anthropogenic production (50 KT) by a factor of 100. Thus organohalogens are an interesting recent case in point since they can influence the ozone budget of the boundary layer, play a role in the production of aerosols and the climate change discussion. An intriguing observation is that most of the atmospheric CH3Cl and CH3Br are of terrestrial rather than of marine origin and that a number of halogenated small organic molecules are produced in soils. The high concentrations of halides in salt soils point to a possibly higher importance of natural halogenation processes as a source of volatile organohalogens. Terrestrial biota, such as fungi, plants, animals and insects, as well as marine algea, bacteria and archaea are known or suspected to be de-novo producers of volatile organohalogens. In recent years we revealed the possibility for VOX to form actively in water and bottom sediments of hyper-saline environments in the course of studying aridization processes during climatic warming. Due to the nature of their production process solar salt works, as to be found along-side the Southern African coast line but also upcountry, combine a variety of semi- and

  17. Molecular basis of biodegradation of chloroaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Sangodkar, U M.X.; Aldrich, T L; Haugland, R A; Johnson, J; Rothmel, R K; Chakrabarty, A M [Illinois Univ., Chicago (USA). Coll. of Medicine; Chapman, P J [Environmental Protection Agency, Gulf Breeze, FL (USA). Microbial Ecology and Biotechnology

    1989-01-01

    Chlorinated aromatic hydrocarbons are widely used in industry and agriculture, and comprise the bulk of environmental pollutants. Although simple aromatic compounds are biodegradable by a variety of degradative pathways, their halogenated counterparts are more resistant to bacterial attack and often necessitate evolution of novel pathways. An understanding of such evolutionary processes is essential for developing genetically improved strains capable of mineralizing highly chlorinated compounds. This article provides an overview of the genetic aspects of dissimilation of chloroaromatic compounds and discusses the potential of gene manipulation to promote enhanced evolution of the degradation pathways. (orig.).

  18. Antibacterial Compounds from Red Seaweeds (Rhodophyta

    Directory of Open Access Journals (Sweden)

    Noer Kasanah

    2015-07-01

    Full Text Available Seaweeds produce great variety of metabolites benefit for human. Red seaweeds (Rhodophyta are well known as producer of phycocolloids such agar, agarose, carragenan and great variety of secondary metabolites. This review discusses the red algal secondary metabolites with antibacterial activity. The chemical constituents of red algae are steroid, terpenoid, acetogenin and dominated by halogenated compounds mainly brominated compounds. Novel compounds with intriguing skeleton are also reported such as bromophycolides and neurymenolides. In summary, red seaweeds are potential sources for antibacterial agents and can serve as lead in synthesis of new natural medicines.

  19. Evaluation of Efficient and Practical Methods for the Preparation of Functionalized Aliphatic Trifluoromethyl Ethers.

    Science.gov (United States)

    Sokolenko, Taras M; Dronkina, Maya I; Magnier, Emmanuel; Yagupolskii, Lev M; Yagupolskii, Yurii L

    2017-05-14

    The "chlorination/fluorination" technique for aliphatic trifluoromethyl ether synthesis was investigated and a range of products with various functional groups was prepared. The results were compared with oxidative desulfurization-fluorination of xanthates with the same structure.

  20. Determinants of the microbial community structure of eutrophic, hyporheic river sediments polluted with chlorinated aliphatic hydrocarbons

    NARCIS (Netherlands)

    Hamonts, K.; Ryngaert, A.; Smidt, H.; Springael, D.; Dejonghe, W.

    2014-01-01

    Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. As biotransformation of CAHs in the impacted river sediments might be an effective remediation strategy, we investigated the determinants of the microbial community structure of eutrophic,

  1. Fully Biobased Unsaturated Aliphatic Polyesters from Renewable Resources : Enzymatic Synthesis, Characterization, and Properties

    NARCIS (Netherlands)

    Jiang, Yi; Alberda van Ekenstein, Gerhard; Woortman, Albert J. J.; Loos, Katja

    2014-01-01

    Fully biobased saturated and unsaturated aliphatic polyesters and oligoesters are successfully prepared by Candida antarctica lipase B (CALB)-catalyzed polycondensations of succinate, itaconate, and 1,4-butanediol. The effects of monomer substrates and polymerization methods on enzymatic

  2. Shape memory polymers based on uniform aliphatic urethane networks

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  3. Recent Advances in 3D Printing of Aliphatic Polyesters.

    Science.gov (United States)

    Chiulan, Ioana; Frone, Adriana Nicoleta; Brandabur, Călin; Panaitescu, Denis Mihaela

    2017-12-24

    3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.

  4. Recent Advances in 3D Printing of Aliphatic Polyesters

    Science.gov (United States)

    Frone, Adriana Nicoleta; Brandabur, Călin

    2017-01-01

    3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed. PMID:29295559

  5. Recent Advances in 3D Printing of Aliphatic Polyesters

    Directory of Open Access Journals (Sweden)

    Ioana Chiulan

    2017-12-01

    Full Text Available 3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid (PLA and polyhydroxyalkanoates (PHA, two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.

  6. Aliphatic polyesters for medical imaging and theranostic applications.

    Science.gov (United States)

    Nottelet, Benjamin; Darcos, Vincent; Coudane, Jean

    2015-11-01

    Medical imaging is a cornerstone of modern medicine. In that context the development of innovative imaging systems combining biomaterials and contrast agents (CAs)/imaging probes (IPs) for improved diagnostic and theranostic applications focuses intense research efforts. In particular, the classical aliphatic (co)polyesters poly(lactide) (PLA), poly(lactide-co-glycolide) (PLGA) and poly(ɛ-caprolactone) (PCL), attract much attention due to their long track record in the medical field. This review aims therefore at providing a state-of-the-art of polyester-based imaging systems. In a first section a rapid description of the various imaging modalities, including magnetic resonance imaging (MRI), optical imaging, computed tomography (CT), ultrasound (US) and radionuclide imaging (SPECT, PET) will be given. Then, the two main strategies used to combine the CAs/IPs and the polyesters will be discussed. In more detail we will first present the strategies relying on CAs/IPs encapsulation in nanoparticles, micelles, dendrimers or capsules. We will then present chemical modifications of polyesters backbones and/or polyester surfaces to yield macromolecular imaging agents. Finally, opportunities offered by these innovative systems will be illustrated with some recent examples in the fields of cell labeling, diagnostic or theranostic applications and medical devices. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Structure and properties of porous films based on aliphatic copolyamide developed for cellular technologies

    Czech Academy of Sciences Publication Activity Database

    Dobrovol`skaya, I.P.; Popryadukhin, P.V.; Yudin, V. E.; Ivankova, E.M.; Elokhovskiy, V.Y.; Weishauptová, Zuzana; Balík, Karel

    2015-01-01

    Roč. 26, č. 1 (2015), article number 46 ISSN 0957-4530 Institutional support: RVO:67985891 Keywords : porous film * aliphatic copolyamide * structure * properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.272, year: 2015 http://www.stem-art.com/Library/Science/Structure%20and%20properties%20of%20porous%20films%20based%20on%20aliphatic%20copolyamide%20developed%20for%20cellular%20technologies.pdf

  8. Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

    Czech Academy of Sciences Publication Activity Database

    Fanfrlík, Jindřich; Holub, Josef; Růžičková, Z.; Řezáč, Jan; Lane, P. D.; Wann, D. A.; Hnyk, Drahomír; Růžička, A.; Hobza, Pavel

    2016-01-01

    Roč. 17, č. 21 (2016), s. 3373-3376 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : bromine * carboranes * halogen bonds * sigma holes * X-ray crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.075, year: 2016

  9. Natural elimination of volatile halogenated hydrocarbons from the environment

    Energy Technology Data Exchange (ETDEWEB)

    Harress, H.M.; Grathwohl, P.; Torunski, H.

    1987-01-01

    Recently carried out field investigations of groundwater contaminations with volatile halogenated hydrocarbons have shown evidence of natural elimination of these hazardous substances. This elimination effects is rare and observed in connection with special geological conditions. With regard to some contaminated sites, the following mechanisms for this behaviour are discussed: 1. Stripping by naturally ascending gases. 2. Sorption on soil organic matter. 3. Biodegradation. The so far compiled knowledge allowed to develop further research programmes, which are pursued in various projects.

  10. Structure-Energy Relationships of Halogen Bonds in Proteins.

    Science.gov (United States)

    Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

    2017-06-06

    The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

  11. First principles study of halogens adsorption on intermetallic surfaces

    International Nuclear Information System (INIS)

    Zhu, Quanxi; Wang, Shao-qing

    2016-01-01

    Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

  12. Development of no halogen incombustible cables for atomic energy

    International Nuclear Information System (INIS)

    Ishii, Nobumasa; Kimura, Hitoshi; Fujimura, Shun-ichi

    1990-01-01

    In upgrading light water reactor technology, it is important to improve the reliability of machinery and equipment, to make regular inspection efficient, to extend the period of continuous operation, to optimize operation cycle and to improve the maintainability of plant facilities. For the cables for nuclear power stations, high incombustibility is required, and at present halogen system incombustible materials are used. Recently the development of no halogen incombustible cables has been advanced, with which the generation of corrosive gas and smoke at the time of fires is slight. In this study, the application of such no halogen incombustible cables to nuclear power stations and the improvement of reliability of the cables were investigated. The cables to be developed are those for electric power, control and instrumentation in BWR plants and insulated electric wires. The required characteristics are incombustibility, no generation of smoke and corrosive gas at the time of fires, radiation resistance and steam resistance in LOCA. The selection of base polymers, metal hydrates and radiation protectors, the evaluation of radiation resistance and steam resistance, the examination of the corrosive and poisonous properties of generated gas and smoke generation and so on are reported. The development was successful. (K.I.)

  13. Halogen doping of II-VI semiconductors during molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Waag, A.; Litz, Th.; Fischer, F.; Heinke, H.; Scholl, S.; Hommel, D.; Landwehr, G. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Bilger, G. (Zentrum fuer Sonnenenergie und Wasserstoff-Forschung, Stuttgart (Germany))

    1994-04-14

    Results on the halogen doping of CdTe, (CdMn)Te as well as (CdMg)Te thin films and quantum well structures are reported. The structures were grown by molecular beam epitaxy. The samples have been investigated by Van der Pauw, photoconductivity, X-ray diffraction, XPS and SIMS measurements. ZnCl[sub 2] and ZnBr[sub 2] have been used as dopant sources. Free carrier concentrations at room temperature above 10[sup 18] cm[sup -3] can easily be achieved for CdTe for a wide range of Cd/Te flux ratios and substrate temperatures. In the ternary alloys, the free carrier concentration decreases drastically with increasing x-values, despite a constant incorporation of the dopant species. In addition, persistent photoconductivity has been observed in n-type doped ternary thin films at low temperatures. The decrease of the free carrier concentration with x-value is common to other wide-gap ternary alloys, and the reason for it is discussed in the frame of DX-like deep donor impurities in ternary II-VI compounds. In first experiments on planar halogen doping of CdTe, a doping level of 5x10[sup 18] cm[sup -3] could be reached in the doped regions, the highest value ever reported for CdTe. A clear influence of dopant incorporation on the structural quality of CdTe thin films has been seen even for dopant concentrations of as low as 10[sup 18] cm[sup -3]. The FWHM of the rocking curves decreased by a factor of 2 with increasing dopant incorporation. SIMS as well as XPS measurements demonstrate that the Cl/Zn and Br/Zn ratio in the doped films is 2/1, but no chemical shift corresponding to Zn-Cl or Zn-Br bonds could be detected. A model for the incorporation of the halogens is proposed on the basis of these results

  14. Synthesis of novel naphthoquinone aliphatic amides and esters and their anticancer evaluation.

    Science.gov (United States)

    Kongkathip, Boonsong; Akkarasamiyo, Sunisa; Hasitapan, Komkrit; Sittikul, Pichamon; Boonyalai, Nonlawat; Kongkathip, Ngampong

    2013-02-01

    Fourteen new naphthoquinone aliphatic amides and seventeen naphthoquinone aliphatic esters were synthesized in nine to ten steps from 1-hydroxy-2-naphthoic acid with 9-25% overall yield for the amides, and 16-21% overall yield for the esters. The key step of the amide synthesis is a coupling reaction between amine and various aliphatic acids using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling agent while for the ester synthesis, DCC/DMAP or CDI was used as the coupling reagent between aliphatic acids and naphthoquinone alcohol. Both naphthoquinone amides and esters were evaluated for their anticancer activity against KB cells. It was found that naphthoquinone aliphatic amides showed stronger anticancer activity than those of the esters when the chains are longer than 7-carbon atoms. The optimum chain of amides is expected to be 16-carbon atoms. In addition, naphthoquinone aliphatic esters with α-methyl on the ester moiety possessed much stronger anticancer activity than the straight chains. Decatenation assay revealed that naphthoquinone amide with 16-carbon atoms chain at 15 μM and 20 μM can completely inhibit hTopoIIα activity while at 10 μM the enzyme activity was moderately inhibited. Molecular docking result also showed the same trend as the cytotoxicity and decatenation assay. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  15. Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

    Science.gov (United States)

    Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

    2018-05-01

    The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

  16. Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

    Czech Academy of Sciences Publication Activity Database

    Riley, Kevin Eugene; Murray, J. S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P.

    2013-01-01

    Roč. 19, č. 11 (2013), s. 4651-4659 ISSN 1610-2940 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : dispersion * electrostatics * halogen bonding * noncovalent interactions Subject RIV: CE - Biochemistry Impact factor: 1.867, year: 2013

  17. Volatile halogenated hydrocarbons over the western Pacific between 43° and 4°N

    Science.gov (United States)

    Quack, Birgit; Suess, Erwin

    1999-01-01

    A spectrum of halogenated hydrocarbon compounds in marine air masses were surveyed over an area in the western Pacific between 43°N, 150°E and 4°N, 113°E in September 1994. The ship's track between northern Japan and Singapore traversed three climatic zones of the northern hemisphere. Recently polluted air, clean marine air derived from the central Pacific Ocean from different latitudes, and marine air from the Indonesian archipelago were collected. Tetrachloroethene and trichloroethene of anthropogenic origin, brominated halocarbons as tribromomethane, dibromochloromethane and bromodichloromethane of anthropogenic and natural sources, and other trace gases were measured in the air samples. Very sparse data on the distribution of these compounds exist for the western Pacific atmosphere. The distribution patterns of the compounds were related to synoptic-scale meteorology, spatial conditions, and origin of the air masses. Anthropogenic and natural sources for both chlorinated and brominated substances were identified. Tetrachloroethene and trichloroethene concentrations and their ratios identify anthropogenic sources. Their mixing ratios were quite low compared to previously published data. They are in agreement with expected low concentrations of photochemically active substances during autumn, with an overall decrease in concentrations toward lower latitudes, and with a decrease of emissions during recent years. Strong evidence for a natural source of trichloroethene was discovered in the tropical region. The concentrations of naturally released brominated species were high compared to other measurements over the Pacific. Gradients toward the coasts and elevated concentrations in air masses influenced by coastal emissions point to significant coastal sources of these compounds. The trace gas composition of anthropogenic and natural compounds clearly identified the air masses which were traversed during the cruise.

  18. Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

    Science.gov (United States)

    Rissanen, Kari; Haukka, Matti

    2015-01-01

    The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

  19. Acid-base thermochemistry of gaseous aliphatic α-aminoacids.

    Science.gov (United States)

    Bouchoux, Guy; Huang, Sihua; Inda, Bhawani Singh

    2011-01-14

    Acid-base thermochemistry of isolated aliphatic amino acids (denoted AAA): glycine, alanine, valine, leucine, isoleucine and proline has been examined theoretically by quantum chemical computations at the G3MP2B3 level. Conformational analysis on neutral, protonated and deprotonated species has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. Comparison of the G3MP2B3 theoretical proton affinities, PA, and ΔH(acid) with experimental results is shown to be correct if experimental thermochemistry is re-evaluated and adapted to the most recent acidity-basicity scales. From this point of view, a set of evaluated proton affinities of 887, 902, 915, 916, 919 and 941 kJ mol(-1), and a set of evaluated ΔH(acid) of 1433, 1430, 1423, 1423, 1422 and 1426 kJ mol(-1), is proposed for glycine, alanine, valine, leucine, isoleucine and proline, respectively. Correlations with structural parameters (Taft's σ(α) polarizability parameter and molecular size) suggest that polarizability of the side chain is the major origin of the increase in PA and decrease in ΔH(acid) along the homologous series glycine, alanine, valine and leucine/isoleucine. Heats of formation of gaseous species AAA, AAAH(+) and [AAA-H](-) were computed at the G3MP2B3 level. The present study provides previously unavailable Δ(f)H°(298) for the ionized species AAAH(+) and [AAA-H](-). Comparison with Benson's estimate, and correlation with molecular size, show that several experimental Δ(f)H°(298) values of neutral or gaseous AAA might be erroneous.

  20. Synthesis of polyhydroxylated compounds from Derythrose: enzymatic inhibition studies

    OpenAIRE

    Noro, Jennifer Martins

    2015-01-01

    Dissertação de mestrado em Química Medicinal This thesis is divided into two parts. At first, two starting synthon compounds were obtained: the benzylidene acetal D-erythrose aldehyde and the unsaturated lactone derived from this aldehyde. Both compounds were obtained following methods reported in the literature. The first part of the work focuses on aldehyde reactions with different primary aliphatic amines, yielding the respective imines. These were reduced to afford the ...

  1. Simple synthesis of multi-halogen pyrazino [1,2-a]indole-1,8(2H,5aH)-dione

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rui Xia; Zhao, Yu Cheng; Kong, Ling Bin; Yan, Sheng Jiao; Lin, Jun [Key Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University), Ministry Education, School of Chemical Science and Technology, Yunnan University, Kunming (China)

    2016-10-15

    A concise and efficient one-pot synthesis of multi-halogen pyrazino[1,2-a]indole-1,8(2H,5aH)-dione (MHPID) derivatives by the reaction of an enamino ester with multi-halogen benzoquinone derivatives is described. MHPIDs 3a–3d were obtained with good yields (78–83%) by refluxing enamino esters 1a and 1b and tetrahalogen-1,4-benzoquinones 2a and 2b for 24 h without the use of catalysts. Compounds 3e–3p were also obtained with excellent yields (69–92%) via the reaction of the phenyl-substituted enamino esters 1c–1h with tetrahalogen-1,4-benzoquinones 2a and 2b in CH3CN catalyzed by Cs2CO3. These two protocols are efficient and effective for the synthesis of MHPIDs.

  2. Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

    Science.gov (United States)

    Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

    2017-03-21

    During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

  3. Influence of the chemical structure on odor qualities and odor thresholds of halogenated guaiacol-derived odorants

    Science.gov (United States)

    Juhlke, Florian; Lorber, Katja; Wagenstaller, Maria; Buettner, Andrea

    2017-12-01

    Chlorinated guaiacol derivatives are found in waste water of pulp mills using chlorine in the bleaching process of wood pulp. They can also be detected in fish tissue, possibly causing off-odors. To date, there is no systematic investigation on the odor properties of halogenated guaiacol derivatives. To close this gap, odor thresholds in air and odor qualities of 14 compounds were determined by gas chromatography-olfactometry. Overall, the investigated compounds elicited smells that are characteristic for guaiacol, namely smoky, sweet, vanilla-like, but also medicinal and plaster-like. Their odor thresholds in air were, however, very low, ranging from 0.00072 to 23 ng/Lair. The lowest thresholds were found for 5-chloro- and 5-bromoguaiacol, followed by 4,5-dichloro- and 6-chloroguaiacol. Moreover, some inter-individual differences in odor threshold values could be observed, with the highest variations having been recorded for the individual values of 5-iodo- and 4-bromoguaiacol.

  4. Determination of halogens, silicon, phosphorus, carbon, sulfur, tributyl phosphate and of free acid in uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Chu Van Vinh

    2003-01-01

    High-purity uranium compounds are widely used in nuclear field in the form of uranyl nitrate or uranium oxides. In production of uranium material the estimation and the control of products quality is necessary and very important. Halogens was separated from uranium compounds by steam distillation and they were later determined by high performance liquid chromatography (HPLC) for Cl - , Br - , I - ions. Br - was also determined by spectrophotometric and iodide by the individual pulse polarography. Silicon and phosphorus in uranyl nitrate solutions were determined by the photometric method. Sulfur was determined as sulfate form by the measurement of turbidity by the titrimetry. TBP in kerosene and free acid in aqueous solution were determined by the titration. (author)

  5. A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

    Energy Technology Data Exchange (ETDEWEB)

    Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Karamahmut, Bingül [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Semerci, Fatih [Department of Energy Systems Engineering, Faculty of Technology, Kırklareli University, 39000 Kırklareli (Turkey); Darcan, Cihan [Department of Molecular Biology and Genetic, Faculty of Arts and Sciences, Bilecik Şeyh Edebali University, Gülümbe-Bilecik (Turkey); Yılmaz, Filiz [Department of Chemistry, Faculty of Sciences, Anadolu University, Eskişehir (Turkey)

    2017-05-15

    /DTA) of the complexes were investigated. - Graphical abstract: In this study, six new silver coordination compounds were synthesized by using saccharinate and flexible aliphatic diamine derivatives. All the compounds were characterized by elemental analysis, IR and single-crystal X-ray analysis. TG/DTA. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes have been investigated. Complexes 1–5a and 6 were synthesized with the same reactant ratio and room temperature by using a mixture of AgNO{sub 3}, sac and different length diamine derivatives. The complex 5b is also synthesized was similar to that of 1 at 80 °C. In the complexes, the diamine derivatives ligands show bis(bridging) coordination mode. The sac ligand exhibits a µ-bridging coordination mode in 1 and N-donor monodentate coordination mode in 2–6. Complexes 1–5 exhibit 1D chain structure while complex 6 are tetranuclear structure. In the crystal packing of complexes, 3D supramolecular frameworks are formed via C-H···Ag, Ag···π and Ag···Ag interactions.

  6. Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

    KAUST Repository

    Baron, Marco

    2016-06-14

    Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    Science.gov (United States)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  8. Teratology study of amide derivatives of branched aliphatic carboxylic acids with 4-aminobenzensulfonamide in NMRI mice.

    Science.gov (United States)

    Onishi, Yuko; Okada, Akinobu; Noyori, Hiroko; Okamura, Ai; Hen, Naama; Yagen, Boris; Bialer, Meir; Fujiwara, Michio

    2013-08-01

    Valproic acid (VPA), widely used to treat epilepsy, bipolar disorders, and migraine prophylaxis, is known to cause neural tube and skeletal defects in humans and animals. Aminobenzensulfonamide derivatives of VPA with branched aliphatic carboxylic acids, namely 2-methyl-N-(4-sulfamoyl-phenyl)-pentanamide (MSP), 2-ethyl-N-(4-sulfamoyl-phenyl)-butyramide (ESB), 2-ethyl-4-methyl-N-(4-sulfamoyl-phenyl)-pentanamide (EMSP), and 2-ethyl-N-(4-sulfamoyl-benzyl)-butyramide (ESBB), have shown more potent anticonvulsant activity than VPA in preclinical testing. Here, we investigated the teratogenic effects of these analogous compounds of VPA in NMRI mice. Pregnant NMRI mice were given a single subcutaneous injection of either VPA at 1.8 or 3.6 mmol/kg, or MSP, ESB, EMSP, or ESBB at 1.8, 3.6, or 4.8 mmol/kg on gestation day (GD) 8. Cesarean section was performed on GD 18, and the live fetuses were examined for external and skeletal malformations. Compared with VPA, which induced neural tube defects (NTDs) in fetuses at 1.8 and 3.6 mmol/kg, the analog derivatives induced no NTDs at dose levels up to 4.8 mmol/kg (except for a single case of exencephaly at 4.8 mmol/kg MSP). Skeletal examination showed several abnormalities mainly at the axial skeletal level with VPA at 1.8 mmol/kg. Fused vertebrae and/or fused ribs were also observed with MSP, ESB, EMSP, and ESBB, they were less severe and seen at a lower incidence that those induced by VPA at the same dose level. In addition to exerting more potent preclinical antiepileptic activity, teratology comparison indicates that aminobenzensulfonamide analogs are generally more weakly teratogenic than VPA. © 2013 Wiley Periodicals, Inc.

  9. Repellency property of long chain aliphatic methyl ketones against ...

    African Journals Online (AJOL)

    -tridecanone and 2-pentadecanone) were more effective than compounds with even carbon atoms (2-decanone and 2- dodecanone). Comparable repellency activity of 2-tridecanone to DEET show that, it may save as Anopheles gambiae s.s. ...

  10. Thermodynamic parameters for binding of some halogenated inhibitors of human protein kinase CK2

    International Nuclear Information System (INIS)

    Winiewska, Maria; Makowska, Małgorzata; Maj, Piotr; Wielechowska, Monika; Bretner, Maria; Poznański, Jarosław; Shugar, David

    2015-01-01

    Highlights: • Two new compounds being potential human CK2a inhibitors are studied. • Their IC50 values were determined in vitro. • The heats of binding and kbind were estimated using DSC. • The increased stability of protein–ligand complexes was followed by fluorescence. • Methylated TBBt derivative (MeBr3Br) is almost as active as TBBt. - Abstract: The interaction of human CK2α with a series of tetrabromobenzotriazole (TBBt) and tetrabromobenzimidazole (TBBz) analogs, in which one of the bromine atoms proximal to the triazole/imidazole ring is replaced by a methyl group, was studied by biochemical (IC 50 ) and biophysical methods (thermal stability of protein–ligand complex monitored by DSC and fluorescence). Two newly synthesized tri-bromo derivatives display inhibitory activity comparable to that of the reference compounds, TBBt and TBBz, respectively. DSC analysis of the stability of protein–ligand complexes shows that the heat of ligand binding (H bind ) is driven by intermolecular electrostatic interactions involving the triazole/imidazole ring, as indicated by a strong correlation between H bind and ligand pK a . Screening, based on fluorescence-monitored thermal unfolding of protein–ligand complexes, gave comparable results, clearly identifying ligands that most strongly bind to the protein. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly, relative to possible intermolecular halogen bonding, in binding of the ligands to the CK2α ATP-binding site

  11. Swift heavy ion induced modification of aliphatic polymers

    International Nuclear Information System (INIS)

    Hossain, Umme Habiba

    2015-01-01

    In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10 10 - 5 x 10 12 ions/cm 2 ). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic species. While

  12. Aliphatic hydrocarbons in surface sediments from South China Sea off Kuching Division, Sarawak

    International Nuclear Information System (INIS)

    Hafidz Yusoff; Zaini Assim; Samsur Mohamad

    2012-01-01

    Eighteen surface sediment samples collected from South China Sea off Kuching Division, Sarawak were analyzed for aliphatic hydrocarbons. These hydrocarbons were recovered from sediment by Soxhlet extraction method and then analyzed using gas chromatography equipped with mass spectrometer (GC/ MS). Total concentrations of aliphatic hydrocarbons in surface sediments from South China Sea off Kuching division are ranged from 35.6 μg/ g to 1466.1 μg/ g dry weights. The sediments collected from Bako Bay, Kuching showed high concentrations of total aliphatic hydrocarbons. Several molecular indices were used to predict the predominant sources of hydrocarbons. Carbon preference index (CPI) value revealed widespread anthropogenic input in this study area (CPI= 0 to 4.1). The ratio of C 31 / C 19 and C 29 / C 31 indicated that major input of aliphatic hydrocarbon mostly transfer by lateral input to the marine environment than atmospheric movements. Generally, the concentrations of aliphatic hydrocarbons in sediment from South China Sea off Kuching division are generally higher compare to other area in the world. (author)

  13. Microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock

    Energy Technology Data Exchange (ETDEWEB)

    Akinlua, A., E-mail: geochemresearch@yahoo.com [Fossil Fuels and Environmental Geochemistry Group, Department of Chemistry, Obafemi Awolowo University, Ile-Ife (Nigeria); Jochmann, M.A.; Laaks, J.; Ewert, A.; Schmidt, T.C. [Instrumental Analytical Chemistry, University Duisburg-Essen, Universitaetsstr, 5, 45141 Essen (Germany)

    2011-04-08

    The extraction of aliphatic hydrocarbons from petroleum source rock using nonionic surfactants with the assistance of microwave was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and kinetic rates have significant effects on extraction yields of aliphatic hydrocarbons. The optimum temperature for microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock was 105 deg. C. The optimum extraction time for the aliphatic hydrocarbons was at 50 min. Concentration of the nonionic surfactant solution and irradiation power had significant effect on the yields of aliphatic hydrocarbons. The yields of the analytes were much higher using microwave assisted nonionic surfactant extraction than with Soxhlet extraction. The recoveries of the n-alkanes and acyclic isoprenoid hydrocarbons for GC-MS analysis from the extractant nonionic surfactant solution by in-tube extraction (ITEX 2) with a TENAX TA adsorbent were found to be efficient. The results show that microwave-assisted nonionic surfactant extraction (MANSE) is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

  14. Microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock

    International Nuclear Information System (INIS)

    Akinlua, A.; Jochmann, M.A.; Laaks, J.; Ewert, A.; Schmidt, T.C.

    2011-01-01

    The extraction of aliphatic hydrocarbons from petroleum source rock using nonionic surfactants with the assistance of microwave was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and kinetic rates have significant effects on extraction yields of aliphatic hydrocarbons. The optimum temperature for microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock was 105 deg. C. The optimum extraction time for the aliphatic hydrocarbons was at 50 min. Concentration of the nonionic surfactant solution and irradiation power had significant effect on the yields of aliphatic hydrocarbons. The yields of the analytes were much higher using microwave assisted nonionic surfactant extraction than with Soxhlet extraction. The recoveries of the n-alkanes and acyclic isoprenoid hydrocarbons for GC-MS analysis from the extractant nonionic surfactant solution by in-tube extraction (ITEX 2) with a TENAX TA adsorbent were found to be efficient. The results show that microwave-assisted nonionic surfactant extraction (MANSE) is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

  15. Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

    Science.gov (United States)

    D’Ambrosio, Steven M.; Han, Chunhua; Pan, Li; Kinghorn, A. Douglas; Ding, Haiming

    2011-01-01

    Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003), was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compound 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not compound 1, prevented EGF-induced activation of EGFR (Tyr1173). When compounds 1 and 2 were combined they synergistically inhibited c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation, and human oral cancer cell proliferation. The present data suggest that the potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins that target two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. PMID:21596018

  16. Cellular effects of halogen blue light from dental curing unit

    International Nuclear Information System (INIS)

    Trosic, I.; Pavicic, I.; Jukic, S.

    2008-01-01

    Full text: Halogen curing lights are the most frequently used polymerization source in dental offices. Light-cured bonding systems have become increasingly popular among clinicians because they offer a number of advantages over self-cured adhesives. The effort to increase polymerization quality releases the commercially available high power light density dental curing units. Emitted visible blue light belongs to the range of nonionizing radiation. Common concern in both, patients and dentist grows with regard to the unfavorable effects on the pulp tissue. The aim of study was to evaluate the time and dose dependence effect of halogen light curing unit (Elipar TriLight, ESPE Dental AG, Germany) at the disposed condition modes in vitro. A quartz-tungsten-halogen light source emits radiation of the wavelengths between 400 and 515 nm. This halogen blue light source operates in the three illumination modes, medium (M), exponential (E) and standard (S), and five illumination times. The total irradiance or the light intensity was measured by the light intensity control area on the control panel of device and mean light intensity given by manufacturer was 800 m W/cm 2 . Continuous culture of V79 cells was illuminated in triplicate. The influence of medium mode (M), exponential (E) and standard (S) illumination during 20, 40 and 80 sec on the cell viability, colony forming ability and proliferation of V79 cell culture was investigated. Trypan blue exclusion test was used to determine cell viability, both, in the treated and control cell samples. Colony forming ability was assessed for each exposure time and mode by colony count on post-exposure day 7. Cell proliferation was determined by cell counts for each time and mode of exposure during five post-exposure days. Statistical difference were determined at p<0.05 (Statistica 7.0, StatSoft Inc., USA). Viability of cells was not affected by blue light in view of exposure time and modes. Regardless to exposure or illumination

  17. Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

    NARCIS (Netherlands)

    Lamont, C.A.; Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, T.W.L.; Andriessen, R.; Groen, P.

    2015-01-01

    For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses

  18. Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

    Science.gov (United States)

    Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

  19. Perfluorinated Compounds as Test Media for Porous Membranes.

    Science.gov (United States)

    Clodt, Juliana I; Filiz, Volkan; Shishatskiy, Sergey

    2017-09-05

    We suggest a failure-free method of porous membranes characterization that gives the researcher the opportunity to compare and characterize properties of any porous membrane. This proposal is supported by an investigation of eight membranes made of different organic and inorganic materials, with nine different perfluorinated compounds. It was found that aromatic compounds, perfluorobenzene, and perfluorotoluene, used in the current study show properties different from other perfluorinated aliphatics. They demonstrate extreme deviation from the general sequence indicating the existence of π-π-interaction on the pore wall. The divergence of the flow for cyclic compounds from ideal e.g., linear compounds can be an indication of the pore dimension.

  20. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li

    2009-01-01

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

  1. Effects of fluoride and other halogen ions on the external stress corrosion cracking of Type 304 austenitic stainless steel

    International Nuclear Information System (INIS)

    Whorlow, K.M.; Hutto, F.B. Jr.

    1997-07-01

    The drip procedure from the Standard Test Method for Evaluating the Influence of Thermal Insulation on External Stress Corrosion Cracking Tendency of Austenitic Stainless Steel (ASTM C 692-95a) was used to research the effect of halogens and inhibitors on the External Stress Corrosion Cracking (ESCC) of Type 304 stainless steel as it applies to Nuclear Regulatory Commission Regulatory Guide 1.36, Nonmetallic Thermal Insulation for Austenitic Stainless Steel. The solutions used in this research were prepared using pure chemical reagents to simulate the halogens and inhibitors found in insulation extraction solutions. The results indicated that sodium silicate compounds that were higher in sodium were more effective for preventing chloride-induced ESCC in Type 304 austenitic stainless steel. Potassium silicate (all-silicate inhibitor) was not as effective as sodium silicate. Limited testing with sodium hydroxide (all-sodium inhibitor) indicated that it may be effective as an inhibitor. Fluoride, bromide, and iodide caused minimal ESCC which could be effectively inhibited by sodium silicate. The addition of fluoride to the chloride/sodium silicate systems at the threshold of ESCC appeared to have no synergistic effect on ESCC. The mass ratio of sodium + silicate (mg/kg) to chloride (mg/kg) at the lower end of the NRC RG 1.36 Acceptability Curve was not sufficient to prevent ESCC using the methods of this research

  2. Special features of self-compensation of halogen donor action in lead telluride

    International Nuclear Information System (INIS)

    Kajdanov, V.I.; Nemov, S.A.; Ravich, Yu.I.; Dereza, A.Yu.

    1985-01-01

    Specific features of self-compensation of halogen donor action in lead telluride are investigasted. Lead telluride samples with chlorine additions (with tellurium excess) and, besides, with bromine- and iodine additions were studied in order to reveal general regularities in alloyind with all halogen donor impurities. Experimental dependences of the difference between the electron and hole concentrations (n-p) in PbTe as a function of an amount of introduced halogen impurities (Ni) are presented for samples with a maximum compensation at 295 K. General features of the n-p=f(Ni) dependence are presented for all halogens. The hypothesis on the kinetic mechanism of increasing the efficiency of self-compensation of halogen donor action in lead telluride is suggested

  3. Long-term Studies of Marine Halogen Release

    Science.gov (United States)

    Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

    2009-04-01

    Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

  4. Aliphatic amine cured PDMS–epoxy interpenetrating network ...

    Indian Academy of Sciences (India)

    Unknown

    Tg, heat-distortion temperature and reduced the percentage weight loss with ... The siliconized epoxy IPN, with better impact and thermal resistance, ... However, these materials also deteriorate ... the method of compounding remains the state of the art. ... geneity and to ascertain any chemical change during storage.

  5. Assessment of indoor levels of volatile organic compounds and carbon dioxide in schools in Kuwait.

    Science.gov (United States)

    Al-Awadi, Layla

    2018-01-01

    Indoor air quality (IAQ) in schools is a matter of concern because children are most vulnerable and sensitive to pollutant exposure. Conservation of energy at the expense of ventilation in heating, ventilation, and air conditioning (HVAC) systems adversely affects IAQ. Extensive use of new materials in building, fitting, and refurbishing emit various pollutants such that the indoor environment creates its own discomfort and health risks. Various schools in Kuwait were selected to assess their IAQ. Comprehensive measurements of volatile organic compounds (VOCs) consisting of 72 organic compounds consisting of aliphatic (C 3 -C 6 ), aromatic (C 6 -C 9 ), halogenated (C 1 -C 7 ), and oxygenated (C 2 -C 9 ) functional groups in indoor air were made for the first time in schools in Kuwait. The concentrations of indoor air pollutants revealed hot spots (science preparation rooms, science laboratories, arts and crafts classes/paint rooms, and woodworking shops/decoration rooms where local sources contributed to the buildup of pollutants in each school. The most abundant VOC pollutant was chlorodifluoromethane (R22; ClF 2 CH), which leaked from air conditioning (AC) systems due to improper operation and maintenance. The other copious VOCs were alcohols and acetone at different locations due to improper handling of the chemicals and their excessive uses as solvents. Indoor carbon dioxide (CO 2 ) levels were measured, and these levels reflected the performance of HVAC systems; a specific rate or lack of ventilation affected the IAQ. Recommendations are proposed to mitigate the buildup of indoor air pollutants at school sites. Indoor air quality in elementary schools has been a subject of extreme importance due to susceptibility and sensibility of children to air pollutants. The schools were selected based on their surrounding environment especially downwind direction from the highly industrialized zone in Kuwait. Extensive sampling from different sites in four schools for

  6. The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes.

    Science.gov (United States)

    Schneider, Lizette M; Adamski, Nikolai M; Christensen, Caspar Elo; Stuart, David B; Vautrin, Sonia; Hansson, Mats; Uauy, Cristobal; von Wettstein-Knowles, Penny

    2016-03-09

    Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley - Cer-c, Cer-q and Cer-u - known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles affect overall protein structure or specific active site residues. The rich diversity of identified mutations will facilitate future studies of three key enzymes involved in synthesis of plant apoplast waxes. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  7. Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

    NARCIS (Netherlands)

    Meindersma, G.W.; Haan, de A.B.

    2012-01-01

    Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coefficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is

  8. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    International Nuclear Information System (INIS)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young

    2017-01-01

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields

  9. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young [Dept. of Energy Systems Research, Ajou University, Suwon (Korea, Republic of)

    2017-03-15

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields.

  10. Kinetic analysis of the reactivity of aliphatic cyclic alcohols and carboxylic acids in the T-for-H exchange reaction

    International Nuclear Information System (INIS)

    Tamura, Kiyoshi; Imaizumi, Hiroshi; Kano, Naoki

    2007-01-01

    In order to quantitatively evaluate the influence of tritium ( 3 He or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly-(vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90degC. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying in A''-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring, the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of

  11. Mono- and polynuclear Co(II) silanethiolates with aliphatic diamines

    Science.gov (United States)

    Pladzyk, Agnieszka; Baranowska, Katarzyna

    2014-01-01

    Four Co(II) complexes, [Co{SSi(OtBu)3}2(dmpda)] 1, [Co{SSi(OtBu)3}2(bda)2]n2 [Co{SSi(OtBu)3}2(pda)2]n3 and [Co{SSi(OtBu)3}2(hda)2]n4 [dmpda = 3-(dimethylamino)-1-propylamine; bda = 1.4-butanediamine; pda = 1.5-pentanediamine; had = 1.6-hexanediamine] have been synthesized and characterized using X-ray diffraction. Complex 1 is mononuclear and contains Co(II) coordinated by dmpda molecule in chelating mode, whereas compounds 3 and 4 are one-dimensional polymers with pda and hda diamines as bridges between the metallic centers respectively. In all complexes tri-tert-butoxysilanethiolate residue acts as terminal S-donor ligand. Full characterization of obtained compounds 1-4 was additionally carried out with the use of IR and UV-vis spectroscopy, elemental and thermal analysis.

  12. Characterization of Predominant Reductants in an Anaerobic Leachate-Contaminated Aquifer by Nitroaromatic Probe Compounds

    DEFF Research Database (Denmark)

    Rügge, Kirsten; Hofstetter, Thomas B.; Haderlein, Stefan B.

    1998-01-01

    The biogeochemical processes controlling the reductive transformation of contaminants in an anaerobic aquifer were inferred from the relative reactivity patterns of redox-sensitive probe compounds. The fate of five nitroaromatic compounds (NACs) was monitored under different redox conditions in a...... results suggest that Fe(ll) associated with ferric iron minerals is a highly reactive reductant in anaerobic aquifers, which may also determine the fate of other classes of reducible contaminants such as halogenated solvents, azo compounds, sulfoxides, chromate, or arsenate....

  13. Substrate-Triggered Formation and Remarkable Stability of the C-H-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2†

    Science.gov (United States)

    Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.; Vaillancourt, Frédéric H.; Walsh, Christopher T.; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin

    2009-01-01

    Aliphatic halogenases activate O2, cleave α-ketoglutarate (αKG) to CO2 and succinate, and form haloferryl [X-Fe(IV)=O; X = Cl, Br] complexes that cleave aliphatic C-H bonds to install halogens during the biosynthesis of natural products by non-ribosomal peptide synthetases (NRPSs). For the related αKG-dependent dioxygenases, it has been shown that reaction of the Fe(II) cofactor with O2 to form the C-H-cleaving ferryl complex is “triggered” by binding of the target substrate. In this study, we have tested for and defined structural determinants of substrate triggering (ST) in the halogenase, SyrB2, from the syringomycin E biosynthetic NRPS of Pseudomonas syringae B301D. As for other halogen ases, the substrate of SyrB2 is complex, consisting of l-Thr tethered via thioester linkage to a covalently bound phosphopantetheine (PPant) cofactor of a carrier protein, SyrB1. Without an appended amino acid, SyrB1 does not trigger formation of the chloroferryl intermediate state in SyrB2, even in the presence of free l-Thr or its analogues, but SyrB1 charged either by l-Thr or by any of several non-native amino acids does trigger the reaction by as much as 8,000-fold (for l-Thr-S-SyrB1). Triggering efficacy is sensitive to the structures of both the amino acid and the carrier protein, being diminished by 5–20-fold when the native l-Thr is replaced by another amino acid and by ∼ 40-fold when SyrB1 is replaced by a heterologous carrier protein, CytC2. The directing effect of the carrier protein and consequent tolerance for profound modifications to the target amino acid allow the chloroferryl state to be formed in the presence of substrates that perturb the ratio of its two putative coordination isomers, lack the target C-H bond (l-Ala-S-SyrB1), or contain a C-H bond of enhanced strength (l-cyclopropylglycyl-S-SyrB1). For the latter two cases, the SyrB2 chloroferryl state so formed exhibits unprecedented stability (t1/2 = 30 – 110 min at 0 °C), can be trapped in

  14. Antennal olfactory responses of adult meadow spittlebug, Philaenus spumarius, to volatile organic compounds (VOCs.

    Directory of Open Access Journals (Sweden)

    Giacinto Salvatore Germinara

    Full Text Available The meadow spittlebug, Philaenus spumarius L. (Hemiptera, Aphrophoridae is a commonly found vector of Xylella fastidiosa Wells et al. (1987 strain subspecies pauca associated with the "Olive Quick Decline Syndrome" in Italy. To contribute to the knowledge of the adult P. spumarius chemoreceptivity, electroantennographic (EAG responses of both sexes to 50 volatile organic compounds (VOCs including aliphatic aldehydes, alcohols, esters, and ketones, terpenoids, and aromatics were recorded. Measurable EAG responses were elicited by all compounds tested. In both sexes, octanal, 2-octanol, 2-decanone, (E-2-hexenyl acetate, and vanillin elicited the strongest antennal amplitude within the chemical groups of aliphatic saturated aldehydes, aliphatic alcohols, aliphatic acetates and aromatics, respectively. Male and female EAG responses to sulcatol, (±linalool, and sulcatone were higher than those to other terpenoinds. In both sexes, the weakest antennal stimulants were phenethyl alcohol and 2-pentanone. Sexual differences in the EAG amplitude were found only for four of test compounds suggesting a general similarity between males and females in antennal sensitivity. The olfactory system of both sexes proved to be sensitive to changes in stimulus concentration, carbon chain length, and compound structure. Compounds with short carbon chain length (C5-C6 elicited lower EAG amplitudes than compounds with higher carbon chain length (C9-C10 in all classes of aliphatic hydrocarbons with different functional groups. The elucidation of the sensitivity profile of P. spumarius to a variety of VOCs provides a basis for future identification of behaviorally-active compounds useful for developing semiochemical-based control strategies of this pest.

  15. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2012-06-01

    Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  16. Incidence of real-world automotive parent and halogenated PAH in urban atmosphere.

    Science.gov (United States)

    Gao, Pan-Pan; Zhao, Yi-Bo; Ni, Hong-Gang

    2018-06-01

    This study reports results from a tunnel experiment impact of real-world traffic-related particle and gas parent and halogenated polycyclic aromatic hydrocarbons (PAHs and HPAHs) on urban air. The traffic related emission characteristics and subsequent environmental behavior of these compounds were investigated. To understand the significance of real-world transport emissions to the urban air, traffic-related mass emissions of PAHs and HPAHs were estimated based on measured emission factors. According to our results, PAHs and HPAHs emissions via particulate phase were greater than those via gaseous phase; particles in 2.1-3.3 μm size fraction, have the major contribution to particulate PAHs and HPAHs emissions. Over all, contribution of traffic-related emission of PAHs (only ∼3% of the total PAHs emission in China) is an overstated source of PAHs pollution in China. Actually, exhaust pipe emission contributed much less than the total traffic-related emission of pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

  17. Alternative sorptive extraction method for gas chromatography determination of halogenated anisoles in water and wine samples

    International Nuclear Information System (INIS)

    Montes, R.; Rodriguez, I.; Rubi, E.; Bollain, M.H.; Cela, R.

    2007-01-01

    An alternative sorptive microextraction method for the determination of five halogenated anisoles in water and wine matrices is proposed. Analytes were concentrated in an inexpensive and disposable piece of bulk polydimethylsiloxane (PDMS), desorbed with a small volume of organic solvent, and determined by gas chromatography with electron-capture detection (GC-ECD) or tandem mass spectrometry (GC-MS/MS). The influence of several factors on the efficiency of extraction and desorption steps was investigated in detail and the observed behaviour justified on the basis of thermodynamics and kinetics of the solid-phase microextraction technique. Under optimised conditions, analytes were first extracted in the headspace (HS) mode, at room temperature, for 2.5 h and then desorbed with 1 mL of n-pentane. This extract was further evaporated to 50 μL. The overall extraction yield of the procedure ranged from 40 to 55% and the limits of quantification remained between 0.5 and 20 ng L -1 , depending on the compound considered and the detection technique. Precision and linearity of the method were excellent for all species with both GC-ECD and GC-MS/MS detection. Matrix effects were evaluated with different water and wine samples; moreover, the suitability of the PDMS sorbent for storage of analytes, under different conditions, was demonstrated

  18. Alternative sorptive extraction method for gas chromatography determination of halogenated anisoles in water and wine samples

    Energy Technology Data Exchange (ETDEWEB)

    Montes, R. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain); Rodriguez, I. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain)], E-mail: qnisaac@usc.es; Rubi, E.; Bollain, M.H.; Cela, R. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain)

    2007-09-05

    An alternative sorptive microextraction method for the determination of five halogenated anisoles in water and wine matrices is proposed. Analytes were concentrated in an inexpensive and disposable piece of bulk polydimethylsiloxane (PDMS), desorbed with a small volume of organic solvent, and determined by gas chromatography with electron-capture detection (GC-ECD) or tandem mass spectrometry (GC-MS/MS). The influence of several factors on the efficiency of extraction and desorption steps was investigated in detail and the observed behaviour justified on the basis of thermodynamics and kinetics of the solid-phase microextraction technique. Under optimised conditions, analytes were first extracted in the headspace (HS) mode, at room temperature, for 2.5 h and then desorbed with 1 mL of n-pentane. This extract was further evaporated to 50 {mu}L. The overall extraction yield of the procedure ranged from 40 to 55% and the limits of quantification remained between 0.5 and 20 ng L{sup -1}, depending on the compound considered and the detection technique. Precision and linearity of the method were excellent for all species with both GC-ECD and GC-MS/MS detection. Matrix effects were evaluated with different water and wine samples; moreover, the suitability of the PDMS sorbent for storage of analytes, under different conditions, was demonstrated.

  19. Halogenated salicylaldehyde azines: The heavy atom effect on aggregation-induced emission enhancement properties

    International Nuclear Information System (INIS)

    Chen, Xiao-tong; Tong, Ai-jun

    2014-01-01

    This study investigates the heavy-atom effect (HAE) on aggregation-induced emission enhancement (AIEE) properties of salicylaldehyde azines. For this purpose, a series of halogenated salicylaldehyde azine derivatives, namely, chloro-salicylaldehyde azine (1), bromo-salicylaldehyde azine (2) and iodo-salicylaldehyde azine (3) are synthesized. 1 and 2 display typical AIEE characteristics of salicylaldehyde azine compounds; whereas for the iodo-substituent in 3, is found to be effective “external” heavy atom quenchers to salicylaldehyde azine fluorescence in aggregated state. Based on its weak fluorescence in aggregated state and relative strong fluorescence in dispersed state, 3 can also be applied as a turn-on fluorescence probe for egg albumin detection attributed to hydrophobic interaction. -- Highlights: • This study investigates the heavy-atom effect (HAE) on aggregation-induced emission enhancement (AIEE) properties of salicylaldehyde azines. • Chloro- and bromo-salicylaldehyde display typical AIEE properties of salicylaldehyde azine, whereas the iodo-substitute quenches AIEE in aggregated state. • Iodo-salicylaldehyde can be applied as a turn-on fluorescence probe for egg albumin detection attributed to hydrophobic interaction

  20. Limitations of the toxic equivalency factor (TEF) approach for risk assessment of halogenated aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Safe, S. [Texas A and M Univ., College Station, TX (United States). Dept. of Veterinary Physiology and Pharmacology

    1995-12-31

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and related halogenated aromatic hydrocarbons (HAHs) are present as complex mixtures of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) in most environmental matrices. Risk management of these mixtures utilize the toxic equivalency factor (TEF) approach in which the TCDD (dioxin) or toxic equivalents of a mixture is a summation of the congener concentration (Ci) times TEF{sub i} (potency relative to TCDD) where. TEQ{sub mixture} = {Sigma}[Cil] {times} TEF{sub i}. TEQs are determined only for those HAHs which are aryl hydrocarbon (Ah) receptor agonists and this approach assumes that the toxic or biochemical effects of individual compounds in a mixture are additive. Several in vivo and in vitro laboratory and field studies with different HAH mixtures have been utilized to validate the TEF approach. For some responses, the calculated toxicities of PCDD/PCDF and PCB mixtures predict the observed toxic potencies. However, for fetal cleft palate and immunotoxicity in mice, nonadditive (antagonistic) responses are observed using complex PCB mixtures or binary mixtures containing an Ah receptor agonist with 2,2{prime},4,4{prime},5,5{prime}-hexachlorobiphenyl (PCB153). The potential interactive effects of PCBs and other dietary Ah receptor antagonist suggest that the TEF approach for risk management of HAHs requires further refinement and should be used selectively.

  1. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

    Directory of Open Access Journals (Sweden)

    Seiya Nagao

    2011-12-01

    Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

  2. Extraterrestrial Organic Compounds in Meteorites

    Science.gov (United States)

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

    2003-01-01

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

  3. Computational Investigation of the Influence of Halogen Atoms on the Photophysical Properties of Tetraphenylporphyrin and Its Zinc(II) Complexes.

    Science.gov (United States)

    De Simone, Bruna C; Mazzone, Gloria; Russo, Nino; Sicilia, Emilia; Toscano, Marirosa

    2018-03-15

    How the tetraphenylporphyrin (TPP) and its zinc(II) complexes (ZnTPP) photophysical properties (absorption energies, singlet-triplet energy gap and spin-orbit coupling contributions) can change due to the presence of an increasing number of heavy atoms in their molecular structures has been investigated by means of density functional theory and its time-dependent formulation. Results show that the increase of the atomic mass of the substituted halogen strongly enhances the spin-orbit coupling values, allowing a more efficient singlet-triplet intersystem crossing. Different deactivation channels have been considered and rationalized on the basis of El-Sayed and Kasha rules. Most of the studied compounds possess the appropriate properties to generate cytotoxic singlet molecular oxygen ( 1 Δ g ) and, consequently, they can be proposed as photosensitizers in photodynamic therapy.

  4. Aromatic-aliphatic copolyesters based on waste poly(ethylene terephthalate) and their biodegradability

    Czech Academy of Sciences Publication Activity Database

    Prokopová, I.; Vlčková, E.; Šašek, Václav; Náhlík, J.; Soukupová-Chaloupková, V.; Skolil, J.

    -, 052 (2008), s. 1-9 ISSN 1618-7229 R&D Projects: GA ČR GA203/03/0508; GA ČR GA203/06/0528 Institutional research plan: CEZ:AV0Z50200510 Keywords : aromatic-aliphatic colpolyesters * rhodococcus erythropolis * biodegradability Subject RIV: EE - Microbiology, Virology Impact factor: 0.661, year: 2008

  5. Influence of molecular weight on the fracture properties of aliphatic polyketone terpolymers

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Homminga, D.S.; Homminga, D.S.; Huetink, Han; Gaymans, R.J.

    2003-01-01

    The influence of polymer molecular weight on the mechanical properties of aliphatic polyketones was investigated. The molecular weight varied from 100,000 to 300,000 g mol21. The crystallinity was found to be independent of polymer molecular weight, as was the glass transition temperature. The yield

  6. OCCUPATIONAL ASTHMA CAUSED BY A HARDENER CONTAINING AN ALIPHATIC AND A CYCLOALIPHATIC DIAMINE

    NARCIS (Netherlands)

    ALEVA, RM; AALBERS, R; KOETER, GH; DEMONCHY, JGR

    An otherwise healthy 44-yr-old man experienced a serious attack of bronchial obstruction after working with resins and hardeners, releasing fumes of a mixture of an aliphatic and a cycloaliphatic diamine hardener. Eight hours after deliberate challenge with the hardener a large increase of airway

  7. Evaluation of Efficient and Practical Methods for the Preparation of Functionalized Aliphatic Trifluoromethyl Ethers

    Directory of Open Access Journals (Sweden)

    Taras M. Sokolenko

    2017-05-01

    Full Text Available The “chlorination/fluorination” technique for aliphatic trifluoromethyl ether synthesis was investigated and a range of products with various functional groups was prepared. The results were compared with oxidative desulfurization-fluorination of xanthates with the same structure.

  8. Modification of eucalyptus pulp fiber using silane coupling agents with aliphatic side chains of different length

    Science.gov (United States)

    The objective of this work was to evaluate the effect of three silane coupling agents with different aliphatic chain lengths on the hydrophobicity of eucalyptus pulp fiber. The three silanes coupling agents used (isobutyltrimethoxysilane, methyltrimethoxysilane, and n-octyltriethoxysilane [OTES]) we...

  9. PcMtr, an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum

    NARCIS (Netherlands)

    Trip, H; Evers, ME; Driessen, AJM

    2004-01-01

    The gene encoding an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum was cloned, functionally expressed and characterized in Saccharomyces cerevisiae M4276. The permease, designated PcMtr, is structurally and functionally homologous to Mtr of Neurospora crassa, and

  10. Electrooxidation of aliphatic alcohols on palladium oxide catalyst prepared by pulsed electrodeposition technique

    International Nuclear Information System (INIS)

    Casella, Innocenzo G.

    2009-01-01

    Palladium film can be deposited on gold polycrystalline electrodes, from a deoxygenated alkaline solution containing 50 mM NaOH plus 0.5 mM K 2 Pd(CN) 4 . A multipulse sequence of potentials of equal amplitude and duration was used for the palladium deposition process. In particular, an optimized waveform of potentials of E 1 = 1.0 V vs. SCE and E 2 = -1.0 V vs. SCE for the relevant pulse duration of t 1 = 0.05 s and t 2 = 0.05 s, for 30 s, was used. Cyclic voltammetry and scanning electron microscopy (SEM) were employed to characterize the gold-palladium modified electrode (Au-Pd) towards the electrooxidation of aliphatic alcohols in alkaline solutions. The voltammetric study suggests that the kinetics involved in the alcohol electrooxidation at the Pd-Au electrode are sensibly higher than those observed on the bare Pd and Au electrodes. In addition, the most interesting aspect of the electrooxidation of aliphatic alcohols at the Au-Pd electrode was that as the number of methylene groups on the homologous series of aliphatic alcohols increased, the molar response also increased. Under pulsed chronoamerometric conditions (PCC), using an optimized triple pulse waveform of potentials the modified electrode exhibits interesting catalytic currents without any apparent poisoning effects during the oxidation of aliphatic alcohols.

  11. High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons

    International Nuclear Information System (INIS)

    Perez, M.; Gonzalez, D.

    1988-01-01

    A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs

  12. Pseudomonas sax genes overcome aliphatic isothiocyanate-mediated non-host resistance in Arabidopsis

    Science.gov (United States)

    Jun Fan; Casey Crooks; Gary Creissen; Lionel Hill; Shirley Fairhurst; Peter Doerner; Chris Lamb

    2011-01-01

    Most plant-microbe interactions do not result in disease; natural products restrict non-host pathogens. We found that sulforaphane (4-methylsulfinylbutyl isothiocyanate), a natural product derived from aliphatic glucosinolates, inhibits growth in Arabidopsis of non-host Pseudomonas bacteria in planta. Multiple sax genes (saxCAB/F/D/G) were identified in Pseudomonas...

  13. Conformational dynamics of semiflexibly bridged electron donor-acceptor systems comprising long aliphatic tails

    NARCIS (Netherlands)

    Bleisteiner, B.; Marian, T.; Schneider, S.; Brouwer, A.M.; Verhoeven, J.W.

    2001-01-01

    In continuation of our previous work on the conformational dynamics (harpooning mechanism) of semiflexibly bridged electron donor-acceptor systems we have studied a derivative with two long aliphatic chains tethered to the donor and acceptor moieties, respectively. The fitting of the time- and

  14. Complex Treatment of Soils, Waste Water and Groundwater Contaminated by Halogenated Organic Compounds.

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, František; Maléterová, Ywetta; Kaštánek, P.; Rott, J.; Jiřičný, Vladimír; Jirátová, Květa

    2007-01-01

    Roč. 211, č. 1-3, (2007) , s. 261-271 ISSN 0011-9164. [Environmental Science and Technology Symposium /9./. Rhodes, 01.09.2005-03.09.2005] R&D Project s: GA ČR(CZ) GA104/03/0407; GA MPO FI-IM3/050 Institutional research plan: CEZ:AV0Z40720504 Keywords : vinyl chloride * waste and underground water * fenton reaction Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.875, year: 2007

  15. Preparation of directly iodinated steroid hormones and related directly halogenated compounds

    International Nuclear Information System (INIS)

    Sahadevan, V.

    1981-01-01

    The preparation of directly iodinated radioactive steroid hormones is described for use in radioimmunoassays or radiolocalization and treatment of human breast tumours. The radioactive iodinated steroid hormone is prepared by reacting a parent steroid hormone with an alkali metal iodide containing radioactive 123 I, 125 I, 130 I or 131 I in the presence of hydrogen peroxide or chloramine-T. The parent steroid hormones include the adrenal corticosteroids, the estrogens, the progestogens, the progestins and the diuretic and antidiuretic agents. The radioactive iodinated steroid hormone is prepared by iodinating the parent steroid hormone directly on the cyclopentanophenanthrene nucleus. The radioactive iodinated steroid hormones have the same antigenicity and receptor site specificity as the parent steroid hormone. The invention is illustrated by 1) the method of iodination of estradiol-17β, 2) results for the percentage labelling of several steroids and steroid hormones, 3) results for the radioimmunoassay of 125 I-estradiol and 4) results for the binding of directly iodinated estradiol-17β in an estrogen receptor assay of human breast cancer. (U.K.)

  16. Benchmarking fully analytic DFT force fields for vibrational spectroscopy: A study on halogenated compounds

    Science.gov (United States)

    Pietropolli Charmet, Andrea; Cornaton, Yann

    2018-05-01

    This work presents an investigation of the theoretical predictions yielded by anharmonic force fields having the cubic and quartic force constants are computed analytically by means of density functional theory (DFT) using the recursive scheme developed by M. Ringholm et al. (J. Comput. Chem. 35 (2014) 622). Different functionals (namely B3LYP, PBE, PBE0 and PW86x) and basis sets were used for calculating the anharmonic vibrational spectra of two halomethanes. The benchmark analysis carried out demonstrates the reliability and overall good performances offered by hybrid approaches, where the harmonic data obtained at the coupled cluster with single and double excitations level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T), are combined with the fully analytic higher order force constants yielded by DFT functionals. These methods lead to reliable and computationally affordable calculations of anharmonic vibrational spectra with an accuracy comparable to that yielded by hybrid force fields having the anharmonic force fields computed at second order Møller-Plesset perturbation theory (MP2) level of theory using numerical differentiation but without the corresponding potential issues related to computational costs and numerical errors.

  17. Molecular-level chemistry of model single-crystal oxide surfaces with model halogenated compounds

    Science.gov (United States)

    Adib, Kaveh

    Synchrotron-based X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD) and low energy electron diffraction (LEED) have been used to investigate, at a molecular level, the chemistry of different terminations of single crystal iron-oxide surfaces with probe molecules (CCl4 and D2O). Comparisons of the reactivity of these surfaces towards CCl4, indicate that the presence of an uncapped surface Fe cation (strong Lewis acid site) and an adjacent oxygen site capped by that cation can effect the C-Cl bond cleavage in CCl4, resulting in dissociatively adsorbed Cl-adatoms and carbon-containing fragments. If in addition to these sites, an uncapped surface oxygen (Lewis base) site is also available, the carbon-containing moiety can then move that site, coordinate itself with that uncapped oxygen, and stabilize itself. At a later step, the carbon-containing fragment may form a strong covalent bond with the uncapped oxygen and may even abstract that surface oxygen. On the other hand, if an uncapped oxygen is not available to stabilize the carbon-containing fragment, the surface coordination will not occur and upon the subsequent thermal annealing of the surface the Cl-adatoms and the carbon-containing fragments will recombine and desorb as CCl4. Finally, the presence of surface deuteroxyls blocking the strong Lewis acid and base sites of the reactive surface, passivates this surface. Such a deuteroxylated surface will be unreactive towards CCl 4. Such a molecular level understanding of the surface chemistry of metal-oxides will have applications in the areas of selective catalysis, including environmental catalysis, and chemical sensor technology.

  18. Different radiosensitization effects of the halogenated compounds on the human chromosome in vitro

    International Nuclear Information System (INIS)

    Kang, Y.S.

    1976-01-01

    Unscheduled DNA synthesis and chromosome aberrations were compared following X- or UV-irradiation or methyl methanesulfonate treatment in cultures of HeLa S 3 or KB cells or human and rabbit lymphocytes. The sensitization by incorporation of the halouridines BUdR and IUdR was also investigated. Unscheduled DNA synthesis occurred in two established cell lines after irradiation with 0 to 10 kR of X-rays. The rate of unscheduled synthesis was dose dependent and differed for the two cell lines. The unscheduled synthesis was not correlated with the modal chromosome number nor with the number of aberrations produced. UV-irradiated rabbit lymphocytes exhibited unscheduled DNA synthesis which saturated after a dose of 250 ergs/mm 2 . In contrast the incorporation of BUdR or IUdR eliminated this saturation and caused an increasing effect with increasing dose up to 1000 ergs/mm 2 . The degree of sensitization varied between the two halo-uridines, BUdR being more effective at high doses while IUdR was a more potent sensitizer at low doses. Chromosome aberrations were not directly related to unscheduled DNA synthesis but were sensitized by halo-uridine incorporation. In this case IUdR was more potent than BUdR at all doses studied. Methyl methanesulfonate was an effective producer of chromosome aberration in human lymphocytes of both the chromosome and chromatid type. Prior incorporation of BUdR or IUdR did not increase the total aberration produced but did increase the number of chromosome type aberration at the expense of the chromatid type

  19. Haloperoxidase-like activity in spruce forest soil. A source of volatile halogenated organic compounds?

    DEFF Research Database (Denmark)

    Laturnus, F.; Mehrtens, G.; Grøn, C.

    1995-01-01

    Haloperoxidase-like activity was monitored in samples from a podzol soil in an uncontaminated spruce forest at Klosterhede, Denmark. Activity for the oxidation of chloride and bromide was found. The pH optima for chlorination and bromination ranged between pH 2.5 and 4: Very high activity, up to 4...

  20. Inhibition of quorum sensing in Pseudomonas aeruginosa biofilm bacteria by a halogenated furanone compound

    DEFF Research Database (Denmark)

    Hentzer, Morten; Riedel, K.; Rasmussen, Thomas Bovbjerg

    2002-01-01

    Novel molecular tools have been constructed which allow for in situ detection of N-acyl homoserine lactone (AHL)-mediated quorum sensing in Pseudomonas aeruginosa biofilms. The reporter responds to AHL activation of LasR lay expression of an unstable version of the green-fluorescent protein (Gfp...

  1. Swift heavy ion induced modification of aliphatic polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hossain, Umme Habiba

    2015-01-15

    In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10{sup 10} - 5 x 10{sup 12} ions/cm{sup 2}). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic

  2. Cycloaddition of CO 2 to challenging N -tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights

    KAUST Repository

    Arayachukiat, Sunatda

    2017-11-06

    An efficient and facile approach to the regioselective synthesis of N-tosyloxazolidinones from the corresponding N-tosylaziridines and CO2 was developed using dual catalytic systems involving an early transition metal coordination compound as a Lewis acid and a nucleophilic cocatalyst. Among the screened Lewis acids, halogen-free niobium pentaethoxide (Nb(OEt)5) displayed the best catalytic activity when used in the presence of tetrabutylammonium iodide (TBAI). Systematic DFT calculations, supported by catalytic experiments, demonstrate that CO2 insertion is the rate determining step for this process and it is highly dependent on the steric hindrance at the niobium center.

  3. Cycloaddition of CO 2 to challenging N -tosyl aziridines using a halogen-free niobium complex: Catalytic activity and mechanistic insights

    KAUST Repository

    Arayachukiat, Sunatda; Yingcharoen, Prapussorn; Vummaleti, Sai V. C.; Cavallo, Luigi; Poater, Albert; D’ Elia, Valerio

    2017-01-01

    An efficient and facile approach to the regioselective synthesis of N-tosyloxazolidinones from the corresponding N-tosylaziridines and CO2 was developed using dual catalytic systems involving an early transition metal coordination compound as a Lewis acid and a nucleophilic cocatalyst. Among the screened Lewis acids, halogen-free niobium pentaethoxide (Nb(OEt)5) displayed the best catalytic activity when used in the presence of tetrabutylammonium iodide (TBAI). Systematic DFT calculations, supported by catalytic experiments, demonstrate that CO2 insertion is the rate determining step for this process and it is highly dependent on the steric hindrance at the niobium center.

  4. Digital solar edge tracker for the Halogen Occultation Experiment

    Science.gov (United States)

    Mauldin, L. E., III; Moore, A. S.; Stump, C. W.; Mayo, L. S.

    1987-01-01

    The optical and electronic design of the Halogen Occultation Experiment (Haloe) elevation sun sensor is described. The Haloe instrument is a gas-correlation radiometer now being developed at NASA Langley for the Upper Atmosphere Research Satellite. The system uses a Galilean telescope to form a solar image on a linear silicon photodiode array. The array is a self-scanned monolithic CCD. The addresses of both solar edges imaged on the array are used by the control/pointing system to scan the Haloe science instantaneous field of view (IFOV) across the vertical solar diameter during instrument calibration and then to maintain the science IFOV 4 arcmin below the top edge during the science data occultation event. Vertical resolution of 16 arcsec and a radiometric dynamic range of 100 are achieved at the 700-nm operating wavelength. The design provides for loss of individual photodiode elements without loss of angular tracking capability.

  5. Use of pyrrole black in zinc-halogen batteries

    Energy Technology Data Exchange (ETDEWEB)

    Mengoli, G.; Musiani, M.M.; Tomat, R.; Valcher, S.; Pletcher, D.

    1985-09-01

    The storage of Br/sub 2//Br/sup -/ and I/sub 2//I/sup -/ couples in a conducting polymer matrix, polypyrrole coated on a reticulated vitreous carbon disc, is described and the application of these positive electrodes in zinc-halogen model batteries is discussed. The cell based on the polypyrrole bromine adduct shows the higher open circuit voltage which, however, depends on the state of charge. Such cells self discharge thus limiting their usefulness. In the case of the iodine cell the self discharge is due to loss of iodine from the polymer to the bulk solution, but with the bromine cell the cause is oxidative bromination and depolymerization of the polypyrrole. 22 references, 6 figures, 2 tables.

  6. Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

    Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

  7. Iron Coordination and Halogen-Bonding Assisted Iodosylbenzene Activation

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Poulsen de Sousa, David; McKenzie, Christine

    catalytic mixtures using soluble terminal oxygen transfer agents. Isolation of a reactive iron-terminal oxidant adduct, an unique Fe(III)-OIPh complex, is facilitated by strong stabilizing supramolecular halogen-bonding. L3-edge XANES suggests +1.6 for the average oxidation state for the iodine atom3......The iron complex of the hexadentate ligand N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena) efficiently catalyzes selective oxidations of electron-rich olefins and sulfides by insoluble iodosylbenzene (PhIO). Surprisingly, these reactions are faster and more selective than homogenous...... in the iron(III)-coordinated PhIO. This represents a reduction of iodine relative to the original “hypervalent” (+3) PhIO. The equivalent of electron density must be removed from the {(tpena)Fe(III)O} moiety, however Mössbauer spectroscopy shows that the iron atom is not high valent....

  8. Fluorescence cell imaging and manipulation using conventional halogen lamp microscopy.

    Directory of Open Access Journals (Sweden)

    Kazuo Yamagata

    Full Text Available Technologies for vitally labeling cells with fluorescent dyes have advanced remarkably. However, to excite fluorescent dyes currently requires powerful illumination, which can cause phototoxic damage to the cells and increases the cost of microscopy. We have developed a filter system to excite fluorescent dyes using a conventional transmission microscope equipped with a halogen lamp. This method allows us to observe previously invisible cell organelles, such as the metaphase spindle of oocytes, without causing phototoxicity. Cells remain healthy even after intensive manipulation under fluorescence observation, such as during bovine, porcine and mouse somatic cell cloning using nuclear transfer. This method does not require expensive epifluorescence equipment and so could help to reduce the science gap between developed and developing countries.

  9. Distribution of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and organochlorinated pollutants in deep-sea sediments of the Southern Cretan margin, Eastern Mediterranean Sea: a baseline assessment.

    Science.gov (United States)

    Mandalakis, Manolis; Polymenakou, Paraskevi N; Tselepides, Anastasios; Lampadariou, Nikolaos

    2014-07-01

    Deep sediments from the southern Cretan margin were analyzed to establish baseline levels for various types of organic pollutants before the anticipated intensification of anthropogenic activities. The total concentration of aliphatic hydrocarbons (ΣAH:326-3758ngg(-1), dry weight) was similar to those reported for deep sediments of the western Mediterranean Sea, while considerably lower levels were measured for polycyclic aromatic hydrocarbons (ΣPAH:9-60ngg(-1)). Source-diagnostic ratios suggested that the aliphatic hydrocarbons in sediments were mainly of terrestrial biogenic origin, while polycyclic aromatic hydrocarbons stemmed from the deposition of long-range transported combustion aerosols. Among the organochlorinated compounds analyzed, β-hexachlorocyclohexane (β-HCH:222-7052pgg(-1)), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT:37-2236pgg(-1)) and polychlorinated biphenyls (ΣPCB:38-1182pgg(-1)) showed the highest abundance in sediments. The presence of HCHs and PCBs was attributed to historical inputs that have undergone extensive weathering, whereas an ongoing fresh input was suggested for p,p'-DDT. Multiple linear regression analysis revealed that the levels of the various pollutants in sediments were controlled by different factors, but with organic carbon content playing a prominent role in most cases. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

    2002-01-01

    fischeri overproduced in Escherichia coli. Whilst a stable interaction between the algal metabolite and the bacterial protein was not found, it was noted by Western analysis that the half-life of the protein is reduced up to 100-fold in the presence of halogenated furanones. This suggests that halogenated...... that the reduction in LuxR concentration is the mechanism by which furanones control expression of AHL-dependent phenotypes. The mode of action by which halogenated furanones reduce cellular concentrations of the LuxR protein remains to be characterized....

  11. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

    Science.gov (United States)

    Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

    2008-10-30

    A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

  12. Basic aspects of photocatalytic detoxification of organic halogens by TiO2 nanocrystallites. Photolytic and radiolytic investigations

    International Nuclear Information System (INIS)

    Rabani, J.

    1998-01-01

    Various forms of TiO 2 (nanocrystallites in colloid solutions, powders and layers) are considered as promising photocatalysts for detoxification of persistent organic chemicals which are present as pollutants in waste water effluents from industrial manufacturers and even from regular households. Such pollutants penetrate and reach water sources and must be removed or destroyed in order to prevent damage to people or to the environment. Some of the toxins, such as organic halogenated compounds is difficult to remove by moderate chemical redox reactions, but can be mineralized by a free radical mechanism. Pilot plants for detoxification of industrial wastes on TiO 2 surface are currently being tested in several countries. In view of this recent development it is of particular interest to investigate yields of the reactive intermediates and reaction mechanisms of reactions of representative organic substrates. Such work is presently going on in many laboratories. In the present contribution we focus on the nature of the primary oxidizing species and the possible ways to increase photolytic yields, with particular attention to chain reactions in organic halogen compounds. Although the work concerns photocatalysis, radiation chemistry may provide useful results regarding kinetic parameters and comparative tests. Thus, comparison between photocatalytic (TiO 2 ), radiolytic and chemical hydroxylations of phenol provides evidence that the reactive hydroxylation agent is an OH· radical adsorbed to the TiO 2 surface. The initial photochemical products are conduction band electrons and valence band holes in the TiO 2 nanocrystallites, which become 'trapped' within less than 30 ps. (author)

  13. Structures and anti-inflammatory properties of 4-halogenated -mofebutazones

    Science.gov (United States)

    Reichelt, Hendrik; Paradies, Henrich H.

    2018-02-01

    The crystal structures of the 4-halogenated (hal: F, Cl, Br)-4-butyl-1-phenyl-1,3-pyrolidine-dione (mofebutazone) are determined, and compared with their solution structures. The racemic 4-halogenated mofebutazone approximants crystallize in a monoclinic space group with four molecules in the unit cell. The 4-hal-mofebutazone molecules reveal strong hydrogen bonding between the hydrogen atom located at the N-2 nitrogen atom and a carbonyl oxygen atom of an adjacent 4-hal-mofebutazone molecule. The hydrogen bond angle for 4-Br-mifebutazone N (2)sbnd H (1)⋯O (1) is 173(3) °, so that the hydrogen bond is essentially linear indicating an infinite chain hydrogen bond network. The 3d and 2d structures are stabilized by π-π and σ-π interactions, short intermolecular distances, and apolar forces between adjacently stacked phenyl rings. Small-angle-X-ray scattering (SAXS) experiments and osmometric measurements reveal the presence of dimers for the 4-hal-mofebutazone molecules. Molecular simulations indicate similar solution structure factors for the 4-hal-mofebutazones solutions, S(Q), and in the solid state. There is a strong indication that the [1,1,0], [1,0,0], and [1,0,0] periodicities of the 4-Brsbnd , 4-Clsbnd and 4-F-mofebutazone in the crystalline solid state were also present in the solution phase. The biochemical and cellular activities of the different 4-hal-mofebutazones were monitored by the magnitude of their inhibition of the PGE2 biosynthesis through the cyclo-oxygenase (COX-1) in macrophages, and on the inhibition of LTD4 (5-lipoxygenase) in polymorphonuclear leukocytes.

  14. Development and application of compact denuder sampling techniques with in situ derivatization followed by gas chromatography-mass spectrometry for halogen speciation in volcanic plumes

    Science.gov (United States)

    Rüdiger, Julian; Bobrowski, Nicole; Hoffmann, Thorsten

    2015-04-01

    Volcanoes are a large source for several reactive atmospheric trace gases including sulphur and halogen containing species. The detailed knowledge of volcanic plume chemistry can give insights into subsurface processes and can be considered as a useful geochemical tool for monitoring of volcanic activity, especially halogen to sulphur ratios (e.g. Bobrowski and Giuffrida, 2012; Donovan et al., 2014). The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable by UV spectrometers at a safe distance. Furthermore it is formed in the plume by a multiphase reaction mechanism under depletion of ozone in the plume. The abundance of BrO changes as a function of the reaction time and therefore distance from the vent as well as the spatial position in the plume. Due to the lack of analytical approaches for the accurate speciation of certain halogens (HBr, Br2, Br, BrCl, HOBr etc.) there are still uncertainties about the magnitude of volcanic halogen emissions and in particular their specificationtheir species and therefore also in the understanding of the bromine chemistry in volcanic plumes (Bobrowski et al., 2007). In this study, the first application of a 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated gas diffusion denuder (Huang and Hoffmann, 2008) on volcanic gases proved to be suitable to collect selectively gaseous bromine species with oxidation states of +1 or 0 (Br2 and BrO(H)), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with bromine gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. The diffusion denuder technique allows sampling of gaseous compounds exclusively without collecting particulate matter. Choosing a flow rate of 500 mL-min-1 and a denuder length of 0.5 m a nearly quantitative collection efficiency was achieved. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography

  15. Dynamic–gravimetric preparation of metrologically traceable primary calibration standards for halogenated greenhouse gases

    Directory of Open Access Journals (Sweden)

    M. Guillevic

    2018-06-01

    Full Text Available For many years, the comparability of measurements obtained with various instruments within a global-scale air quality monitoring network has been ensured by anchoring all results to a unique suite of reference gas mixtures, also called a primary calibration scale. Such suites of reference gas mixtures are usually prepared and then stored over decades in pressurised cylinders by a designated laboratory. For the halogenated gases which have been measured over the last 40 years, this anchoring method is highly relevant as measurement reproducibility is currently much better ( <  1 %, k  =  2 or 95 % confidence interval than the expanded uncertainty of a reference gas mixture (usually  >  2 %. Meanwhile, newly emitted halogenated gases are already measured in the atmosphere at pmol mol−1 levels, while still lacking an established reference standard. For compounds prone to adsorption on material surfaces, it is difficult to evaluate mixture stability and thus variations in the molar fractions over time in cylinders at pmol mol−1 levels.To support atmospheric monitoring of halogenated gases, we create new primary calibration scales for SF6 (sulfur hexafluoride, HFC-125 (pentafluoroethane, HFO-1234yf (or HFC-1234yf, 2,3,3,3-tetrafluoroprop-1-ene, HCFC-132b (1,2-dichloro-1,1-difluoroethane and CFC-13 (chlorotrifluoromethane. The preparation method, newly applied to halocarbons, is dynamic and gravimetric: it is based on the permeation principle followed by dynamic dilution and cryo-filling of the mixture in cylinders. The obtained METAS-2017 primary calibration scales are made of 11 cylinders containing these five substances at near-ambient and slightly varying molar fractions. Each prepared molar fraction is traceable to the realisation of SI units (International System of Units and is assigned an uncertainty estimate following international guidelines (JCGM, 2008, ranging from 0.6 % for SF6 to 1.3 % (k

  16. Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

    Directory of Open Access Journals (Sweden)

    Anon Namin

    2012-01-01

    Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

  17. UPLC-ESI-MS/MS method for the quantitative measurement of aliphatic diamines, trimethylamine N-oxide, and β-methylamino-l-alanine in human urine.

    Science.gov (United States)

    Bhandari, Deepak; Bowman, Brett A; Patel, Anish B; Chambers, David M; De Jesús, Víctor R; Blount, Benjamin C

    2018-04-15

    This work describes a quantitative high-throughput analytical method for the simultaneous measurement of small aliphatic nitrogenous biomarkers, i.e., 1,6-hexamethylenediamine (HDA), isophoronediamine (IPDA), β-methylamino-l-alanine (BMAA), and trimethylamine N-oxide (TMAO), in human urine. Urinary aliphatic diamines, HDA and IPDA, are potential biomarkers of environmental exposure to their corresponding diisocyanates. Urinary BMAA forms as a result of human exposure to blue-green algae contaminated food. And, TMAO is excreted in urine due to the consumption of carnitine- and choline-rich diets. These urinary biomarkers represent classes of small aliphatic nitrogen-containing compounds (N-compounds) that have a high aqueous solubility, low logP, and/or high basic pK a . Because of the highly polar characteristics, analysis of these compounds in complex sample matrices is often challenging. We report on the development of ion-pairing chemistry based ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS) method for the simultaneous measurement of these biomarkers in human urine. Chromatographic separation was optimized using heptafluorobutyric acid-(HFBA-) based mobile phase and a reversed-phase C18 column. All four analytes were baseline separated within 2.6 min with an overall run time of 5 min per sample injection. Sample preparation involved 4 h of acid hydrolysis followed by automated solid phase extraction (SPE) performed using strong cation exchange sorbent bed with 7 N ammonia solution in methanol as eluent. Limits of detection ranged from 0.05 ng/mL to 1.60 ng/mL. The inter-day and intra-day accuracy were within 10%, and reproducibility within 15%. The method is accurate, fast, and well-suited for biomonitoring studies within targeted groups, as well as larger population-based studies such as the U. S. National Health and Nutrition Examination Survey (NHANES). Published by Elsevier B.V.

  18. Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation.

    Science.gov (United States)

    Le Roux, Julien; Gallard, Hervé; Croué, Jean-Philippe

    2011-05-01

    Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH(2)Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl(2)) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e

  19. Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization.

    Science.gov (United States)

    Kauppila, Tiina J; Haack, Alexander; Kroll, Kai; Kersten, Hendrik; Benter, Thorsten

    2016-03-01

    In a preceding work with dopant assisted-atmospheric pressure photoionization (DA-APPI), an abundant ion at [M + 77](+) was observed in the spectra of pyridine and quinoline with chlorobenzene dopant. This contribution aims to reveal the identity and route of formation of this species, and to systematically investigate structurally related analytes and dopants. Compounds containing N-, O-, and S-lone pairs were investigated with APPI in the presence of fluoro-, chloro-, bromo-, and iodobenzene dopants. Computational calculations on a density functional theory (DFT) level were carried out to study the reaction mechanism for pyridine and the different halobenzenes. The experimental and computational results indicated that the [M + 77](+) ion was formed by nucleophilic aromatic ipso-substitution between the halobenzene radical cation and nucleophilic analytes. The reaction was most efficient for N-heteroaromatic compounds, and it was weakened by sterical effects and enhanced by resonance stabilization. The reaction was most efficient with chloro-, bromo-, and iodobenzenes, whereas with fluorobenzene the reaction was scarcely observed. The calculated Gibbs free energies for the reaction between pyridine and the halobenzenes were shown to increase in the order I < Br < Cl < F. The reaction was found endergonic for fluorobenzene due to the strong C-F bonding, and exergonic for the other halobenzenes. For fluoro- and chlorobenzenes the reaction was shown to proceed through an intermediate state corresponding to [M + dopant](+), which was highly stable for fluorobenzene. For the bulkier bromine and iodine, this intermediate did not exist, but the halogens were shown to detach already during the approach by the nucleophile.

  20. Halogenated and parent polycyclic aromatic hydrocarbons in vegetables: Levels, dietary intakes, and health risk assessments.

    Science.gov (United States)

    Wang, Li; Li, Chunmei; Jiao, Bining; Li, Qiwan; Su, Hang; Wang, Jing; Jin, Fen

    2018-03-01

    Halogenated polycyclic aromatic hydrocarbons (HPAHs) are attracting increasing concern because of their greater toxicity than their corresponding parent PAHs. However, human exposure to HPAHs via food consumption is not fully understood. In this study, daily intake via vegetable ingestion of 11 HPAHs and 16 PAHs and subsequent cancer risk were assessed for population in Beijing. A total of 80 vegetable samples were purchased from markets, including five leafy vegetables and three root vegetables. The concentrations of total HPAHs (∑HPAHs) were 0.357-0.874ng/g in all vegetables, lower than that of total PAHs (∑PAHs, 10.6-47.4ng/g). ∑HPAHs and ∑PAHs concentrations in leafy vegetables were higher than those in root vegetables, suggesting that the atmospheric deposition might be the dominant source of PAHs and HPAHs in leafy vegetables. Among the HPAH congeners, 2-BrFle and 9-ClFle were the predominant compounds and frequently detected in the vegetable samples. HPAHs and PAHs were also found in certificated vegetables at the concentrations of 0.466-0.751ng/g and 10.6-38.9ng/g, respectively, which were lower than those in non-certificated vegetables except for spinach. For leafy vegetables from local farms, the ∑PAHs and ∑HPAHs levels in the rape and Chinese cabbage samples significantly decreased with increasing the distance away from the incineration plant. The incremental lifetime cancer risks of HPAHs were below the acceptable risk level (10 -6 ), suggesting that there might be little or no risk to consumers from these compounds in vegetables. For all population groups, children were the most sensitive population to PAHs and HPAHs, and their health issues should be paid more attention. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation

    KAUST Repository

    Le Roux, Julien

    2011-05-01

    Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH2Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl2) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e

  2. Thermodynamic parameters for binding of some halogenated inhibitors of human protein kinase CK2

    Energy Technology Data Exchange (ETDEWEB)

    Winiewska, Maria; Makowska, Małgorzata [Institute of Biochemistry and Biophysics PAS, Warszawa (Poland); Maj, Piotr [Institute of Biochemistry and Biophysics PAS, Warszawa (Poland); Nencki Institute of Experimental Biology PAS, Warszawa (Poland); Wielechowska, Monika; Bretner, Maria [Warsaw University of Technology, Faculty of Chemistry, Warszawa (Poland); Poznański, Jarosław, E-mail: jarek@ibb.waw.pl [Institute of Biochemistry and Biophysics PAS, Warszawa (Poland); Shugar, David [Institute of Biochemistry and Biophysics PAS, Warszawa (Poland)

    2015-01-02

    Highlights: • Two new compounds being potential human CK2a inhibitors are studied. • Their IC50 values were determined in vitro. • The heats of binding and kbind were estimated using DSC. • The increased stability of protein–ligand complexes was followed by fluorescence. • Methylated TBBt derivative (MeBr3Br) is almost as active as TBBt. - Abstract: The interaction of human CK2α with a series of tetrabromobenzotriazole (TBBt) and tetrabromobenzimidazole (TBBz) analogs, in which one of the bromine atoms proximal to the triazole/imidazole ring is replaced by a methyl group, was studied by biochemical (IC{sub 50}) and biophysical methods (thermal stability of protein–ligand complex monitored by DSC and fluorescence). Two newly synthesized tri-bromo derivatives display inhibitory activity comparable to that of the reference compounds, TBBt and TBBz, respectively. DSC analysis of the stability of protein–ligand complexes shows that the heat of ligand binding (H{sub bind}) is driven by intermolecular electrostatic interactions involving the triazole/imidazole ring, as indicated by a strong correlation between H{sub bind} and ligand pK{sub a}. Screening, based on fluorescence-monitored thermal unfolding of protein–ligand complexes, gave comparable results, clearly identifying ligands that most strongly bind to the protein. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly, relative to possible intermolecular halogen bonding, in binding of the ligands to the CK2α ATP-binding site.

  3. Electrospun Polyurethane Fibers for Absorption of Volatile Organic Compounds from Air

    NARCIS (Netherlands)

    Scholten, E.; Bromberg, L.; Rutledge, G.C.; Hatton, T.A.

    2011-01-01

    Electrospun polyurethane fibers for removal of volatile organic compounds (VOC) from air with rapid VOC absorption and desorption have been developed. Polyurethanes based on 4,4-methylenebis(phenylisocyanate) (MDI) and aliphatic isophorone diisocyanate as the hard segments and butanediol and

  4. Dependence of negative muon depolarization on molecular weight and temperature in organic compounds

    International Nuclear Information System (INIS)

    Djuraev, A.A.; Evseev, V.S.; Obukhov, Yu.V.; Roganov, V.S.

    2009-01-01

    An atomic capture of negative muons in the aliphatic spirit series, the dependence of muon rest polarization on the molecular weight of spirit have been studied. The temperature dependence of depolarization in benzole and styrene has been obtained. The results on depolarization are being interpreted basing on notions about chemical interactions of mesic atoms in organic compounds. (author)

  5. The role of metasomatism in the balance of halogens in ore-forming process at porphyry Cu-Mo deposits

    Science.gov (United States)

    Berzina, A. N.

    2009-04-01

    Volatile components play an important role in the evolution of ore-magmatic systems and their ore potential. Of special interest are fluorine and chlorine compounds that principally control the transportation of ore elements by the fluid in a magmatic process and under high-temperature hydrothermal conditions. Study of the evolution of fluorine-chlorine activity in the ore-forming process and their source is usually based on analysis of their magmatic history, whereas the additional source of fluorine and chlorine released during metasomatic alteration of rocks hosting mineralization is poorly discussed in the existing literature. Based on microprobe data on Cl and F abundances in halogen-containing minerals (biotite, amphibole, apatite, titanite) in intrusive rocks and their hydrothermally altered varieties, the role of metasomatic processes in the balance of volatiles in the ore-forming system is discussed by the example of porphyry Cu-Mo deposits of Siberia (Russia) and Mongolia. Two groups of the deposits are considered: copper-molybdenum (Erdenetiin Ovoo, Mongolia and Aksug, Russia) with prevailing propylitic and phyllic alteration and molybdenum-copper (Sora, Russia), with predominant potassic alteration. All types of hydrothermal alterations have led to drastic decrease in Cl contents in metasomatic minerals as compared with halogen-containing magmatic minerals. All studied deposits (particularly those where propylitic and phyllic alteration were developed) show a nearly complete chlorine removal from altered halogen-containing rock-forming minerals (biotite and amphibole). The Cl content in amphibole decreases several times at the stage of replacement with actinolite in the process of propylitization. In the later chlorites (ripidolite and brunsvigite) that replace amphibole, actinolite, and biotite, chlorine is not detected by microprobe (detection limit 0.01-0.02% Cl). Chlorine was also not detected in white micas (muscovite-phengite series) in quartz

  6. Tuning different kinds of entangled metal-organic frameworks by modifying the spacer group of aliphatic dicarboxylate ligands and the reactant ratio.

    Science.gov (United States)

    Yang, Jin-Xia; Zhai, Ji-Quan; Zhang, Xin; Qin, Ye-Yan; Yao, Yuan-Gen

    2016-01-14

    Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (), {[Cd(fum)(bpp)2]·(H2O)5}n (), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (), {[Cd(suc)(bpp)2]·(H2O)1.5}n (), {[Cd2(glu)2(bpp)3]·10H2O}n (), and {Cd(adp)(bpp)(H2O)}n () have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds and are comprised of undulated 2D 4(4)-sql networks. In the structure of compound , two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For , the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (4(2)·6(3)·8)(4(2)·6) topology. Compound presents an unusual 2D self-threading network with a novel 4-connected {4(2)·6(3)·8} topology. Compound displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of have been examined in the solid state at room temperature.

  7. STRUCTURAL PHASE TRANSITION OF ALIPHATIC NYLONS VIEWED FROM THE WAXD/SAXS AND VIBRATIONAL SPECTRAL MEASUREMENTS AND MOLECULAR DYNAMICS CALCULATION

    Institute of Scientific and Technical Information of China (English)

    Kohji Tashiro

    2007-01-01

    The crystalline phase transition of aliphatic nylon 10/10 has been investigated on the basis of the simultaneous measurement of wide-angle and small-angle X-ray scatterings, the infrared spectral measurement and the molecular dynamics calculation. An interpretation of infrared spectra taken for a series of nylon samples and the corresponding model compounds was successfully made, allowing us to assign the infrared bands of the planar-zigzag methylene segments reasonably. As a result the methylene segmental parts of molecular chains were found to experience an order-to-disorder transition in the Brill transition region, where the intermolecular hydrogen bonds are kept alive although the bond strength becomes weaker at higher temperature. The small-angle X-ray scattering data revealed a slight change in lamellar stacking mode in the transition region. The crystal structure has been found to change more remarkably in the temperature region immediately below the melting point, where the conformationally disordered chains experienced drastic rotational and translational motions without any constraints by hydrogen bonds, and the lamellar thickness increased largely along the chain axis. These experimental results were reasonably reproduced by the molecular dynamics calculation performed at the various temperatures.

  8. Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid.

    Science.gov (United States)

    Reinsch, Helge; Pillai, Renjith S; Siegel, Renée; Senker, Jürgen; Lieb, Alexandra; Maurin, Guillaume; Stock, Norbert

    2016-03-14

    The new aluminium based metal-organic framework [Al(OH)(O2C-C4H8-CO2)]·H2O denoted as Al-MIL-53-ADP-lp (lp stands for large pore) was synthesised under solvothermal conditions. This solid is an analogue of the archetypical aluminium terephthalate Al-MIL-53 based on the aliphatic single-chain linker molecule adipic acid (H2ADP, hexanedioic acid). In contrast to its aromatic counterparts, Al-MIL-53-ADP exhibits a structural breathing behaviour solely upon dehydration/rehydration. The crystal structure of the anhydrous compound denoted as Al-MIL-53-ADP-np (np stands for narrow pore) was determined by a combination of forcefield-based computations and Rietveld refinement of the powder X-ray diffraction data while the structure of the hydrated form Al-MIL-53-ADP-lp was derived computationally by a combination of force field based methods and Density Functional Theory calculations. Both structures were further supported by (1)H, (13)C and (27)Al high-resolution NMR MAS 1D data coupled again with simulations. Al-MIL-53-ADP was further characterised by means of vibrational spectroscopy, elemental analysis, thermogravimetry and water vapour sorption.

  9. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J

    1989-01-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

  10. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    International Nuclear Information System (INIS)

    McKinlay, A.F.; Whillock, M.J.; Meulemans, C.C.E.

    1989-07-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard. (author)

  11. ANTIMICROBIAL REAGENTS AS FUNCTIONAL FINISHING FOR TEXTILES INTENDED FOR BIOMEDICAL APPLICATIONS. I. SYNTHETIC ORGANIC COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Madalina Zanoaga

    2014-06-01

    Full Text Available This article offers an overview of some contemporary antimicrobial (biocides and biostatics agents used as functional finishing for textiles intended for biomedical applications. It reviews only synthetic agents, namely quaternary ammonium compounds, halogenated phenols, polybiguanides, N-halamines, and renewable peroxides, as a part of an extensive study currently in progress.

  12. Ion conducting material, new compounds contained in it, its manufacture and use. Ionenleitermaterial, darin enthaltene neue Verbindungen, ihre Herstellung und Verwendung

    Energy Technology Data Exchange (ETDEWEB)

    Wichelhaus, W; Weppner, W; Hartwig, P

    1980-07-24

    The invention concerns a solid ion conducting material, new compounds and its manufacture and use in the context of a battery. Lithium nitride and lithium halogen compounds are mixed in the required mol ratio under an inert gas, compressed and the compressed substance is quickly heated in a nitrogen atmosphere to 460 to 550/sup 0/C, and then tempered at 350 to 450/sup 0/C until the reaction is finished. The lithium halogen compound and lithium metal can also be mixed in the required mol ratio and heated under nitrogen. Here the required temperature is 150 to 500/sup 0/C. The lithium nitride halogen compounds exist as crystals. They are suitable for use as the electrolyte in batteries. The battery according to the invention contains a lithium or lithium alloy electrode and a positive electrode made of sulphited titanium or molybdenum.

  13. Skin exposure to aliphatic polyisocyanates in the auto body repair and refinishing industry: II. A quantitative assessment.

    Science.gov (United States)

    Bello, Dhimiter; Redlich, Carrie A; Stowe, Meredith H; Sparer, Judy; Woskie, Susan R; Streicher, Robert P; Hosgood, H Dean; Liu, Youcheng

    2008-03-01

    Skin exposure to isocyanates, in addition to respiratory exposures, may contribute to sensitization and asthma. Quantitative skin exposure data are scarce and quantitative methods limited. As part of the Survey of Painters and Repairers of Autobodies by Yale study, a method to sample and quantify human isocyanate skin exposure was developed (based on NIOSH 5525 method) and used to evaluate aliphatic isocyanate skin exposure in 81 auto body shop painters and body technicians. Wipe samples were collected from unprotected skin and from under PPE (gloves, clothing and respirator) using a polypropylene glycol-impregnated wipe. Hexamethylene diisocyanate (HDI), its polyisocyanates [HDI-derived polyisocyanates (pHDI)], isophorone diisocyanate (IPDI) and its polyisocyanates and IPDI-derived polyisocyanates (pIPDI) were quantified separately and also expressed as the total free isocyanate groups (total NCO). For unprotected skin areas, 49 samples were collected for spray painting, 13 for mixing, 27 for paint-related tasks (e.g. sanding and compounding) and 53 for non-paint-related tasks. Forty-three samples were also collected under PPE. The geometric mean (GM) [geometric standard deviation (GSD)] total NCO concentrations (ng NCO cm(-2)) for unprotected skin (hands, face and forearms) was 1.9 (10.9) and range 0.0-64.4. pHDI species were the major contributor to the total NCO content. Levels were very variable, with the highest concentrations measured for clear coating and paint mixing tasks. Isocyanate skin exposure was also commonly detected under PPE, with 92% of samples above the limit of detection. Levels were very variable with the overall GM (GSD) total NCO (ng NCO cm(-2)) under PPE 1.0 (5.2) and range (0.0-47.0) and similar under the different PPE (glove, respirator and clothing). The highest concentrations were detected for mixing and spraying tasks, 6.9 (5.3) and 1.0 (5.2), respectively. Levels under PPE were generally lower than unpaired samples obtained with no

  14. First-principles studies on the effects of halogen adsorption on monolayer antimony.

    Science.gov (United States)

    Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

    2017-09-27

    Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

  15. Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts

    International Nuclear Information System (INIS)

    Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

    2015-01-01

    Halogenated nitrogenous disinfection byproducts (N-DBPs) raise concerns regarding their mutagenicity and carcinogenicity threatening public health. However, environmental consequence of their mutagenicity has received less attention. In this study, the effect of halogenated N-DBPs on bacterial antibiotic resistance (BAR) was investigated. After exposure to bromoacetamide (BAcAm), trichloroacetonitrile (TCAN) or tribromonitromethane (TBNM), the resistance of Pseudomonas aeruginosa PAO1 to both individual and multiple antibiotics (ciprofloxacin, gentamicin, polymyxin B, rifampin, tetracycline, ciprofloxacin + gentamicin and ciprofloxacin + tetracycline) was increased, which was predominantly ascribed to the overexpression of efflux pumps. The mechanism of this effect was demonstrated to be mutagenesis through sequencing and analyzing antibiotic resistance genes. The same induction phenomena also appeared in Escherichia coli, suggesting this effect may be universal to waterborne pathogens. Therefore, more attention should be given to halogenated N-DBPs, as they could increase not only genotoxicological risks but also epidemiological risks of drinking water. - Highlights: • The halogenated N-DBPs could induce bacterial antibiotic resistance. • Both individual and multiple resistances could be induced. • Efflux mechanism played an important role in the induced antibiotic resistance. • The halogenated N-DBPs induced bacterial antibiotic resistance via mutagenesis. • Effects of N-DBPs on antibiotic resistance may be universal to waterborne pathogens. - Halogenated N-DBPs could increase antibiotic resistance, even multidrug resistance via mutagenesis, contributing to the enrichment of antibiotic resistant bacteria in drinking water

  16. Evaluation of remaining behavior of halogen on the fabrication of MOX pellet containing Am

    International Nuclear Information System (INIS)

    Ozaki, Yoko; Osaka, Masahiko; Obayashi, Hiroshi; Tanaka, Kenya

    2004-11-01

    It is important to limit the content of halogen elements, namely fluorine and chlorine that are sources of making cladding material corrode, in nuclear fuel from the viewpoint of quality assurance. The halogen content should be more carefully limited in the MOX fuel containing Americium (Am-MOX), which is fabricated in the Alpha-Gamma Facility (AGF) for irradiation testing to be conducted in the experimental fast reactor JOYO, because fluorine may remain in the sintered pellets owing to a formation of AmF 3 known to have a low vapor pressure and may exceeds the limit of 25 ppm. In this study, a series of experimental determination of halogen element in Am-MOX were performed by a combination method of pyrolysis and ion-chromatography for the purpose of an evaluation of behavior of remaining halogen through the sintering process. Oxygen potential, temperature and time were changed as experimental parameters and their effects on the remaining behavior of halogen were examined. It was confirmed that good pellets, which contained small amount of halogen, could be obtained by the sintering for 3 hour at 1700degC in the oxygen potential range from -520 to -390 kJ/mol. In order to analysis of fluorine chemical form in green pellet, thermal analysis was performed. AmF 3 and PuF 3 have been confirmed to remain in the green pellet. (author)

  17. Measurements of activity coefficients at infinite dilution of aromatic and aliphatic hydrocarbons, alcohols, and water in the new ionic liquid [EMIM][SCN] using GLC

    International Nuclear Information System (INIS)

    Domanska, Urszula; Marciniak, Andrzej

    2008-01-01

    A new ionic liquid was chosen for the separation of aromatic hydrocarbons from aliphatic hydrocarbons. The activity coefficients at infinite dilution, γ 13 ∞ for 29 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, and water in the ionic liquid 1-ethyl-3-methyl-imidazolium thiocyanate [EMIM][SCN] were determined by gas-liquid chromatography at the temperatures from 298.15 K to 368.15 K. The values of the partial molar excess enthalpies at infinite dilution ΔH 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The selectivities for the hexane/benzene and cyclohexane/benzene separation problems were calculated from the γ 13 ∞ and compared to the other ionic liquids, NMP and sulfolane, taken from the recent literature. This work demonstrates that with chosen ionic liquid it is possible to separate different organic compounds with the highest selectivity ever published

  18. Use of halide transport in epitaxial growth of InP and related compounds

    Energy Technology Data Exchange (ETDEWEB)

    Somogyi, K. [Hungarian Academy of Sciences, Budapest (Hungary). Research Inst. for Technical Physics

    1996-12-31

    In this paper methods and results in the InP (and related) growth practice are reviewed, classified and summarized on the basis of the recent literature. The aim is to show the present place and role of the halogen transport in the epitaxial growth. In the case of InP the importance of the classical hydride method is still high. Though MOVPE technique dominates in the case of growth of the compounds with In content, atomic layer epitaxy and selective area growth are successful with auxiliary application of the halogen transport. Chlorine assisted MOVPE has an increasing role.

  19. The ozonolysis of primary aliphatic amines in fine particles

    Science.gov (United States)

    Zahardis, J.; Geddes, S.; Petrucci, G. A.

    2008-02-01

    The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3- (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

  20. The ozonolysis of primary aliphatic amines in fine particles

    Directory of Open Access Journals (Sweden)

    J. Zahardis

    2008-02-01

    Full Text Available The oxidative processing by ozone of the particulate amines octadecylamine (ODA and hexadecylamine (HDA is reported. Ozonolysis of these amines resulted in strong NO2 and NO3 ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3 (HNO3. For ozonized mixed particles containing ODA or HDA + oleic acid (OL, with pO3≥3×10–7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines and stabilized Criegee intermediates (SCI or secondary ozonides (for amides from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10−3 atm for 17 s. This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3, formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

  1. Anthropogenic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Hutzinger, O

    1982-01-01

    The chapters about lead and arsenic, beryllium, selenium and vanadium describe production, use and natural occurrence, chemistry, analytical methods, transport behavior in the environment, physical, chemical and photochemical reactions, metabolism, exposure and accumulation and toxicity. The chapter of C/sub 1/ and C/sub 2/ halocarbons deals with use patterns and losses to the environment, occurrence in the environment, distribution and degradation and effects on living organisms. The chapter of halogenated aromatics treats production and properties, uses and losses to and occurrence in the environment, distribution and degradation in the environment, effects on biological systems. The chapter of volatile aromatics involves production and emissions, concentration in the environment, metabolism and biological effects in mammals. The chapter on surfactants is divided in two parts: chemistry and environment.

  2. Colorless triphenylamine-based aliphatic thermoset epoxy for multicolored and near-infrared electrochromic applications.

    Science.gov (United States)

    Chuang, Ya-Wen; Yen, Hung-Ju; Wu, Jia-Hao; Liou, Guey-Sheng

    2014-03-12

    In this study, two novel colorless thermoset epoxy resins with anodically electrochromism were prepared from the thermal curing of two triphenylamine-based diamine monomers, 4,4'-diamino-4″-methoxytriphenylamine (1) and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine (2) with aliphatic epoxy triglycidyl isocyanurate, respectively. The resulting thermoset epoxy resins showed excellent softening temperature (Ts, 270 and 280 °C) due to the rigid structure and highly crosslinking density. In addition, novel colorless epoxy resin films revealed good reversible electrochemical oxidation and interesting multi-electrochromic behavior with high contrast ratio both in visible and near-infrared regions. The aliphatic thermoset epoxy resins also exhibited high transparency in visible region as colorless and great potential for practical electrochromic applications.

  3. Oxyfunctionalization of the Remote C-H Bonds of Aliphatic Amines by Decatungstate Photocatalysis.

    Science.gov (United States)

    Schultz, Danielle M; Lévesque, François; DiRocco, Daniel A; Reibarkh, Mikhail; Ji, Yining; Joyce, Leo A; Dropinski, James F; Sheng, Huaming; Sherry, Benjamin D; Davies, Ian W

    2017-11-27

    Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H 2 O 2 or O 2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  5. Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT): Overview of a wintertime air chemistry field study in the front range urban corridor of Colorado

    Science.gov (United States)

    Brown, Steven S.; Thornton, Joel A.; Keene, William C.; Pszenny, Alexander A. P.; Sive, Barkley C.; Dubé, William P.; Wagner, Nicholas L.; Young, Cora J.; Riedel, Theran P.; Roberts, James M.; VandenBoer, Trevor C.; Bahreini, Roya; Öztürk, Fatma; Middlebrook, Ann M.; Kim, Saewung; Hübler, Gerhard; Wolfe, Daniel E.

    2013-07-01

    The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) field experiment took place during late winter, 2011, at a site 33 km north of Denver, Colorado. The study included fixed-height measurements of aerosols, soluble trace gases, and volatile organic compounds near surface level, as well as vertically resolved measurements of nitrogen oxides, aerosol composition, soluble gas-phase acids, and halogen species from 3 to 270 m above ground level. There were 1928 individual profiles during the three-week campaign to characterize trace gas and aerosol distributions in the lower levels of the boundary layer. Nitrate and ammonium dominated the ionic composition of aerosols and originated primarily from local or regional sources. Sulfate and organic matter were also significant and were associated primarily with longer-range transport to the region. Aerosol chloride was associated primarily with supermicron size fractions and was always present in excess of gas-phase chlorine compounds. The nighttime radical reservoirs, nitryl chloride, ClNO2, and nitrous acid, HONO, were both consistently present in nighttime urban air. Nitryl chloride was especially pronounced in plumes from large point sources sampled aloft at night. Nitrous acid was typically most concentrated near the ground surface and was the dominant contributor (80%) to diurnally averaged primary OH radical production in near-surface air. Large observed mixing ratios of light alkanes, both in near-surface air and aloft, were attributable to local emissions from oil and gas activities.

  6. Extraction-spectrophotometric determination of purine alkaloids in water solutions using aliphatic alcohols

    Directory of Open Access Journals (Sweden)

    Y. I. Korenman

    2012-01-01

    Full Text Available For extraction of caffeine, theobromin and theophylline from water solutions are applied aliphatic alcohols С3 – С9. Water concentrates analyzed method UF- spectrophotometry. Factors of distribution and extraction degree are calculated. Influence of length of a hydrocarbonic radical in a solvent and nature olecule salting-out agent on interphase distribution of alkaloids is studied. Dependence of quantitative characteristics extraction from number active groups in structure alkaloids is established.

  7. The effect of mechanical loads on the degradation of aliphatic biodegradable polyesters.

    Science.gov (United States)

    Li, Ying; Chu, Zhaowei; Li, Xiaoming; Ding, Xili; Guo, Meng; Zhao, Haoran; Yao, Jie; Wang, Lizhen; Cai, Qiang; Fan, Yubo

    2017-06-01

    Aliphatic biodegradable polyesters have been the most widely used synthetic polymers for developing biodegradable devices as alternatives for the currently used permanent medical devices. The performances during biodegradation process play crucial roles for final realization of their functions. Because physiological and biochemical environment in vivo significantly affects biodegradation process, large numbers of studies on effects of mechanical loads on the degradation of aliphatic biodegradable polyesters have been launched during last decades. In this review article, we discussed the mechanism of biodegradation and several different mechanical loads that have been reported to affect the biodegradation process. Other physiological and biochemical factors related to mechanical loads were also discussed. The mechanical load could change the conformational strain energy and morphology to weaken the stability of the polymer. Besides, the load and pattern could accelerate the loss of intrinsic mechanical properties of polymers. This indicated that investigations into effects of mechanical loads on the degradation should be indispensable. More combination condition of mechanical loads and multiple factors should be considered in order to keep the degradation rate controllable and evaluate the degradation process in vivo accurately. Only then can the degradable devise achieve the desired effects and further expand the special applications of aliphatic biodegradable polyesters.

  8. Distribution of aliphatic and polycyclic aromatic hydrocarbon in South China sea sediments

    International Nuclear Information System (INIS)

    Md Suhaimi Elias; Ab Khalik Wood; Zaleha Hashim; Wee Boon Siong; Nazaratul Ashifa; Mohd Suhaimi Hamzah; Shamsiah Ab Rahman; Ariffin Talib

    2006-01-01

    Petroleum hydrocarbon (Hcp) consist of three major components namely alkanes, cyclo-alkanes and aromatics. HCP are pollutant and can cause adverse effect to the marine organisms. The study was done to identify the source of pollution in the South China Sea coastal area. The South China Sea is one of the major oil production area in Malaysia. Sampling was done at 15 stations along the coastal area of South China Sea off Peninsular Malaysia, which involved two zone namely coastal (zone 1) and offshore (zone 2) areas. Samples were analyzed using GC-MS for determination of HCP. The results showed, that concentration of aliphatic and polycyclic aromatic hydrocarbon at coastal area, range from 0.51 - 1.31 mg/g and 0.18 - 0.42 mg/g dry weight, respectively whilst, concentration of aliphatic and polycyclic aromatic hydrocarbon at offshore area, range from 0.44 - 1.09 mg/g and 0.20 - 0.49 mg/g dry weight, respectively. SHCP (Aliphatic + PAH) concentration in the sediment at the study area range from 0.64 - 1.68 mg/g dry weight. In this study, it was found that, pollution source for the South China Sea off Peninsular Malaysia was originated from pyrolytic sources (combustion fossil fuel), while some other area had been polluted by pyrolytic or petrogenic (unburned fossil) sources. (Author)

  9. Sea ice dynamics influence halogen deposition to Svalbard

    Directory of Open Access Journals (Sweden)

    A. Spolaor

    2013-10-01

    Full Text Available Sea ice is an important parameter in the climate system and its changes impact upon the polar albedo and atmospheric and oceanic circulation. Iodine (I and bromine (Br have been measured in a shallow firn core drilled at the summit of the Holtedahlfonna glacier (Northwest Spitsbergen, Svalbard. Changing I concentrations can be linked to the March–May maximum sea ice extension. Bromine enrichment, indexed to the Br / Na sea water mass ratio, appears to be influenced by changes in the seasonal sea ice area. I is emitted from marine biota and so the retreat of March–May sea ice coincides with enlargement of the open-ocean surface which enhances marine primary production and consequent I emission. The observed Br enrichment could be explained by greater Br emissions during the Br explosions that have been observed to occur mainly above first year sea ice during the early springtime. In this work we present the first comparison between halogens in surface snow and Arctic sea ice extension. Although further investigation is required to characterize potential depositional and post-depositional processes, these preliminary findings suggest that I and Br can be linked to variability in the spring maximum sea ice extension and seasonal sea ice surface area.

  10. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  11. Halogenated source gases measured by FTIR at the Jungfraujoch station: updated trends and new target species

    Science.gov (United States)

    Mahieu, Emmanuel; Bader, Whitney; Bovy, Benoît; Franco, Bruno; Lejeune, Bernard; Servais, Christian; Notholt, Justus; Palm, Mathias; Toon, Geoffrey C.

    2015-04-01

    The atmospheric abundances of chlorine and fluorine increased very significantly during the second half of last century, following large emissions of long-lived halogenated source gases used in numerous industrial and domestic applications. Given the phase-out schedule of ozone depleting substances adopted by the Montreal Protocol, its Amendments and Adjustments, the loading of the CFCs in the Earth's atmosphere is now slowly decreasing. In contrast, their first replacement products, the HCFCs, are still on the rise, with current rates of increase substantially larger than at the beginning of the 21st century. As potent greenhouse gases, a suite of fluorinated compounds are targeted by the Kyoto Protocol. At present, they continue to accumulate in the atmosphere (Montzka et al., 2011). Given their environmental impacts, continuous monitoring of the abundances of these gases is of primary importance. In addition to the in situ networks, remote sensing techniques operated from space, balloon or from the ground provide valuable information to assess the long-term tropospheric and lower stratospheric trends of an increasing number of halogenated source gases, as well as of the reservoirs resulting from their photolysis in the stratosphere (e.g. Mahieu et al., 2014a). In this contribution, we will present decadal time series of halogenated source gases monitored at the high altitude station of the Jungfraujoch (46.5° N, 8° E, 3580 m asl) with Fourier Transform Infared (FTIR) spectrometers, within the framework of the Network for the Detection of Atmospheric Composition Change (NDACC, see http://www.ndacc.org). Total column trends presented in previous studies for CFC-11, -12 and HCFC-22 (Zander at al., 2008), CCl4 (Rinsland et al., 2012), HCFC-142b (Mahieu et al., 2013), CF4 (Mahieu et al., 2014b) and SF6 (Zander et al., 2008) will be updated using the latest available Jungfraujoch solar observations. Investigations dealing with the definition of approaches to

  12. Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

    Science.gov (United States)

    Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

    2016-09-01

    Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Behaviour of antimony during thermal treatment of Sb-rich halogenated waste

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J. [Laboratoire Gestion des Risques et Environnement, 25 rue de Chemnitz, 68200 Mulhouse (France); Dorge, S., E-mail: sophie.dorge@uha.fr [Laboratoire Gestion des Risques et Environnement, 25 rue de Chemnitz, 68200 Mulhouse (France); Trouve, G. [Laboratoire Gestion des Risques et Environnement, 25 rue de Chemnitz, 68200 Mulhouse (France); Venditti, D.; Durecu, S. [TREDI Departement de Recherche, Technopole de Nancy-Brabois, 9 avenue de la Foret de Haye, BP 184, 54505 Vandoeuvre-les-Nancy (France)

    2009-07-30

    Antimony compounds have a wide range of industrial applications, particularly as additives in flame retardants. To ensure environmentally friendly waste incineration of Sb-rich wastes, it is essential to strengthen the knowledge about the fate of antimony and the potential formation of harmful species. Investigations should be conducted particularly in relation with the main operational parameters controlling the process, chiefly temperature, residence time and air supply in the oven and in the post-combustion zone, prior final adapted cleaning of the flue-gas stream. Experimental studies focusing on antimony behaviour were undertaken through laboratory-scale thermal treatment at 850 deg. C and 1100 deg. C of a Sb-rich halogenated waste, originating from the sector of flame retardants formulation. The configuration of our laboratory experimental device allowed to achieve only low oxidative conditions in the waste bed, but high oxidative strength coupled with high temperature and sufficient gas residence time in the post-combustion zone, as prescribed during the incineration of hazardous wastes. Atomic absorption spectroscopy was used to assess the partition of antimony in the different compartments of the process. The oxidation degree of antimony in the gas-phase was determined by the use of electrochemical techniques, namely polarography coupled with anodic stripping voltamperometry. The partition of antimony between the residual ash and the gas-phase under moderate oxidative conditions in the waste bed was constant, whatever the temperature: the volatilization rate for antimony was {approx}64%, while a {approx}36% fraction remained in the residual bottom ashes. But interestingly, while at 850 {sup o}C, antimony was mainly present in the gas-phase at a +III oxidation degree, an increase in temperature of 250 {sup o}C favoured the presence of antimony to its highest oxidation degree +V in the flue-gas stream, a valence known to be involved in less toxic species.

  14. Behaviour of antimony during thermal treatment of Sb-rich halogenated waste

    International Nuclear Information System (INIS)

    Klein, J.; Dorge, S.; Trouve, G.; Venditti, D.; Durecu, S.

    2009-01-01

    Antimony compounds have a wide range of industrial applications, particularly as additives in flame retardants. To ensure environmentally friendly waste incineration of Sb-rich wastes, it is essential to strengthen the knowledge about the fate of antimony and the potential formation of harmful species. Investigations should be conducted particularly in relation with the main operational parameters controlling the process, chiefly temperature, residence time and air supply in the oven and in the post-combustion zone, prior final adapted cleaning of the flue-gas stream. Experimental studies focusing on antimony behaviour were undertaken through laboratory-scale thermal treatment at 850 deg. C and 1100 deg. C of a Sb-rich halogenated waste, originating from the sector of flame retardants formulation. The configuration of our laboratory experimental device allowed to achieve only low oxidative conditions in the waste bed, but high oxidative strength coupled with high temperature and sufficient gas residence time in the post-combustion zone, as prescribed during the incineration of hazardous wastes. Atomic absorption spectroscopy was used to assess the partition of antimony in the different compartments of the process. The oxidation degree of antimony in the gas-phase was determined by the use of electrochemical techniques, namely polarography coupled with anodic stripping voltamperometry. The partition of antimony between the residual ash and the gas-phase under moderate oxidative conditions in the waste bed was constant, whatever the temperature: the volatilization rate for antimony was ∼64%, while a ∼36% fraction remained in the residual bottom ashes. But interestingly, while at 850 o C, antimony was mainly present in the gas-phase at a +III oxidation degree, an increase in temperature of 250 o C favoured the presence of antimony to its highest oxidation degree +V in the flue-gas stream, a valence known to be involved in less toxic species.

  15. Relationship between centrifugation and drying of sludge and the organic halogens

    Directory of Open Access Journals (Sweden)

    Karel Hrich

    2010-01-01

    Full Text Available This work is focused on determination of adsorbable organic halogens (AOX concentration in the digested sludge from the sewage treatment plant and the losses of this component during dewatering and drying of sludge. Drying of the sludge from wastewater treatment plant is not extended too much in Czech Republic. In this work, the AOX are monitored, because AOX is one of the limits restraining use of the sludge on an agricultural land. Another reason is technological demand for using the sludge in cement processing, because chlorine in AOX can cause decrease in a heat transfer effect in a cement kiln. It is clear from the results that both centrifuged and dried sludge from the sewage treatment plant Brno fulfilled limits for using sludge on agriculture land. They can also be composted, in case they meet other requirements. If not, it is a possibility of co-incineration in cement kiln. In such case, limit for total chlorine including the AOX is required too. This limit was not exceeded. Another aim was to calculate a mass balance of AOX during the centrifugation and drying processes. It was found out, that after centrifugation the main part of AOX remained in the centrifuged sludge (96.4 %. The rest was drawn-off with reject water. 60 % of AOX in the reject water were dissolved compounds. A similar situation occurred during the drying process. More than 99 % of AOX was bound in the dried sludge. The air and vaporised water contained such quantity of AOX, which corresponded with the amount of the dust in the air and the amount of particles of sludge in vaporised water.

  16. Algae form brominated organic compounds in surface waters

    Energy Technology Data Exchange (ETDEWEB)

    Huetteroth, A; Putschew, A; Jekel, M [Tech. Univ. Berlin (Germany)

    2004-09-15

    Monitoring of organic halogen compounds, measured as adsorbable organic bromine (AOBr) revealed seasonal high concentrations of organic bromine compounds in a surface water (Lake Tegel, Berlin, Germany). Usually, in late summer, concentrations are up to five times higher than during the rest of the year. The AOBr of the lake inflows (throughout the year less then 6 {mu}g/L) were always lower then those in the lake, which indicates a production of AOBr in the lake. A correlation of the AOBr and chlorophyll-a concentration (1) in the lake provides first evidence for the influence of phototrophic organisms. The knowledge of the natural production of organohalogens is relatively recent. Up to now there are more then 3800 identified natural organohalogen compounds that have been detected in marine plants, animals, and bacteria and also in terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and humans. Halogenated organic compounds are commonly considered to be of anthropogenic origin; derived from e.g. pharmaceuticals, herbicides, fungicides, insecticides, flame retardants, intermediates in organic synthesis and solvents. Additionally they are also produced as by-products during industrial processes and by waste water and drinking water disinfection. Organohalogen compounds may be toxic, persistent and/or carcinogenic. In order to understand the source and environmental relevance of naturally produced organobromine compounds in surface waters, the mechanism of the formation was investigated using batch tests with lake water and algae cultures.

  17. Scientific Opinion on the safety and efficacy of straight-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing saturated alcohols and acetals containing saturated aldehydes (chemical group 1) when used as flavourings for all animal species

    OpenAIRE

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP)

    2013-01-01

    Chemical group 1 (CG 1) consists of straight-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing saturated alcohols and acetals containing saturated aldehydes of which 86 are currently authorised for use as flavours in food. The FEEDAP Panel was unable to perform an assessment of ethyl oleate because of its insufficient purity. The following compounds are considered to be safe for all animal species at the use level proposed for feed flavourings: formic...

  18. Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

    Science.gov (United States)

    Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

    2015-10-20

    Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.

  19. Biodegradable compounds: Rheological, mechanical and thermal properties

    Science.gov (United States)

    Nobile, Maria Rossella; Lucia, G.; Santella, M.; Malinconico, M.; Cerruti, P.; Pantani, R.

    2015-12-01

    Recently great attention from industry has been focused on biodegradable polyesters derived from renewable resources. In particular, PLA has attracted great interest due to its high strength and high modulus and a good biocompatibility, however its brittleness and low heat distortion temperature (HDT) restrict its wide application. On the other hand, Poly(butylene succinate) (PBS) is a biodegradable polymer with a low tensile modulus but characterized by a high flexibility, excellent impact strength, good thermal and chemical resistance. In this work the two aliphatic biodegradable polyesters PBS and PLA were selected with the aim to obtain a biodegradable material for the industry of plastic cups and plates. PBS was also blended with a thermoplastic starch. Talc was also added to the compounds because of its low cost and its effectiveness in increasing the modulus and the HDT of polymers. The compounds were obtained by melt compounding in a single screw extruder and the rheological, mechanical and thermal properties were investigated. The properties of the two compounds were compared and it was found that the values of the tensile modulus and elongation at break measured for the PBS/PLA/Talc compound make it interesting for the production of disposable plates and cups. In terms of thermal resistance the compounds have HDTs high enough to contain hot food or beverages. The PLA/PBS/Talc compound can be, then, considered as biodegradable substitute for polystyrene for the production of disposable plates and cups for hot food and beverages.

  20. Analysis of Halogen-Mercury Reactions in Flue Gas

    Energy Technology Data Exchange (ETDEWEB)

    Paula Buitrago; Geoffrey Silcox; Constance Senior; Brydger Van Otten

    2010-01-01

    Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using a wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation

  1. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Science.gov (United States)

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  2. Influence of the Chemical Structure on Odor Qualities and Odor Thresholds of Halogenated Guaiacol-Derived Odorants

    Directory of Open Access Journals (Sweden)

    Florian Juhlke

    2017-12-01

    Full Text Available Chlorinated guaiacol derivatives are found in waste water of pulp mills using chlorine in the bleaching process of wood pulp. They can also be detected in fish tissue, possibly causing off-odors. To date, there is no systematic investigation on the odor properties of halogenated guaiacol derivatives. To close this gap, odor thresholds in air and odor qualities of 14 compounds were determined by gas chromatography-olfactometry. Overall, the investigated compounds elicited smells that are characteristic for guaiacol, namely smoky, sweet, vanilla-like, but also medicinal and plaster-like. Their odor thresholds in air were, however, very low, ranging from 0.00072 to 23 ng/Lair. The lowest thresholds were found for 5-chloro- and 5-bromoguaiacol, followed by 4,5-dichloro- and 6-chloroguaiacol. Moreover, some inter-individual differences in odor threshold values could be observed, with the highest variations having been recorded for the individual values of 5-iodo- and 4-bromoguaiacol.

  3. Simultaneous determination of radioactive halogen isotopes and 99Tc

    International Nuclear Information System (INIS)

    Kabai, E.; Vajda, N.; Gaca, P.

    2003-01-01

    The purpose of this study was to develop a simplified method for simultaneous determination of radiologically important halogen isotopes and 99 Tc from different types of samples like environmental, biological and waste samples. Due to their long half-lives (longer than 10 5 years) they play important role in the nuclear cycle, especially in environmental monitoring and protection. For a rapid response in the evaluation of 129 I, 36 Cl and 99 Tc contamination levels of these samples it is advantageous to combine the existing individual methods. According to the present procedure, iodine, chlorine and technetium are separated selectively from the same sample aliquot followed by the β spectrometry of the purified fractions. Increased sensitivities can be achieved by neutron activation (NA) especially in the case of 129 I. Our work intends to solve the problem by combining the well-known hot acidic distillation method for iodine separation with the organic extraction process characteristic for technetium separation. The major objective of the work was to separate the disturbing halides from iodine. For this purpose a selective oxidant was applied. For the sample destruction and fractionated distillation an air flow-through installation was used with hot concentrated sulphuric and nitric acids. The trap for iodine contained 3 M NaOH solution. After iodine separation the trap was exchanged for a new one containing the same solution for trapping chlorine or bromine with an addition of 0.01 M KMnO 4 solution as an oxidative agent. As expected, the main part of technetium was contained in the acidic residue after distillation. Tc purification was performed by organic extraction with TBP and TEVA column. (author)

  4. 13C separation by IRMPD of halogenated difluoromethanes

    International Nuclear Information System (INIS)

    Ma Peihua; Chen Guancheng; Wu Bin; Liu Julin; Jing Yan; Chu Minxiong; Arai, Shigeyoshi.

    1995-01-01

    Isotopically-selective consecutive two-stage infrared multiphoton dissociation (IRMPD) of halogenated difluoromethanes in the presence of scavengers produces carbon-13 over 95 %. The reaction mechanism for the IRMPD of mixture of CHClF 2 and HI can be explained by a series of first-order dissociation reactions and followed radical-scavenger reactions occurred in a continuous irradiation procedure. Furthermore, 13 C enrichment at laboratory scaling-up level by the 13 C selective IRMPD of CHClF 2 /Br 2 mixture has been investigated in a flow reactor. The 13 C production rates, 13 C atomic fractions in the CBr 2 F 2 products and 13 C depletions in the CHClF 2 reactants at different flow rates and laser repetition frequencies were examined to optimize the parameters suitable for large-scale production of carbon isotope. The data obtained from the flow tests demonstrated a 40 mg h -1 production rate for CB 2 F 2 at 65 % carbon-13 by using a 40 W (4J, 10 Hz) laser beam focused with a lens of focal length 120 cm. If a reliable TEA CO 2 laser can be operated with 100 W (10 J, 10 Hz) output, the production rate of CBr 2 F 2 for carbon-13 at 60 % can attain 200 mg h -1 . The measurements of spatial profile of focused laser beam imply a 2 g h -1 production rate for the 60 % carbon-13 product for an incident power of 200 W (20 J, 10 Hz). (author)

  5. Biosynthesis of polybrominated aromatic organic compounds by marine bacteria

    Science.gov (United States)

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

    2014-01-01

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

  6. Screening halogenated environmental contaminants in biota based on isotopic pattern and mass defect provided by high resolution mass spectrometry profiling

    Energy Technology Data Exchange (ETDEWEB)

    Cariou, Ronan, E-mail: laberca@oniris-nantes.fr; Omer, Elsa; Léon, Alexis; Dervilly-Pinel, Gaud; Le Bizec, Bruno

    2016-09-14

    In the present work, we addressed the question of global seeking/screening organohalogenated compounds in a large panel of complex biological matrices, with a particular focus on unknown chemicals that may be considered as potential emerging hazards. A fishing strategy was developed based on untargeted profiling among full scan acquisition datasets provided by high resolution mass spectrometry. Since large datasets arise from such profiling, filtering useful information stands as a central question. In this way, we took advantage of the exact mass differences between Cl and Br isotopes. Indeed, our workflow involved an innovative Visual Basic for Applications script aiming at pairing features according to this mass difference, in order to point out potential organohalogenated clusters, preceded by an automated peak picking step based on the centWave function (xcms package of open access R programming environment). Then, H/Cl-scale mass defect plots were used to visualize the datasets before and after filtering. The filtering script was successfully applied to a dataset generated upon liquid chromatography coupled to ESI(−)-HRMS measurement from one eel muscle extract, allowing for realistic manual investigations of filtered clusters. Starting from 9789 initial obtained features, 1994 features were paired in 589 clusters. Hexabromocyclododecane, chlorinated paraffin series and various other compounds have been identified or tentatively identified, allowing thus broad screening of organohalogenated compounds in this extract. Although realistic, manual review of paired clusters remains time consuming and much effort should be devoted to automation. - Highlights: • We address the screening of halogenated compounds in large Full Scan HRMS datasets. • The workflow involves peak picking, pairing script and review of paired features. • The pairing script is based on exact mass differences between Cl and Br isotopes. • H/Cl scale mass defect plots are used to

  7. Screening halogenated environmental contaminants in biota based on isotopic pattern and mass defect provided by high resolution mass spectrometry profiling

    International Nuclear Information System (INIS)

    Cariou, Ronan; Omer, Elsa; Léon, Alexis; Dervilly-Pinel, Gaud; Le Bizec, Bruno

    2016-01-01

    In the present work, we addressed the question of global seeking/screening organohalogenated compounds in a large panel of complex biological matrices, with a particular focus on unknown chemicals that may be considered as potential emerging hazards. A fishing strategy was developed based on untargeted profiling among full scan acquisition datasets provided by high resolution mass spectrometry. Since large datasets arise from such profiling, filtering useful information stands as a central question. In this way, we took advantage of the exact mass differences between Cl and Br isotopes. Indeed, our workflow involved an innovative Visual Basic for Applications script aiming at pairing features according to this mass difference, in order to point out potential organohalogenated clusters, preceded by an automated peak picking step based on the centWave function (xcms package of open access R programming environment). Then, H/Cl-scale mass defect plots were used to visualize the datasets before and after filtering. The filtering script was successfully applied to a dataset generated upon liquid chromatography coupled to ESI(−)-HRMS measurement from one eel muscle extract, allowing for realistic manual investigations of filtered clusters. Starting from 9789 initial obtained features, 1994 features were paired in 589 clusters. Hexabromocyclododecane, chlorinated paraffin series and various other compounds have been identified or tentatively identified, allowing thus broad screening of organohalogenated compounds in this extract. Although realistic, manual review of paired clusters remains time consuming and much effort should be devoted to automation. - Highlights: • We address the screening of halogenated compounds in large Full Scan HRMS datasets. • The workflow involves peak picking, pairing script and review of paired features. • The pairing script is based on exact mass differences between Cl and Br isotopes. • H/Cl scale mass defect plots are used to

  8. Reactive and organic halogen species in three different European coastal environments

    Directory of Open Access Journals (Sweden)

    C. Peters

    2005-01-01

    Full Text Available We present results of three field campaigns using active longpath DOAS (Differential Optical Absorption Spectroscopy for the study of reactive halogen species (RHS BrO, IO, OIO and I2. Two recent field campaigns took place in Spring 2002 in Dagebüll at the German North Sea Coast and in Spring 2003 in Lilia at the French Atlantic Coast of Brittany. In addition, data from a campaign in Mace Head, Ireland in 1998 was partly re-evaluated. During the recent field campaigns volatile halogenated organic compounds (VHOCs were determined by a capillary gas chromatograph coupled with an electron capture detector and an inductively coupled plasma mass spectrometer (GC/ECD-ICPMS in air and water. Due to the inhomogeneous distribution of macroalgae at the German North Sea Coast we found a clear connection between elevated levels of VHOCs and the appearance of macroalgae. Extraordinarily high concentrations of several VHOCs, especially CH3I and CH3Br of up to 1830 pptv and 875 pptv, respectively, were observed at the coast of Brittany, demonstrating the outstanding level of bioactivity there. We found CH2I2 at levels of up to 20 pptv, and a clear anti-correlation with the appearance of IO. The IO mixing ratio reached up to 7.7±0.5 ppt(pmol/mol during the day, in reasonable agreement with model studies designed to represent the meteorological and chemical conditions in Brittany. For the two recent campaigns the DOAS spectra were evaluated for BrO, OIO and I2, but none of these species could be clearly identified (average detection limits around 2 ppt, 3 ppt, 20 ppt, resp., significantly higher in individual cases. Only in the Mace Head spectra evidence was found for the presence of OIO. Since macroalgae under oxidative stress are suggested to be a further source for I2 in the marine boundary layer, we re-analyzed spectra in the 500–600 nm range taken during the 1998 PARFORCE campaign in Mace Head, Ireland, which had not previously been analyzed for I2. We

  9. Reactive and Organic Halogen Species in Three Different European Coastal Environments

    Science.gov (United States)

    Platt, U.; Peters, C.; Pechtl, S.

    2005-12-01

    Within this contribution results of three field campaigns using active longpath DOAS (Differential Optical Absorption Spectroscopy) for the study of reactive halogen species (RHS) BrO, IO, OIO and I2 are presented. Two recent field campaigns took place in Spring 2002 in Dagebuell at the German North Sea Coast and 2003 in Lilia at the French Atlantic Coast of Brittany. Both sites represent coastal environments, characterized by extended intertidal zones and a moderately polluted atmosphere, with NO2 levels of up to 8 ppb. However, the sites show strong differences in their respective bioactivity. A great variety of macroalgae appeared over extended areas in Brittany, whereas algae were localized in small and rare spots at the German North Sea Coast. During these field campaigns volatile halogenated organic compounds (VHOCs) were determined by GC/ECD-ICPMS in air and water. Due to the spatial distribution of macroalgae at the German North Sea Coast clear evidence was for a connection between elevated levels of VHOCs and the appearance of macroalgae. Extraordinarily high concentrations of several VHOCs, specially CH3I and CH3Br of up to 1830 pptv and 875 pptv, respectively, were observed at the coast of Brittany, demonstrating the outstanding level of bioactivity there. CH2I2, an important source species for reactive iodine in the atmosphere due its short photolytic lifetime of only a few minutes, could be detected of up to 20 pptv. The IO mixing ratio reached up to 7.7±0.5 ppt (pmol/mol) during the day, in reasonable agreement with model studies designed to represent the meteorological and chemical conditions in Brittany. Since macroalgae under oxidative stress are suggested to be a further source for I2 in the marine boundary layer, spectra in the 500-600 nm range were re-analyzed taken during the 1998 PARFORCE campaign in Mace Head, Ireland, which had not previously been analyzed for I2. Molecular iodine could be clearly identified above the detection limit (~20

  10. Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

    International Nuclear Information System (INIS)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D.; DeYoung, Paul A.; Blum, Arlene; Stapleton, Heather M.; Peaslee, Graham F.

    2015-01-01

    A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams

  11. Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

    Science.gov (United States)

    Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

    2015-08-03

    Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

    2007-01-01

    Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

  13. Development of halogen-free, heat-resistant, low-voltage wire for automotive use

    International Nuclear Information System (INIS)

    Ueno, Keiji; Suzuki, Sizuo; Takahagi, Masatoshi; Uda, Ikujiro

    1995-01-01

    The environmental load of our motorized society is of major concern, and includes considerations of recycling of automotive parts as the industrial wastes. The total average length of AV, AVX (electrical wire insulated with PVC, cross-linked PVC), and AEX (electrical wire insulated with cross-linked polyolefin) wires required for the harnesses in modern automobiles is approximately 2,000-3,000 meters per unit. However these electrical wires contain a large amount of halogen, which can generate the smoke and corrosive gas. In response to this problem the authors have developed the electron beam irradiated halogen-free, heat-resistant, low-voltage electrical wire which does not contain any halogen based polymer or flame retardants. The developed wire features the reliability equivalent to AEX wire with minimum environmental load. (Author)

  14. Development of Halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1992-01-01

    Conventional flame-retardant cables release a large volume of corrosive and toxic gases as well as smoke while combusted. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and have already been used in telecommunication service, subway and shipboard applications. However, for cables for nuclear power plant, covering materials should also have radiation resistance and other properties, including long-term physical stability. We have developed halogen-free flame-retardant cables for BWR nuclear power plant with sufficient flame retardancy radiation resistance and environmental resistance including steam-exposure resistance all of which are in accordance with Japanese specifications for BWR nuclear cables and have such characteristics as low corrosiveness, low toxicity and low smoke emission. (author)

  15. Development of halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1991-01-01

    Conventional flame-retardant cables release a large amount of corrosive and toxic gases and also smoke during combustion on fire. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and already used in telecommunication plant, subway and shipboard applications. In the case of nuclear power plant application, cable covering materials should also have radiation resistance and other properties including long-term physical stability. We have developed halogen-free flame-retardant cables for nuclear power plant with sufficient flame retardancy, radiation resistance, and environmental resistance including steam-exposure resistance, all of which are in accordance with Japanese specifications for nuclear cables, and with characteristics as low corrosiveness, low toxicity, and low smoke evolution. (author)

  16. Recoil halogen reactions in liquid and frozen aqueous solutions of biomolecules

    International Nuclear Information System (INIS)

    Arsenault, L.J.; Blotcky, A.J.; Firouzbakht, M.L.; Rack, E.P.; Nebraska Univ., Omaha

    1982-01-01

    Reactions of recoil 38 Cl, 80 Br and 128 I have been studied in crystalline systems of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as well as liquid and frozen aqueous solutions of these halogenated biomolecules. In all systems expect crystalline 5-iuodouracil the major product was the radio-labelled halide ion. There was no evidence for other halogen inorganic species. The major labelled organic product was the parent molecule. A recoil atom tracer technique was developed to acquire site information of the biomolecule solutes in the liquid and frozen aqueous systems. For all liquid and frozen aqueous systems, the halogenated biomolecules tended to aggregate. For liquid systems, the tendency for aggregation diminished as the solute concentration approached zero, where the probable state of the solute approached a monomolecular dispersion. Unlike the liquid state, the frozen ice lattice demonstated a ''caging effect'' for the solute aggregates which resulted in constant product yields over the whole concentration range. (orig.)

  17. Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

    Energy Technology Data Exchange (ETDEWEB)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D. [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States); DeYoung, Paul A. [Department of Physics, Hope College, 27 Graves Place, Holland, MI 49423 (United States); Blum, Arlene [Green Science Policy Institute, Box 5455, Berkeley, CA 94705 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Duke University, LSRC Box 90328, Durham, NC 27708 (United States); Peaslee, Graham F., E-mail: peaslee@hope.edu [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)

    2015-09-01

    A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams.

  18. Halogen degassing during ascent and eruption of water-poor basaltic magma

    Science.gov (United States)

    Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

    2009-01-01

    A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

  19. Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

    Science.gov (United States)

    Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

    2016-07-01

    The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

  20. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

    International Nuclear Information System (INIS)

    1985-01-01

    Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

  1. Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error.

    Science.gov (United States)

    Otero-de-la-Roza, A; Johnson, Erin R; DiLabio, Gino A

    2014-12-09

    Halogen bonds are formed when a Lewis base interacts with a halogen atom in a different molecule, which acts as an electron acceptor. Due to its charge transfer component, halogen bonding is difficult to model using many common density-functional approximations because they spuriously overstabilize halogen-bonded dimers. It has been suggested that dispersion-corrected density functionals are inadequate to describe halogen bonding. In this work, we show that the exchange-hole dipole moment (XDM) dispersion correction coupled with functionals that minimize delocalization error (for instance, BH&HLYP, but also other half-and-half functionals) accurately model halogen-bonded interactions, with average errors similar to other noncovalent dimers with less charge-transfer effects. The performance of XDM is evaluated for three previously proposed benchmarks (XB18 and XB51 by Kozuch and Martin, and the set proposed by Bauzá et al.) spanning a range of binding energies up to ∼50 kcal/mol. The good performance of BH&HLYP-XDM is comparable to M06-2X, and extends to the "extreme" cases in the Bauzá set. This set contains anionic electron donors where charge transfer occurs even at infinite separation, as well as other charge transfer dimers belonging to the pnictogen and chalcogen bonding classes. We also show that functional delocalization error results in an overly delocalized electron density and exact-exchange hole. We propose intermolecular Bader delocalization indices as an indicator of both the donor-acceptor character of an intermolecular interaction and the delocalization error coming from the underlying functional.

  2. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.

    2014-05-15

    Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin-film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin-film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X-ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 dw, where dw represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting "edge-on" versus "face-on" molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the "edge-on" self-assembly of molecules forms uniform, (001) lamellar-textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the "face-on" oriented crystallites increases. The role of interfacial halogenation in mediating texture formation and the self-patterning of organic semiconductor films, as well as the resulting effects on charge transport in organic thin-film transistors, are explored. The presence of two or more anchoring sites between a halogenated semiconductor and a halogenated self-assembled monolayer, closer than about twice the corresponding van der Waals distance, alter the microstructure and improve electrical properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Global impacts of tropospheric halogens (Cl, Br, I on oxidants and composition in GEOS-Chem

    Directory of Open Access Journals (Sweden)

    T. Sherwen

    2016-09-01

    Full Text Available We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I. Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016 we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3 concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 % due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 % but Cl oxidation of other VOCs (ethane, acetone, and propane can be significant (∼  15–27 %. Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

  4. Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α.

    Science.gov (United States)

    Winiewska, Maria; Kucińska, Katarzyna; Makowska, Małgorzata; Poznański, Jarosław; Shugar, David

    2015-10-01

    The interaction of human CK2α (hCK2α) with nine halogenated benzotriazoles, TBBt and its analogues representing all possible patterns of halogenation on the benzene ring of benzotriazole, was studied by biophysical methods. Thermal stability of protein-ligand complexes, monitored by calorimetric (DSC) and optical (DSF) methods, showed that the increase in the mid-point temperature for unfolding of protein-ligand complexes (i.e. potency of ligand binding to hCK2α) follow the inhibitory activities determined by biochemical assays. The dissociation constant for the ATP-hCK2α complex was estimated with the aid of microscale thermophoresis (MST) as 4.3±1.8 μM, and MST-derived dissociation constants determined for halogenated benzotriazoles, when converted according to known ATP concentrations, perfectly reconstruct IC50 values determined by the biochemical assays. Ligand-dependent quenching of tyrosine fluorescence, together with molecular modeling and DSC-derived heats of unfolding, support the hypothesis that halogenated benzotriazoles bind in at least two alternative orientations, and those that are efficient hCK2α inhibitors bind in the orientation which TBBt adopts in its complex with maize CK2α. DSC-derived apparent heat for ligand binding (ΔΔHbind) is driven by intermolecular electrostatic interactions between Lys68 and the triazole ring of the ligand, as indicated by a good correlation between ΔΔHbind and ligand pKa. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly (~40 kJ/mol), relative to possible intermolecular halogen/hydrogen bonding (less than 10 kJ/mol), in binding of halogenated benzotriazoles to the ATP-binding site of hCK2α. This article is part of a Special Issue entitled: Inhibitors of Protein Kinases. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Quantitative prediction of solvation free energy in octanol of organic compounds.

    Science.gov (United States)

    Delgado, Eduardo J; Jaña, Gonzalo A

    2009-03-01

    The free energy of solvation, DeltaGS0, in octanol of organic compounds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a DeltaGS0 range from about -50 to 0 kJ.mol(-1). The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ.mol(-1), just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

  6. Laboratory Study of Aliphatic Organic Spectral Signatures and Applications to Ceres and Primitive Asteroids

    Science.gov (United States)

    Kaplan, H. H.; Milliken, R.

    2017-12-01

    Aliphatic organics were recently discovered on the surface of Ceres with Dawn's Visible and InfraRed (VIR) mapping spectrometer, which has implications for prebiotic chemistry of Ceres and other asteroids. An absorption in the spectrum at 3.4 µm was used to identify and provide initial estimates of the amount of organic material. We have studied the 3.4 µm absorption in reflectance spectra of bulk rock and meteorite powders and isolated organic materials in the NASA RELAB facility at Brown University to determine how organic composition and abundance affects absorption strength. Reflectance spectra of insoluble organic matter (IOM) extracted from carbonaceous chondrites were measured from 0.35 - 25 µm. These IOM have known elemental (H, C, N, O) and isotopic compositions that were compared with spectral properties. Bulk meteorites were measured as chips and particulates over the same wavelength range. Despite overall low reflectance values (albedo IOM samples, specifically those with a H/C ratio greater than 0.4. The absorption strength (band depth) increases with increasing H/C ratio, which corroborates similar findings in our previous study of sedimentary rocks and isolated kerogens. The absorption strength in the bulk meteorites reflects both H/C of the IOM and the concentration of IOM in the inorganic (mineral) matrix. Overlapping absorptions from carbonates and phyllosilicates (OH/H2O) can also influence the aliphatic organic bands in bulk rocks and meteorites. This laboratory work provides a foundation that can be used to constrain the composition of Ceres' aliphatic organic matter using band depth as a proxy for H/C. Reflectance spectra collected for this work will also be used to model the Dawn VIR data and obtain abundance and H/C estimates assuming that the organic material on Ceres' surface is similar to carbonaceous chondrite IOM. These spectra and findings can aid interpretation of reflectance data from Ceres and other asteroid missions, such as

  7. Molecular Characterization of MYB28 Involved in Aliphatic Glucosinolate Biosynthesis in Chinese Kale (Brassica oleracea var. alboglabra Bailey

    Directory of Open Access Journals (Sweden)

    Ling Yin

    2017-06-01

    Full Text Available Glucosinolates are Brassicaceae-specific secondary metabolites that act as crop protectants, flavor precursors, and cancer-prevention agents, which shows strong evidences of anticarcinogentic, antioxidant, and antimicrobial activities. MYB28, the R2R3-MYB28 transcription factor, directly activates genes involved in aliphatic glucosinolate biosynthesis. In this study, the MYB28 homology (BoaMYB28 was identified in Chinese kale (Brassica oleracea var. alboglabra Bailey. Analysis of the nucleotide sequence indicated that the cDNA of BoaMYB28 was 1257 bp with an ORF of 1020 bp. The deduced BoaMYB28 protein was a polypeptide of 339 amino acid with a putative molecular mass of 38 kDa and a pI of 6.87. Sequence homology and phylogenetic analysis showed that BoaMYB28 was most closely related to MYB28 homologs from the Brassicaceae family. The expression levels of BoaMYB28 varies across the tissues and developmental stages. BoaMYB28 transcript levels were higher in leaves and stems compared with those in cotyledons, flowers, and siliques. BoaMYB28 was expressed across all developmental leaf stages, with higher transcript accumulation in mature and inflorescence leaves. Over-expression and RNAi studies showed that BoaMYB28 retains the basic MYB28 gene function as a major transcriptional regulator of aliphatic glucosinolate pathway. The results indicated that over-expression and RNAi lines showed no visible difference on plant morphology. The contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes increased in over-expression lines and decreased in RNAi lines. In over-expression lines, aliphatic glucosinolate contents were 1.5- to 3-fold higher than those in the wild-type, while expression levels of aliphatic glucosinolate biosynthesis genes were 1.5- to 4-fold higher than those in the wild-type. In contrast, the contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate

  8. Molecular Characterization of MYB28 Involved in Aliphatic Glucosinolate Biosynthesis in Chinese Kale (Brassica oleracea var. alboglabra Bailey).

    Science.gov (United States)

    Yin, Ling; Chen, Hancai; Cao, Bihao; Lei, Jianjun; Chen, Guoju

    2017-01-01

    Glucosinolates are Brassicaceae-specific secondary metabolites that act as crop protectants, flavor precursors, and cancer-prevention agents, which shows strong evidences of anticarcinogentic, antioxidant, and antimicrobial activities. MYB28 , the R2R3-MYB28 transcription factor, directly activates genes involved in aliphatic glucosinolate biosynthesis. In this study, the MYB28 homology ( BoaMYB28 ) was identified in Chinese kale ( Brassica oleracea var. alboglabra Bailey). Analysis of the nucleotide sequence indicated that the cDNA of BoaMYB28 was 1257 bp with an ORF of 1020 bp. The deduced BoaMYB28 protein was a polypeptide of 339 amino acid with a putative molecular mass of 38 kDa and a pI of 6.87. Sequence homology and phylogenetic analysis showed that BoaMYB28 was most closely related to MYB28 homologs from the Brassicaceae family. The expression levels of BoaMYB28 varies across the tissues and developmental stages. BoaMYB28 transcript levels were higher in leaves and stems compared with those in cotyledons, flowers, and siliques. BoaMYB28 was expressed across all developmental leaf stages, with higher transcript accumulation in mature and inflorescence leaves. Over-expression and RNAi studies showed that BoaMYB28 retains the basic MYB28 gene function as a major transcriptional regulator of aliphatic glucosinolate pathway. The results indicated that over-expression and RNAi lines showed no visible difference on plant morphology. The contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes increased in over-expression lines and decreased in RNAi lines. In over-expression lines, aliphatic glucosinolate contents were 1.5- to 3-fold higher than those in the wild-type, while expression levels of aliphatic glucosinolate biosynthesis genes were 1.5- to 4-fold higher than those in the wild-type. In contrast, the contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes in

  9. Vapour pressures and heat capacity measurements on the C7-C9 secondary aliphatic alcohols

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Schick, Christoph

    2007-01-01

    Molar enthalpies of vaporization of secondary C 7 -C 9 alkanols were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. The measured data sets were checked for internal consistency successfully. A large number of the primary experimental results on temperature dependences of vapour pressures of secondary alcohols have been collected from the literature and have been treated uniform in order to derive their vaporization enthalpies at the reference temperature 298.15 K. This collection, together with our experimental results, have helped to ascertain the database for branched aliphatic alcohols

  10. Efficient 'One Pot' Nitro Reduction-Protection of γ-Nitro Aliphatic Methyl Esters

    OpenAIRE

    Díaz-Coutiño, Francisco D.; Escalante, Jaime

    2009-01-01

    A simple and efficient protocol has been developed for the direct conversion of γ-nitro aliphatic methyl esters to N-(tert-butoxycarbonyl)amine methyl esters using NH4+HCO2- and Pd/C in the presence of (Boc)2O. There was a significant decrease in the reaction time under these conditions, increased yields and the purity of the products using this 'one pot' procedure. Un protocolo simple y eficiente de síntesis ha sido desarrollado para la conversión directa de metil ésteres de γ-nitro alifá...

  11. Analysis of TPH and Aliphatic and Aromatic Hydrocarbons Fractions in Environmental Interest Matrices

    International Nuclear Information System (INIS)

    Pindado, O.; Perez, R. M.; Garcia, S.

    2014-01-01

    Analytical methods to analyze TPH and several aliphatic and aromatic fractions present in soil and groundwater samples contaminated by hydrocarbons are showed. As a part of BIOXISOIL project, analyzing these parameters is fundamental and indispensable to know the initial contamination level, design an adequate method to decontaminate it and eventually assess decontamination accomplished. Analysis of both matrices involve different extraction stages such as microwave radiation, clean up steps based on solid phase extraction and finally a chromatograph analysis with flame ion detector. Analytical procedures have showed satisfactory analytical quality parameters and have been validated against several certified reference materials. (Author)

  12. Preparation and characterization of aliphatic diphenyl esters intended as precursors for polyesters

    DEFF Research Database (Denmark)

    Hvilsted, S.; Andruzzi, F.; Cerrai, P.

    1991-01-01

    An extensive number of aliphatic diphenyl esters, C6H5OOC(CH2)nCOOC6H5 (n = O,...,8,10,11,12,14), have been prepared in pure form. The crystalline melting points these esters exhibit an odd-even temperature behaviour, with the higher-melting even series (n even) displaying a minimum for n = 8 while...... based on similar data from phenyl esters, interpreted as the results of an apparent macrocyclic conformation of the larger diphenyl esters. High-performance size exclusion chromatography (s.e.c.) of diphenyl esters, phenyl esters, aromatic and linear hydrocarbons in tetrahydrofuran, toluene...

  13. Abilities of some higher plants to hydrolyze the acetates of phenols and aromatic-aliphatic alcohols

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available In the biotransformations carried out under the same conditions, the whole intact plants of Spirodela punctata, Nephrolepis exaltata, Cyrtomium falcatum, Nephrolepis cordifolia and the suspension cultures of Helianthus tuberosus, Daucus carota and Petunia hybrida hydrolyze (partially or totally the ester bonds of the acetates of phenols and aromatic-aliphatic alcohols and also the menthyl acetate. Nevertheless, the methyl esters of aromatic acids, structurally similar to the former substrates, do not undergo hydrolysis. At the same time, the viability of first four plants was observed for different levels of acetate concentration. The method of continuous preparative hydrolysis of the same acetates was worked out in Cyrtomium falcatum culture.

  14. Kinetics and mechanism of the selective oxidation of primary aliphatic alcohols under phase transfer catalysis

    Directory of Open Access Journals (Sweden)

    K. Bijudas

    2014-03-01

    Full Text Available Kinetics of the oxidation of primary aliphatic alcohols has been carried out using phase transferred monochromate in benzene. Tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB are used as phase transfer catalysts (PT catalyst. The reaction shows first order dependence on both [alcohol] and [monochromate ion]. The oxidation leads to the formation of corresponding aldehyde and no traces of carboxylic acid has been detected. The reaction mixture failed to induce the polymerization of added acrylonitrile which rules out the presence radical intermediates in the reaction. Various thermodynamic parameters have been evaluated and a suitable mechanism has been proposed.

  15. Simultaneous determination of aliphatic hydrocarbons, PCBs and PCTs in pork liver by gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Barros, C [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Alvarez Pineiro, M E [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Simal Lozano, J [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Lage Yusty, M A [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain)

    1996-10-01

    A multicomponent extraction/concentration procedure has been developed for the enrichment of PCBs, PCTs and aliphatic hydrocarbons (pristane, C{sub 18}, C{sub 19}, C{sub 20}, C{sub 22}, C{sub 24}, C{sub 28}, C{sub 32} and C{sub 36}) in pork liver. These components of the enriched extract were then simultaneously determined by gas chromatography. Mean recoveries ranged from 81.5% for pristane to 93% for PCBs; CV % (0.9-6.7) indicated the method to be both precise and reproducible. (orig.)

  16. Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

    International Nuclear Information System (INIS)

    Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

    2007-01-01

    The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

  17. A 19F NMR study of C-I....pi- halogen bonding

    DEFF Research Database (Denmark)

    Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.

    2011-01-01

    The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

  18. Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

    Science.gov (United States)

    Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

    2017-06-01

    The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

  19. Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

    Directory of Open Access Journals (Sweden)

    Janet E. Del Bene

    2017-11-01

    Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

  20. Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

    Science.gov (United States)

    Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

    2018-04-01

    The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.