WorldWideScience

Sample records for reported halogenated furanone

  1. 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

    ). Gfp-based reporter technology has been applied for non-destructive, single-cell-level detection of quorum sensing in laboratory-based P. aeruginosa biofilms. It is reported that a synthetic halogenated furanone compound, which is a derivative of the secondary metabolites produced by the Australian...

  2. 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......). Gfp-based reporter technology has been applied for non-destructive, single-cell-level detection of quorum sensing in laboratory-based P. aeruginosa biofilms. It is reported that a synthetic halogenated furanone compound, which is a derivative of the secondary metabolites produced by the Australian...

  3. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, Michael; Rasmussen, Thomas Bovbjerg; Henzter, Morten

    2002-01-01

    N-acyl-L-homoserine lactones (AHLs) are co-regulatory ligands required for control of the expression of genes encoding virulence traits in many Gram-negative bacterial species. Recent studies have indicated that AHLs modulate the cellular concentrations of LuxR-type regulatory proteins by binding...... and fortifying these proteins against proteolytic degradation (Zhu & Winans, 2001 ). Halogenated furanones produced by the macroalga Delisea pulchra inhibit AHL-dependent gene expression. This study assayed for an in vivo interaction between a tritiated halogenated furanone and the LuxR protein of Vibrio...... furanones modulate LuxR activity but act to destabilize, rather than protect, the AHL-dependent transcriptional activator. The furanone-dependent reduction in the cellular concentration of the LuxR protein was associated with a reduction in expression of a plasmid encoded P(luxI)-gfp(ASV) fusion suggesting...

  4. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

    2002-01-01

    N-acyl-L-homoserine lactones (AHLs) are co-regulatory ligands required for control of the expression of genes encoding virulence traits in many Gram-negative bacterial species. Recent studies have indicated that AHLs modulate the cellular concentrations of LuxR-type regulatory proteins by binding...... and fortifying these proteins against proteolytic degradation (Zhu & Winans, 2001). Halogenated furanones produced by the macroallga Delisea pulchra inhibit AHL-dependent gene expression. This study assayed for an in vivo interaction between a tritiated halogenated furanone and the LuxR protein of Vibrio...... furanones modulate LuxR activity but act to destabilize, rather than protect, the AHL-dependent transcriptional activator. The furanone-dependent reduction in the cellular concentration of the LuxR protein was associated with a reduction in expression of a plasmid encoded P-luxl-gfp(ASV) fusion suggesting...

  5. Occurrence of halogenated furanones in U.S. drinking waters.

    Science.gov (United States)

    Onstad, Gretchen D; Weinberg, Howard S; Krasner, Stuart W

    2008-05-01

    Chlorinated and brominated forms of MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) were detected in the disinfected waters of six pairs of U.S. drinking watertreatment plants, with MX as high as approximately 310 ng/L in finished water. The strength of this study is in its comparison between pairs of plants that drew water from the same or similar watersheds and treated the raw source water with two contrasting disinfection and/or treatment schemes. As expected, the brominated MX-analogues were produced in greater abundance than MX from raw source waters with high bromide concentrations. Disinfection of waters with free chlorine produced more MX-analogues than disinfection with monochloramine. Use of chloramines as the residual disinfectant appeared to stabilize MX-analogues once they were formed. Pretreatment with ozone and biologically active granular activated carbon minimized MX-analogue formation upon subsequent chlorination or chloramination, either because MX precursors were altered by ozone, removed by granular activated carbon, or degraded by biological filtration. Pretreatment with chlorine dioxide did not minimize MX-analogue formation. In plant effluent samples, MX and chloroform were positively correlated (molar R = 0.7, N = 6). Similar formation patterns of MX-analogues, trihalomethanes, and haloacetic acids in these water treatment plants suggest that the three classes of disinfection byproduct follow a common formation mechanism from natural organic matter and chlorine.

  6. Inhibition of quorum sensing in Pseudomonas aeruginosa biofilm bacteria by a halogenated furanone compound

    DEFF Research Database (Denmark)

    Hentzer, Morten; Riedel, Kathrin; Rasmussen, Thomas B;

    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 by expression of an unstable version of the green-fluorescent protein (Gfp...... macroalga Delisea pulchra, is capable of interfering with AHL-mediated quorum sensing in P. aeruginosa. It is demonstrated that the furanone compound specifically represses expression of a PlasB-gfp reporter fusion without affecting growth or protein synthesis. In addition, it reduces the production...

  7. Halogenated furanones from the red alga, Delisea pulchra, inhibit carbapenem antibiotic synthesis and exoenzyme virulence factor production in the phytopathogen Erwinia carotovora

    DEFF Research Database (Denmark)

    Manefield, M.; Welch, M.; Givskov, Michael Christian

    2001-01-01

    The plant pathogen Erwinia carotovora regulates expression of virulence factors and antibiotic production via an N-3- oxohexanoyl-L-homoserine lactone (3-oxo-C6-HSL) dependent quorum sensing mechanism. The marine alga Delisea pulchra produces halogenated furanones known to antagonise 3-oxo-C6-HSL...... activity. We have tested the effects of a halogenated furanone on the production of carbapenem, cellulase and protease in E. carotovora. Despite differences in the regulatory mechanisms controlling carbapenem and exoenzyme production each was inhibited by the algal metabolite. We present evidence...... to suggest that the furanone dependent inhibition of carbapenem production is a result of the disruption of the 3-oxo-C6-HSL dependent expression of the carABCDEFGH operon....

  8. Halogenated furanones from the red alga, Delisea pulchra, inhibit carbapenem antibiotic synthesis and exoenzyme virulence factor production in the phytopathogen Erwinia carotovora

    DEFF Research Database (Denmark)

    Manefield, M.; Welch, M.; Givskov, Michael Christian

    2001-01-01

    The plant pathogen Erwinia carotovora regulates expression of virulence factors and antibiotic production via an N-3- oxohexanoyl-L-homoserine lactone (3-oxo-C6-HSL) dependent quorum sensing mechanism. The marine alga Delisea pulchra produces halogenated furanones known to antagonise 3-oxo-C6-HSL...

  9. Fabrication and in vitro release behavior of a novel antibacterial coating containing halogenated furanone-loaded poly(L-lactic acid nanoparticles on microarc-oxidized titanium

    Directory of Open Access Journals (Sweden)

    Cheng YC

    2012-11-01

    Full Text Available Yicheng Cheng,1 Jiang Wu,1 Bo Gao,1 Xianghui Zhao,2 Junyan Yao,3 Shenglin Mei,1 Liang Zhang,4 Huifang Ren1 1Department of Prosthodontics, School of Stomatology, Fourth Military Medical University, 2Institute of Neuroscience, School of Basic Medicine, Fourth Military Medical University, 3Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, 4Department of Orthodontics, School of Stomatology, Fourth Military Medical University, Xi'an, ChinaYicheng Cheng and Jiang Wu contributed equally to this workBackground: Dental implants have become increasingly common for the management of missing teeth. However, peri-implant infection remains a problem, is usually difficult to treat, and may lead eventually to dental implant failure. The aim of this study was to fabricate a novel antibacterial coating containing a halogenated furanone compound, ie, (Z--4-bromo-5-(bromomethylene-2(5H-furanone (BBF-loaded poly(L-lactic acid (PLLA nanoparticles on microarc-oxidized titanium and to evaluate its release behavior in vitro.Methods: BBF-loaded PLLA nanoparticles were prepared using the emulsion solvent-evaporation method, and the antibacterial coating was fabricated by cross-linking BBF-loaded PLLA nanoparticles with gelatin on microarc-oxidized titanium.Results: The BBF-loaded PLLA nanoparticles had a small particle size (408 ± 14 nm, a low polydispersity index (0.140 ± 0.008, a high encapsulation efficiency (72.44% ± 1.27%, and a fine spherical shape with a smooth surface. The morphology of the fabricated antibacterial coating showed that the BBF-loaded PLLA nanoparticles were well distributed in the pores of the microarc oxidation coating, and were cross-linked with each other and the wall pores by gelatin. The release study indicated that the antibacterial coating could achieve sustained release of BBF for 60 days, with a slight initial burst release during the first 4 hours.Conclusion: The novel antibacterial coating

  10. How Delisea pulchra furanones affect quorum sensing and swarming motility in Serratia liquefaciens MG1

    DEFF Research Database (Denmark)

    Rasmussen, T B; Manefield, M; Andersen, Jens Bo

    2000-01-01

    Halogenated furanones produced by the benthic marine macroalga Delisea pulchra inhibit swarming motility of Serratia liquefaciens MG1. This study demonstrates that exogenously added furanones control transcription of the quorum sensing regulated gene swrA in competition with the cognate signal...... molecule N:-butanoyl-L-homoserine lactone. This in turn results in reduced production of the surface-active compound serrawettin W2, which is crucial for surface translocation of the differentiated swarm cells. It is demonstrated that furanones interfere with interspecies communication during swarming...

  11. Halogen control in integrated hot gas cleaning: final report

    Energy Technology Data Exchange (ETDEWEB)

    Nieminen, M.; Kangasmaa, K.; Laatikainen-Luntama, J.; Kurkela, E. [VTT Energy (Finland)

    1998-12-31

    A simple and cost effective dry-scrubbing halogen control method for hot gasification gas cleaning applications was developed. The work aimed to develop a dry scrubbing method for integration into a hot gas cleaning system including particulate removal by cyclones, filtration and possibly a desulphurisation system. Work started by determining the behaviour of halogen compounds in a reducing gasification atmosphere to evaluate the fate of halogens on downstream components, to understand the role of halogens as precursors for environmental emissions, and to give background information for developing halogen control methods. New halogen sampling and analysis methods for pressurised gasification gas conditions were also developed. Mass balances were determined for several gasification conditions, with and without calcium-based bed additives. Several potential dry scrubbing sorbent candidates were evaluated. Chemical, technical, economical and environmental aspects were used as selection criteria, calcium-based sorbents being chosen for development of the halogen removal system. The process concept was based on sorbent feeding into the product gas prior to the hot gas filter unit, where the final step of halogen capture takes place and both sorbent and particulates are removed from the gas. Preliminary screening of calcium-based sorbents and preoptimisation of process conditions was performed in a laboratory scale dry scrubbing test rig. Finally, the performance of the developed dry scrubbing halogen removal system was verified in a PDU scale pressurised fluidised bed gasification and gas cleaning test rig. Preliminary verification showed that, in favourable conditions, the system developed formed a potential halogen control system that could be easily integrated into the other hot gas cleaning systems. 2 refs., 9 figs., 2 tabs.

  12. 粘质沙雷氏菌AS-1中SpnR功能及卤化呋喃对其群体感应的抑制%The function of SpnR and the inhibitory effects by halogenated furanone on quorum sensing in Serratia marcescens AS-1

    Institute of Scientific and Technical Information of China (English)

    陶寅璐; 诸星知宏; 加藤纪弘; 池田宰; 庄惠生

    2008-01-01

    By secretion and detection of a series of signaling molecules,bacteria are able to Coordinate gene expression as a community,to regulate a variety of important phenotypes,from virulence factor production to biofilm formation to symbiosis related behaviours such as bioluminescence.This widespread signaling mechanism is called quorum sensing.There are several quorum sensing systems described in Serratia.Serratia marcescens AS-1,isolated from soil,had the LuxI/LuxR homologues called SpnI/SpnR.S. marcescens AS-1 produced two kinds of N-acyl-L-homoserine lactones,N-hexanoyl-L-homoserine lactone and N-(3-oxohexanoyl)-L-homoserine lactone as signal molecules,which involved in quorum sensing to control the gene expression in response to increased cell density.By gene replacement method,the spnR mutant was constructed,named S.marcescens AS-1R.SpnR acted as a negative regulator for the production of prodigiosin,swarming motility and biofilm formation,which were regulated by quorum sensing.Halogenated furanone,known as a natural inhibitor of quorum sensing,could effectively inhibit the quorum sensing of S.marcescens AS-1 but without interrupting AHL-SpnR interaction.All results will be helpful to understand the mechanisms of halogenated furanone inhibition on quorum sensing and the potential application of halogenated furanone in effectively preventing infection disease caused by Serratia strains.%通过分泌和感知一系列信号分子,细菌能够根据自身菌体密度的变化调控基因的表达,从而控制一系列重要的表现型,包括毒力因子的产生,生物膜的形成以及菌体发光等.这种广泛存在的信号机制被称为群体感应.在沙雷氏菌种中已经发现了多套群体感应机制.粘质沙雷氏菌AS-1从土壤中分离,其中含有LuxI/LuxR的同类蛋白,被称为SpnI/SpnR.粘质沙雷氏菌AS-1合成AHLs分子N-hexanoy1-L-homoserinelactone(C6-HSL)和N-(3.oxohexanoyl)-L-homoserine lactone(3-oxo-C6-HSL)作为其信号分子,通

  13. High energy decomposition of halogenated hydrocarbons FY93 final report

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, B.J.; Arbon, R.E.; Meikrantz, D.H.

    1993-09-01

    The purpose of this program is to demonstrate a viable process for the decomposition of hazardous organochlorine compounds to nonhazardous products. This process has applicability to the treatment of mixed wastes containing both chlorinated hydrocarbons and radioactive constituents. The organics may be decomposed leaving only the radioactive constituents in the waste. Further, the use of spent nuclear fuel as a gamma-ray source presents a potentially cost effective energy source and elegantly allows the fuel to be considered a resource rather than a liability. During FY93 more than 400 samples were irradiated with fission product gamma-rays. Many of these samples were individual PCB congeners dissolved in isopropanol. These samples were studied to gain an understanding of the mechanism and kinetics of, and to provide a mass balance for, the PCB radiolysis reaction. In addition to research findings this report also contains a summary of efforts expended on technology transfer, professional publications and conference presentations.

  14. Synthesis of 4-Halo-2 ( 5H )-furanones and Their Suzuki-Coupling Reactions with Organoboronic Acids.A General Route to 4-Aryl-2 ( 5 H ) - furanones

    Institute of Scientific and Technical Information of China (English)

    MA,Sheng-Ming(麻生明); SHI,zhang-Jie(施章杰)

    2001-01-01

    4-Halo-2(5H)-furanones were prepared by the halolactoniza-tion of 2,3-allenoic acids.The subsequent Suzuki coupling reaction of 4-halo-2(5H)-furanones with aryl boronic acids was carried out to produce 4-aryl-2(5H).furanones in excellent yields.``

  15. Lipase Catalyzed Enantioselective Transesterification of 5-Acyloxy-2(5H)-Furanones

    NARCIS (Netherlands)

    Deen, Hanneke van der; Hof, Robert P.; Oeveren, Arjan van; Kellogg, Richard M.; Feringa, Bernard

    1994-01-01

    Several lipases catalyse the transesterification of gamma-acyloxyfuranones in organic solvents with high enantioselectivities. This method has been used for the kinetic resolution of 5-acetoxy-2(5H)-furanone, 5-acetoxy-4-methyl-2(5H)-furanone and 5-propionyloxy-2(5H)-furanone, in e.e.'s ranging from

  16. Synthesis of furanone-based natural product analogues with quorum sensing antagonist activity

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Persson, T.; Rasmussen, Thomas Bovbjerg;

    2003-01-01

    The synthesis of 5- and 3-(1'-hydroxyalkyl)-substituted 5H-furan-2-ones 4a-d and 8a-d as well as 5-alkylidene-5H-furan-2-ones 5a-d is described. A study of the structure-activity relationship of these furanone-based natural product analogues towards two different quorum sensing systems is reported....... Although the synthesized compounds are not as potent quorum sensing inhibitors as some natural counterparts and a synthetic analogue hereof, interesting structure-activity relationships are seen....

  17. 40 CFR 721.8675 - Halogenated pyridines.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated pyridines. 721.8675... Substances § 721.8675 Halogenated pyridines. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated pyridine (PMN P-83-1163)...

  18. Effect of brominated furanones on the formation of biofilm by Escherichia coli on polyvinyl chloride materials.

    Science.gov (United States)

    Lianhua, Ye; Yunchao, Huang; Geng, Xu; Youquang, Zhou; Guangqiang, Zhao; Yujie, Lei

    2013-01-01

    To study the influence of brominated furanones on the biofilm (BF) formation by Escherichia coli (E. coli) on polyvinyl chloride (PVC) material, and to provide new ways of surface modification of materials to clinically prevent biomaterial centered infection. Three brominated furanones, dissolved in ethanol, furanone-1(3,4-dibromo-5-hydroxyl-furanone), furanone-2(4-bromo-5-(4-methoxypheny)-3-(methylamino)-furanone), and furanone-3(3,4-dibromo-5,5-dimethoxypheny-2(5H)-furanone) with representative chemical structure, were coated on the surfaces of separate PVC materials (1 × 1 cm), respectively. The surface-modified PVC materials were incubated with E. coli and for controls, 75 % ethanol-treated PVC materials were used. This treatment played as control group. The cultivation incubations were for 6, 12, 18, and 24 h. The thickness of bacterial BF and bacterial community quantity unit area on the PVC materials was determined by confocal laser scanning microscopy (CLSM), and the surface structure of bacterial BF formation was examined by scanning electron microscopy (SEM). The results of CLSM indicated the thickness of bacterial BF and bacterial community quantity unit area on PVC materials treated with furanone-3 were significantly lower than that of control at all time points (P 0.05). The results of SEM indicated that after 6 h incubation, the quantity of bacterial attachment to the surface of PVC material treated with furanone-3 was lower than the control group. By 18 h incubation there was completely formed BF structure on the surface of control PVC material. However, there was no significant BF formation on the surface of PVC material treated with furanone-3. The impact of different brominated furanones on SA biofilm formation on the surface of PVC materials are different, furanone-3 can inhibit E. coli biofilm formation on the surface of PVC material.

  19. ASYMMETRIC DIELS-ALDER REACTIONS WITH 5-MENTHYLOXY-2(5H)-FURANONE

    NARCIS (Netherlands)

    Jong, Johannes C. de; Bolhuis, Fré van; Feringa, Bernard

    1991-01-01

    A new class of chiral dienophiles, 5-alkoxy-2(5H)-furanones, has been developed. Both enantiomers of 5-menthyloxy-2(5H)-furanone are readily available in enantiomerically pure form, starting from furfural and d- or l-menthol. Excellent diastereoselectivities (d.e. greater-than-or-equal-to 99%) are o

  20. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated benzyl ester acrylate... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for...

  1. 40 CFR 721.535 - Halogenated alkane (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane (generic). 721.535... Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  2. 40 CFR 721.536 - Halogenated phenyl alkane.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated phenyl alkane. 721.536... Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  3. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkyl pyridine. 721.8700... Substances § 721.8700 Halogenated alkyl pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkyl pyridine (PMN P-83-237)...

  4. Halogenation of microcapsule walls

    Science.gov (United States)

    Davis, T. R.; Schaab, C. K.; Scott, J. C.

    1972-01-01

    Procedure for halogenation of confining walls of both gelatin and gelatin-phenolic resin capsules is similar to that used for microencapsulation. Ten percent halogen content renders capsule wall nonburning; any higher content enhances flame-retardant properties of selected internal phase material. Halogenation decreases permeability of wall material to encapsulated materials.

  5. The naturally occurring furanones: formation and function from pheromone to food.

    Science.gov (United States)

    Colin Slaughter, J

    1999-08-01

    Three closely related 4-hydroxy-3(2H)-furanones have been found in a range of highly cooked foodstuffs where they are important flavour compounds with aroma threshold values as low as 20 micrograms kg-1 water (approximately 0.14 mumol l-1). The compounds are formed mainly as a result of the operation of the Maillard reactions between sugars and amino acids during heating but one compound, 5-(or 2)-ethyl-2-(or 5)-methyl-4-hydroxy-3(2H)-furanone, appears in practice to be produced by yeast, probably from a Maillard intermediate, during the fermentation stages in the production of soy sauce and beer. The compounds are also important in the flavour of strawberry, raspberry, pineapple and tomato but the route of biosynthesis is unknown. Two 3-hydroxy-2(5H)-furanones, emoxyfuranone and sotolon, which are produced spontaneously from amino acids such as threonine and 4-hydroxy-L-leucine are major contributors to meaty and spicy/nutty flavours in foods. The biosynthesis of 5-(1,2-dihydroxyethyl)-3,4-dihydroxy-2(5H)-furanone (ascorbic acid, vitamin C) and 5-hydroxymethyl-3,4-dihydroxy-2(5H)-furanone (erythroascorbic acid) from sugars in plants and yeast, respectively, has been characterized to the enzymic level. After treatment with chlorine, humic waters contain a range of chloro-furanones, some of which, particularly 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX), are powerful mutagens. The furanones which occur in foods are also mutagenic to bacteria and cause DNA damage in laboratory tests. However, these compounds are, in practice, very effective anti-carcinogenic agents in the diets of animals which are being treated with known cancer-inducing compounds such as benzo[alpha]pyrene or azoxymethane. Two of the food-derived furanones have antioxidant activity comparable to that of ascorbic acid. A biological function has been discovered for some of the furanones besides vitamin C. 5-Methyl-4-hydroxy-3(2H)-furanone is a male pheromone in the cockroach Eurycolis

  6. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

    Directory of Open Access Journals (Sweden)

    Jubi John

    2014-06-01

    Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

  7. Cross-reactivity of Halogenated Platinum Salts

    Science.gov (United States)

    Halogenated platinum (Pt) salts are well-known respiratory sensitizers associated with the development of asthma. People may be exposed to a variety of platinum compounds in different contexts (e.g. occupationally, automobile exhaust). Published reports suggest that sensitizati...

  8. EPA's (Environmental Protection Agency's) draft drinking-water criteria document for monochlorobenzene. Technical comments of the Halogenated Organics Subcommittee. Final report

    Energy Technology Data Exchange (ETDEWEB)

    1987-01-16

    The Halogenated Organics Subcommittee evaluated the animal evidence for carcinogencity of chlorobenzene to be inadequate under EPA's new guidelines based on the lack of a statistically significant increase in the incidence of tumors in female mice, male mice and female rats, and on the basis of the perception of a diminished biologic significance of reported malignant neoplastic nodules of the liver in the highest dose-treated male rats. The evidence would place chlorobenzene into the overall weight-of-the-evidence category D (not classified).

  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. Natural 4-Hydroxy-2,5-dimethyl-3(2H-furanone (Furaneol®

    Directory of Open Access Journals (Sweden)

    Wilfried Schwab

    2013-06-01

    Full Text Available 4-Hydroxy-2,5-dimethyl-3(2H-furanone (HDMF, furaneol® and its methyl ether 2,5-dimethyl-4-methoxy-3(2H-furanone (DMMF are import aroma chemicals and are considered key flavor compounds in many fruit. Due to their attractive sensory properties they are highly appreciated by the food industry. In fruits 2,5-dimethyl-3(2H-furanones are synthesized by a series of enzymatic steps whereas HDMF is also a product of the Maillard reaction. Numerous methods for the synthetic preparation of these compounds have been published and are applied by industry, but for the development of a biotechnological process the knowledge and availability of biosynthetic enzymes are required. During the last years substantial progress has been made in the elucidation of the biological pathway leading to HDMF and DMMF. This review summarizes the latest advances in this field.

  11. A Serendipitous Synthesis of Bis-Heterocyclic Spiro 3(2H)-Furanones.

    Science.gov (United States)

    Picado, Alfredo; Li, ShengJian; Dieter, R Karl

    2016-02-19

    (Z) Enol triflates 6, 11b-d, (E) enol triflate 11e, and phenol triflate 11a, derived from β-keto esters or 2-carboalkoxy phenols, respectively, react with N-Boc 2-lithiopyrrolidine (5a), N-Boc N-methylaminomethyllithium (5b), or 2-lithio-1,3-dithiane (14) to afford 3(2H)-furanones in modest to good yields (38-81%). Product and carbanion reagent studies suggest that the 3(2H)-furanone is formed in a cascade of reactions involving nucleophilic acyl substitution, enolate formation, trifluoromethyl transfer, iminium or sulfenium ion formation, and subsequent ring closure to form the 3(2H)-furanone. The use of 2-lithio-1,3-dithiane affords a cyclic α-keto-S,S,O-orthoester in which the functionality can be selectively manipulated for synthetic applications.

  12. 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...... and separation method. This review covers separation by solid phase chromatography, gel permeation chromatography, and liquid-liquid extraction, followed by halogen determination. All studies performed according to this outline have indicated that the major organohalogen compounds are chlorinated fatty acids...... bound in different lipids. For the detection and identification of individual, halogenated fatty acid methyl esters (FAMEs) liberated from the lipids, gas chromatography (GC) has been employed together with detection methods such as electron capture detection, electrolytic conductivity detection (ELCD...

  13. Halogens in the atmosphere

    Science.gov (United States)

    Cicerone, R. J.

    1981-01-01

    Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

  14. Halogens in the atmosphere

    Science.gov (United States)

    Cicerone, R. J.

    1981-01-01

    Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

  15. Photosensitized addition of isopropanol to furanones in a 365 nm UV-LED microchip.

    Science.gov (United States)

    Shvydkiv, Oksana; Yavorskyy, Alexander; Nolan, Kieran; Youssef, Ali; Riguet, Emmanuel; Hoffmann, Norbert; Oelgemöller, Michael

    2010-12-01

    The DMBP-sensitized addition of isopropanol to furanones was studied in a novel LED-driven microchip reactor. Complete conversions were achieved after just 2.5 to 5 min of irradiation with 6 × 365 nm high-power LEDs. The results were compared to analogous experiments using a conventional batch reactor.

  16. Halogens in the troposphere.

    Science.gov (United States)

    Finlayson-Pitts, Barbara J

    2010-02-01

    Although inorganic halogen gases are believed to play key roles in the chemistry of the lower atmosphere, many of them have not yet been detected or measured in ambient air. This article describes some of the current techniques and future needs for inorganic halogens in air. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  17. Pulvinulin A, graminin C, and cis-gregatin B--new natural furanones from Pulvinula sp. 11120, a fungal endophyte of Cupressus arizonica.

    Science.gov (United States)

    Wijeratne, E M Kithsiri; Xu, Yaming; Arnold, A Elizabeth; Gunatilaka, A A Leslie

    2015-01-01

    Three new natural furanones, pulvinulin A (1), graminin C (2), and cis-gregatin B (3), together with the known fungal metabolites, graminin B (4) and 10-norparvulenone (5), were isolated from Pulvinula sp. 11120, an endophytic fungal strain occurring in healthy foliage of Cupressus arizonica (Arizona cypress). The structures of 1 and 2 were elucidated by the analysis of their spectroscopic data and chemical interconversions, and that of 3 was determined by comparison with data for synthetic cis-gregatin B. Comparison of spectroscopic data of 4 and 5 with those reported identified them as graminin B and 10-norparvulenone, respectively. Metabolites 1-4 exhibited antibacterial activity against E. coli.

  18. FaQR, required for the biosynthesis of the strawberry flavor compound 4-hydroxy-2,5-dimethyl-3(2H)-furanone, encodes an enone oxidoreductase.

    Science.gov (United States)

    Raab, Thomas; López-Ráez, Juan Antonio; Klein, Dorothée; Caballero, Jose Luis; Moyano, Enriqueta; Schwab, Wilfried; Muñoz-Blanco, Juan

    2006-04-01

    The flavor of strawberry (Fragaria x ananassa) fruit is dominated by an uncommon group of aroma compounds with a 2,5-dimethyl-3(H)-furanone structure. We report the characterization of an enzyme involved in the biosynthesis of 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF; Furaneol), the key flavor compound in strawberries. Protein extracts were partially purified, and the observed distribution of enzymatic activity correlated with the presence of a single polypeptide of approximately 37 kD. Sequence analysis of two peptide fragments showed total identity with the protein sequence of a strongly ripening-induced, auxin-dependent putative quinone oxidoreductase, Fragaria x ananassa quinone oxidoreductase (FaQR). The open reading frame of the FaQR cDNA consists of 969 bp encoding a 322-amino acid protein with a calculated molecular mass of 34.3 kD. Laser capture microdissection followed by RNA extraction and amplification demonstrated the presence of FaQR mRNA in parenchyma tissue of the strawberry fruit. The FaQR protein was functionally expressed in Escherichia coli, and the monomer catalyzed the formation of HDMF. After chemical synthesis and liquid chromatography-tandem mass spectrometry analysis, 4-hydroxy-5-methyl-2-methylene-3(2H)-furanone was confirmed as a substrate of FaQR and the natural precursor of HDMF. This study demonstrates the function of the FaQR enzyme in the biosynthesis of HDMF as enone oxidoreductase and provides a foundation for the improvement of strawberry flavor and the biotechnological production of HDMF.

  19. Occurrence of halogenated alkaloids.

    Science.gov (United States)

    Gribble, Gordon W

    2012-01-01

    Once considered to be isolation artifacts or chemical "mistakes" of nature, the number of naturally occurring organohalogen compounds has grown from a dozen in 1954 to >5000 today. Of these, at least 25% are halogenated alkaloids. This is not surprising since nitrogen-containing pyrroles, indoles, carbolines, tryptamines, tyrosines, and tyramines are excellent platforms for biohalogenation, particularly in the marine environment where both chloride and bromide are plentiful for biooxidation and subsequent incorporation into these electron-rich substrates. This review presents the occurrence of all halogenated alkaloids, with the exception of marine bromotyrosines where coverage begins where it left off in volume 61 of The Alkaloids. Whereas the biological activity of these extraordinary compounds is briefly cited for some examples, a future volume of The Alkaloids will present full coverage of this topic and will also include selected syntheses of halogenated alkaloids. Natural organohalogens of all types, especially marine and terrestrial halogenated alkaloids, comprise a rapidly expanding class of natural products, in many cases expressing powerful biological activity. This enormous proliferation has several origins: (1) a revitalization of natural product research in a search for new drugs, (2) improved compound characterization methods (multidimensional NMR, high-resolution mass spectrometry), (3) specific enzyme-based and other biological assays, (4) sophisticated collection methods (SCUBA and remote submersibles for deep ocean marine collections), (5) new separation and purification techniques (HPLC and countercurrent separation), (6) a greater appreciation of traditional folk medicine and ethobotany, and (7) marine bacteria and fungi as novel sources of natural products. Halogenated alkaloids are truly omnipresent in the environment. Indeed, one compound, Q1 (234), is ubiquitous in the marine food web and is found in the Inuit from their diet of whale

  20. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated substituted pyridine. 721... Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses... pyridine (PMN P-86-838) is subject to reporting under this section for the significant new uses...

  1. Halogenated solvent remediation

    Science.gov (United States)

    Sorenson, Kent S.

    2004-08-31

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

  2. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  3. Cytotoxicity of halogenated graphenes

    Science.gov (United States)

    Teo, Wei Zhe; Khim Chng, Elaine Lay; Sofer, Zdeněk; Pumera, Martin

    2013-12-01

    Graphene and its family of derivatives possess unique and remarkable physicochemical properties which make them valuable materials for applications in many areas like electronics, energy storage and biomedicine. In response to the possibility of its large-scale manufacturing as commercial products in the future, an investigation was conducted to determine the cytotoxicity of one particular family of graphene derivatives, the halogenated graphenes, for the first time. Halogenated graphenes were prepared through thermal exfoliation of graphite oxide in gaseous chlorine, bromine or iodine atmospheres to yield chlorine- (TRGO-Cl), bromine- (TRGO-Br) and iodine-doped graphene (TRGO-I) respectively. 24 h exposure of human lung carcinoma epithelial cells (A549) to the three halogenated graphenes and subsequent cell viability assessments using methylthiazolyldiphenyl-tetrazolium bromide (MTT) and water-soluble tetrazolium salt (WST-8) assays revealed that all the halogenated graphenes examined are rather cytotoxic at the concentrations tested (3.125 μg mL-1 to 200 μg mL-1) and the effects are dose-dependent, with TRGO-Cl reducing the cell viability to as low as 25.7% at the maximum concentration of 200 μg mL-1. Their levels of cytotoxicity can be arranged in the order of TRGO-Cl > TRGO-Br > TRGO-I, and it is suggested that the amount of halogen present in the graphene material is the determining factor for the observed trend. Control experiments were carried out to test for possible nanomaterial-induced interference as a consequence of reaction between the halogenated graphenes and the viability markers (MTT/WST-8 reagent) or binding of the formazan products under cell-free conditions. The data obtained eliminate the probability of significant influence by these interferents as the change in the normalized percentage of formazan formed is relatively small and thorough washings were performed prior to the viability assessments to reduce the amount of halogenated

  4. Halogenation of cobalt dicarbollide

    Science.gov (United States)

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  5. Toxicokinetic studies on some mixed-halogenated dioxins. Final report; Toxikokinetische Untersuchungen einiger gemischt-halogenierter Dibenzodioxine. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Neubert, D. [Freie Univ. Berlin (Germany). Inst. fuer Toxikologie und Embryonalpharmakologie; Hutzinger, O. [Bayreuth Univ. (Germany). Lehrstuhl fuer Oekologische Chemie und Geochemie

    1996-12-31

    The goal was to provide first information on the kinetics of mixed-halogenated dibenzodioxins in mammals, as a basis for a risk assessment. Out of the multitude of mixed-halogenated dioxins, the following tri- and tetrahalogenated congeners were selected: 2,3-Br{sub 2}-7,8-Cl{sub 2}DD compared with 2,3,7,8-TCDD and 2,3,7,8-TBDD, as well as 2,3,7-trichlorodibenzo-p-dioxin (Cl{sub 3}DD), 2,3,7-tribromodibenzo-p-dioxin (Br{sub 3}DD) and 2,3-dichloro-7-bromodibenzo-p-dioxin (Cl{sub 2}Br{sub 1}DD). For a risk assessment data on kinetics are essential. These were established in two animal species (rat and marmoset-monkey) by analyzing the time course of tissue concentrations subsequent to single or multiple administrations. The studies performed with the trihalogenated congeners in this research project are among the first systematic studies in viva. The studies revealed for these congeners a quite different kinetics than for the 2,3,7,8-substituted ones. The kinetic properties of the tested 3 trihalogenated congeners Cl{sub 3}DD, Br{sub 3}DD, and Cl{sub 2}Br{sub 1}DD were almost identical in the rat. However, large differences existed in the organ distribution between liver, adipose tissue, and thymus. Following intravenous injection of Cl{sub 3}DD, Br{sub 3}DD, and Cl{sub 2}Br{sub 1}DD, a 8-fold increase in hepatic EROD-activity was observed. However, the induction did not correlate with the concentration within the liver. Due to the very short elimination half-life, the hepatic concentration had already considerably declined before the maximum of the enzyme induction was reached. This finding is unusual, and it differs considerably from all previous investigations performed with the 2,3,7,8-substituted congeners. For these substances always a perfect correlation was obtained. (orig./MG) [Deutsch] Es war das Ziel, erste Kenntnisse zur Pharmakokinetik gemischt-halogenierter Dibenzodioxine im Saeugerorganismus zu gewinnen, um Voraussetzungen fuer eine Risikoabschaetzung

  6. Halogen Chemistry in Volcanic Plumes (Invited)

    Science.gov (United States)

    Roberts, Tjarda

    2017-04-01

    Volcanoes release vast amounts of gases and particles in the atmosphere. Volcanic halogens (HF, HCl, HBr, HI) are co-emitted alongside SO2, and observations show rapid formation of BrO and OClO in the plume as it disperses into the troposphere. The development of 1D and Box models (e.g. PlumeChem) that simulate volcanic plume halogen chemistry aims to characterise how volcanic reactive halogens form and quantify their atmospheric impacts. Following recent advances, these models can broadly reproduce the observed downwind BrO/SO2 ratios using "bromine-explosion" chemistry schemes, provided they use a "high-temperature initialisation" to inject radicals (OH, Cl, Br and possibly NOx) which "kick-start" the low-temperature chemistry cycles that convert HBr into reactive bromine (initially as Br2). The modelled rise in BrO/SO2 and subsequent plateau/decline as the plume disperses downwind reflects cycling between reactive bromine, particularly Br-BrO, and BrO-HOBr-BrONO2. BrCl is produced when aerosol becomes HBr-depleted. Recent model simulations suggest this mechanism for reactive chlorine formation can broadly account for OClO/SO2 reported at Mt Etna. Predicted impacts of volcanic reactive halogen chemistry include the formation of HNO3 from NOx and depletion of ozone. This concurs with HNO3 widely reported in volcanic plumes (although the source of NOx remains under question), as well as observations of ozone depletion reported in plumes from several volcanoes (Mt Redoubt, Mt Etna, Eyjafjallajokull). The plume chemistry can transform mercury into more easily deposited and potentially toxic forms, for which observations are limited. Recent incorporation of volcanic halogen chemistry in a 3D regional model of degassing from Ambrym (Vanuatu) also predicts how halogen chemistry causes depletion of OH to lengthen the SO2 lifetime, and highlights the potential for halogen transport from the troposphere to the stratosphere. However, the model parameter-space is vast and

  7. Skin Sensitizing Potency of Halogenated Platinum Salts.

    Science.gov (United States)

    The relationship between occupational exposure to halogenated platinum (Pt) salts and Pt-specific allergic sensitization is well-established. Although human case reports and clinical studies demonstrate that Pt salts are potent skin sensitizers, no studies have been published tha...

  8. 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......, chlorinated lipids have been found in meat exposed to hypochlorite disinfected water, and in chlorine-treated flour and in products made from such flour. Following exposure to chlorine bleached pulp mill effluents, aquatic organisms may have elevated concentrations of chlorinated fatty acids in their lipids....... However, a natural production of halogenated fatty acids is also possible. In this paper we summarize the present knowledge of the occurrence of halogenated fatty acids in lipids and suggested ways of their formation. In Part II (Trends Anal. Chem. 16 (1997) 274) we deal with methods...

  9. Synthesis of 2(5H)-Furanone Derivatives with Bis-1,2,3-triazole Structure%Synthesis of 2(5H)-Furanone Derivatives with Bis-1,2,3-triazole Structure

    Institute of Scientific and Technical Information of China (English)

    霍景沛; 吕梅香; 王朝阳; 李意忠

    2012-01-01

    A series of new chiral 2(5H)-furanone derivatives containing bis-l,2,3-triazole moiety were designed and syn- thesized from (5S)-5-alkoxy-3,4-dihalo-2(5H)-furanones 1, dicarboxyl amino acids 2, propargyl bromide, and or- ganic azides 5 under mild conditions via the sequential three steps, including asymmetric Michael addi- tion-elimination, substitution and no-ligand click reaction. Twelve new intermediates, including N-[5-alkoxy- 2(5H)-furanonyl] dicarboxyl amino acids 3 and their corresponding propargyl esters 4, and twelve target molecules 6 were characterized by FTIR, 1H NMR, 13C NMR, MS and elemental analysis. The influences of different syn- thetic conditions and substrates in each step were investigated. The research provides a new method and idea for the synthesis of 2(5H)-furanone compounds with polyheterocyclic structure due to the diversities of four basic unit molecules.

  10. Halogen Chemistry in the CMAQ Model

    Science.gov (United States)

    Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

  11. 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.

  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. Role of computational efficiency indices and pose clustering in effective decision making: An example of annulated furanones in Pf-DHFR space.

    Science.gov (United States)

    Kumar, Manoj; Kaur, Tanpreet; Sharma, Anuj

    2017-04-01

    In the present report, the role of computationally estimated efficiency indices and pose clustering has been demonstrated in effective decision making, resource management and chemical prioritization. As an example, 720 annulated furanones from six different scaffold classes were computationally docked against Pf-DHFR active site using AutoDock 4.2. Many trends were established by navigating efficiency indices (BEI and SEI) in 2D planes. These trends were then explained by comparing interaction profiles of docked poses with that of known actives/inhibitors. Cases where trends emerged from efficiency plots resonated well with the pattern of a particular cluster diagram were considered as guidelines for optimization purpose. These kind of guidelines can help medicinal chemists in prioritization their work and in effective management of time, energy and chemical resources. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. The Synthetic of 5H -Furanone%5H -呋喃酮的合成

    Institute of Scientific and Technical Information of China (English)

    张广省

    2015-01-01

    The compounds with structure of 5H -furanones exist in a large number of natural products , and show a wide range of biological activities .5 H -furanone is organic synthesis of five ring lactone compounds key intermediates , some spices can be used for material and natural product synthesis , drug and biological substances is important in the Status . This text used in the synthesis of a new line to furfural and N ,N -Dimethyla cetamide and Formic acid and Hydrogen peroxide as the main raw material, the oxide of cis -obtained target product.%含5H -呋喃酮结构的化合物广泛存在于天然物质当中,具有多种生物活性。5H -呋喃酮是有机合成中合成五元内酯化合物的重要中间体,可用于一些香料物质和天然产物的合成,在药物和生物活性物质中具有重要的地位。本文中采用了全新的合成路线,以糠醛、二甲基乙醇胺、甲酸、双氧水为主要的原料,经氧化合成得到目标产物。

  15. Screening of Furanone in Cucurbita melo and Evaluation of its Bioactive Potential Using In Silico Studies.

    Science.gov (United States)

    Singh, Nidhi; Sudandiradoss, C; Abraham, Jayanthi

    2016-12-01

    The work presented here attempts to screen for the presence of 4-Hydroxy-2,5-dimethyl-3(2H)-furanone in fruits and also any bioactive potential present in the fruit extracts. Curcurbita melo was selected for the study, and the fruit was crushed, filtered and extracted with ethyl acetate as the solvent. The resulting extract was subjected to disk diffusion test using Kirby Bauer method for checking its antimicrobial potential. Melon extract showed promising results against different clinical pathogens, 19-mm zone being the largest against Klebsiella pneumoniae and 17 mm against Shigella dysenteriae. GC-MS data of the melon extract confirmed the existence of furanone derivative in the extract. To evaluate the antimicrobial activity, in silico studies were performed using AutoDock 4.0 software, and topoisomerase was used as the target protein molecule for the isolated compound and 3-methyl-2-(2-oxopropyl)furan as the ligand. Further, the results were interpreted using PyMol and Ligplot plus softwares. The results confirmed the presence of molecular interactions between the protein molecule and the ligand. It can be envisaged that these interactions are responsible for the inhibitory effects of the extract .

  16. QSAR analysis of furanone derivatives as potential COX-2 inhibitors: kNN MFA approach

    Directory of Open Access Journals (Sweden)

    Ruchi Bhatiya

    2014-12-01

    Full Text Available A series of thirty-two furanone derivatives with their cyclooxygenase-2 inhibitory activity were subjected to quantitative structural–activity relationship analysis to derive a correlation between biological activity as a dependent variable and various descriptors as independent variables by using V-LIFE MDS3.5 software. The significant 2D QSAR model showed correlation coefficient (r2 = 0.840, standard error of estimation (SEE = 0.195, and a cross-validated squared correlation coefficient (q2 = 0.773. The descriptors involved in the building of 2D QSAR model are retention index for six membered rings, total number of oxygen connected with two single bonds, polar surface area excluding P and S plays a significant role in COX-2 inhibition. 3D-QSAR performed via Step Wise K Nearest Neighbor Molecular Field Analysis [(SW kNN MFA] with partial least-square (PLS technique showed high predictive ability (r2 = 0.7622, q2 = 0.7031 and standard error = 0.3660 explaining the majority of the variance in the data with two principle components. The results of the present study may be useful in the design of more potent furanone derivatives as COX-2 inhibitors.

  17. Halogen Bonding Promotes Higher Dye-Sensitized Solar Cell Photovoltages.

    Science.gov (United States)

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

    2016-08-24

    We report here an enhancement in photovoltage for dye-sensitized solar cells (DSSCs) where halogen-bonding interactions exist between a nucleophilic electrolyte species (I(-)) and a photo-oxidized dye immobilized on a TiO2 surface. The triarylamine-based dyes under investigation showed larger rate constants for dye regeneration (kreg) by the nucleophilic electrolyte species when heavier halogen substituents were positioned on the dye. The open-circuit voltages (VOC) tracked these kreg values. This analysis of a homologous series of dyes that differ only in the identity of two halogen substituents provides compelling evidence that the DSSC photovoltage is sensitive to kreg. This study also provides the first direct evidence that halogen-bonding interactions between the dye and the electrolyte can bolster DSSC performance.

  18. PHENYLSULFONYL-SUBSTITUTED 5-ALKOXY-2(5H)-FURANONES - A NEW CLASS OF HIGHLY REACTIVE CHIRAL DIENOPHILES

    NARCIS (Netherlands)

    DEJONG, JC; VANDENBERG, KJ; FERINGA, BL; van Leusen, A.M.

    1991-01-01

    The synthesis of enantiomerically pure (5S)-5-(d-menthyloxy)-4-(phenylsulfonyl)-2(5H)-furanone (4) and the application of 4 as efficient dienophile in Diels-Alder reactions under mild conditions with enantioselectivities > 98% e.e. are described.

  19. Phenylsulfonyl-substituted 5-Alkoxy-2(5H)-furanones; a New Class of Highly Reactive Chiral Dienophiles.

    NARCIS (Netherlands)

    de Jong, Johannes C.; Berg, Keimpe J. van den; Leusen, Albert M. van; Feringa, Bernard

    1991-01-01

    The synthesis of enantiomerically pure (5S)-5-(d-menthyloxy)-4-(phenylsulfonyl)-2(5H)-furanone (4) and the application of 4 as efficient dienophile in Diels-Alder reactions under mild conditions with enantioselectivities >98% e.e. are described.

  20. Asymmetric 1,3-Dipolar Cycloadditions to 5-(R)-Menthyloxy-2(5H)-Furanone

    NARCIS (Netherlands)

    Rispens, Minze T.; Keller, Erik; Lange, Ben de; Zijlstra, Robert W.J.; Feringa, Bernard

    Various diazo compounds, nitrile oxides, nitrones and azomethine ylides were examined in 1,3-dipolar cycloadditions to enantiomerically pure 5-(R)-menthyloxy-2(5H)-furanone 1a. Pyrazoline 9 was obtained in 100% c.y. as a mixture of 2 diastereoisomers in ratios up to 72 : 28, whereas pyrazoline 16

  1. Novel 4-Aroyl-3-alkoxy-2(5H-furanones as Precursors for the Preparation of Furo[3,4-b][1,4]-diazepine Ring System

    Directory of Open Access Journals (Sweden)

    Adel Amer

    2003-10-01

    Full Text Available A general synthesis of tetronic acid derivatives, namely 4-aroyl-3-alkoxy-2(5H-furanones, is achieved via the treatment of an anhydrous dimethylformamide (DMF solution of 4-aroyl-3-hydroxy-2(5H-furanones with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU as base at -10-0°C, followed by the addition of alkyl iodide. Their structural assignments are based on spectroscopic data and confirmed by X-ray crystallography. These furanones were used as starting materials for the preparation of furodiazepines.

  2. Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites.

    Science.gov (United States)

    Schöler, Heinz F; Nkusi, Gerard; Niedan, Volker W; Müller, German; Spitthoff, Bianca

    2005-09-01

    The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.

  3. Quinoline based furanones and their nitrogen analogues: Docking, synthesis and biological evaluation

    Directory of Open Access Journals (Sweden)

    Sukhbir Lal Khokra

    2016-11-01

    Full Text Available A small library of twenty-four quinoline based butenolides also known as furanones and their nitrogen analogues was prepared by using two different aroylpropionic acids, viz. 3-(2-naphthoylpropionic acid (3 and 3-(biphenyl-4-ylpropionic acid (4, as starting materials. The 3-aroylpropionic acids were reacted with different 6-substituted-2-chloroquinolin-3-carbaldehydes (2a–d to obtain the corresponding furan-2(3H-ones (5a–h. The purified and characterized furanones were then converted into their corresponding 2(3H-pyrrolones (6a–h and N-benzyl-pyrrol-2(3H-ones (7a–h. The antimicrobial activities of the title compounds were evaluated against two strains of each Gram +ve (Staphylococcus aureus and Bacillus subtilis, Gram −ve bacteria (Escherichia coli and Pseudomonas aeruginosa and against fungal strains of Aspergillus niger and Aspergillus flavus. In vivo anti-inflammatory potential of the title compounds was investigated by standard method. Majority of the compounds showed significant antibacterial activity against both the Gram +ve strains. Eight most potent anti-inflammatory compounds (5b, 5d, 5h, 6b, 7b, 7d, 7f, 7h which exhibited >53% inhibition in edema, were also screened for their in vivo analgesic activity. All the tested compounds were found to have significant reduction in ulcerogenic action but only three compounds (5d, 5h and 7h showed comparable analgesic activity to standard drug, diclofenac. The results were also validated using in silico approach and maximum mol doc score was obtained for compounds 7a–h. On comparing the in vivo and in silico anti-inflammatory results of synthesized compounds, N-benzyl pyrrolones (7a–h emerged as the potent anti-inflammatory agents. It was also observed that compounds that possess electron withdrawing group such as Cl or NO2 are more biologically active.

  4. The Halogen Occultation Experiment

    Science.gov (United States)

    Russell, James M., III; Gordley, Larry L.; Park, Jae H.; Drayson, S. R.; Hesketh, W. D.; Cicerone, Ralph J.; Tuck, Adrian F.; Frederick, John E.; Harries, John E.; Crutzen, Paul J.

    1993-01-01

    The Halogen Occultation Experiment (HALOE) uses solar occultation to measure vertical profiles of O3, HCl, HF, CH4, H2O, NO, NO2, aerosol extinction, and temperature versus pressure with an instantaneous vertical field of view of 1.6 km at the earth limb. Latitudinal coverage is from 80 deg S to 80 deg N over the course of 1 year and includes extensive observations of the Antarctic region during spring. The altitude range of the measurements extends from about 15 km to about 60-130 km, depending on channel. Experiment operations have been essentially flawless, and all performance criteria either meet or exceed specifications. Internal data consistency checks, comparisons with correlative measurements, and qualitative comparisons with 1985 atmospheric trace molecule spectroscopy (ATMOS) results are in good agreement. Examples of pressure versus latitude cross sections and a global orthographic projection for the September 21 to October 15, 1992, period show the utility of CH4, HF, and H2O as tracers, the occurrence of dehydration in the Antarctic lower stratosphere, the presence of the water vapor hygropause in the tropics, evidence of Antarctic air in the tropics, the influence of Hadley tropical upwelling, and the first global distribution of HCl, HF, and NO throughout the stratosphere. Nitric oxide measurements extend through the lower thermosphere.

  5. Structural perspective on enzymatic halogenation.

    Science.gov (United States)

    Blasiak, Leah C; Drennan, Catherine L

    2009-01-20

    Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% ( Harris , C. M. ; Kannan , R. ; Kopecka , H. ; Harris , T. M. J. Am. Chem. Soc. 1985 , 107 , 6652 - 6658 ). This Account analyzes how structure underlies mechanism in halogenases, the molecular machines designed by nature to incorporate halogens into diverse substrates. Traditional synthetic methods of integrating halogens into complex molecules are often complicated by a lack of specificity and regioselectivity. Nature, however, has developed a variety of elegant mechanisms for halogenating specific substrates with both regio- and stereoselectivity. An improved understanding of the biological routes toward halogenation could lead to the development of novel synthetic methods for the creation of new compounds with enhanced functions. Already, researchers have co-opted a fluorinase from the microorganism Streptomyces cattleya to produce (18)F-labeled molecules for use in positron emission tomography (PET) ( Deng , H. ; Cobb , S. L. ; Gee , A. D. ; Lockhart , A. ; Martarello , L. ; McGlinchey , R. P. ; O'Hagan , D. ; Onega , M. Chem. Commun. 2006 , 652 - 654 ). Therefore, the discovery and characterization of naturally occurring enzymatic halogenation mechanisms has become an active area of research. The catalogue of known halogenating enzymes has expanded from the familiar haloperoxidases to include oxygen-dependent enzymes and fluorinases. Recently, the discovery of a nucleophilic halogenase that catalyzes chlorinations has expanded the repertoire of biological halogenation chemistry ( Dong , C. ; Huang , F. ; Deng , H. ; Schaffrath , C. ; Spencer , J. B. ; O'Hagan , D. ; Naismith , J. H. Nature 2004 , 427 , 561 - 565 ). Structural

  6. Halogenated compounds from marine algae.

    Science.gov (United States)

    Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

    2010-08-09

    Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds.

  7. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Science.gov (United States)

    2010-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  8. The mechanism of halogen liberation in the polar troposphere

    Directory of Open Access Journals (Sweden)

    E. Lehrer

    2004-06-01

    Full Text Available Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a 1-D model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently 'recycles' less reactive bromine species (e.g. HBr and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

  9. Halogen Bonding in Organic Synthesis and Organocatalysis.

    Science.gov (United States)

    Bulfield, David; Huber, Stefan M

    2016-10-01

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  10. A vibrational circular dichroism approach to the determination of the absolute configurations of flavorous 5-substituted-2(5H)-furanones.

    Science.gov (United States)

    Nakahashi, Atsufumi; Yaguchi, Yoshihiro; Miura, Nobuaki; Emura, Makoto; Monde, Kenji

    2011-04-25

    Sotolon (1) and maple furanone (2) are naturally occurring chiral furanones. These 5-substituted-2(5H)-furanones are industrially significant aroma compounds due to their characteristic organoleptic properties and extraordinarily low odor thresholds. Each enantiomer of 1 and 2 was successfully obtained by preparative enantioselective supercritical fluid chromatography. The absolute configuration of 1 was confirmed as (R)-(-)-1 and (S)-(+)-1 by adopting the vibrational circular dichroism (VCD) approach. The absolute configuration of 2, which has remained ambiguous since its discovery in 1957, was determined as (R)-(+)-2 and (S)-(-)-2 for the first time by the VCD technique. Surprisingly, the signs of the optical rotation of 2 are opposite of those of 1 regardless of their identical absolute configurations. This observation emphasizes the risk in absolute configurational assignments based on comparison of optical rotation signs of similar structures. Odor evaluation of the enantiomers of 2 revealed different odor intensities.

  11. 3-Hydroxy-4,5-dimethyl-2(5H)-furanone: a key odorant of the typical aroma of oxidative aged Port wine.

    Science.gov (United States)

    Silva Ferreira, A C; Barbe, Jean-Christophe; Bertrand, Alain

    2003-07-16

    Application of aroma extract dilution analysis (AEDA) on organic extracts from Port wines barrel-aged over 40 years revealed 5 odor-active compounds corresponding to descriptors used to qualify the characteristic old wine aroma. One of the compounds, described as "nutty" and "spicy-like", and present in at least 9 dilutions above the others, was perceived as particularly important. The compound responsible for this flavor was identified as 3-hydroxy-4,5-dimethyl-2(5H)-furanone (sotolon). The levels ranged from 5 to 958 microg/L for wines between 1 and 60 years old. It was also observed that during oxidative aging the concentration of this compound increased with time according to a linear trend (r > 0.95). Although the presence of 2-ketobutyric acid was verified, the constant rate of formation of sotolon with aging and its high correlation with sugar derivates (HMF, furfural) suggests other mechanisms, different from those reported for other wines. The flavor threshold of sotolon was evaluated in Port wine at 19 microg/L. Sensorial tests provided valuable information concerning sotolon impact on Port wine aroma. Samples supplemented with this substance were consistently ranked as older. In view of these results it can be expected that sotolon plays a pre-eminent role in the characteristic old Port wine aroma.

  12. 3-Hydroxy-4, 5-dimethyl-2 (5 H)-furanone levels in fortified Madeira wines: Relationship to sugar content

    OpenAIRE

    2004-01-01

    The maturation of Madeira wines usually involves exposure to relatively high temperatures and humidity levels >70%, which affect the aroma and flavor composition and lead to the formation of the typical and characteristic bouquet of these wines. To estimate the levels of sotolon [3-hydroxy4,5-dimethyl-2(5 H )-furanone] and their behavior over time, 86 aged Madeira wines samples (1-25 years old), with different sugar concentrations, respectively, 90 g L-1 for Boal, 110 g L-1 for Malvazia, 25 g...

  13. [Halogenated natural products from the marine-derived actinobacteria and their halogenation mechanism].

    Science.gov (United States)

    Tan, Yi; Zhou, Hong-xia; Wang, Yi-guang; Gan, Mao-luo; Yang, Zhao-yong

    2013-09-01

    In the last decade, along with the development of taxonomy research in marine-derived actinobacteria, more and more halogenated natural products were discovered from marine actinobacteria. Most of them showed good biological activity and unique structure compared to those from land. The special halogenation mechanism in some compounds' biosynthesis has drawn great attention. So in this review, we focus on the halogenated natural products from marine actinobacteria and their halogenation mechanisms.

  14. How do halogen bonds (S-O⋯I, N-O⋯I and C-O⋯I) and halogen-halogen contacts (C-I⋯I-C, C-F⋯F-C) subsist in crystal structures? A quantum chemical insight.

    Science.gov (United States)

    Pandiyan, B Vijaya; Deepa, P; Kolandaivel, P

    2017-01-01

    Thirteen X-ray crystal structures containing various non-covalent interactions such as halogen bonds, halogen-halogen contacts and hydrogen bonds (I⋯N, I⋯F, I⋯I, F⋯F, I⋯H and F⋯H) were considered and investigated using the DFT-D3 method (B97D/def2-QZVP). The interaction energies were calculated at MO62X/def2-QZVP and MP2/aug-cc-pvDZ level of theories. The higher interaction and dispersion energies (2nd crystal) of -9.58 kcal mol(-1) and -7.10 kcal mol(-1) observed for 1,4-di-iodotetrafluorobenzene bis [bis (2-phenylethyl) sulfoxide] structure indicates the most stable geometrical arrangement in the crystal packing. The electrostatic potential values calculated for all crystal structures have a positive σ-hole, which aids understanding of the nature of σ-hole bonds. The significance of the existence of halogen bonds in crystal packing environments was authenticated by replacing iodine atoms by bromine and chlorine atoms. Nucleus independent chemical shift analysis reported on the resonance contribution to the interaction energies of halogen bonds and halogen-halogen contacts. Hirshfeld surface analysis and topological analysis (atoms in molecules) were carried out to analyze the occurrence and strength of all non-covalent interactions. These analyses revealed that halogen bond interactions were more dominant than hydrogen bonding interactions in these crystal structures. Graphical Abstract Molecluar structure of 1,4-Di-iodotetrafluorobenzene bis(thianthrene 5-oxide) moelcule and its corresponding molecular electrostatic potential map for the view of σ-hole.

  15. Synthesis, reactions and biological activity of 3-arylidene-5-(4-methylphenyl-2(3H-furanones

    Directory of Open Access Journals (Sweden)

    ASIF HUSAIN

    2009-02-01

    Full Text Available 3-Arylidene-5-(4-methylphenyl-2(3H-furanones 2a–m were prepared from 3-(4-methyl-benzoylpropanoic acid 1 and several aromatic aldehydes. Some of the selected furanones were reacted with ammonia gas and benzylamine to give corresponding 3-arylidene-1,3-dihydro-5-(4-methylphenyl-2H-pyrrol-2-ones 3a–h and 3-arylidene-1-benzyl-1,3-dihydro-5-(4-methylphenyl-2H-pyrrol-2-ones 4a–f, respectively, which were characterized on the basis of IR, 1H-NMR, mass spectral data and elemental analysis results. These compounds were tested for their anti-inflammatory and antibacterial activities. The compounds, which showed significant anti-inflammatory activity, were further screened for their analgesic and ulcerogenic activities. Three new compounds (2e, 2h and 4d, out of twenty-seven showed very good anti-inflammatory activity in the carrageenan induced rat paw edema test, with significant analgesic activity in the acetic acid induced writhing test together with negligible ulcerogenic action. The antibacterial activity is expressed as the corresponding MIC values.

  16. Volatile halogenated hydrocarbons in foods

    Energy Technology Data Exchange (ETDEWEB)

    Miyahara, Makoto; Toyoda, Masatake; Saito, Yukio [National Institute of Health Services, Tokyo (Japan)] [and others

    1995-02-01

    Volatile halogenated organic compounds were determined in foods. Statistical treatment of the data for 13 sampled from 20 families living in suburban Tokyo (Saitama prefecture) indicated that the foods were contaminated by water pollution and/or substances introduced by the process of food production. Butter and margarine were contaminated by chlorinated ethylene, ethane, and related compounds released by dry cleaning and other operations. Soybean sprouts and tofu (soybean curd) contained chloroform and related trihalomethanes absorbed during the production process. 27 refs., 6 figs., 5 tabs.

  17. Copper-Catalyzed [4 + 1] Annulation between α-Hydroxy Ketones and Nitriles: An Approach to Highly Substituted 3(2H)-Furanones.

    Science.gov (United States)

    He, Haitao; Qi, Chaorong; Hu, Xiaohan; Ouyang, Lu; Xiong, Wenfang; Jiang, Huanfeng

    2015-05-15

    A copper-catalyzed [4 + 1] annulation between α-hydroxy ketones and nitriles has been developed. The reaction provides a facile and efficient method for the construction of a wide range of highly substituted 3(2H)-furanones, a class of important compounds known to be associated with several biological activities.

  18. EFSA EFSA ; Scientific Opinion on Flavouring Group Evaluation 99 (FGE.99): Consideration of furanone derivatives evaluated by the JECFA (63rd, 65th and 69th meetings)

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of five furanone derivatives evaluated by the JECFA at their 63rd, 65th and 69th meetings. The substances were evaluated through a stepwise approach that integrates information...

  19. Halogenation generates effective modulators of amyloid-Beta aggregation and neurotoxicity.

    Directory of Open Access Journals (Sweden)

    H Edward Wong

    Full Text Available Halogenation of organic compounds plays diverse roles in biochemistry, including selective chemical modification of proteins and improved oral absorption/blood-brain barrier permeability of drug candidates. Moreover, halogenation of aromatic molecules greatly affects aromatic interaction-mediated self-assembly processes, including amyloid fibril formation. Perturbation of the aromatic interaction caused by halogenation of peptide building blocks is known to affect the morphology and other physical properties of the fibrillar structure. Consequently, in this article, we investigated the ability of halogenated ligands to modulate the self-assembly of amyloidogenic peptide/protein. As a model system, we chose amyloid-beta peptide (Aβ, which is implicated in Alzheimer's disease, and a novel modulator of Aβ aggregation, erythrosine B (ERB. Considering that four halogen atoms are attached to the xanthene benzoate group in ERB, we hypothesized that halogenation of the xanthene benzoate plays a critical role in modulating Aβ aggregation and cytotoxicity. Therefore, we evaluated the modulating capacities of four ERB analogs containing different types and numbers of halogen atoms as well as fluorescein as a negative control. We found that fluorescein is not an effective modulator of Aβ aggregation and cytotoxicity. However, halogenation of either the xanthenes or benzoate ring of fluorescein substantially enhanced the inhibitory capacity on Aβ aggregation. Such Aβ aggregation inhibition by ERB analogs except rose bengal correlated well to the inhibition of Aβ cytotoxicity. To our knowledge, this is the first report demonstrating that halogenation of aromatic rings substantially enhance inhibitory capacities of small molecules on Aβ-associated neurotoxicity via Aβ aggregation modulation.

  20. Stereoselective Halogenation in Natural Product Synthesis.

    Science.gov (United States)

    Chung, Won-jin; Vanderwal, Christopher D

    2016-03-24

    At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp(3) -hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.

  1. Halogen Chemistry on Catalytic Surfaces.

    Science.gov (United States)

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling.

  2. Halogen versus halide electronic structure

    Institute of Scientific and Technical Information of China (English)

    Willem-Jan; van; Zeist; F.Matthias; Bickelhaupt

    2010-01-01

    Halide anions X-are known to show a decreasing proton affinity(PA),as X descends in the periodic table along series F,Cl,Br and I.But it is also well-known that,along this series,the halogen atom X becomes less electronegative(or more electropositive).This corresponds to an increasing energy of the valence np atomic orbital(AO) which,somewhat contradictorily,suggests that the electron donor capability and thus the PA of the halides should increase along the series F,Cl,Br,I.To reconcile these contradictory observations,we have carried out a detailed theoretical analysis of the electronic structure and bonding capability of the halide anions X-as well as the halogen radicals X-,using the molecular orbital(MO) models contained in Kohn-Sham density functional theory(DFT,at SAOP/TZ2P as well as OLYP/TZ2P levels) and ab initio theory(at the HF/TZ2P level).We also resolve an apparent intrinsic contradiction in Hartree-Fock theory between orbital-energy and PA trends.The results of our analyses are of direct relevance for understanding elementary organic reactions such as nucleophilic substitution(SN2) and base-induced elimination(E2) reactions.

  3. Halogenated coumarin derivatives as novel seed protectants.

    Science.gov (United States)

    Brooker, N; Windorski, J; Bluml, E

    2008-01-01

    Development of new and improved antifungal compounds that are target-specific is backed by a strong Federal, public and commercial mandate. Many plant-derived chemicals have proven fungicidal properties, including the coumarins (1,2-Benzopyrone) found in a variety of plants such as clover, sweet woodruff and grasses. Preliminary research has shown the coumarins to be a highly active group of molecules with a wide range of antimicrobial activity against both fungi and bacteria. It is believed that these cyclic compounds behave as natural pesticidal defence molecules for plants and they represent a starting point for the exploration of new derivative compounds possessing a range of improved antifungal activity. Within this study, derivatives of coumarin that were modified with halogenated side groups were screened for their antifungal activity against a range of soil-borne plant pathogenic fungi. Fungi included in this in vitro screen included Macrophomina phaseolina (charcoal rot), Phytophthora spp. (damping off and seedling rot), Rhizoctonia spp. (damping off and root rot) and Pythium spp. (seedling blight), four phylogenetically diverse and economically important plant pathogens. Studies indicate that these halogenated coumarin derivatives work very effectively in vitro to inhibit fungal growth and some coumarin derivatives have higher antifungal activity and stability as compared to the original coumarin compound alone. The highly active coumarin derivatives are brominated, iodinated and chlorinated compounds and results suggest that besides being highly active, very small amounts can be used to achieve LD100 rates. In addition to the in vitro fungal inhibition assays, results of polymer seed coating compatibility and phytotoxicity testing using these compounds as seed treatments will also be reported. These results support additional research in this area of natural pesticide development.

  4. 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.

  5. Halogen Bonding in Hypervalent Iodine Compounds.

    Science.gov (United States)

    Catalano, Luca; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe; Terraneo, Giancarlo

    Halogen bonds occur when electrophilic halogens (Lewis acids) attractively interact with donors of electron density (Lewis bases). This term is commonly used for interactions undertaken by monovalent halogen derivatives. The aim of this chapter is to show that the geometric features of the bonding pattern around iodine in its hypervalent derivatives justify the understanding of some of the longer bonds as halogen bonds. We suggest that interactions directionality in ionic and neutral λ(3)-iodane derivatives is evidence that the electron density distribution around iodine atoms is anisotropic, a region of most positive electrostatic potential exists on the extensions of the covalent bonds formed by iodine, and these positive caps affect, or even determine, the crystal packing of these derivatives. For instance, the short cation-anion contacts in ionic λ(3)-iodane and λ(5)-iodane derivatives fully match the halogen bond definition and geometrical prerequisites. The same holds for the short contacts the cation of ionic λ(3)-iodanes forms with lone-pair donors or the short contacts given by neutral λ(3)-iodanes with incoming nucleophiles. The longer and weaker bonds formed by iodine in hypervalent compounds are usually called secondary bondings and we propose that the term halogen bond can also be used. Compared to the term secondary bond, halogen bond may possibly be more descriptive of some bonding features, e.g., its directionality and the relationships between structure of interacting groups and interaction strength.

  6. Does fluorine participate in halogen bonding?

    Science.gov (United States)

    Eskandari, Kiamars; Lesani, Mina

    2015-03-16

    When R is sufficiently electron withdrawing, the fluorine in the R-F molecules could interact with electron donors (e.g., ammonia) and form a noncovalent bond (F⋅⋅⋅N). Although these interactions are usually categorized as halogen bonding, our studies show that there are fundamental differences between these interactions and halogen bonds. Although the anisotropic distribution of electronic charge around a halogen is responsible for halogen bond formations, the electronic charge around the fluorine in these molecules is spherical. According to source function analysis, F is the sink of electron density at the F⋅⋅⋅N BCP, whereas other halogens are the source. In contrast to halogen bonds, the F⋅⋅⋅N interactions cannot be regarded as lump-hole interactions; there is no hole in the valence shell charge concentration (VSCC) of fluorine. Although the quadruple moment of Cl and Br is mainly responsible for the existence of σ-holes, it is negligibly small in the fluorine. Here, the atomic dipole moment of F plays a stabilizing role in the formation of F⋅⋅⋅N bonds. Interacting quantum atoms (IQA) analysis indicates that the interaction between halogen and nitrogen in the halogen bonds is attractive, whereas it is repulsive in the F⋅⋅⋅N interactions. Virial-based atomic energies show that the fluorine, in contrast to Cl and Br, stabilize upon complex formation. According to these differences, it seems that the F⋅⋅⋅N interactions should be referred to as "fluorine bond" instead of halogen bond.

  7. Informative document halogenated hydrocarbon-containing waste

    NARCIS (Netherlands)

    Verhagen H

    1992-01-01

    This "Informative document halogenated hydrocarbon-containing waste" forms part of a series of "Informative documents waste materials". These documents are conducted by RIVM on the instructions of the Directorate General for the Environment, Waste Materials Directorate, in behal

  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......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......, 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....

  9. 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.

  10. Latest generation of halogen-containing pesticides.

    Science.gov (United States)

    Jeschke, Peter

    2017-02-01

    Agriculture is confronted with enormous challenges, from production of enough high-quality food to water use, environmental impacts and issues combined with a continually growing world population. Modern agricultural chemistry has to support farmers by providing innovative agrichemicals, used in applied agriculture. In this context, the introduction of halogen atoms into an active ingredient is still an important tool to modulate the properties of new crop protection compounds. Since 2010, around 96% of the launched products (herbicides, fungicides, insecticides/acaricides and nematicides) contain halogen atoms. The launched nematicides contain the largest number of halogen atoms, followed by insecticides/acaricides, herbicides and fungicides. In this context, fungicides and herbicides contain in most cases fluorine atoms, whereas nematicides and insecticides contain in most cases 'mixed' halogen atoms, for example chlorine and fluorine. This review gives an overview of the latest generation of halogen-containing pesticides launched over the past 6 years and describes current halogen-containing development candidates. © 2017 Society of Chemical Industry.

  11. Pop-like halogenated natural products in antarctic sponges

    Energy Technology Data Exchange (ETDEWEB)

    Vetter, W. [Hohenheim Univ., Stuttgart (Germany); Janussen, D. [Senckenbergische Naturforschende Gesellschaft (Natur-Museum und Forschungs-Institut), Frankfurt am Main (Germany)

    2004-09-15

    Persistent organic pollutants (POPs) are major contaminants of our days. This group of chemicals comprises a number of halogenated compounds used as pesticides (DDT, lindane, chlordane, toxaphene and others) as well as industrial chemicals (PCBs, PCNs, CPs, and brominated flameretardants). Although the list of known POPs including isomers and metabolites is long, there are frequent reports on the detection of unknown organohalogen compounds in the literature. Recent work demonstrated that some of these unknown peaks in gas chromatograms originate from halogenated natural products (HNPs). Sometimes, HNPs have been found at remarkably high concentrations in marine birds, mammals and fish. Due to the structural similarities with anthropogenic POPs, these substances may possess a potential risk for wildlife and man. HNPs are known to be produced with an overwhelming variety by marine organisms such as algae, sponges, microorganisms and others. In this study we have screened different species of Antarctic sponges on the occurrence of halogenated compounds which may be of environmental concern. Thus, we were only interested in lipophilic and persistent HNPs. Following that, we applied our standard sample clean-up procedure for the analysis of nonpolar POPs. Two steps on deactivated and activated silica yielded compounds with similar polarity as PCBs, chloropesticides and brominated analogues in the sample extracts. Additionally, all samples were treated with concentrated sulphuric acid in order to eliminate labile (non-presistent) HNPs.

  12. Quorum sensing-disrupting brominated furanones protect the gnotobiotic brine shrimp Artemia franciscana from pathogenic Vibrio harveyi, Vibrio campbellii, and Vibrio parahaemolyticus isolates.

    Science.gov (United States)

    Defoirdt, Tom; Crab, Roselien; Wood, Thomas K; Sorgeloos, Patrick; Verstraete, Willy; Bossier, Peter

    2006-09-01

    Autoinducer 2 (AI-2) quorum sensing was shown before to regulate the virulence of Vibrio harveyi towards the brine shrimp Artemia franciscana. In this study, several different pathogenic V. harveyi, Vibrio campbellii, and Vibrio parahaemolyticus isolates were shown to produce AI-2. Furthermore, disruption of AI-2 quorum sensing by a natural and a synthetic brominated furanone protected gnotobiotic Artemia from the pathogenic isolates in in vivo challenge tests.

  13. Treatment System for Removing Halogenated Compounds from Contaminated Sources

    Science.gov (United States)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor)

    2015-01-01

    A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

  14. 2(5H-Furanone: a prospective strategy for biofouling-control in membrane biofilm bacteria by quorum sensing inhibition

    Directory of Open Access Journals (Sweden)

    Kannan Ponnusamy

    2010-03-01

    Full Text Available Biofouling of membranes demands costly periodic cleaning and membrane replacement. A sustainable and environmentally friendly solution for maintenance is not available and would be of great interest for many purposes including economical. As complex biofilm formation by environmental strains is the major cause of biofouling and biofilm formation in most cases are controlled by N-Acylhomoserine lactone (AHLmediated Quorum Sensing (QS. An effort was made to understand the appropriateness of 2(5H-furanone, to use against biofouling of membranes. QS inhibition activity by 2(5H-furanone was studied using bioindicator strains and known AHLs of different acyl chain lengths. The biofilm inhibition was studied by growth analysis on polystyrene plate of Aeromonas hyrdrophila, an environmental biofilm strain isolated from a bio-fouled reverse osmosis (RO membrane. Results showed a QS inhibition activity against a wide range of AHLs and also biofilm formation by 2(5H-furanone, which is believed to act as a potential quorum inhibition agent in a bacterial biofilm community.

  15. Negative Halogen Ions for Fusion Applications

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. A QTAIM exploration of the competition between hydrogen and halogen bonding in halogenated 1-methyluracil: Water systems

    Science.gov (United States)

    Huan, Guo; Xu, Tianlv; Momen, Roya; Wang, Lingling; Ping, Yang; Kirk, Steven R.; Jenkins, Samantha; van Mourik, Tanja

    2016-10-01

    Using QTAIM we show that the hydrogen bonding complexes of 5-halogenated-1-methyluracil (XmU; X = F, Cl, Br, I or At) with a water molecule were always stronger than the corresponding halogen bonds. The strength of the hydrogen bond decreased with increasing halogen size. The hydrogen bonds displayed an admixture of covalent character but all the halogen bonds were purely electrostatic in nature. An F---O halogen bond was found and was facilitated by an intermediate F---H bonding interaction. The metallicity ξ(rb) of the C = O bonds neighboring the hydrogen bonds and of the C-X bonds contiguous with the halogen bonds was explored.

  17. Halogen-bonding-triggered supramolecular gel formation.

    Science.gov (United States)

    Meazza, Lorenzo; Foster, Jonathan A; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W

    2013-01-01

    Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel ('co-gel') is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a 'tipping point' in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

  18. Evaluation of Halogenated Coumarins for Antimosquito Properties

    Directory of Open Access Journals (Sweden)

    Venugopala K. Narayanaswamy

    2014-01-01

    Full Text Available Mosquitoes are the major vectors of parasites and pathogens affecting humans and domestic animals. The widespread development of insecticide resistance and negative environmental effects of most synthetic compounds support an interest in finding and developing alternative products against mosquitoes. Natural coumarins and synthetic coumarin analogues are known for their several pharmacological properties, including being insecticidal. In the present study halogenated coumarins (3-mono/dibromo acetyl, 6-halogenated coumarin analogues were screened for larvicidal, adulticidal, and repellent properties against Anopheles arabiensis, a zoophilic mosquito that is one of the dominant vectors of malaria in Africa. Five compounds exerted 100% larval mortality within 24 h of exposure. All coumarins and halogenated coumarins reversibly knocked down adult mosquitoes but did not kill them after 24 h of exposure. Repellent properties could not be evidenced. Five compounds were considered potential larvicidal agents for further research and development, while adulticidal activity was considered only mild to moderate.

  19. Fiscal 1997 report on the results of the international standardization R and D. Development of a test method of halogen-free flame-retardant cables and a study of the cable standards; 1997 nendo seika hokokusho kokusai hyojun soseigata kenkyu kaihatsu. Non halogen nannen cable no shiken hoho kaihatsu narabini cable kikaku no kento

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-03-01

    As for halogen-free flame-retardant cables with high recyclability and safety (HFFR cables), the development is being promoted in many countries as a next generation cable. The standard of HFFR cables has been set up by some countries and groups in the U.S. and Europe, but the international standard has not yet been established independently. The purpose of this R and D is the development of a test method to appropriately evaluate the performance of HFFR cables and its standardization, and the proposal of the international standardization on common items of the cable standard. A study group was sent to the U.S. and Europe to investigate the development, application status and test methods of the HFFR cable overseas. The ion chromatography and FT-IR method were studied as methods to evaluate corrosivity/toxicity of the gases emitted in combustion. The performance of HFFR cables in Japan and abroad was also evaluated mainly by IEC standards. Further, considering the results of the overseas surveys, the structure and details of the international standard plan on HFFR cables were studied, and approaches to the international standardization were studied. 32 refs., 31 figs., 54 tabs.

  20. On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

    2015-06-28

    In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

  1. On the directionality of halogen bonding.

    Science.gov (United States)

    Huber, Stefan M; Scanlon, Joseph D; Jimenez-Izal, Elisa; Ugalde, Jesus M; Infante, Ivan

    2013-07-07

    The origin of the high directionality of halogen bonding was investigated quantum chemically by a detailed comparison of typical adducts in two different orientations: linear (most stable) and perpendicular. Energy decomposition analyses revealed that the synergy between charge-transfer interactions and Pauli repulsion are the driving forces for the directionality, while electrostatic contributions are more favourable in the less-stable, perpendicular orientation.

  2. Halogen Bonding in (Z-2-Iodocinnamaldehyde

    Directory of Open Access Journals (Sweden)

    Miriam Rossi

    2013-07-01

    Full Text Available Based on the bulkiness of the iodine atom, a non-planar conformation was expected for the title compound. Instead, its molecular structure is planar, as experimentally determined using single crystal X-ray diffraction, and confirmed theoretically by DFT calculations on the single molecule and the halogen pair paired molecules, therefore ruling out crystal packing forces as a principal factor leading to planarity. Indeed, planarity is ascribed to the carbonyl double bond, as when this bond is saturated on forming the related alcohol derivative, the molecule loses planarity. The X-ray molecular structure shows an intermolecular separation between the iodine and the oxygen of the carbonyl shorter than the corresponding van der Waals distance suggesting a weak halogen bond interaction. DFT minimization of this 2-molecule arrangement shows the iodine--oxygen distance much shorter than that observed in the crystal interaction and confirming its stronger halogen bond nature. A trend between increasing I•••O(carbonyl separation and decreasing C-I•••O(carbonyl angle is demonstrated, further confirming the existence of a halogen bond.

  3. Syntheses of very dense halogenated liquids.

    Science.gov (United States)

    Ye, Chengfeng; Shreeve, Jean'ne M

    2004-09-17

    A family of halogenated liquids with densities ranging from 1.95 to 2.80 g cm(-3) was readily synthesized by a one-pot procedure. These liquids exhibit characteristics of ionic liquids with melting/transition points lower than room temperature, long liquid ranges, and marked hydrolytic and thermal stabilities.

  4. Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen-Bonded Anions.

    Science.gov (United States)

    Cavallo, Gabriella; Terraneo, Giancarlo; Monfredini, Alessandro; Saccone, Marco; Priimagi, Arri; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Bruce, Duncan W

    2016-05-17

    Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen-bonded supramolecular anions [Cn F2 n+1 -I⋅⋅⋅I⋅⋅⋅I-Cn F2 n+1 ](-) are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen-bonded liquid crystals, and 2) imidazolium-based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.

  5. 3-(4-Methyl-3-pentenyl)-2(5H)-furanone, alpha,alpha-acariolide and 4-(4-methyl-3-pentenyl)-2(5H)-furanone, alpha,beta-acariolide: new monoterpene lactones from the astigmatid mites, Schwiebea araujoae and Rhizoglyphus sp. (Astigmata: Acaridae).

    Science.gov (United States)

    Tarui, Hirokazu; Mori, Naoki; Nishida, Ritsuo; Okabe, Kimiko; Kuwahara, Yasumasa

    2002-01-01

    A new monoterpene lactone from the acarid mite, Schwiebea araujoae, was elucidated without its isolation by GC/FT-IR and GC/MS analyses to be 3-(4-methyl-3-pentenyl)-2(5H)-furanone (1) and tentatively named as alpha,alpha-acariolide. The structure of 1 was identified by its synthesis from alpha-bromo-gamma-butyrolactone via 4 reaction steps. The synthesized compound gave the same GC/MS and GC/FT-IR spectra as those of the natural product. The other monoterpene lactone was likewise elucidated from the unidentified Rhizoglyphus mite to be 4-(4-methyl-3-pentenyl)-2(5H)-furanone (2) and named as alpha,beta-acariolide; it was also identified by its synthesis in 5 reaction steps from the same butyrolactone as the starting material. GC/MS and GC/FT-IR spectra of the preparation were identical to those of the natural product.

  6. Halogen bonding origin properties and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hobza, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague (Czech Republic); Regional Center of Advanced Technologies and Materials, Department of Physical Chemistry, Palacky University, 77146 Olomouc (Czech Republic)

    2015-12-31

    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well.

  7. 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.

  8. Asymmetric 1,4-Additions to 5-Alkoxy-2(5H)-furanones Enantioselective Synthesis and Absolute Configuration Determination of β-Amino-γ-butyrolactones and Amino Diols

    NARCIS (Netherlands)

    Lange, B. de; Bolhuis, F. van; Feringa, Bernard

    1989-01-01

    The synthesis of enantiomerically pure β-amino-γ-butyrolactones via asymmetric conjugate addition of various amines to 5-menthyloxy-2(5H)-furanone is described. This route provides access to new multifunctional homochiral building blocks. The absolute configuration of the β-amino-γ-butyrolactones is

  9. MX [3-Chloro-4-(Dichloromethyl)-5-Hydroxy-2[5H]-Furanone], A Drinking-Water Carcinogen, Does Not Induce Mutations in the Liver of Cii Transgenic Medaka (Oryzias latipes)

    Science.gov (United States)

    Mutagenicity assays with Salmonella have shown that 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone (MX), a drinking water disinfection by-product is a potent mutagen, accounting for about one third of the mutagenic potency/potential of chlorinated drinking water. The abilit...

  10. The pharmacology of halogenated salicylanilides and their anthelmintic use in animals : review article

    Directory of Open Access Journals (Sweden)

    G.E. Swan

    1999-07-01

    Full Text Available The halogenated salicylanilides are a large group of compounds developed mainly for their antiparasitic activity in animals. Several halogenated salicylanilides with potent antiparasitic activity have been synthesised of which only closantel, niclosamide, oxyclozanide, rafoxanide and resorantel are commercially available. Closantel and rafoxanide, which represent the most important drugs in the group, are used extensively for the control of Haemonchus spp. and Fasciola spp. infestations in sheep and cattle and Oestrus ovis in sheep in many parts of the world. Niclosamide is used extensively for its anticestodal activity in a wide range of animals. Antiparasitic activity of the halogenated salicylanilides has also been demonstrated against a large number of other internal parasites, in particular haematophagous helminths, and external parasites including ticks and mites, in a variety of animal species. Several cases of toxicity and mortality have been reported for closantel and rafoxanide in sheep and goats. Their unique pharmacokinetic behaviour appears to play an important role in the efficacy and safety of these compounds. The chemical and physical characteristics, mode of action, pharmacokinetics, antiparasitic activity and toxicity of the halogenated salicylanilides in animals are reviewed.

  11. Halogen bonds in crystal engineering: like hydrogen bonds yet different.

    Science.gov (United States)

    Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R

    2014-08-19

    The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen···halogen interactions (X···X) and halogen···heteroatom interactions (X···B). Many X···X and almost all X···B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms-halogen and hydrogen-are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X···X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen···halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be

  12. Recent Progress in Metal-Catalyzed Reactions of 2(5H)-Furanones%金属催化的2(5H)-呋喃酮反应研究进展

    Institute of Scientific and Technical Information of China (English)

    毛超旭; 汪朝阳; 谭越河; 薛福玲

    2011-01-01

    2(5H)-呋喃酮结构单元广泛存在于天然产物中,同时许多2(5H)-呋喃酮类化合物也是重要的有机合成中间体.因此,基于常见2(5H)-呋喃酮的有机合成研究近年来引起了人们的关注,尤其是金属催化的2(5H)-呋喃酮反应的地位日趋彰显重要,从而成为众多化学工作者的研究热点.按照反应类型的不同,对近年来金属催化的2(5H)-呋喃酮反应的研究进展进行了综述,主要包括Sonogashira,Suzuki,Stille等偶联反应,以及Michael加成反应、Friedel-Crafts烷基化反应、Baylis-Hillman反应、亲核取代反应、还原反应等.%The unique carbon skeleton of 2(5H)-furanone is widely present in a variety of natural products, and many compounds containing 2(5H)-furanone skeleton are important synthetic intermediates. Recently, more and more attentions have been attracted to the organic synthesis based on 2(5H)-furanones, especially via the metal-catalyzed reactions of 2(5H)-furanones. Classified as different types, the recent progress in metal-catalyzed reactions of 2(5H)-furanones, mainly including Sonogashira reaction, Suzuki reaction, Stille reaction, Michael addition, Friedel-Crafts alkylation, Baylis-Hillman reaction, nucleophilic substitution, and reduction reaction, is reviewed in this paper.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. Photoresponsive liquid crystals based on halogen bonding of azopyridines.

    Science.gov (United States)

    Chen, Yinjie; Yu, Haifeng; Zhang, Lanying; Yang, Huai; Lu, Yunfeng

    2014-09-04

    A series of photoresponsive halogen-bonded liquid crystals (LCs) were successfully constructed using molecular halogen and azopyridine compounds, which show interesting properties of photoinduced phase transition upon UV irradiation. In addition, bromine-bonded LCs were first obtained with high mesophase stability.

  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. Hydrogen bond and halogen bond inside the carbon nanotube

    Science.gov (United States)

    Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

    2011-02-01

    The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

  1. [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.

  2. Protection of halogenated DNA from strand breakage and sister-chromatid exchange induced by the topoisomerase I inhibitor camptothecin

    Energy Technology Data Exchange (ETDEWEB)

    Orta, Manuel Luis; Mateos, Santiago; Cantero, Gloria [Department of Cell Biology, Faculty of Biology, University of Seville (Spain); Wolff, Lisa J. [Sweet Briar College, VA (United States); Cortes, Felipe [Department of Cell Biology, Faculty of Biology, University of Seville (Spain)], E-mail: cortes@us.es

    2008-01-01

    The fundamental nuclear enzyme DNA topoisomerase I (topo I), cleaves the double-stranded DNA molecule at preferred sequences within its recognition/binding sites. We have recently reported that when cells incorporate halogenated nucleosides analogues of thymidine into DNA, it interferes with normal chromosome segregation, as shown by an extraordinarily high yield of endoreduplication, and results in a protection against DNA breakage induced by the topo II poison m-AMSA [F. Cortes, N. Pastor, S. Mateos, I. Dominguez, The nature of DNA plays a role in chromosome segregation: endoreduplication in halogen-substituted chromosomes, DNA Repair 2 (2003) 719-726; G. Cantero, S. Mateos, N. Pastor; F. Cortes, Halogen substitution of DNA protects from poisoning of topoisomerase II that results in DNA double-strand breaks (DSBs), DNA Repair 5 (2006) 667-674]. In the present investigation, we have assessed whether the presence of halogenated nucleosides in DNA diminishes the frequency of interaction of topo I with DNA and thus the frequency with which the stabilisation of cleavage complexes by the topo I poison camptothecin (CPT) takes place, in such a way that it protects from chromosome breakage and sister-chromatid exchange. This protective effect is shown to parallel a loss in halogen-substituted cells of the otherwise CPT-increased catalytic activity bound to DNA.

  3. A one dimensional model study of the mechanism of halogen liberation and vertical transport in the polar troposphere

    Directory of Open Access Journals (Sweden)

    E. Lehrer

    2004-01-01

    Full Text Available Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a one dimensional model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently 'recycles' less reactive bromine species (e.g. HBr and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

  4. A New Approach to the Asymmetric Reaction of the Chiron 5-L-Menthyloxy-2(5H)-furanones with Horner-Emmons Reagent

    Institute of Scientific and Technical Information of China (English)

    李学强; 王凤荣; 何兰; 陈庆华

    2003-01-01

    The asymmetric reaction of the chiron 2(5H )-furanones (4a-4c) with the Horner-Emmons reagents (5a-5b) has been investigated. The newly chirai organophosphorus derivatives 6 and 7 were obtained using the phosphoryl-stabilized carbanion as a building block in DMSO under mild conditions. Through the asymmetric introduction, the Horner-Emmons reagent could be transformed to a chiral building block to afford the novel functionalized phosphorus derivatives. The structures of the synthesized compounds 6 and 7 were identified on the basis of their elementary and spectroscopic data, such as IR,1H NMR, 13C NMR, MS and X-ray crystallography. These resuits provided a valuable approach to the synthesis of potentially interesting chirai organophosphorus derivatives and probing their biological activities.

  5. 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....

  6. Survey of reproductive hazards among oil, chemical, and atomic workers exposed to halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Savitz, D.A.; Harley, B.; Krekel, S.; Marshall, J.; Bondy, J.; Orleans, M.

    1984-01-01

    Several halogenated hydrocarbons are suspected of causing adverse reproductive effects. Because of such concerns, the Oil, Chemical, and Atomic Workers International Union surveyed the reproductive histories of two groups of workers. One group worked at plants engaged in the production or use of halogenated hydrocarbons (exposed) whereas the others had no such opportunity for exposure (nonexposed). Although a low response rate precludes firm conclusions, the 1,280 completed questionnaires provide useful data for generating hypotheses in this developing field of interest. A history of diagnosed cancer was reported more frequently among exposed workers. The infant mortality rate was also significantly elevated among the offspring of exposed workers. No risk gradient was observed for episodes of infertility, fetal loss, congenital defects, or low-birthweight offspring. Concerns with nonresponse, exposure characterization, possible confounding factors, and limited statistical power are addressed. The results provide further suggestions which help to direct studies of occupational reproductive risks.

  7. Halogen bonding interactions between brominated ion pairs and CO2 molecules: implications for design of new and efficient ionic liquids for CO2 absorption.

    Science.gov (United States)

    Zhu, Xiang; Lu, Yunxiang; Peng, Changjun; Hu, Jun; Liu, Honglai; Hu, Ying

    2011-04-14

    In recent years, several novel halogenated liquids with characteristics of ionic liquids (ILs) were reported. To explore their performance in the absorption of CO(2), in this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between experimentally available brominated ion pairs and CO(2) molecules. It is shown that, as compared to B3LYP, the functional PBE yields geometrical and energetic data more close to those of MP2 for cation-CO(2) systems. The cation of brominated ILs under study can interact with CO(2) molecules through Br···O interactions, possibly making an important impact on the physical solubility of CO(2) in brominated ILs. The optimized geometries of the complexes of the ion pair with CO(2) molecules are quite similar to those of the corresponding complexes of the cation, especially for the essentially linear C-Br···O contacts. However, much weaker halogen bonds are predicted in the former systems, as indicated by the longer intermolecular distances and the smaller interaction energies. Charges derived from NBO analysis reveal the origin of the different optimized conformations and halogen bonding interactions for the CO(2) molecule. Based on the electrostatic potential results, the substitution of hydrogen atoms with fluorine atoms constituting the cation is then applied to enhance halogen bond strength. The QTAIM analysis further validates the existence of halogen bonding interaction in all complexes. The topological properties at the halogen bond critical points indicate that the Br···O interactions in the complexes are basically electrostatic in nature and belong to conventional weak halogen bonds. This study would be helpful for designing new and effective ILs for CO(2) physical absorption.

  8. Weak acidity of vinyl CH bonds enhanced by halogen substitution.

    Science.gov (United States)

    Craig, Norman C; Matlin, Albert R

    2014-02-21

    As shown by the rates of proton-deuteron exchange in ethylenes with halogen substituents, the weak acidity of vinyl CH bonds is enhanced by halogen substitution. Relative rates of exchange in basic deuterium oxide reflect the relative acidities. Substitution in the α position has the strongest effect. Less electronegative halogens such as bromine increase the acidity more than does fluorine. The vinyl CH acid strengths correlate closely with the energies of deprotonation of isolated molecules into isolated anions, as computed with the MP2/cc-pVQZ model. The smaller deprotonation energies are associated with the stronger acids. Atomic charges from a natural bond order analysis done with the MP2/aug-cc-pVQZ model show that the negative charge becomes more dispersed in the anions of the stronger acids. Results are given for 13 haloethylenes and for 6 halogen-substituted butadienes, cyclopropenes, and a cyclobutene.

  9. 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...

  10. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    Science.gov (United States)

    Goodman, M.M.; Faraj, B.

    1999-07-06

    Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

  11. Progress in the Formation of Carbon-Hetero Bond Based on 2(5H)-Furanones%基于2(5H)-呋喃酮的碳-杂成键反应研究进展

    Institute of Scientific and Technical Information of China (English)

    谭越河; 李建晓; 洪文坤; 汪朝阳

    2011-01-01

    2(5H)-呋喃酮结构单元广泛存在于天然产物中,同时许多2(5H)-呋喃酮类化合物也是重要的有机合成中间体.因此,基于常见2(5H)-呋喃酮(1)的有机合成研究近年来引起了人们的关注.根据在有机合成反应中成键方式的不同,综述了在2(5H)-呋喃酮(1)环上形成C-O,C-N,C-S,C-P,C-Se,C-Si等碳-杂键的反应研究进展.%Recently, the organic synthesis based on 2(5H)-furanones (1) has attracted much attention owing to the unique carbon skeleton of 2(5H)-furanone which is widely present in a variety of natural products and their utility as valuable synthetic intermediates.Classified as different bond kinds, the progress in the formation reactions of carbon-oxygen bond, carbon-nitrogen bond, carbon-sulfur bond, carbon-phosphorus bond, carbon-selenium bond and carbon-silicon bond on 2(5H)-furanone ring is reviewed.

  12. Halogen Bonding: An AIM Analysis of the Weak Interactions

    Institute of Scientific and Technical Information of China (English)

    ZOU, Jian-Wei; LU, Yun-Xiang; YU, Qing-Sen; ZHANG, Hua-Xin; JIANG, Yong-Jun

    2006-01-01

    A series of complexes formed between halogen-containing molecules and ammonia have been investigated by means of the atoms in molecules (AIM) approach to gain a deeper insight into halogen bonding. The existence of the halogen bond critical points (XBCP) and the values of the electron density (ρb) and Laplacian of electron density (▽2pb) at the XBCP reveal the closed-shell interactions in these complexes. Integrated atomic properties such as charge, energy, polarization moment, volume of the halogen bond donor atoms, and the corresponding changes (△) upon complexation have been calculated. The present calculations have demonstrated that the halogen bond represents different AIM properties as compared to the well-documented hydrogen bond. Both the electron density and the Laplacian of electron density at the XBCP have been shown to correlate well with the interaction energy, which indicates that the topological parameters at the XBCP can be treated as a good measure of the halogen bond strength.In addition, an excellent linear relationship between the interatomic distance d(X…N) and the logarithm of ρb has been established.

  13. Halogen chemistry reduces tropospheric O3 radiative forcing

    Science.gov (United States)

    Sherwen, Tomás; Evans, Mat J.; Carpenter, Lucy J.; Schmidt, Johan A.; Mickley, Loretta J.

    2017-01-01

    Tropospheric ozone (O3) is a global warming gas, but the lack of a firm observational record since the preindustrial period means that estimates of its radiative forcing (RFTO3) rely on model calculations. Recent observational evidence shows that halogens are pervasive in the troposphere and need to be represented in chemistry-transport models for an accurate simulation of present-day O3. Using the GEOS-Chem model we show that tropospheric halogen chemistry is likely more active in the present day than in the preindustrial. This is due to increased oceanic iodine emissions driven by increased surface O3, higher anthropogenic emissions of bromo-carbons, and an increased flux of bromine from the stratosphere. We calculate preindustrial to present-day increases in the tropospheric O3 burden of 113 Tg without halogens but only 90 Tg with, leading to a reduction in RFTO3 from 0.43 to 0.35 Wm-2. We attribute ˜ 50 % of this reduction to increased bromine flux from the stratosphere, ˜ 35 % to the ocean-atmosphere iodine feedback, and ˜ 15 % to increased tropospheric sources of anthropogenic halogens. This reduction of tropospheric O3 radiative forcing due to halogens (0.087 Wm-2) is greater than that from the radiative forcing of stratospheric O3 (˜ 0.05 Wm-2). Estimates of RFTO3 that fail to consider halogen chemistry are likely overestimates (˜ 25 %).

  14. Persistence, bioaccumulation, and toxicity of halogen-free flame retardants.

    Science.gov (United States)

    Waaijers, Susanne L; Kong, Deguo; Hendriks, Hester S; de Wit, Cynthia A; Cousins, Ian T; Westerink, Remco H S; Leonards, Pim E G; Kraak, Michiel H S; Admiraal, Wim; de Voogt, Pim; Parsons, John R

    2013-01-01

    Polymers are synthetic organic materials having a high carbon and hydrogen content, which make them readily combustible. Polymers have many indoor uses and their flammability makes them a fire hazard. Therefore, flame retardants (FRs) are incorporated into these materials as a safety measure. Brominated flame retardants (BFRs), which accounted for about 21% of the total world market of FRs, have several unintended negative effects on the environment and human health. Hence, there is growing interest in finding appropriate alternative halogen-free flame retardants (HFFRs). Many of these HFFRs are marketed already, although their environ- mental behavior and toxicological properties are often only known to a limited extent, and their potential impact on the environment cannot yet be properly assessed. Therefore, we undertook this review to make an inventory of the available data that exists (up to September 2011) on the physical-chemical properties, pro- duction volumes, persistence, bioaccumulation, and toxicity (PBT) of a selection of HFFRs that are potential replacements for BFRs in polymers. Large data gaps were identified for the physical-chemical and the PBT properties of the reviewed HFFRs. Because these HFFRs are currently on the market, there is an urgent need to fill these data gaps. Enhanced transparency of methodology and data are needed to reevaluate certain test results that appear contradictory, and, if this does not provide new insights, further research should be performed. TPP has been studied quite extensively and it is clearly persistent, bioaccumulative, and toxic. So far, RDP and BDP have demonstrated low to high ecotoxicity and persistence. The compounds ATH and ZB exerted high toxicity to some species and ALPI appeared to be persistent and has low to moderate reported ecotoxicity. DOPO and MPP may be persistent, but this view is based merely on one or two studies, clearly indicating a lack of information. Many degradation studies have been

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

    Science.gov (United States)

    Cartoni, Antonella; Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo

    2014-05-14

    In this paper an investigation of the photofragmentation of dihalomethanes CH2X2 (X = F, Cl, Br, I) and chlorinated methanes (CH(n)Cl(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 CH2F2 as a source of both fluorine and hydrogen atoms and the characteristic formation of I2(+) and CH2(+) ions from the photofragmentation of the CH2I2 molecule.

  16. 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.

  17. The chemistry of halogens on diamond: effects on growth and electron emission

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, W.L.; Pan, L.S.; Brown, L.A. [Sandia National Labs., Livermore, CA (United States)] [and others

    1997-02-01

    Diamond growth using halogenated precursors was studied in several diamond growth reactors. In a conventionao plasma reactor, diamond growth using the following gas mixtures was studied: CF{sub 4}/H{sub 2}, CH{sub 4}/H{sub 2}, CH{sub 3}F/H{sub 2}, and CH{sub 3}CL/H{sub 2}. Both the diamond growth measurements demonstrated ineffective transport of halogen radicals to the diamond surface during the growth process. In order to transport radical halogen species to the diamond surface during growth, a flow-tube reactor was constructed which minimized gas phase reactions. Also, the flow-tube reactor enabled pulsed gs transport to the diamond surface by fast-acting valves. Molecular beam mass spectroscopy was used to find condition which resulted in atomic hydrogen and/or atomic fluorine transport to the growing diamond surface. Although such conditions were found, they required very low pressures (0.5 Torr and below); these low pressures produce radical fluxes which are too low to sustain a reasonable diamond growth rate. The sequential reactor at Stanford was modified to add a halogen-growth step to the conventinoal atomic hydrogen/atomic carbon diamond growth cycle. Since the atomic fluorine, hydrogen and carbon environments are independent in the sequential reactor, the effect of fluorine on diamond growth could be studied independently of gas phase reactions. Although the diamond growth rate was increased by the use of fluorine, the film quality was seen to deteriorate as well as the substrate surface. Moreover, materials incompatibilities with fluorine significantly limited the use of fluorine in this reactor. A diamond growth model incorporating both gas phase and surface reactions was developed for the halocarbon system concurrent with the film growth efforts. In this report, we review the results of the growth experiments, the modeling, and additional experiments done to understand fluorine with diamond surfaces.

  18. Synthesis of Soluble Halogenated Polyphenylenes. Mechanism for the Coupling Halogenated Lithiobenzenes

    Science.gov (United States)

    1993-11-22

    the halogen content in these polymers was lowered using larger amounts of tert- butyllithium. TGA analysis (N2 , 20C/rmin) of I1 showed a 10% weight...iodide for every three aryl rings. DSC analysis (N2 , 20°C/min) for 1 8 showed no transitions on either the first or second heating scans to 230"C. TGA ... analysis (N2. 20C/rmin) showed a 10% weight loss at 3220C and char yields of 46% at 900"C. Visual analysis of the charred material did indicate that

  19. Catalytic mechanisms, basic roles, and biotechnological and environmental significance of halogenating enzymes

    Institute of Scientific and Technical Information of China (English)

    Xianping Chen; Karl-Heinz van Pée

    2008-01-01

    The understanding of enzymatic incorporation of halogen atoms into organic molecules has increased during the last few years. Two novel types of halogenating enzymes, flavindependent halogenases and α-ketoglutarate-dependent halogenases, are now known to play a significant role in enzyme-catalyzed halogenation. The recent advances on the halogenating enzymes RebH, SyrB2, and CytC3 have suggested some new mechanisms for enzymatic halogenations. This review concentrates on the occurrence, catalytic mechanisms, and biotechnological applications of the halogenating enzymes that are currently known.

  20. Designer Metallic Acceptor-Containing Halogen Bonding: General Strategies.

    Science.gov (United States)

    Zhang, Xinxing; Bowen, Kit H

    2017-03-13

    Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB has could also be applied to XB. However, there has been no report on a metallic XB acceptor but metal anions have been observed to be good HB acceptors. This missing mosaic piece of XB is because common metal anions are reactive for XB donors. In view of this, we propose two strategies for designing metallic acceptor-containing XB using ab initio calculations. The first one is to utilize a metal cluster anion with a high electron detachment energy, such as the superatom, Al13- as the XB acceptor. The second strategy is to design a ligand passivated/protected metal core while it still can maintain the negative charge; several exotic clusters, such as PtH5-, PtZnH5- and PtMgH5-, are utilized as examples. Based on these two strategies, we anticipate that more metallic acceptor-containing XB will be discovered.

  1. Metal hydrides form halogen bonds: measurement of energetics of binding.

    Science.gov (United States)

    Smith, Dan A; Brammer, Lee; Hunter, Christopher A; Perutz, Robin N

    2014-01-29

    The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS° = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = -7.3 ± 0.1 kJ/mol, ΔS° = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M(-1), respectively.

  2. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Science.gov (United States)

    2010-07-01

    ... alcohol, halogenated alkane, substituted epoxide, and amino compound (generic). 721.10145 Section 721... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  3. Brønsted Acidic Ionic Liquid Accelerated Halogenation of Organic Compounds with N-Halosuccinimides (NXS)

    National Research Council Canada - National Science Library

    Stojan Stavber; Kenneth K. Laali; Dejan Vražič; Marjan Jereb

    2012-01-01

    ...;-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H)][OTf] ionic liquid (IL...

  4. Brønsted acidic ionic liquid accelerated halogenation of organic compounds with N-Halosuccinimides (NXS)

    National Research Council Canada - National Science Library

    Vražič, Dejan; Jereb, Marjan; Laali, Kenneth K; Stavber, Stojan

    2012-01-01

    ...-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO(3)H)][OTf] ionic liquid (IL...

  5. A theoretical model on the formation mechanism and kinetics of highly toxic air pollutants from halogenated formaldehydes reacted with halogen atoms

    Science.gov (United States)

    Ji, Y. M.; Wang, H. H.; Gao, Y. P.; Li, G. Y.; An, T. C.

    2013-11-01

    The atmospheric reactions of halogenated formaldehydes with halogen atoms were investigated by high-accuracy molecular orbital calculation. Our studies showed that compared to X-addition pathway, the H-abstraction pathway was demonstrated to be more preferred to form halogenated formyl radicals and hydrogen halides (HX). In specific areas with abundant halogen atoms, such as the marine boundary layer (MBL), halogenated formyl radical was reacted easily with halogen atoms and finally transformed into HX and CO2 in the presence of water; otherwise, this radical was degraded to CO2, halogen gas, and halogenated oxide in the presence of O2 and halogen atoms. By using the canonical variational transition state theory, the kinetics calculations were performed within a wide atmospheric temperature range of 200-368 K, and theoretical values agreed well with the available experimental data. Under atmospheric conditions, rate constants decreased as altitude increased, and especially the rate constants of halogen atoms reacted with FCHO quickly reduced. The kinetic results showed that although the reactions of halogenated formaldehydes with F atoms occurred more easily than did those with Cl and Br atoms, the two latter reactions were still important atmospheric degradation process, especially in the MBL. The modified Arrhenius equations of rate constants within the atmospheric temperature range were fitted, which helped to understand the established atmospheric model and estimated the contribution of title reactions to atmospheric chemistry pollution.

  6. Investigating Planetary Volatile Accretion Mechanisms Using the Halogens

    Science.gov (United States)

    Ballentine, C. J.; Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Day, J. M.

    2014-12-01

    Depletion of the volatile elements in the Earth relative to the CI chondrites is roughly correlated with volatility, or decreasing condensation temperature. For the heavy halogen group elements (Cl, Br and I), volatility alone does not account for their apparent depletion, which early data has suggested is far greater than predicted [1-2]. Such depletion has been used to argue for the preferential loss of halogens by, amongst other processes, impact-driven erosive loss from Earth's surface [2]. Little consensus exists as to why the halogens should exhibit such preferential behavior during accretionary processes. Early efforts to constrain halogen abundance and understand their behavior in both Earth and planetary materials [3-6] have been hampered by their typically low abundance (ppb level) in most geologic materials. We present the results of halogen analysis of 23 chondrite samples, selected to represent diverse groups and petrologic type. Halogen abundances were measured by neutron irradiation noble gas mass spectrometry (NI-NGMS). Significant concentration heterogeneity is observed within some samples. However, a single Br/Cl and I/Cl ratio of 1.9 ± 0.2 (x 10-3) and 335 ± 10 (x 10-6) can be defined for carbonaceous chondrites with a good correlation between Br and Cl (R2 = 0.97) and between I and Cl (R2 = 0.84). Ratios of I/Cl overlap with terrestrial estimates of Bulk Silicate Earth and Mid Ocean Ridge Basalts. Similarly, good correlations are derived for enstatite (E) chondrites and a sulfide- and halogen- rich subset of E-chondrites. Chlorine abundances of CI (Orgueil) in this study are lower by factor of ~ 3 than the value of ~ 700 ppm Cl (compilation in [1]). Our results are similar to early discarded low values for Ivuna and Orgueil from [5,6] and agree more closely with values for CM chondrites. Halogens may not be as depleted in Earth as previously suggested, or a high degree of heterogeneity in the abundance of these volatile elements in

  7. Thermochemical properties and phase behavior of halogenated polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Fu, Jinxia; Suuberg, Eric M

    2012-03-01

    Knowledge of vapor pressure of organic pollutants is essential in predicting their fate and transport in the environment. In the present study, the vapor pressures of 12 halogenated polycyclic aromatic compounds (PACs), 9-chlorofluorene, 2,7-dichlorofluorene, 2-bromofluorene, 9-bromofluorene, 2,7-dibromofluorene, 2-bromoanthracene, 9-chlorophenanthrene, 9-bromophenanthrene, 9,10-dibromophenanthrene, 1-chloropyrene, 7-bromobenz[a]anthracene, and 6,12-dibromochrysene, were measured using the Knudsen effusion method over the temperature range of 301 to 464 K. Enthalpies and entropies of sublimation of these compounds were determined via application of the Clausius-Clapeyron equation. The data were also compared with earlier published literature values to study the influence of halogen substitution on vapor pressure of PACs. As expected, the halogen substitution decreases vapor pressure compared with parent compounds but does not necessarily increase the enthalpy of sublimation. Furthermore, the decrease of vapor pressure also depends on the substitution position and the substituted halogen, and the di-substitution of chlorine and/or bromine decreases the vapor pressure compared with single halogen-substituted polycyclic aromatic hydrocarbons. In addition, the enthalpy of fusion and melting temperature of these 12 PACs were determined using differential scanning calorimetry and melting point analysis.

  8. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

    Science.gov (United States)

    Smith, G. B.

    1996-01-01

    The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

  9. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    Science.gov (United States)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl- and Br- by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  10. Behavior of halogens during the degassing of felsic magmas

    Science.gov (United States)

    Balcone-Boissard, H.; Villemant, B.; Boudon, G.

    2010-09-01

    Residual concentrations of halogens (F, Cl, Br, I) and H2O in glass (matrix glass and melt inclusions) have been determined in a series of volcanic clasts (pumice and lava-dome fragments) of plinian, vulcanian and lava dome-forming eruptions. Felsic magmas from calc-alkaline, trachytic and phonolitic systems have been investigated: Montagne Pelée and Soufrière Hills of Montserrat (Lesser Antilles), Santa Maria-Santiaguito (Guatemala), Fogo (Azores) and Vesuvius (Italy). The behavior of halogens during shallow H2O degassing primarily depends on their incompatible character and their partitioning between melt and exsolved H2O vapor. However, variations in pre-eruptive conditions, degassing kinetics, and syn-eruptive melt crystallization induce large variations in the efficiency of halogen extraction. In all systems studied, Cl, Br and I are not fractionated from each other by differentiation or by degassing processes. Cl/Br/I ratios in melt remain almost constant from the magma reservoir to the surface. The ratios measured in erupted clasts are thus characteristic of pre-eruptive magma compositions and may be used to trace deep magmatic processes. F behaves as an incompatible element and, unlike the other halogens, is never significantly extracted by degassing. Cl, Br and I are efficiently extracted from melts at high pressure by H2O-rich fluids exsolved from magmas or during slow effusive magma degassing, but not during rapid explosive degassing. Because H2O and halogen mobility depends on their speciation, which strongly varies with pressure in both silicate melts and exsolved fluids, we suggest that the rapid pressure decrease during highly explosive eruptions prevents complete equilibrium between the diverse species of the volatiles and consequently limits their degassing. Conversely, degassing in effusive eruptions is an equilibrium process and leads to significant halogen output in volcanic plumes.

  11. Fine tuning of graphene properties by modification with aryl halogens

    Science.gov (United States)

    Bouša, D.; Pumera, M.; Sedmidubský, D.; Šturala, J.; Luxa, J.; Mazánek, V.; Sofer, Z.

    2016-01-01

    Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06295k

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Halogen bonded two-dimensional supramolecul arassemblies studied by high resolution scanning tunneling microscopy

    Institute of Scientific and Technical Information of China (English)

    YANG XunYu; WANG Fang; CHEN QiuXia; WANG LiYan; WANG ZhiQiang

    2007-01-01

    We described the formation of self-organized two-dimensional (2D) assemblies of N-(2,3,5,6-tetrafluoro- 4-iodophenyl)hexadecylamine and 1-dodecyl-imidazole at the liquid/HOPG interface. The two-dimen- sional assemblies showed a fishbone-like pattern structure as revealed by high-resolution scanning tunneling microscopy. Although different interactions can drive the formation of 2D assemblies,as far as we know,this is the first report on halogen bond-driven 2D assemblies.

  14. Halogen and Cl isotopic systematics in Martian phosphates: Implications for the Cl cycle and surface halogen reservoirs on Mars

    Science.gov (United States)

    Bellucci, J. J.; Whitehouse, M. J.; John, T.; Nemchin, A. A.; Snape, J. F.; Bland, P. A.; Benedix, G. K.

    2017-01-01

    The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive δ37Cl anomalies (+1.1 to + 2.5 ‰). These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (<600 Ma) have negative δ37Cl anomalies (-0.2 to - 5.6 ‰). Phosphates with the largest negative δ37Cl anomalies display zonation in which the rims of the grains are enriched in all halogens and have significantly more negative δ37Cl anomalies suggestive of interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average δ37Cl of - 0.6 ‰, supporting a similar initial Cl isotope composition for Mars, the Earth, and the Moon. Oxidation and reduction of chlorine are the only processes known to strongly fractionate Cl isotopes, both positively and negatively, and perchlorate has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have been documented on the Martian surface, has been active throughout Martian

  15. Nucleophilic reactivity and electrocatalytic reduction of halogenated organic compounds by nickel o-phenylenedioxamidate complexes.

    Science.gov (United States)

    Das, Siva Prasad; Ganguly, Rakesh; Li, Yongxin; Soo, Han Sen

    2016-09-14

    A growing number of halogenated organic compounds have been identified as hazardous pollutants. Although numerous advanced oxidative processes have been developed to degrade organohalide compounds, reductive and nucleophilic molecular approaches to dehalogenate organic compounds have rarely been reported. In this manuscript, we employ nickel(ii)-ate complexes bearing the o-phenylenebis(N-methyloxamide) (Me2opba) tetraanionic ligand as nucleophilic reagents that can react with alkyl halides (methyl up to the bulky isobutyl) by O-alkylation to give their respective imidate products. Four new nickel(ii) complexes have been characterized by X-ray crystallography, and the salient structural parameters and FT-IR vibrational bands (∼1655 cm(-1)) concur with their assignment as the imidate tautomeric form. To the best of our knowledge, this is the first report on the nucleophilic reactivity of Ni(II)(Me2opba) with halogenated organic compounds. The parent nickel(ii) Me2opba complex exhibits reversible electrochemical oxidation and reduction behavior. As a proof of concept, Ni(II)(Me2opba) and its alkylated congeners were utilized for the electrocatalytic reduction of chloroform, as a representative, simple polyhalogenated organic molecule that could arise from the oxidative treatment of organic compounds by chlorination. Modest turnover numbers of up to 6 were recorded, with dichloromethane identified as one of the possible products. Future efforts are directed towards bulkier -ate complexes that possess metal-centered instead of ligand-centered nucleophilic activity to create more effective electrocatalysts for the reduction of halogenated organic compounds.

  16. 3-Hydroxy-4,5-dimethyl-2(5H)-furanone levels in fortified Madeira wines: relationship to sugar content.

    Science.gov (United States)

    Câmara, José Sousa; Marques, José C; Alves, María A; Silva Ferreira, Antonio C

    2004-11-03

    The maturation of Madeira wines usually involves exposure to relatively high temperatures and humidity levels >70%, which affect the aroma and flavor composition and lead to the formation of the typical and characteristic bouquet of these wines. To estimate the levels of sotolon [3-hydroxy-4,5-dimethyl-2(5H)-furanone] and their behavior over time, 86 aged Madeira wines samples (1-25 years old), with different sugar concentrations, respectively, 90 g L(-)(1) for Boal, 110 g L(-)(1) for Malvazia, 25 g L(-)(1) for Sercial, and 65 g L(-)(1) for Verdelho varieties, were analyzed. Isolation was performed by liquid-liquid extraction with dichloromethane followed by chromatographic analysis by GC-MS. The reproducibility of the method was found to be 4.9%. The detection and quantification limits were 1.2 and 2.0 microg L(-)(1), respectively. The levels of sotolon found ranged from not detected to 2000 microg L(-)(1) for wines between 1 and 25 years old. It was observed that during aging, the concentration of sotolon increased with time in a linear fashion (r = 0.917). The highest concentration of sotolon was found in wines with the highest residual sugar contents, considering the same time of storage. The results show that there is a strong correlation between sotolon and sugar derivatives: furfural, 5-methylfurfural, 5-hydroxymethylfurfural, and 5-ethoxymethylfurfural. These compounds are also well correlated with wine aging. These findings indicate that the kinetics of sotolon formation is closely related with residual sugar contents, suggesting that this molecule may come from a component like sugar.

  17. Alkali and Halogen Chemistry in Volcanic Gases on Io

    CERN Document Server

    Schaefer, L

    2004-01-01

    We use chemical equilibrium calculations to model the speciation of alkalis and halogens in volcanic gases emitted on Io. The calculations cover wide temperature (500-2000 K) and pressure (10^-6 to 10^+1 bars) ranges, which overlap the nominal conditions at Pele (T = 1760 K, P = 0.01 bars). About 230 compounds of 11 elements (O, S, Li, Na, K, Rb, Cs, F, Cl, Br, I) are considered. We predict the major alkali and halogen species in a Pele-like volcanic gas and the major alklai and halogen condensates. We also model disequilibrium chemistry of the alkalis and halogens in the volcanic plume. Based on this work and our prior modeling for Na, K, and Cl in a volcanic plume, we predict the major loss processes for the alkali halide gases are photolysis and/or condensation onto grains. On the basis of elemental abundances and photochemical lifetimes, we recommend searching for gaseous KCl, NaF, LiF, LiCl, RbF, RbCl, CsF, and CsCl around volcanic vents during eruptions. Based on abundance considerations and observation...

  18. First negative halogen beams produced at PSBooster-ISOLDE

    CERN Document Server

    Stora, T; Bouquerel, E; Catherall, R; Eller, M; Lettry, J; Menna, M

    Chemically pure radioactive halogen beams have interesting potentials for solid state and nuclear physics, for instance for implantation studies or in precise -decay measurements. They can be produced as positive ions by the ISOL approach, with possible isobaric contaminations, or as pure negative ion beams, with a LaB6 negative surface ion source...

  19. Influence of saponins on the biodegradation of halogenated phenols.

    Science.gov (United States)

    Kaczorek, Ewa; Smułek, Wojciech; Zdarta, Agata; Sawczuk, Agata; Zgoła-Grześkowiak, Agnieszka

    2016-09-01

    Biotransformation of aromatic compounds is a challenge due to their low aqueous solubility and sorptive losses. The main obstacle in this process is binding of organic pollutants to the microbial cell surface. To overcome these, we applied saponins from plant extract to the microbial culture, to increase pollutants solubility and enhance diffusive massive transfer. This study investigated the efficiency of Quillaja saponaria and Sapindus mukorossi saponins-rich extracts on biodegradation of halogenated phenols by Raoultella planticola WS2 and Pseudomonas sp. OS2, as an effect of cell surface modification of tested strains. Both strains display changes in inner membrane permeability and cell surface hydrophobicity in the presence of saponins during the process of halogenated phenols biotransformation. This allows them to more efficient pollutants removal from the environment. However, only in case of the Pseudomonas sp. OS2 the addition of surfactants to the culture improved effectiveness of bromo-, chloro- and fluorophenols biodegradation. Also introduction of surfactant allowed higher biodegradability of halogenated phenols and can shorten the process. Therefore this suggests that usage of plant saponins can indicate more successful halogenated phenols biodegradation for selected strains.

  20. Manganese Catalyzed C-H Halogenation.

    Science.gov (United States)

    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-Mn(V)═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 formation. Indeed, this idea

  1. 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

  2. Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere

    Science.gov (United States)

    Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil; Coburn, Sean; Dix, Barbara; Koenig, Theodore K.; Apel, Eric; Bowdalo, Dene; Campos, Teresa; Eloranta, Ed; Evans, Mathew J.; Digangi, Joshua P.; Zondlo, Mark A.; Gao, Ru-shan; Haggerty, Julie A.; Hall, Samuel R.; Hornbrook, Rebecca S.; Jacob, Daniel; Morley, Bruce; Pierce, Bradley; Reeves, Mike; Romashkin, Pavel; Ter Schure, Arnout; Volkamer, Rainer

    2015-01-01

    Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

  3. Ruthenium-catalyzed intramolecular selective halogenation of O-methylbenzohydroximoyl halides: a new route to halogenated aromatic nitriles.

    Science.gov (United States)

    Chinnagolla, Ravi Kiran; Pimparkar, Sandeep; Jeganmohan, Masilamani

    2013-04-18

    The intramolecular halogenation of O-methylbenzohydroximoyl halides in the presence of a Ru catalyst and the ligand diphenylacetylene afforded halo substituted aromatic nitriles in a highly regioselective manner. Further, substituted nitriles were converted into substituted tetrazole derivatives in the presence of NaN3 and I2.

  4. All-metal clusters that mimic the chemistry of halogens.

    Science.gov (United States)

    Zhao, Tianshan; Li, Yawei; Wang, Qian; Jena, Puru

    2013-10-07

    Owing to their s(2)p(5) electronic configuration, halogen atoms are highly electronegative and constitute the anionic components of salts. Whereas clusters that contain no halogen atoms, such as AlH(4), mimic the chemistry of halogens and readily form salts (e.g., Na(+)(AlH(4))(-)), clusters that are solely composed of metal atoms and yet behave in the same manner as a halogen are rare. Because coinage-metal atoms (Cu, Ag, and Au) only have one valence electron in their outermost electronic shell, as in H, we examined the possibility that, on interacting with Al, in particular as AlX(4) (X=Cu, Ag, Au), these metal atoms may exhibit halogen-like properties. By using density functional theory, we show that AlAu(4) not only mimics the chemistry of halogens, but also, with a vertical detachment energy (VDE) of 3.98 eV in its anionic form, is a superhalogen. Similarly, analogous to XHX superhalogens (X=F, Cl, Br), XAuX species with VDEs of 4.65, 4.50, and 4.34 eV in their anionic form, respectively, also form superhalogens. In addition, Au can also form hyperhalogens, a recently discovered species that show electron affinities (EAs) that are even higher than those of their corresponding superhalogen building blocks. For example, the VDEs of M(AlAu(4))(2)(-) (M=Na and K) and anionic (FAuF)Au(FAuF) range from 4.06 to 5.70 eV. Au-based superhalogen anions, such as AlAu(4)(-) and AuF(2)(-), have the additional advantage that they exhibit wider optical absorption ranges than their H-based analogues, AlH(4)(-) and HF(2)(-). Because of the catalytic properties and the biocompatibility of Au, Au-based superhalogens may be multifunctional. However, similar studies that were carried out for Cu and Ag atoms have shown that, unlike AlAu(4), AlX(4) (X=Cu, Ag) clusters are not superhalogens, a property that can be attributed to the large EA of the Au atom. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Photoacoustic/laser spectra of halogens and mixed halogens for energy purposes: Progress report to date/annual performance report

    Energy Technology Data Exchange (ETDEWEB)

    Venkateswarlu, P.; George, M.C.; Chakrapani, G.; Okafor, C.

    1986-01-01

    Photoacoustic spectroscopy of iodine molecule has been studied in gas phase using nitrogen laser pumped tunable dye laser. The experiment has yielded the complete vibrational spectrum corresponding to X /sup 1/..sigma../sub g//sup +/(0/sub g//sup +/) ..-->.. B /sup 3/PI/sub u/(0/sub u//sup +/) transitions up to the dissociation limit. The vibrational assignments to the band head positions have been made by comparing with wavenumbers calculated using Luc's constants. Some of these vibrational bands have been partially resolved and two of these resolved bands have been rotationally analyzed. The analysis was based on the highly resolved spectrum of Luc and Gerstenkorn. The structure observed in the spectrum in the 20,150 to 27,750 cm/sup -1/ which is beyond the dissociation limit of X /sup 1/..sigma../sub g//sup +/(0/sub g//sup +/) ..-->.. B /sup 3/PI/sub u/(0/sub u//sup +/) transitions has been associated to be due to stepwise two photon absorption since there are no discrete levels in the range 20,150 to 30,000 cm/sup -1/ in the iodine molecule. On the basis of the assumption, most of the bands could be assigned to two transitions both originating in the ground state and terminating in two different electronic states 1/sub g/ at T/sub e/ = 40,821 cm/sup -1/ (or T/sub 0/ = 41,355 cm/sup -1/) and ..sigma..(0/sub g//sup +/) at T/sub e/ = 41,411 cm/sup -1/ (or T/sub 0/ = 41,355 cm/sup -1/) respectively.

  6. 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.

  7. Synthesis and cytotoxic properties of halogen and aryl-/heteroarylpiperazinyl derivatives of benzofurans.

    Science.gov (United States)

    Krawiecka, Mariola; Kuran, Bozena; Kossakowski, Jerzy; Cieslak, Marcin; Kazmierczak-Baranska, Julia; Krolewska, Karolina; Nawrot, Barbara

    2015-01-01

    A series of seven derivatives of 1,1'-(5,6-dimethoxy-3-methyl-1-benzofuran-2,7-diyl)diethanone was synthesized and characterized by (1)HNMR and ESI MS spectra and elemental analyses. The obtained new compounds and three halogen derivatives of benzofuran, reported in our earlier work, were tested for their cytotoxic properties in human chronic (K562) and acute (HL60) leukemia cells, human cervical cancer (HeLa), and normal endothelial cells (HUVEC). Four compounds (2, 3, 4, 5), which contain halogens in their structure showed significant anticancer activity. The most promising was 1,1'-[3- (bromomethyl)-5,6-dimethoxy-1-benzofuran-2,7-diyl]diethanone (2), which was highly and selectively toxic for K562 cells (IC50 of 5µM) and HL60 cells (IC50 of 0.1µM), which showed no cytotoxicity toward HeLa and HUVEC cells. Moreover, the observed remarkable cytotoxicity of this compound toward K562 cells resulted from cells apoptosis.

  8. Halogenation effects on electron collisions with CF3Cl, CF2Cl2, and CFCl3

    Science.gov (United States)

    Freitas, T. C.; Lopes, A. R.; Azeredo, A. D.; Bettega, M. H. F.

    2016-04-01

    We report differential and integral elastic cross sections for low-energy electron collisions with CF3Cl, CF2Cl2, and CFCl3 molecules for energies ranging from 0.1 eV to 30 eV. The calculations were performed using the Schwinger multichannel method with pseudopotentials in the static-exchange and static-exchange plus polarization approximations. The influence of the permanent electric dipole moment on the cross sections was included using the Born closure scheme. A very good agreement between our calculations and the experimental results of Jones [J. Chem. Phys. 84, 813 (1986)], Mann and Linder [J. Phys. B 25, 1621 (1992); 25, 1633 (1992)] and Hoshino et al. [J. Chem. Phys. 138, 214305 (2013)] was found. We also compare our results with the calculations of Beyer et al. [Chem. Phys. 255, 1 (2000)] using the R-matrix method, where we find good agreement with respect to the location of the resonances, and with the calculations of Hoshino et al. using the independent atom method with screening corrected additivity rule, where we find qualitative agreement at energies above 20 eV. Additional electronic structure calculations were carried out in order to help in the interpretation of the scattering results. The stabilization the lowest σ∗ resonance due to the exchange of fluorine by chlorine atoms (halogenation effect) follows a simple linear relation with the energy of the lowest unoccupied molecular orbitals and can be considered as a signature of the halogenation effect.

  9. Solution phase synthesis of halogenated graphene and the electrocatalytic activity for oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Kuang-Hsu Wu; Da-Wei Wang; Qingcong Zeng; Yang Li; Ian R. Gentle

    2014-01-01

    Metal-free carbon electrocatalyts for the oxygen reduction reaction (ORR) are attractive for their high activity and economic advantages. However, the origin of the activity has never been clearly elucidated in a systematic manner. Halogen group elements are good candidates for elucidating the effect, although it has been a difficult task due to safety issues. In this report, we demonstrate the synthesis of Cl-, Br-and I-doped reduced graphene oxide through two solution phase syntheses. We have evaluated the effectiveness of doping and performed electrochemical measurements of the ORR activity on these halogenated graphene materials. Our results suggest that the high electroneg-ativity of the dopant is not the key factor for high ORR activity;both Br-and I-doped graphene pro-moted ORR more efficiently than Cl-doped graphene. Furthermore, an unexpected sulfur-doping in acidic conditions suggests that a high level of sulfide can degrade the ORR activity of the graphene material.

  10. Laboratory Studies of Halogen Oxides Important to Stratospheric Ozone Depletion

    Science.gov (United States)

    Wilmouth, D. M.; Klobas, J. E.; Anderson, J. G.

    2016-12-01

    Inorganic chlorine and bromine molecules are primarily responsible for stratospheric ozone destruction, with BrO, ClO, and ClOOCl comprising the two reaction cycles that cause most polar ozone losses. Despite comprehensive international treaties regulating CFCs and halons, seasonal polar ozone depletion will likely continue for decades to come. Accurate spectroscopic and kinetic measurements of inorganic bromine and chlorine molecules obtained in the laboratory are essential for reducing uncertainty in atmospheric models, better interpreting atmospheric field measurements, and forming trusted projections of future ozone changes. Here we present results from recent work in our laboratory using absorption spectroscopy and atomic resonance fluorescence detection to determine rate constants of halogen reactions, the equilibrium constant of ClO/ClOOCl, and absorption cross sections of several halogen oxides using a new cold trap-thermal desorption approach.

  11. Radiochemical photon activation analysis of Halogens in meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Oura, Yasuji; Latif, S.A.; Setoguchi, Mina; Nakamoto, Tomoshi; Ebihara, Mitsuru; Nakahara, Hiromichi [Tokyo Metropolitan Univ. (Japan). Faculty of Science; Ohtsuki, Tsutomu

    1999-12-01

    Halogens (F, Cl, Br and I) in meteorites and rocks are determined by a radiochemical photon activation analysis (RPAA) and compared with that of NPAA. We tried to determine all halogen elements at one time by one irradiation with 20 or 30 MeV maximum energy (E{sub 0}) by controlling irradiation for 2 or 6 hours with cooling. Average current is about 110 {mu}A. After irradiation, the sample was separated by radiochemical analysis. Allende meteorite, JR-I and d-41-7 were analyzed. The value of F, Cl and Br showed good reproducibility and agreed with the value in the reference. However, I showed small value. It may indicate volatilizing of I. (S.Y.)

  12. Polarographic behaviour of pesticides with carbon-halogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Jehring, H.; La Chevallerie-Haaf, U. de; Meyer, A.; Henze, G.

    1989-01-01

    The dp-polarographic behaviour of different pesticides with carbon-halogen bonds was investigated in dimethylsulfoxide and methanol-water as solvents; the peak-potentials are demonstrated graphically. From peak-height the pesticides are detectable up to 100 ng.ml/sup -1/. The investigations are of interest for the development of multistage-combined procedures by h.p.l.c. with amperometric detection.

  13. Reactive halogen species in the troposphere - Are there general principles?

    Science.gov (United States)

    Platt, Ulrich

    2017-04-01

    Reactive halogen species (RHS, e.g. BrO, IO, HOBr) are abundant in many parts of the troposphere (as well as in the stratosphere), these 'halogen compartments' include polar regions, coastal areas, vicinity of salt pans, parts of the free troposphere, and volcanic plumes. These RHS have been shown to have a profound impact on tropospheric chemistry. During the recent years much progress has been made with respect to elucidating the spatial and temporal distribution of RHS, their origin, and their chemical interactions in these compartments as well as in the theoretical understanding of these processes. However many unanswered questions remain, for instance: Why is there an Antarctic - Arctic asymmetry of reactive iodine species? Does the bromine explosion only occur during polar springtime? What is the influence of the shrinking Sea Ice area? What drives the autocatalytic bromine release from halogenides (the bromine explosion)? What is the effect of coupling cycles involving different halogens? How wide-spread are RHS in the free troposphere? We give an overview of ground- aircraft- and satellite- based observations and recent advances modeling illustrating the above questions. It is attempted to identify common features of the RHS-related processes in the different compartments and thus to derive answers to some of the questions.

  14. Transepidermal water loss during halogen spotlight phototherapy in preterm infants.

    Science.gov (United States)

    Grünhagen, Dirk J; de Boer, Mark G J; de Beaufort, Arnout Jan; Walther, Frans J

    2002-03-01

    Among preterm infants there is a relationship between skin blood flow and transepidermal water loss (TEWL). The aim of this study was to assess whether halogen spotlight phototherapy without significant heat stress increases TEWL and affects maintenance fluid requirements in preterm infants. TEWL was measured noninvasively before the start and after 1 h of halogen spotlight phototherapy in a group of preterm infants, nursed in double-walled incubators with moderately high relative humidity. Relative humidity and ambient temperature in the incubator were tightly controlled. Mean +/- SD birth weight of the 18 infants was 1412 +/- 256 g, gestational age 30.6 +/- 1.6 wk, and age at measurement 5 +/- 3 d. Nine infants received ventilatory assistance. Relative humidity was 40-80% (mean 52%). Average TEWL increased from 13.6 to 16.5 g/m(2)/h during phototherapy. These data show that TEWL increases by approximately 20% during phototherapy despite constant skin temperature and relative humidity. Maintenance fluids of preterm infants should be increased by 0.35 mL/kg/h during exposure to halogen spotlight phototherapy.

  15. Converting a conventional wired-halogen illuminated indirect ophthalmoscope to a wireless-light emitting diode illuminated indirect ophthalmoscope in less than 1000/- rupees

    Directory of Open Access Journals (Sweden)

    Mihir Kothari

    2015-01-01

    Full Text Available Aim: To report the "do it yourself" method of converting an existing wired-halogen indirect ophthalmoscope (IO to a wireless-light emitting diode (LED IO and report the preferences of the patients and the ophthalmologists. Subjects and Methods: In this prospective observational study, a conventional IO was converted to wireless-LED IO using easily available, affordable electrical components. Conventional and the converted IO were then used to perform photo-stress test and take the feedback of subjects and the ophthalmologists regarding its handling and illumination characteristics. Results: The cost of conversion to wireless-LED was 815/- rupees. Twenty-nine subjects, mean age 34.3 ΁ 10 years with normal eyes were recruited in the study. Between the two illumination systems, there was no statistical difference in the magnitude of the visual acuity loss and the time to recovery of acuity and the bleached vision on photo-stress test, although the visual recovery was clinically faster with LED illumination. The heat sensation was more with halogen illumination than the LED (P = 0.009. The ophthalmologists rated wireless-LED IO higher than wired-halogen IO on the handling, examination comfort, patient′s visual comfort and quality of the image. Twenty-two (81% ophthalmologists wanted to change over to wireless-LED IO. Conclusions: Converting to wireless-LED IO is easy, cost-effective and preferred over a wired-halogen indirect ophthalmoscope.

  16. 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)

  17. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria

    OpenAIRE

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-01-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas bio...

  18. Halogens, Barium and Uranium in Mantle Fluid Inclusions

    Science.gov (United States)

    Villa, I. M.; Peverelli, V.; Oglialoro, E.; Pettke, D. T.; Frezzotti, M. L.

    2016-12-01

    Halogens are an underexplored geochemical marker. A way to measure halogens at ng/g levels is measuring Ar, Kr and Xe in irradiated samples [1,2]. We derive absolute halogen amounts from rare gas amounts via scapolite monitor SY [2]. Kr-Xe systematics also yield Ba and U concentrations. We combined irradiation with stepheating on carbonate-sulfate-rich fluid inclusions (FI)-bearing xe­no­liths from El Hierro, Canarias: spinel harzburgite XML-7 and spinel dunite XML-1 [3]. Three components are recognized in the rare gas release. (1) Atmospheric surface contamination occurs up to 1000 °C. (2) FI decrepitation by laboratory heating occurs above 1200 °C [4], corresponding to the release of 80,82Kr and 128Xe in the 1200 and 1400 °C steps. Br whole-rock concentrations are 3-8 ng/g; the molar Br/Cl and I/Cl ratios in the harzburgite FI, 9 E-4 resp. 2 E-4, are identical to those in the dunite FI. This sets the halogens in our FI apart from MORB [2]. Halogen-derived rare gases are closely associated to artificial 131Xe from Ba; Ba has a high affinity of for CO2-rich fluids. Daughter minerals in multiphase FI were identified by Raman micro­spectroscopy [4]. The calculated Ba concentrations are 2-6 µg/g. (3) The third component is U-derived 134,136Xe and 86Kr released in a spike at 1000 °C, decoupled from FI. This requires a different carrier than FI, e.g. Ti oxides. As U concentrations are 10-20 pg/g, the U-bearing phase needs to be below a ppm, invisible by petro­graphy. The 136Xe/134Xe ratio > 1 suggests retention of radio­genic Xe. However, analysis of an unirradiated sample detected no radiogenic Xe. It is likely that Xe-U produced in the core of the McMaster reactor (thermal, epithermal and fast neutrons) has a different isotopic composition from that in textbooks, as proposed by [2].[1] Jeffery & Reynolds (1961) J.Geophys. Res. 66, 3582 [2] Kendrick (2012) Chem. Geol. 292, 116 [3] Oglialoro et al (2015) AGU Fall Meeting abstract V21C-3046 [4] Roedder (1965

  19. The pharmacology of halogenated salicylanilides and their anthelmintic use in animals

    National Research Council Canada - National Science Library

    Swan, G E

    1999-01-01

    .... Several halogenated salicylanilides with potent antiparasitic activity have been synthesised of which only closantel, niclosamide, oxyclozanide, rafoxanide and resorantel are commercially available...

  20. The pharmacology of halogenated salicylanilides and their anthelmintic use in animals : review article

    National Research Council Canada - National Science Library

    G.E. Swan

    1999-01-01

    .... Several halogenated salicylanilides with potent antiparasitic activity have been synthesised of which only closantel, niclosamide, oxyclozanide, rafoxanide and resorantel are commercially available...

  1. New halogenated additives to propylene carbonate-based electrolytes for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Naji, A.; Ghanbaja, J.; Billaud, D. [Universite Henri Poincare, Vandoeuvre les Nancy (France). LCSM; Willmann, P. [CNES, Toulouse (France)

    2000-07-01

    Lithium cannot be electrointercalated into graphite in an electrolyte containing propylene carbonate (PC) as the only solvent species. In order to improve the cyclability of graphite electrodes in the presence of PC two methods were used: use of solvent mixtures containing PC and halogen-substituted solvent molecules ({alpha}-bromo-{gamma}-butyrolactone and methyl chloroformate); impregnation of the graphite electrode by halogenated solvents prior to cycling in PC-based electrolytes. It appears that the reversible capacity is increased by {approx}10% when such halogenated solvent molecules are used. Moreover, the cyclability is dependent on the nature of lithium salt, the concentration of halogen solvent and the specific current.

  2. Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

    Science.gov (United States)

    Han, Yi-Jen; Lin, Chia-Yu; Liang, Mong; Liu, Ying-Ling

    2016-05-01

    This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

  3. Identification of methyl triclosan and halogenated analogues in male common carp (Cyprinus carpio) from Las Vegas Bay and semipermeable membrane devices from Las Vegas Wash, Nevada.

    Science.gov (United States)

    Leiker, Thomas J; Abney, Sonja R; Goodbred, Steven L; Rosen, Michael R

    2009-03-01

    Methyl triclosan and four halogenated analogues have been identified in extracts of individual whole-body male carp (Cyprinus carpio) tissue that were collected from Las Vegas Bay, Nevada, and Semipermeable Membrane Devices (SPMD) that were deployed in Las Vegas Wash, Nevada. Methyl triclosan is believed to be the microbially methylated product of the antibacterial agent triclosan (2, 4, 4'-trichloro-4-hydroxydiphenyl ether, Chemical Abstract Service Registry Number 3380-34-5, Irgasan DP300). The presence of methyl triclosan and four halogenated analogues was confirmed in SPMD extracts by comparing low- and high-resolution mass spectral data and Kovats retention indices of methyl triclosan with commercially obtained triclosan that was derivatized to the methyl ether with ethereal diazomethane. The four halogenated analogues of methyl triclosan detected in both whole-body tissue and SPMD extracts were tentatively identified by high resolution mass spectrometry. Methyl triclosan was detected in all 29 male common carp from Las Vegas Bay with a mean concentration of 596 microg kg(-1) wet weight (ww) which is more than an order of magnitude higher than previously reported concentrations in the literature. The halogenated analogs were detected less frequently (21%-76%) and at much lower concentrations (<51 microg kg(-1) ww). None of these compounds were detected in common carp from a Lake Mead reference site in Overton Arm, Nevada.

  4. Identification of methyl triclosan and halogenated analogues in male common carp (Cyprinus carpio) from Las Vegas Bay and semipermeable membrane devices from Las Vegas Wash, Nevada

    Science.gov (United States)

    Leiker, T.J.; Abney, S.R.; Goodbred, S.L.; Rosen, Michael R.

    2009-01-01

    Methyl triclosan and four halogenated analogues have been identified in extracts of individual whole-body male carp (Cyprinus carpio) tissue that were collected from Las Vegas Bay, Nevada, and Semipermeable Membrane Devices (SPMD) that were deployed in Las Vegas Wash, Nevada. Methyl triclosan is believed to be the microbially methylated product of the antibacterial agent triclosan (2, 4, 4'-trichloro-4-hydroxydiphenyl ether, Chemical Abstract Service Registry Number 3380-34-5, Irgasan DP300). The presence of methyl triclosan and four halogenated analogues was confirmed in SPMD extracts by comparing low- and high-resolution mass spectral data and Kovats retention indices of methyl triclosan with commercially obtained triclosan that was derivatized to the methyl ether with ethereal diazomethane. The four halogenated analogues of methyl triclosan detected in both whole-body tissue and SPMD extracts were tentatively identified by high resolution mass spectrometry. Methyl triclosan was detected in all 29 male common carp from Las Vegas Bay with a mean concentration of 596????g kg- 1 wet weight (ww) which is more than an order of magnitude higher than previously reported concentrations in the literature. The halogenated analogs were detected less frequently (21%-76%) and at much lower concentrations (< 51????g kg- 1 ww). None of these compounds were detected in common carp from a Lake Mead reference site in Overton Arm, Nevada.

  5. (13)C and (19)F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles.

    Science.gov (United States)

    Szell, Patrick M J; Gabriel, Shaina A; Gill, Russell D D; Wan, Shirley Y H; Gabidullin, Bulat; Bryce, David L

    2017-03-01

    Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. (13)C and (19)F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from (19)F to (13)C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional (1)H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental (13)C and (19)F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

  6. Spatial Gradients in Halogen Oxides Across the North Slope of Alaska Indicate That Halogen Activated Airmasses are Spatially Large

    Science.gov (United States)

    Simpson, W. R.; Hoenninger, G. S.; Platt, U.

    2005-12-01

    Reactive halogens are important oxidizers in the polar atmosphere during springtime. They deplete tropospheric ozone, oxidize hydrocarbons, and oxidize gas-phase mercury, causing it to deposit to the snow pack. We want to understand the mechanism by which halides in on snow/ice crystals and/or in aerosol particles are converted to reactive halogen species. This understanding can assist in prediction of mercury deposition and how that deposition depends on environmental variables like sea-ice extent and temperature. This mechanistic knowledge is particularly important in the context of a changing Arctic system. To study halogen activation, we are working in the Studies of the Northern Alaskan Coastal System (SNACS) project and here show results from 2005 including the LEADX experiment. A number of studies have implicated leads (cracks in the sea ice) as a source of halogen activation, but it is unclear if halogens are directly activated on ice surfaces at the lead (e.g. frost flowers) or if the lead is less directly involved. To address the role of leads in halogen activation, we measured bromine monoxide (BrO) using Multiple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) at Barrow and Atqasuk, Alaska over a four-month period. The locations of these sites, either on the coast near a recurring lead in the case of Barrow, or 100km inland in the case of Atqasuk provides an ability to measure spatial gradients on the 100km length scale. In addition, the Barrow instrument was the first implementation of fully automated two dimensional MAX-DOAS where both elevation and azimuth were scanned. Because the MAX-DOAS method typically detects path-averaged BrO amounts between the instrument and a range of approximately 10km, differences in BrO between viewing azimuths allows us to determine short-length scale BrO gradients. From the 2-D MAX-DOAS observations at Barrow, we find that there are very small if any spatial gradients on the 10km length scale. From the

  7. Halogenated Explosives to Defeat Biological Agents

    Science.gov (United States)

    2015-09-01

    of TFM-RDX were carried out using Cheetah 6.0 code by estimating a density of TFM-RDX, which had not been reported as experimentally measured...HMX (1.861 g∙cm−3).35 The density of TFM-RDX (1), needed for Cheetah calculations, was preliminarily estimated by adding three-quarters of the overall...enhancement of those four CF3 groups (0.323 g∙cm−3) to the known density of RDX: ρ(TFM-RDX) ~ 1.816 + ¾(0.323) ≈ 2.06 g∙cm−3. Then Cheetah

  8. 3-Hydroxy-4,5-dimethyl-2(5H)-furanone (Sotolon) causing an off-flavor: elucidation of its formation pathways during storage of citrus soft drinks.

    Science.gov (United States)

    König, T; Gutsche, B; Hartl, M; Hübscher, R; Schreier, P; Schwab, W

    1999-08-01

    Gas chromatography/olfactometry (GCO) and gas chromatography-mass spectrometry (HRGC-MS) revealed 3-hydroxy-4, 5-dimethyl-2(5H)-furanone (sotolon) to be responsible for the "burnt" and "spicy" off-flavor observed in citrus soft drinks during storage. Among the ingredients of citrus soft drinks, ethanol and ascorbic acid were identified as the essential precursors of sotolon. Two formation pathways were postulated by studies using (2)H (D)- and (13)C-labeled ethanol and ascorbic acid; i.e., sotolon is formed from two molecules of ethanol and carbons 2 and 3 of ascorbic acid (pathway 1), or it is generated from one molecule of ethanol and carbons 3-6 of ascorbic acid (pathway 2).

  9. The physiological and ecological roles of volatile halogen production by marine diatoms

    Science.gov (United States)

    Hughes, Claire; Sun, Shuo

    2015-04-01

    Sea-to-air halogen flux is known to have a major impact on catalytic ozone cycling and aerosol formation in the troposphere. The biological production of volatile organic (e.g. bromoform, diiodomethane) and reactive inorganic halogens (e.g. molecular iodine) is believed to play an important role in mediating halogen emissions from the marine environment. Marine diatoms in particular are known to produce the organic and inorganic volatile halogens at high rates in pelagic waters and sea-ice systems. The climate-induced changes in diatom communities that have already been observed and are expected to occur throughout the world's oceans as warming progresses are likely to alter sea-to-air halogen flux. However, we currently have insufficient understanding of the physiological and ecological functions of volatile halogen production to develop modelling tools that can predict the nature and magnitude of the impact. The results of a series of laboratory studies aimed at establishing the physiological and ecological role of volatile halogen production in two marine polar diatoms (Thalassiosira antarctica and Porosira glacialis) will be described in this presentation. We will focus on our work investigating how the activity of the haloperoxidases, a group of enzymes known to be involved in halogenation reactions in marine organisms, is altered by environmental conditions. This will involve exploring the antioxidative defence role proposed for marine haloperoxidases by showing specifically how halogenating activity varies with photosynthetic rate and changes in the ambient light conditions in the two model marine diatoms. We will also present results from our experiments designed to investigate how volatile halogen production is impacted by and influences diatom-bacterial interactions. We will discuss how improved mechanistic understanding like this could pave the way for future volatile halogen-ecosystem model development.

  10. University of Maryland Wall Washer Retrofit - LED Modules Replace Halogen Lamps in a Performing Arts Center

    Energy Technology Data Exchange (ETDEWEB)

    Wilkerson, Andrea M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Abell, Thomas C. [Univ. of Maryland, College Park, MD (United States); Perrin, Tess E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-08-03

    The University of Maryland (UMD) began retrofitting halogen wall washers in the Clarice Smith Performing Arts Center (CSPAC) in April 2014. The U.S. Department of Energy (DOE) Solid-State Lighting (SSL) GATEWAY program documented this process through the final installation in March 2015, summarized in this report. The wall washers illuminate hallways lining the atrium, providing task illuminance for transitioning between spaces and visual interest to the atrium boundaries. The main goals of the retrofit were to maintain the visual appearance of the space while reducing maintenance costs – energy savings was considered an additional benefit by UMD Facilities Management. UMD Facilities Management is pleased with the results of this retrofit, and continues to initiate LED retrofit projects across the UMD campus.

  11. Persistent halogenated organic contaminants and mercury in northern fulmars (Fulmarus glacialis) from the Canadian Arctic.

    Science.gov (United States)

    Braune, Birgit M; Mallory, Mark L; Butt, Craig M; Mabury, Scott A; Muir, Derek C G

    2010-12-01

    Northern fulmars from two breeding colonies in the Canadian Arctic, Cape Vera and Prince Leopold Island, were analyzed for organochlorine pesticides, PCBs, perfluorinated compounds (PFCs) and total mercury (Hg). Hepatic concentrations of organochlorines and Hg were highest in the male fulmars from Cape Vera. Perfluorooctane sulfonate (PFOS) concentrations did not vary significantly between sexes or colonies. However, concentrations of the perfluorinated carboxylates (PFCAs) were higher in fulmars from Cape Vera than Prince Leopold Island. The C(11)-C(15) PFCAs averaged 90% of the PFCA profile at both colonies. Polychorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs (NO-PCBs) were measured only in birds from Prince Leopold Island. Concentrations of PCDDs, PCDFs, NO-PCBs and Toxic Equivalents (TEQs) did not differ significantly between sexes. ΣTEQ was comprised mainly of ΣTEQ(PCDF). Concentrations of Hg and the persistent halogenated compounds reported in this study were below published toxicological threshold values for wild birds.

  12. Abiotic and biotic reductive dehalogenation of halogenated methanes

    Energy Technology Data Exchange (ETDEWEB)

    Matheson, L.J.

    1994-01-01

    Reductive dehalogenation is an important reaction that generally leads to detoxification of many halogenated methanes. Halogenated methanes are widely used in industrial and commercial applications and the inadvertent or deliberate release of these chemicals has caused contamination of the atmosphere, soil and groundwater. The research presented here details the study of several systems for reductive dehalogenation of chlorinated methanes. The first system described in this dissertation involves reductive dechlorination of chlorinated methanes by laboratory cultures of methanogens. A vessel was constructed that allowed maintenance of anaerobic conditions and minimized losses of the volatile chlorocarbons. Methylene chloride was not dechlorinated in the presence of pure cultures of methanogens. Similarly, dechlorination did not occur in enrichments made with samples from several different anaerobic digesters. Abiotic dehalogenation studies showed that cobalamins, cobalt-centered macrocyclic compounds, catalyzed the reductive dechlorination of several halomethanes in anaerobic, closed batch systems. These studies focused on immobilization of cobalamins to several types of supports for use in pollution remediation strategies. Cyanocobalamin bound to Epoxy-Activated Sepharose 6B and talc catalyzed the rapid reduction of carbon tetrachloride and methylene chloride to sequentially reduced products. Corroding iron metal was also studied as a reductant for halogenated methanes. Several chlorinated methanes were reductively dechlorinated in closed, anaerobic, laboratory-scale model systems containing granular iron. Carbon tetrachloride was sequentially dehalogenated, via chloroform, to methylene chloride. The initial rate of each reaction was pseudo-first order in substrate and declined substantially with each dehalogenation step. Trichloroethene was also dechlorinated by iron, although more slowly than carbon tetrachloride.

  13. Theoretical and Experimental Study of the Friction Behavior of Halogen-Free Ionic Liquids in Elastohydrodynamic Regime

    National Research Council Canada - National Science Library

    Janardhanan, Karthik; Iglesias, Patricia

    2016-01-01

    .... Halogen-free ionic liquids have recently been considered as more environmentally stable than their halogenated counterparts, which tend to form highly toxic and corrosive acids when exposed to moisture...

  14. Preliminary assessment of halogenated alkanes as vapor-phase tracers

    Energy Technology Data Exchange (ETDEWEB)

    Adams, Michael C.; Moore, Joseph N.; Hirtz, Paul

    1991-01-01

    New tracers are needed to evaluate the efficiency of injection strategies in vapor-dominated environments. One group of compounds that seems to meet the requirements for vapor-phase tracing are the halogenated alkanes (HCFCs). HCFCs are generally nontoxic, and extrapolation of tabulated thermodynamic data indicate that they will be thermally stable and nonreactive in a geothermal environment. The solubilities and stabilities of these compounds, which form several homologous series, vary according to the substituent ratios of fluorine, chlorine, and hydrogen. Laboratory and field tests that will further define the suitability of HCFCs as vapor-phase tracers are under way.

  15. 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...... 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....

  16. New halogenated agents: should I change my practice?

    Science.gov (United States)

    Feiss, P

    2000-05-01

    Sevoflurane and Desflurane are relatively new halogenated agents which make induction and control of depth of anaesthesia easier, recovery rapid and of good quality and they have less side-effects and toxicity. In children sevoflurane could replace halothane because it provides smooth and rapid induction with less cardiovascular depression and arrhythmias. Desflurane is not used because of its pungent odour. In adults sevoflurane could be preferred to desflurane because it allows rapid induction and laryngeal mask insertion or tracheal intubation without myorelaxants, a similar time of recovery, no clinical evidence for renal and hepatic toxicity, no more costs for anaesthesia for a lower MAC.

  17. Molecular dynamics of halogenated graphene - hexagonal boron nitride nanoribbons

    Science.gov (United States)

    Nemnes, G. A.; Visan, Camelia; Anghel, D. V.; Manolescu, A.

    2016-08-01

    The hybrid graphene - hexagonal boron nitride (G-hBN) systems offer new routes in the design of nanoscale electronic devices. Using ab initio density functional theory calculations we investigate the dynamics of zig-zag nanoribbons a few interatomic distances wide. Several structures are analyzed, namely pristine graphene, hBN and G-hBN systems. By passivating the nanoribbon edges with hydrogen and different halogen atoms, one may tune the electronic and mechanical properties, like the band gap energies and the natural frequencies of vibration.

  18. Halogen free benzoxazine based curable compositions for high T.sub.g applications

    Energy Technology Data Exchange (ETDEWEB)

    Tietze, Roger; Nguyen, Yen-Loan

    2016-08-16

    A method for forming a halogen-free curable composition containing a benzoxazine monomer, at least one epoxy resin, a catalyst, a toughening agent and a solvent. The halogen-free curable composition is especially suited for use in automobile and aerospace applications since the composition, upon curing, produces a composite having a high glass transition temperature.

  19. Toxicity of gaseous halogenated organic compounds. (Latest citations from the NTIS bibliographic database). Published Search

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-02-01

    The bibliography contains citations concerning the toxicology of halogenated hydrocarbons and their health effects. Topics cover halogenated gases used as industrial chemicals, fire extinguishers, anesthetics, solvents, pesticides, and aerosol propellants. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

  20. 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...

  1. Investigation of non-halogenated solvent mixtures for high throughput fabrication of polymerfullerene solar cells

    NARCIS (Netherlands)

    Schmidt-Hansberg, B.; Sanyal, M.; Grossiord, N.; Galagan, Y.O.; Baunach, M.; Klein, M.F.G.; Colsmann, A.; Scharfer, P.; Lemmer, U.; Dosch, H.; Michels, J.J; Barrena, E.; Schabel, W.

    2012-01-01

    The rapidly increasing power conversion efficiencies of organic solar cells are an important prerequisite towards low cost photovoltaic fabricated in high throughput. In this work we suggest indane as a non-halogenated replacement for the commonly used halogenated solvent o-dichlorobenzene. Indane w

  2. Anaerobic microbial transformation of halogenated aromatics and fate prediction using electron density modeling.

    Science.gov (United States)

    Cooper, Myriel; Wagner, Anke; Wondrousch, Dominik; Sonntag, Frank; Sonnabend, Andrei; Brehm, Martin; Schüürmann, Gerrit; Adrian, Lorenz

    2015-05-19

    Halogenated homo- and heterocyclic aromatics including disinfectants, pesticides and pharmaceuticals raise concern as persistent and toxic contaminants with often unknown fate. Remediation strategies and natural attenuation in anaerobic environments often build on microbial reductive dehalogenation. Here we describe the transformation of halogenated anilines, benzonitriles, phenols, methoxylated, or hydroxylated benzoic acids, pyridines, thiophenes, furoic acids, and benzenes by Dehalococcoides mccartyi strain CBDB1 and environmental fate modeling of the dehalogenation pathways. The compounds were chosen based on structural considerations to investigate the influence of functional groups present in a multitude of commercially used halogenated aromatics. Experimentally obtained growth yields were 0.1 to 5 × 10(14) cells mol(-1) of halogen released (corresponding to 0.3-15.3 g protein mol(-1) halogen), and specific enzyme activities ranged from 4.5 to 87.4 nkat mg(-1) protein. Chlorinated electron-poor pyridines were not dechlorinated in contrast to electron-rich thiophenes. Three different partial charge models demonstrated that the regioselective removal of halogens is governed by the least negative partial charge of the halogen. Microbial reaction pathways combined with computational chemistry and pertinent literature findings on Co(I) chemistry suggest that halide expulsion during reductive dehalogenation is initiated through single electron transfer from B12Co(I) to the apical halogen site.

  3. Investigation of non-halogenated solvent mixtures for high throughput fabrication of polymerfullerene solar cells

    NARCIS (Netherlands)

    Schmidt-Hansberg, B.; Sanyal, M.; Grossiord, N.; Galagan, Y.O.; Baunach, M.; Klein, M.F.G.; Colsmann, A.; Scharfer, P.; Lemmer, U.; Dosch, H.; Michels, J.J; Barrena, E.; Schabel, W.

    2012-01-01

    The rapidly increasing power conversion efficiencies of organic solar cells are an important prerequisite towards low cost photovoltaic fabricated in high throughput. In this work we suggest indane as a non-halogenated replacement for the commonly used halogenated solvent o-dichlorobenzene. Indane w

  4. Impacts of halogen additions on mercury oxidation, in a slipstream selective catalyst reduction (SCR), reactor when burning sub-bituminous coal.

    Science.gov (United States)

    Cao, Yan; Gao, Zhengyang; Zhu, Jiashun; Wang, Quanhai; Huang, Yaji; Chiu, Chengchung; Parker, Bruce; Chu, Paul; Pant, Wei-Ping

    2008-01-01

    This paper presents a comparison of impacts of halogen species on the elemental mercury (Hg(0)) oxidation in a real coal-derived flue gas atmosphere. It is reported there is a higher percentage of Hg(0) in the flue gas when burning sub-bituminous coal (herein Powder River Basin (PRB) coal) and lignite, even with the use of selective catalytic reduction (SCR). The higher Hg(0)concentration in the flue gas makes it difficult to use the wet-FGD process for the mercury emission control in coal-fired utility boilers. Investigation of enhanced Hg(0) oxidation by addition of hydrogen halogens (HF, HCl, HBr, and HI) was conducted in a slipstream reactor with and without SCR catalysts when burning PRB coal. Two commercial SCR catalysts were evaluated. SCR catalyst no. 1 showed higher efficiencies of both NO reduction and Hg(0) oxidation than those of SCR catalyst no. 2. NH3 addition seemed to inhibit the Hg(0) oxidation, which indicated competitive processes between NH3 reduction and Hg(0) oxidation on the surface of SCR catalysts. The hydrogen halogens, in the order of impact on Hg(0) oxidation, were HBr, HI, and HCl or HF. Addition of HBr at approximately 3 ppm could achieve 80% Hg(0) oxidation. Addition of HI at approximately 5 ppm could achieve 40% Hg(0) oxidation. In comparison to the empty reactor, 40% Hg(0) oxidation could be achieved when HCl addition was up to 300 ppm. The enhanced Hg(0) oxidation by addition of HBr and HI seemed not to be correlated to the catalytic effects by both evaluated SCR catalysts. The effectiveness of conversion of hydrogen halogens to halogen molecules or interhalogens seemed to be attributed to their impacts on Hg(0) oxidation.

  5. Principles and applications of halogen bonding in medicinal chemistry and chemical biology.

    Science.gov (United States)

    Wilcken, Rainer; Zimmermann, Markus O; Lange, Andreas; Joerger, Andreas C; Boeckler, Frank M

    2013-02-28

    Halogen bonding has been known in material science for decades, but until recently, halogen bonds in protein-ligand interactions were largely the result of serendipitous discovery rather than rational design. In this Perspective, we provide insights into the phenomenon of halogen bonding, with special focus on its role in drug discovery. We summarize the theoretical background defining its strength and directionality, provide a systematic analysis of its occurrence and interaction geometries in protein-ligand complexes, and give recent examples where halogen bonding has been successfully harnessed for lead identification and optimization. In light of these data, we discuss the potential and limitations of exploiting halogen bonds for molecular recognition and rational drug design.

  6. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false List of Halogenated Organic Compounds... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining the... defined the HOCs that must be included in a calculation as any compounds having a carbon-halogen...

  7. 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

  8. Emerging halogenated flame retardants and hexabromocyclododecanes in food samples from an e-waste processing area in Vietnam.

    Science.gov (United States)

    Tao, Fang; Matsukami, Hidenori; Suzuki, Go; Tue, Nguyen Minh; Viet, Pham Hung; Takigami, Hidetaka; Harrad, Stuart

    2016-03-01

    This study reports concentrations of selected emerging halogenated flame retardants (HFRs) and hexabromocyclododecanes (HBCDs) in foodstuffs sourced from an e-waste processing area in Vietnam and two reference sites in Vietnam and Japan. Concentrations of all target HFRs in e-waste-impacted samples in this study exceed significantly (p e-waste processing activities exert a substantial impact on local environmental contamination and human dietary exposure. Significant linear positive correlations in concentrations of syn-Dechlorane Plus (DP) and anti-DP were found between soils and those in co-located chicken samples (p e-waste processing sites and non-e-waste processing areas elsewhere.

  9. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    Science.gov (United States)

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-05

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process.

  10. Novel Halogenated Pyrazine-Based Chalcones as Potential Antimicrobial Drugs

    Directory of Open Access Journals (Sweden)

    Marta Kucerova-Chlupacova

    2016-10-01

    Full Text Available Chalcones, i.e., compounds with the chemical pattern of 1,3-diphenylprop-2-en-1-ones, exert a wide range of bio-activities, e.g., antioxidant, anti-inflammatory, anticancer, anti-infective etc. Our research group has been focused on pyrazine analogues of chalcones; several series have been synthesized and tested in vitro on antifungal and antimycobacterial activity. The highest potency was exhibited by derivatives with electron withdrawing groups (EWG in positions 2 and 4 of the ring B. As halogens also have electron withdrawing properties, novel halogenated derivatives were prepared by Claisen-Schmidt condensation. All compounds were submitted for evaluation of their antifungal and antibacterial activity, including their antimycobacterial effect. In the antifungal assay against eight strains of selected fungi, growth inhibition of Candida glabrata and Trichophyton interdigitale (formerly T. mentagrophytes was shown by non-alkylated derivatives with 2-bromo or 2-chloro substitution. In the panel of selected bacteria, 2-chloro derivatives showed the highest inhibitory effect on Staphylococcus sp. In addition, all products were also screened for their antimycobacterial activity against Mycobacterium tuberculosis H37RV My 331/88, M. kansasii My 235/80, M. avium 152/80 and M. smegmatis CCM 4622. Some of the examined compounds, inhibited growth of M. kansasii and M. smegmatis with minimum inhibitory concentrations (MICs comparable with those of isoniazid.

  11. Emission location dependent ozone depletion potentials for very short-lived halogenated species

    Directory of Open Access Journals (Sweden)

    I. Pisso

    2010-12-01

    Full Text Available We present trajectory-based estimates of Ozone Depletion Potentials (ODPs for very short-lived halogenated source gases as a function of surface emission location. The ODPs are determined by the fraction of source gas and its degradation products which reach the stratosphere, depending primarily on tropospheric transport and chemistry, and the effect of the resulting reactive halogen in the stratosphere, which is determined by stratospheric transport and chemistry, in particular by stratospheric residence time. Reflecting the different timescales and physico-chemical processes in the troposphere and stratosphere, the estimates are based on calculation of separate ensembles of trajectories for the troposphere and stratosphere. A methodology is described by which information from the two ensembles can be combined to give the ODPs.

    The ODP estimates for a species with a fixed 20 d lifetime, representing a compound like n-propyl bromide, are presented as an example. The estimated ODPs show strong geographical and seasonal variation, particularly within the tropics. The values of the ODPs are sensitive to the inclusion of a convective parametrization in the trajectory calculations, but the relative spatial and seasonal variation is not. The results imply that ODPs are largest for emissions from south and south-east Asia during Northern Hemisphere summer and from the western Pacific during Northern Hemisphere winter. Large ODPs are also estimated for emissions throughout the tropics with non-negligible values also extending into northern mid-latitudes, particularly in the summer. These first estimates, whilst made under some simplifying assumptions, show larger ODPs for certain emission regions, particularly south Asia in NH summer, than have typically been reported by previous studies which used emissions distributed evenly over land surfaces.

  12. A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil.

    Science.gov (United States)

    Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

    2016-06-29

    In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications.

  13. Halogens and their role in polar boundary-layer ozone depletion

    Directory of Open Access Journals (Sweden)

    W. R. Simpson

    2007-03-01

    Full Text Available During springtime in the polar regions, unique photochemistry converts inert halide salts ions (e.g. Br into reactive halogen species (e.g. Br atoms and BrO that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

  14. 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.

  15. Evaluating the potential for halogen bonding in ketosteroid isomerase’s oxyanion hole using unnatural amino acid mutagenesis

    Science.gov (United States)

    Kraut, Daniel A; Churchil, Michael J; Dawson, Phillip E

    2009-01-01

    There has recently been an increasing interest in controlling macromolecular conformations and interactions through halogen bonding. Halogen bonds are favorable electrostatic interactions between polarized, electropositive chlorine, bromine or iodine atoms and electronegative atoms such as oxygen or nitrogen. These interactions have been likened to hydrogen bonds both in terms of their favored acceptor molecules, their geometries, and their energetics. We asked whether a halogen bond could replace a hydrogen bond in the oxyanion hole of ketosteroid isomerase, using semi-synthetic enzyme containing para-halogenated phenylalanine derivatives to replace the tyrosine hydrogen bond donor. Formation of a halogen bond to the oxyanion in the transition state would be expected to rescue the effects of mutation to phenylalanine, but all of the halogenated enzymes were comparable in activity to the phenylalanine mutant. We conclude that, at least in this active site, a halogen bond cannot functionally replace a hydrogen bond. PMID:19260691

  16. Vertical ionization energies of halogen anions in solution

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Based on the constrained equilibrium state theory,the nonequilibrium solvation energy is derived in the framework of the continuum model.The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption.The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X(X = Cl,Br,I,Cl2,Br2,I2) in aqueous solution.According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum,our final estimated vertical ionization energies in solution are very close to the experimental observations,while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies.

  17. 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.

  18. 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.

  19. 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.

  20. The Brenner Moor - A saline bog as a source for halogenated and non-halogenated volatile compounds

    Science.gov (United States)

    Krause, T.; Studenroth, S.; Furchner, M.; Hoffman, A.; Lippe, S.; Kotte, K.; Schöler, H. F.

    2012-04-01

    The Brenner Moor is a small bog in the catchment area of the river Trave located in Schleswig-Holstein, North Germany, between Baltic and North Sea. The bog is fed by several saline springs with chloride concentrations up to 15 g/L. The high chloride concentrations and the high organic content of the peat make the Brenner Moor an ideal source for the abiotic formation of volatile organic halogenated compounds (VOX). VOX play an important role in the photochemical processes of the lower atmosphere and information on the atmospheric input from saline soils like the Brenner Moor will help to understand the global fluxes of VOX. Soil samples were taken in spring 2011 from several locations and depths in the vicinity of the Brenner Moor. The samples were freeze-dried, ground and incubated in water emphasising an abiotic character for the formation of volatile organic compounds. 1,2-dichloroethane and trichloromethane are the main halogenated compounds emitted from soils of the Brenner Moor. The abiotic formation of trichloromethane as well as other trihalomethanes has been part of intensive studies. A well known source is the decarboxylation of trichloroacetic acid and trichloroacetyl-containing compounds to trichloromethane [1]. Huber et al. discovered another pathway in which catechol, as a model compound for organic substances, is oxidised under Fenton-like conditions with iron(III), hydrogen peroxide and halides to form trihalomethanes [2]. Besides the halogenated compounds, the formation of sulphur compounds such as dimethyl sulfide and dimethyl disulfide and several furan derivatives could be detected which also have an impact on atmospheric chemistry, especially particle formation of clouds. Furan, methylfuran and dimethylfuran are compounds that can be obtained under Fenton-like oxidation from catechol, methyl- and dimethylcatechol and are known to be produced in natural soils [3]. A novel class of furan derivatives that are formed under abiotic conditions from

  1. 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.

  2. Martian fluid and Martian weathering signatures identified in Nakhla, NWA 998 and MIL 03346 by halogen and noble gas analysis

    Science.gov (United States)

    Cartwright, J. A.; Gilmour, J. D.; Burgess, R.

    2013-03-01

    We report argon (Ar) noble gas, Ar-Ar ages and halogen abundances (Cl, Br, I) of Martian nakhlites Nakhla, NWA 998 and MIL 03346 to determine the presence of Martian hydrous fluids and weathering products. Neutron-irradiated samples were either crushed and step-heated (Nakhla only), or simply step-heated using a laser or furnace, and analysed for noble gases using an extension of the 40Ar-39Ar technique to determine halogen abundances. The data obtained provide the first isotopic evidence for a trapped fluid that is Cl-rich, has a strong correlation with 40ArXS (40ArXS = 40Armeasured - 40Arradiogenic) and displays 40ArXS/36Ar of ˜1000 - consistent with the Martian atmosphere. This component was released predominantly in the low temperature and crush experiments, which may suggest a fluid inclusion host. For the halogens, we observe similar Br/Cl and I/Cl ratios between the nakhlites and terrestrial reservoirs, which is surprising given the absence of crustal recycling, organic matter and frequent fluid activity on Mars. In particular, Br/Cl ratios in our Nakhla samples (especially olivine) are consistent with previously analysed Martian weathering products, and both low temperature and crush analyses show a similar trend to the evaporation of seawater. This may indicate that surface brines play an important role on Mars and on halogen assemblages within Martian meteorites and rocks. Elevated I/Cl ratios in the low temperature NWA 998 and MIL 03346 releases may relate to in situ terrestrial contamination, though we are unable to distinguish between low temperature terrestrial or Martian components. Whilst estimates of the amount of water present based on the 36Ar concentrations are too high to be explained by a fluid component alone, they are consistent with a mixed-phase inclusion (gas and fluid) or with shock-implanted Martian atmospheric argon. The observed fluid is dilute (low salinity, but high Br/Cl and I/Cl ratios), contains a Martian atmospheric component

  3. Synthesis of 2(5H)-Furanone Derivatives with Biphenyl Ether Unit%含联苯醚结构2(5H)-呋喃酮衍生物的合成

    Institute of Scientific and Technical Information of China (English)

    关丽涛; 莫广珍; 吴彦城; 梁欣榆; 罗俏芳; 汪朝阳

    2015-01-01

    Sixteen 5-(4'-alkoxybiphenyl-4-yloxy)-3,4-dihalo-2(5H)-furanones are synthesized via the direct dehydrative etherification reactions of 4'-alkoxybiphenyl-4-ol with mucochloric acid and mucobromic acid, respectively, using sulfuric acid as catalyst at reflux in toluene from 30% to 58% yields (mostly over 47%). The moderate yields may be due to that this ac-id-catalyzed etherification should be a SN2 nucleophilic substitution reaction. The structures of all newly synthesized com-pounds are elucidated and confirmed by FTIR, UV,1H NMR,13C NMR, and elemental analysis. The synthetic procedures af-ford not only an important strategy for the synthesis of 2(5H)-furanone derivatives having potential bioactivity, but also a sim-ple method for the synthesis of aromatic ether from two different hydroxyl compounds.%以硫酸为催化剂,不同4'-烷氧基-4-羟基联苯与粘卤酸在甲苯溶剂中回流,经脱水醚化反应合成了16个新型的5-(4'-烷氧基-4-联苯氧基)-3,4-二卤-2(5H)-呋喃酮化合物,产率30%~58%(大部分47%以上)。中等产率可能与该酸催化的反应为SN2亲核取代反应有关。新化合物的结构经FTIR, UV,1H NMR,13C NMR和元素分析确证。这些具有不同生物活性基团化合物的设计与合成,为新型2(5H)-呋喃酮衍生物的合成,以及由不同羟基化合物合成芳香醚类化合物提供了参考。

  4. Comment on "Cosmic-ray-driven reaction and greenhouse effect of halogenated molecules: Culprits for atmospheric ozone depletion and global climate change"

    Science.gov (United States)

    Müller, Rolf; Grooß, Jens-Uwe

    2014-04-01

    Lu's "cosmic-ray-driven electron-induced reaction (CRE) theory" is based on the assumption that the CRE reaction of halogenated molecules (e.g., chlorofluorocarbons (CFCs), HCl, ClONO2) adsorbed or trapped in polar stratospheric clouds in the winter polar stratosphere is the key step in forming photoactive halogen species that are the cause of the springtime ozone hole. This theory has been extended to a warming theory of halogenated molecules for climate change. In this comment, we discuss the chemical and physical foundations of these theories and the conclusions derived from the theories. First, it is unclear whether the loss rates of halogenated molecules induced by dissociative electron attachment (DEA) observed in the laboratory can also be interpreted as atmospheric loss rates, but even if this were the case, the impact of DEA-induced reactions on polar chlorine activation and ozone loss in the stratosphere is limited. Second, we falsify several conclusions that are reported on the basis of the CRE theory: There is no polar ozone loss in darkness, there is no apparent 11-year periodicity in polar total ozone measurements, the age of air in the polar lower stratosphere is much older than 1-2 years, and the reported detection of a pronounced recovery (by about 20-25%) in Antarctic total ozone measurements by the year 2010 is in error. There are also conclusions about the future development of sea ice and global sea level which are fundamentally flawed because Archimedes' principle is neglected. Many elements of the CRE theory are based solely on correlations between certain datasets which are no substitute for providing physical and chemical mechanisms causing a particular behavior noticeable in observations. In summary, the CRE theory cannot be considered as an independent, alternative mechanism for polar stratospheric ozone loss and the conclusions on recent and future surface temperature and global sea level change do not have a physical basis.

  5. Development of Non-Halogen Flame Retardant Optical Fiber and Optical Fiber Cord

    Institute of Scientific and Technical Information of China (English)

    Kazunori; Tanaka; Kaoru; Okuno; Tomoyuki; Hattori; Kiyoaki; Moriuchi; Hiroshi; Hayami; Wataru; Katsurashima; Yoshikyo; Tamekuni

    2003-01-01

    A non-halogen highly flame-retardant 0.9mm optical fiber and 2.0mm simplex optical cord, which are harmonized with the ecosystem, have been developed. The characteristics of them are presented in this paper.

  6. Highly Regioselective Halogenation of Pyridine N-Oxide: Practical Access to 2-Halo-Substituted Pyridines.

    Science.gov (United States)

    Chen, Ying; Huang, Jinkun; Hwang, Tsang-Lin; Chen, Maosheng J; Tedrow, Jason S; Farrell, Robert P; Bio, Matthew M; Cui, Sheng

    2015-06-19

    A highly efficient and regioselective halogenation reaction of unsymmetrical pyridine N-oxide under mild conditions is described. The methodology provides a practical access to various 2-halo-substituted pyridines, which are pharmaceutically important intermediates.

  7. Mechanisms of halogen-based covalent self-assembly on metal surfaces.

    Science.gov (United States)

    Björk, Jonas; Hanke, Felix; Stafström, Sven

    2013-04-17

    We computationally study the reaction mechanisms of halogen-based covalent self-assembly, a major route for synthesizing molecular nanostructures and nanographenes on surfaces. Focusing on biphenyl as a small model system, we describe the dehalogenation, recombination, and diffusion processes. The kinetics of the different processes are also investigated, in particular how diffusion and coupling barriers affect recombination rates. Trends across the periodic table are derived from three commonly used close-packed (111) surfaces (Cu, Ag, and Au) and two halogens (Br and I). We show that the halogen atoms can poison the surface, thus hindering long-range ordering of the self-assembled structures. Finally, we present core-level shifts of the relevant carbon and halogen atoms, to provide reference data for reliably detecting self-assembly without the need for atomic-resolution scanning tunneling microscopy.

  8. Halogen behaviours during andesitic magma degassing: from magma chamber to volcanic plume

    Science.gov (United States)

    Balcone-Boissard, H.; Villemant, B.; Boudon, G.; Michel, A.

    2009-04-01

    Halogen (F, Cl, Br and I) behaviours during degassing of H2O-rich silicic magmas are investigated using volatile content analysis in glass (matrix glass and melt inclusions) of volcanic clasts (pumice and lava-dome fragments) in a series of plinian, vulcanian and lava dome-forming eruptions. Examples are taken from andesitic systems in subduction zones: Montagne Pelée and Soufrière Hills of Montserrat (Lesser Antilles) and Santa Maria-Santiaguito (Guatemala). Halogens behaviour during shallow degassing primarily depends on their incompatible character in melts and on H2O solubility. But variations in pre-eruptive conditions, degassing kinetics and syn-eruptive melt crystallisation, induce large variations in halogen extraction efficiency during H2O degassing, up to prevent halogen loss. In all studied systems, Cl, Br and I are not fractionated neither by differentiation nor by degassing processes: thus Cl/Br/I ratios remain well preserved in melts from reservoirs to eruption. These ratios measured in erupted clasts are characteristic of pre-eruptive magma compositions and may be used to trace deep magmatic processes. Moreover, during plinian eruptions, Cl, Br and I are extracted by H2O degassing but less efficiently than predicted by available experimental fluid-melt partition coefficients, by a factor as high as 5. F behaves as an incompatible element and, contrary to other halogens, is never significantly extracted by degassing. Degassing during lava dome-forming eruptions of andesitic magmas occurs mainly at equilibrium and is more efficient at extracting halogens and H2O than explosive degassing. The mobility of H2O and halogens depends on their speciation in both silicate melts and exsolved fluids which strongly varies with pressure. We suggest that the rapid pressure decrease during highly explosive eruptions prevents complete volatile speciation at equilibrium and consequently strongly limits halogen degassing.

  9. 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...

  10. Advances in Metal-Catalyzed Cross-Coupling Reactions of Halogenated Quinazolinones and Their Quinazoline Derivatives

    Directory of Open Access Journals (Sweden)

    Malose Jack Mphahlele

    2014-10-01

    Full Text Available Halogenated quinazolinones and quinazolines are versatile synthetic intermediates for the metal-catalyzed carbon–carbon bond formation reactions such as the Kumada, Stille, Negishi, Sonogashira, Suzuki-Miyaura and Heck cross-coupling reactions or carbon-heteroatom bond formation via the Buchwald-Hartwig cross-coupling to yield novel polysubstituted derivatives. This review presents an overview of the application of these methods on halogenated quinazolin-4-ones and their quinazolines to generate novel polysubstituted derivatives.

  11. Halogenated cytisine derivatives as agonists at human neuronal nicotinic acetylcholine receptor subtypes.

    Science.gov (United States)

    Slater, Y E; Houlihan, L M; Maskell, P D; Exley, R; Bermúdez, I; Lukas, R J; Valdivia, A C; Cassels, B K

    2003-03-01

    Cytisine (cy) is a potent and competitive partial agonist at alpha4 subunit-containing nicotinic acetylcholine (nACh) receptors while at homomeric alpha7-nACh receptors it behaves as a full agonist with a relatively lower potency. In the present study, we assessed the effects of bromination or iodination of the pyridone ring of cy and N-methylcytisine (N-Me-cy) on the effects of these compounds on recombinant human (h) alpha7, halpha4beta2 and halpha4beta4 nACh receptors expressed in clonal cell lines and Xenopus oocytes. Halogenation at C(3) of cy or N-Me-cy usually brings about a marked increase in both affinity and efficacy at halpha7, halpha4beta2 and halpha4beta4 nACh, the extent of which depends on whether the halogen is bromine or iodine, and upon receptor subtype. The effects of halogenation at C(5) are strongly influenced by the specific halogen substituent so that bromination causes a decrease in both affinity and efficacy while iodination decreases affinity but its effects on efficacy range from a decrease (halpha7, halpha4beta4 nACh receptors) to a marked increase (halpha4beta2 nACh receptors). Based on these findings, which differ from those showing that neither the affinity nor efficacy of nicotine, 3-(2-azetidinylmethoxy)-pyridine or epibatidine are greatly affected by halogenation, dehalogenation or halogen exchange at equivalent positions, we suggest that cy, N-Me-cy and their halo-isosteres bind to neuronal nACh receptors in a different orientation allowing the halogen atom to interact with a hydrophobic halogen-accepting region within the predominantly hydrophobic agonist-binding pocket of the receptors.

  12. Plant selective uptake of halogenated flame retardants at an e-waste recycling site in southern China.

    Science.gov (United States)

    Wang, Shaorui; Wang, Yan; Luo, Chunling; Li, Jun; Yin, Hua; Zhang, Gan

    2016-07-01

    The concentrations and homolog patterns of halogenated flame retardants (HFRs) in vegetables grown at an e-waste contaminated site were investigated. Polybrominated diphenyl ethers (PBDEs) were the dominant HFRs in vegetable tissues, with concentrations ranging from 10.3 to 164 ng g(-1) and 1.16-107 ng g(-1) in shoots and roots, respectively, followed by novel brominated flame retardants (NBFRs) and dechlorane plus (DPs). This is an indication that PBDE contamination in vegetables grown around e-waste recycling sites may pose a risk to the local terrestrial ecosystem and residents. In addition, this is the first report on the concentrations and compositions of NBFRs in vegetables around e-waste recycling sites. The HFRs concentrations in vegetables varied greatly with the vegetable species, with the highest concentrations observed in Brassica oleracea var. capitata. Root concentration factors (RCF) decreased with increasing log Kow of HFRs, which indicated that the uptake of HFRs was controlled mainly by log Kow. Dissimilar HFRs profiles in shoots and roots suggested that the uptake and translocation of HFRs by plants were selective, with lower halogenated congeners prone to accumulation in vegetable tissues. Positive relationships between PBDEs and their substitutes were observed in vegetable tissues, suggesting that the replacement of PBDEs by NBFRs has not resulted in an obvious transition in plants within the study area.

  13. 卤键弱作用浅谈%Brief discussion on halogen bonding weak interaction

    Institute of Scientific and Technical Information of China (English)

    王亚琴; 邵群

    2015-01-01

    Halogen bonding, a noncovalent, int ermolecular weak interaction analogues to hydrogen bonding, exists between σ antibonding orbital of halogen atoms and atoms with lone-pair electron and πelectron system, which exerts unique effect in the field of desigh of functional materials and biomedicine. In this paper, the interaction essence of halogen bonding was simply introduced, the developing history of halogen bonding was elaborated and the basic character of halogen bonding was depicted, looking forward to much more comprehension toward halogen bonding.%卤键是与氢键相似的一种分子间非共价作用,存在于卤原子的σ反键轨道与具有孤电子对的原子或π电子体系之间,在功能材料与生物药物设计方面发挥了独特作用。介绍卤键的作用本质,阐述卤键发展简史,并描述卤键的基本特征。

  14. QSARS for Acute Toxicity of Halogenated Benzenes to Bacteria in Natural Waters

    Institute of Scientific and Technical Information of China (English)

    GUAN-GHUA LU; CHAO WANG; YU-MEI LI

    2006-01-01

    Objective To measure the acute toxicity of halogenated benzenes to bacteria in natural waters and to study quantitative relationships between the structure and activity of chemicals. Methods The concentration values causing 50% inhibition of bacteria growth (24h-IC50) were determined according to the bacterial growth inhibition test method. The energy of the lowest unoccupied molecular orbital and the net charge of carbon atom of 20 halogenated benzenes were calculated by the quantum chemical MOPAC program. Results The log1/IC50 values ranged from 4.79 for 2,4-dinitrochlorobenzene to 3.65 for chlorobenzene. A quantitative structure-activity relationship model was derived from the toxicity and structural parameters: log1/IC50 =-0.531(ELUMO)+1.693(Qc)+0.163(logP)+3.375. This equation was found to fit well (r2=0.860, s=0.106), and the average percentage error was only 1.98%. Conclusion Halogenated benzenes and alkyl halogenated benzenes are non-polar narcotics, and have hydrophobicity-dependent toxicity. The halogenated phenols and anilines exhibit a higher toxic potency than their hydrophobicity, whereas 2,4-dinitrochlorobenzene is electrophile with the halogen acting as the leaving group.

  15. Benchmarking DFT methods with small basis sets for the calculation of halogen-bond strengths.

    Science.gov (United States)

    Siiskonen, Antti; Priimagi, Arri

    2017-02-01

    In recent years, halogen bonding has become an important design tool in crystal engineering, supramolecular chemistry and biosciences. The fundamentals of halogen bonding have been studied extensively with high-accuracy computational methods. Due to its non-covalency, the use of triple-zeta (or larger) basis sets is often recommended when studying halogen bonding. However, in the large systems often encountered in supramolecular chemistry and biosciences, large basis sets can make the calculations far too slow. Therefore, small basis sets, which would combine high computational speed and high accuracy, are in great demand. This study focuses on comparing how well density functional theory (DFT) methods employing small, double-zeta basis sets can estimate halogen-bond strengths. Several methods with triple-zeta basis sets are included for comparison. Altogether, 46 DFT methods were tested using two data sets of 18 and 33 halogen-bonded complexes for which the complexation energies have been previously calculated with the high-accuracy CCSD(T)/CBS method. The DGDZVP basis set performed far better than other double-zeta basis sets, and it even outperformed the triple-zeta basis sets. Due to its small size, it is well-suited to studying halogen bonding in large systems.

  16. Human fibroblasts and 900 MHz radiofrequency radiation: evaluation of DNA damage after exposure and co-exposure to 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5h)-furanone (MX).

    Science.gov (United States)

    Sannino, A; Di Costanzo, G; Brescia, F; Sarti, M; Zeni, O; Juutilainen, J; Scarfì, M R

    2009-06-01

    The aim of this study was to investigate DNA damage in human dermal fibroblasts from a healthy subject and from a subject affected by Turner's syndrome that were exposed for 24 h to radiofrequency (RF) radiation at 900 MHz. The RF-radiation exposure was carried out alone or in combination with 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX), a well-known environmental mutagen and carcinogen produced during the chlorination of drinking water. Turner's syndrome fibroblasts were also exposed for a shorter time (1 h). A signal similar to that emitted by Global System for Mobile Communications (GSM) mobile phones was used at a specific absorption rate of 1 W/kg under strictly controlled conditions of temperature and dosimetry. To evaluate DNA damage after RF-radiation exposure alone, the alkaline comet assay and the cytokinesis-block micronucleus assay were used. In the combined-exposure experiments, MX was given at a concentration of 25 microM for 1 h immediately after the RF-radiation exposure, and the effects were evaluated by the alkaline comet assay. The results revealed no genotoxic and cytotoxic effects from RF radiation alone in either cell line. As expected, MX treatment induced an increase in DNA migration in the comet assay, but no enhancement of the MX-induced DNA damage was observed in the cells exposed to RF radiation.

  17. The Relationship between MX [3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone], Routinely Monitored Trihalomethanes, and Other Characteristics in Drinking Water in a Long-Term Survey.

    Science.gov (United States)

    Smith, Rachel B; Bennett, James E; Rantakokko, Panu; Martinez, David; Nieuwenhuijsen, Mark J; Toledano, Mireille B

    2015-06-01

    MX (3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) is a drinking water disinfection byproduct (DBP). It is a potent mutagen and is of concern to public health. Data on MX levels in drinking water, especially in the UK, are limited. Our aim was to investigate factors associated with variability of MX concentrations at the tap, and to evaluate if routinely measured trihalomethanes (THMs) are an appropriate proxy measure for MX. We conducted quarterly water sampling at consumers' taps in eight water supply zones in and around Bradford, UK, between 2007 and 2010. We collected 79 samples which were analyzed for MX using GC-HRMS. Other parameters such as pH, temperature, UV-absorbance and free chlorine were measured concurrently, and total THMs were modeled from regulatory monitoring data. To our knowledge this is the longest MX measurement survey undertaken to date. Concentrations of MX varied between 8.9 and 45.5 ng/L with a median of 21.3 ng/L. MX demonstrated clear seasonality with concentrations peaking in late summer/early fall. Multivariate regression showed that MX levels were associated with total trihalomethanes, UV-absorbance and pH. However, the relationship between TTHM and MX may not be sufficiently consistent across time and location for TTHM to be used as a proxy measure for MX in exposure assessment.

  18. Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

    Science.gov (United States)

    Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

    2015-11-01

    A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater).

  19. Persistent halogenated compounds in captive Chinese alligators (Alligator sinensis) from China.

    Science.gov (United States)

    Wu, Ting; Hong, Bing; Wu, Xiaobing; Wu, Jiangping; Wang, Xinming; Yi, Zhigang; Zhao, Juan; Zhan, Miao; Mai, Bixian

    2014-09-01

    While a number of studies have reported residual levels of persistent halogenated compounds (PHCs) in crocodilia, there is still a dearth of information on the Chinese alligator, a critically endangered crocodilian species. In the present study, several PHCs, including polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and dichlorodiphenyltrichloroethane and its metabolites (DDTs), were detected in the adult tissues, neonates, and eggs of captive Chinese alligators from China. The concentrations of ΣPBDEs, ΣPCBs, and ΣDDTs in Chinese alligators ranged from 0.11 to 16.1, 1.12 to 22.2, and 6.03 to 1020ngg(-1) wet weight, respectively, with higher levels of ΣPCBs and ΣDDTs in the neonates and eggs than in muscle tissues. The ΣDDT residues in the studied Chinese alligators were at the high end of reported ranges from crocodilia around the world, and some results exceeded levels known to cause a female-biased sex ratio in crocodilians.

  20. Discovery, SAR, and Radiolabeling of Halogenated Benzimidazole Carboxamide Antagonists as Useful Tools for (alpha)4(beta)1 Integrin Expressed on T- and B-cell Lymphomas

    Energy Technology Data Exchange (ETDEWEB)

    Carpenter, R D; Natarajan, A; Lau, E Y; Andrei, M; Solano, D M; Lightstone, F C; DeNardo, S J; Lam, K S; Kurth, M J

    2010-02-08

    The cell surface receptor {alpha}{sub 4}{beta}{sub 1} integrin is an attractive yet poorly understood target for selective diagnosis and treatment of T- and B-cell lymphomas. This report focuses on the rapid microwave preparation of medicinally pertinent benzimidazole heterocycles, structure-activity relationships (SAR) of novel halobenzimidazole carboxamide antagonists 3-6, and preliminary biological evaluation of radioiodinated agents 7, 8, and 18. The I-125 derivative 18 had good tumor uptake (12 {+-} 1% ID/g at 24 h; 4.5 {+-} 1% ID/g at 48 h) and tumor:kidney ratio ({approx}4:1 at 24 h; 2.5:1 at 48 h) in xenograft murine models of B-cell lymphoma. Molecular homology models of {alpha}{sub 4}{beta}{sub 1} integrin have predicted that docked halobenzimidazole carboxamides have the halogen atom in a suitable orientation for halogen-hydrogen bonding. These high affinity ({approx} pM binding) halogenated ligands are attractive tools for medicinal and biological use; the fluoro and iodo derivatives are potential radiodiagnostic ({sup 18}F) or radiotherapeutic ({sup 131}I) agents, whereas the chloro and bromo analogues could provide structural insight into integrin-ligand interactions through photoaffinity cross-linking/mass spectroscopy experiments, as well as co-crystallization X-ray studies.

  1. Potent methyl oxidation of 5-methyl-2'-deoxycytidine by halogenated quinoid carcinogens and hydrogen peroxide via a metal-independent mechanism.

    Science.gov (United States)

    Shao, Jie; Huang, Chun-Hua; Kalyanaraman, Balaraman; Zhu, Ben-Zhan

    2013-07-01

    Halogenated quinones are a class of carcinogenic intermediates and are newly identified chlorination disinfection by-products in drinking water. We found recently that the highly reactive and biologically important hydroxyl radical ((•)OH) can be produced by halogenated quinones and H2O2 independent of transition metal ions. However, it is not clear whether these quinoid carcinogens and H2O2 can oxidize the nucleoside 5-methyl-2'-deoxycytidine (5mdC) to its methyl oxidation products and, if so, what the underlying molecular mechanism is. Here we show that three methyl oxidation products, 5-(hydroperoxymethyl)-, 5-(hydroxymethyl)-, and 5-formyl-2'-deoxycytidine, could be produced when 5mdC was treated with tetrachloro-1,4-benzoquinone (TCBQ) and H2O2. The formation of the oxidation products was markedly inhibited by typical (•)OH scavengers and under anaerobic conditions. Analogous effects were observed with other halogenated quinones and the classic Fenton system. Based on these data, we propose that the oxidation of 5mdC by TCBQ/H2O2 might be through the following mechanism: (•)OH produced by TCBQ/H2O2 may first abstract hydrogen from the methyl group of 5mdC, leading to the formation of 5-(2'-deoxycytidylyl)methyl radical, which may combine with O2 to form the peroxyl radical. The unstable peroxyl radical transforms into the corresponding hydroperoxide 5-(hydroperoxymethyl)-2'-deoxycytidine, which reacts with TCBQ and results in the formation of 5-(hydroxymethyl)-2'-deoxycytidine and 5-formyl-2'-deoxycytidine. This is the first report that halogenated quinoid carcinogens and H2O2 can induce potent methyl oxidation of 5mdC via a metal-independent mechanism, which may partly explain their potential carcinogenicity. Copyright © 2013 Elsevier Inc. All rights reserved.

  2. Halogen bonds in some dihalogenated phenols: applications to crystal engineering.

    Science.gov (United States)

    Mukherjee, Arijit; Desiraju, Gautam R

    2014-01-01

    3,4-Dichlorophenol (1) crystallizes in the tetragonal space group I41/a with a short axis of 3.7926 (9) Å. The structure is unique in that both type I and type II Cl⋯Cl interactions are present, these contact types being distinguished by the angle ranges of the respective C-Cl⋯Cl angles. The present study shows that these two types of contacts are utterly different. The crystal structures of 4-bromo-3-chlorophenol (2) and 3-bromo-4-chlorophenol (3) have been determined. The crystal structure of (2) is isomorphous to that of (1) with the Br atom in the 4-position participating in a type II interaction. However, the monoclinic P21/c packing of compound (3) is different; while the structure still has O-H⋯O hydrogen bonds, the tetramer O-H⋯O synthon seen in (1) and (2) is not seen. Rather than a type I Br⋯Br interaction which would have been mandated if (3) were isomorphous to (1) and (2), Br forms a Br⋯O contact wherein its electrophilic character is clearly evident. Crystal structures of the related compounds 4-chloro-3-iodophenol (4) and 3,5-dibromophenol (5) were also determined. A computational survey of the structural landscape was undertaken for (1), (2) and (3), using a crystal structure prediction protocol in space groups P21/c and I41/a with the COMPASS26 force field. While both tetragonal and monoclinic structures are energetically reasonable for all compounds, the fact that (3) takes the latter structure indicates that Br prefers type II over type I contacts. In order to differentiate further between type I and type II halogen contacts, which being chemically distinct are expected to have different distance fall-off properties, a variable-temperature crystallography study was performed on compounds (1), (2) and (4). Length variations with temperature are greater for type II contacts compared with type I. The type II Br⋯Br interaction in (2) is stronger than the corresponding type II Cl⋯Cl interaction in (1), leading to elastic bending

  3. Halogen bonds in some dihalogenated phenols: applications to crystal engineering

    Directory of Open Access Journals (Sweden)

    Arijit Mukherjee

    2014-01-01

    Full Text Available 3,4-Dichlorophenol (1 crystallizes in the tetragonal space group I41/a with a short axis of 3.7926 (9 Å. The structure is unique in that both type I and type II Cl...Cl interactions are present, these contact types being distinguished by the angle ranges of the respective C—Cl...Cl angles. The present study shows that these two types of contacts are utterly different. The crystal structures of 4-bromo-3-chlorophenol (2 and 3-bromo-4-chlorophenol (3 have been determined. The crystal structure of (2 is isomorphous to that of (1 with the Br atom in the 4-position participating in a type II interaction. However, the monoclinic P21/c packing of compound (3 is different; while the structure still has O—H...O hydrogen bonds, the tetramer O—H...O synthon seen in (1 and (2 is not seen. Rather than a type I Br...Br interaction which would have been mandated if (3 were isomorphous to (1 and (2, Br forms a Br...O contact wherein its electrophilic character is clearly evident. Crystal structures of the related compounds 4-chloro-3-iodophenol (4 and 3,5-dibromophenol (5 were also determined. A computational survey of the structural landscape was undertaken for (1, (2 and (3, using a crystal structure prediction protocol in space groups P21/c and I41/a with the COMPASS26 force field. While both tetragonal and monoclinic structures are energetically reasonable for all compounds, the fact that (3 takes the latter structure indicates that Br prefers type II over type I contacts. In order to differentiate further between type I and type II halogen contacts, which being chemically distinct are expected to have different distance fall-off properties, a variable-temperature crystallography study was performed on compounds (1, (2 and (4. Length variations with temperature are greater for type II contacts compared with type I. The type II Br...Br interaction in (2 is stronger than the corresponding type II Cl...Cl interaction in (1, leading to elastic

  4. Formation of halogenated acetones in the lower troposphere

    Science.gov (United States)

    Sattler, Tobias; Wittmer, Julian; Krause, Torsten; Schöler, Heinz Friedrich; Kamilli, Katharina; Held, Andreas; Zetzsch, Cornelius; Ofner, Johannes; Atlas, Elliot

    2015-04-01

    Western Australia is a semi-/arid region that is heavily influenced by climate change and agricultural land use. The area is known for its saline lakes with a wide range of hydrogeochemical parameters and consists of ephemeral saline and saline groundwater fed lakes with a pH range from 2.5 to 7.1. In 2012 a novel PTFE-chamber was setup directly on the lakes. The 1.5 m³ cubic chamber was made of UV transparent PTFE foil to permit photochemistry while preventing dilution of the air due to lateral wind transport. This experimental setup allows linking measured data directly to the chemistry of and above the salt lakes. Air samples were taken using stainless steel canisters and measured by GC-MS/ECD. Sediment, crust and water samples were taken for investigation of potential VOC and VOX emissions in the laboratory using GC-MS. Several lakes were investigated and canister samples were taken over the day to see diurnal variations. The first samples were collected at 6 a.m. and from this time every 2 hours a canister was filled with chamber air. Concentrations of chloroacetone up to 15 ppb and of bromoacetone up to 40 ppb in the air samples were detected. The concentrations vary over the day and display their highest values around noon. Soil and water samples showed a variety of highly volatile and semi-volatile VOC/VOX but no halogenated acetones. An abiotic formation of these VOC/VOX seems conclusive due to iron-catalysed reactions below the salt crust [1]. The salt crust is the interface through which VOC/VOX pass from soil/groundwater to the atmosphere where they were photochemically altered. This explains the finding of halo acetones only in the air samples and not in water and soil samples measured in the laboratory. The main forming pathway for these haloacetones is the direct halogenation due to atomic chlorine and bromine above the salt lakes [2]. A minor pathway is the atmospheric degradation of chloropropane and bromopropane [3]. These halopropanes were found

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

    Energy Technology Data Exchange (ETDEWEB)

    Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue [College of Chemistry, Beijing Normal University, Beijing 100875 (China); Jin Weijun, E-mail: wjjin@bnu.edu.cn [College of Chemistry, Beijing Normal University, Beijing 100875 (China)

    2012-11-13

    Highlights: Black-Right-Pointing-Pointer Halogen bonding (XB) is firstly utilised in solid phase extraction. Black-Right-Pointing-Pointer The perfluorinated iodine alkanes can be extracted by C-I Midline-Horizontal-Ellipsis Cl{sup -} halogen bonding. Black-Right-Pointing-Pointer The C-I Midline-Horizontal-Ellipsis Cl{sup -} halogen bond is well characterised by spectroscopy methods. Black-Right-Pointing-Pointer 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, {sup 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 Midline-Horizontal-Ellipsis Cl{sup -} 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{sup -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{sup -}. 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{sup -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{sup -1} in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid

  6. Gas chromatography mass spectrometry computer analysis of volatile halogenated hydrocarbons in man and his environment--A multimedia environmental study.

    Science.gov (United States)

    Barkley, J; Bunch, J; Bursey, J T; Castillo, N; Cooper, S D; Davis, J M; Erickson, M D; Harris, B S; Kirkpatrick, M; Michael, L C; Parks, S P; Pellizzari, E D; Ray, M; Smith, D; Tomer, K B; Wagner, R; Zweidinger, R A

    1980-04-01

    As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatography mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined.

  7. 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.

  8. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    Science.gov (United States)

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices.

  9. 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.

  10. Hydroxyl radical substitution in halogenated carbonyls: oxalic acid formation.

    Science.gov (United States)

    Christiansen, Carrie J; Dalal, Shakeel S; Francisco, Joseph S; Mebel, Alexander M; Gaffney, Jeffrey S

    2010-03-04

    An ab initio study of OH radical substitution reactions in halogenated carbonyls is conducted. Hydroxyl radical substitution into oxalyl dichloride [ClC(O)C(O)Cl] and oxalyl dibromide [BrC(O)C(O)Br], resulting in the formation of oxalic acid, is presented. Analogous substitution reactions in formyl chloride [ClCH(O)], acetyl chloride [ClC(O)CH(3)], formyl bromide [BrCH(O)], and acetyl bromide [BrC(O)CH(3)] are considered. Energetics of competing hydrogen abstraction reactions for all applicable species are computed for comparison. Geometry optimizations and frequency computations are performed using the second-order Møller-Plesset perturbation theory (MP2) and the 6-31G(d) basis set for all minimum species and transition states. Single point energy computations are performed using fourth-order Møller-Plesset perturbation theory (MP4) and coupled cluster theory [CCSD(T)]. Potential energy surfaces, including activation energies and enthalpies, are determined from the computations. These potential energy surfaces show that OH substitution into ClC(O)C(O)Cl and BrC(O)C(O)Br, resulting in the formation of oxalic acid and other minor products, is energetically favorable. Energetics of analogous reactions with ClCH(O), BrCH(O), ClC(O)CH(3), and BrC(O)CH(3) are also computed.

  11. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    Science.gov (United States)

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Sea ice dynamics influence halogen deposition to Svalbard

    Directory of Open Access Journals (Sweden)

    A. Spolaor

    2013-03-01

    Full Text Available Sea ice is an important parameter in the climate system and its changes impact upon the polar albedo and the atmospheric and oceanic circulation. Iodine (I and bromine (Br have been measured in a shallow ice core drilled at the summit of the Holtedahlfonna glacier (Northwest Spitsbergen, Svalbard. Changing I concentrations can be linked to the spring 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 spring sea ice coincides with enlargement of the open ocean surface which enhances marine primary production and consequent I emission. The observed Br enrichment can be explained by greater Br emissions during the Br explosion that have been observed to occur 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.

  13. ASCORBIC ACID TREATMENT TO REDUCE RESIDUAL HALOGEN-BASED OXIDANTS PRIOR TO THE DETERMINATION OF HALOGENATED DISINFECTION BYPRODUCTS IN POTABLE WATER

    Science.gov (United States)

    Treatment of potable water samples with ascorbic acid has been investigated as a means for reducing residual halogen-based oxidants (disinfectants)i.e., HOCl, Cl2, Brw and BrCl, prior to determination of EPA Method 551.1A and 551.1B analytes. These disinfection byproducts include...

  14. Boiling of simulated tap water: effect on polar brominated disinfection byproducts, halogen speciation, and cytotoxicity.

    Science.gov (United States)

    Pan, Yang; Zhang, Xiangru; Wagner, Elizabeth D; Osiol, Jennifer; Plewa, Michael J

    2014-01-01

    Tap water typically contains numerous halogenated disinfection byproducts (DBPs) as a result of disinfection, especially of chlorination. Among halogenated DBPs, brominated ones are generally significantly more toxic than their chlorinated analogues. In this study, with the aid of ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 79/81, whole spectra of polar brominated DBPs in simulated tap water samples without and with boiling were revealed. Most polar brominated DBPs were thermally unstable and their levels were substantially reduced after boiling via decarboxylation or hydrolysis; the levels of a few aromatic brominated DBPs increased after boiling through decarboxylation of their precursors. A novel adsorption unit for volatile total organic halogen was designed, which enabled the evaluation of halogen speciation and mass balances in the simulated tap water samples during boiling. After boiling for 5 min, the overall level of brominated DBPs was reduced by 62.8%, of which 39.8% was volatilized and 23.0% was converted to bromide; the overall level of chlorinated DBPs was reduced by 61.1%, of which 44.4% was volatilized and 16.7% was converted to chloride; the overall level of halogenated DBPs was reduced by 62.3%. The simulated tap water sample without boiling was cytotoxic in a chronic (72 h) exposure to mammalian cells; this cytotoxicity was reduced by 76.9% after boiling for 5 min. The reduction in cytotoxicity corresponded with the reduction in overall halogenated DBPs. Thus, boiling of tap water can be regarded as a "detoxification" process and may reduce human exposure to halogenated DBPs through tap water ingestion.

  15. Determination of volatile halogenated organic compounds in the tropical terrestrial ecosystem

    Energy Technology Data Exchange (ETDEWEB)

    Quintana, A.; Lopez-Garriga, J. [Univ. of Puerto Rico, Mayaguez (Puerto Rico)

    1995-12-01

    Volatile Halogenated Organic Compounds are discharged into our biosphere by plants, marine organisms, fungi and by other natural processes. Due to the high rate of evaporation of the tropical terrestrial ecosystem, the production of VHOC by fungi, higher plants and other organisms may be one of the most important sources of the total amount of VHOC released to the atmosphere from biogenic origin. The main goal of this research was to determine the VHOC`s released to the surroundings from biogenic origin in the tropical terrestrial ecosystem. Using vacuum distillation with cryogenic trapping and a thermal desorption unit coupled to a GC-ECD, we found that samples of air, water and soil contains 36.418 ng/L, 0.222 ng/mL and 9.156 ng/g (wet) of chloroform. Microorganisms such as the Actinomycetes and Halobacterium salinarium were also analyzed for VHOC`S contents. Carbontetrachloride, 1,1-dichloroethene, dichlorodifluoromethane, trichlorofluoromethane and other VHOC`S of environmental importance were determined. This is the first time that the presence of VHOC`S is reported in pure cultured bacteria.

  16. Halogenated pentamethine cyanine dyes exhibiting high fidelity for G-quadruplex DNA.

    Science.gov (United States)

    Nanjunda, Rupesh; Owens, Eric A; Mickelson, Leah; Alyabyev, Sergey; Kilpatrick, Nancy; Wang, Siming; Henary, Maged; Wilson, W David

    2012-12-15

    Design and optimization of quadruplex-specific small molecules is developing into an attractive strategy for anti-cancer therapeutics with some promising candidates in clinical trials. A number of therapeutically favorable features of cyanine molecules can be effectively exploited to develop them as promising quadruplex-targeting agents. Herein, the design, synthesis and evaluation of a series of dimethylindolenine cyanine dyes with varying halogen substitutions are reported. Their interactions with telomeric and c-myc quadruplexes as well as a reference duplex sequence have been evaluated using thermal melting, biosensor-surface plasmon resonance, circular dichroism, isothermal titration calorimetry and mass spectrometry. Thermal melting analysis indicates that these ligands exhibit significant quadruplex stabilization and a very low duplex binding, with the dimethyl incorporation of paramount importance for decreased duplex affinity. Circular dichroism studies showed that the interaction of cyanines with quadruplex structures are primarily through stacking at one or both ends of the terminal tetrads with the two (trimethylammonium)propyl groups interacting in the accessible quadruplex grooves. Surface plasmon resonance and mass spectral studies shows the formation of an initial strong 1:1 complex followed by a significantly weaker secondary binding. Isothermal calorimetry studies show that the interaction of cyanines is predominantly entropy driven. In line with the design principles, this work provides new insights for further developing potent, highly selective cyanines as promising quadruplex-specific agents.

  17. Persistent halogenated organic contaminants and mercury in northern fulmars (Fulmarus glacialis) from the Canadian Arctic

    Energy Technology Data Exchange (ETDEWEB)

    Braune, Birgit M., E-mail: birgit.braune@ec.gc.c [Environment Canada, National Wildlife Research Centre, Carleton University, Raven Road, Ottawa, Ontario, K1A 0H3 (Canada); Mallory, Mark L. [Environment Canada, Box 1714, Iqaluit, Nunavut, X0A 0H0 (Canada); Butt, Craig M.; Mabury, Scott A. [Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 (Canada); Muir, Derek C.G. [Environment Canada, Canada Centre for Inland Waters, 867 Lakeshore Road, Burlington, Ontario, L7R 4A6 (Canada)

    2010-12-15

    Northern fulmars from two breeding colonies in the Canadian Arctic, Cape Vera and Prince Leopold Island, were analyzed for organochlorine pesticides, PCBs, perfluorinated compounds (PFCs) and total mercury (Hg). Hepatic concentrations of organochlorines and Hg were highest in the male fulmars from Cape Vera. Perfluorooctane sulfonate (PFOS) concentrations did not vary significantly between sexes or colonies. However, concentrations of the perfluorinated carboxylates (PFCAs) were higher in fulmars from Cape Vera than Prince Leopold Island. The C{sub 11}-C{sub 15} PFCAs averaged 90% of the PFCA profile at both colonies. Polychorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs (NO-PCBs) were measured only in birds from Prince Leopold Island. Concentrations of PCDDs, PCDFs, NO-PCBs and Toxic Equivalents (TEQs) did not differ significantly between sexes. {Sigma}TEQ was comprised mainly of {Sigma}TEQ{sub PCDF}. Concentrations of Hg and the persistent halogenated compounds reported in this study were below published toxicological threshold values for wild birds. - Northern fulmars in the Canadian Arctic demonstrate sex-specific, colony-specific, and regional differences in contaminant profiles.

  18. A QSRR Study on the Relative Retention Time of Halogenated Methyl-phenyl Ethers

    Institute of Scientific and Technical Information of China (English)

    XU Hui-Ying; YU Qing-Sen; ZOU Jian-Wei; WANG Yan-Hua; WANG Hong-Qing; CHEN Xue-Song

    2006-01-01

    Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 42 halogenated anisoles at the HF/6-31 G* level. A number of statistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.

  19. Quantifying the effects of halogen bonding by haloaromatic donors on the acceptor pyrimidine.

    Science.gov (United States)

    Ellington, Thomas L; Reves, Peyton L; Simms, Briana L; Wilson, Jamey L; Watkins, Davita L; Tschumper, Gregory S; Hammer, Nathan I

    2017-02-28

    The effects of intermolecular interactions by a series of haloaromatic halogen bond donors on the normal modes and chemical shifts of the acceptor pyrimidine are investigated by Raman and NMR spectroscopies and electronic structure computations. Halogen bond interactions with pyrimidine's nitrogen atoms shift normal modes to higher energy and shift 1H and 13C NMR peaks upfield in adjacent nuclei. This perturbation of vibrational normal modes is reminiscent of the effects of hydrogen bonded networks of water, methanol, or silver on pyrimidine. The unexpected observation of vibrational red shifts and downfield 13C NMR shifts in some complexes suggests that other intermolecular forces such as pi-interactions are competing with halogen bonding. Natural bond orbital analyses indicate a wide range of charge transfer from pyrimidine to different haloaromatic donors is possible and computed halogen bond binding energies can be larger than a typical hydrogen bond. These results emphasize the importance in strategic selection of substituents and electron withdrawing groups in developing supramolecular structures based on halogen bonding.

  20. Seaonal Sea Ice as a source of organo-halogens during Polar night

    Science.gov (United States)

    Abrahamsson, Katarina; Granfors, Anna; Ahnoff, Martin

    2016-04-01

    The release of bromine from snow and sea ice surfaces has mainly been attributed to the reaction of hypobromous acid with bromide at acidic conditions to form Br2. Little attention has been given to the role of volatile halogenated organic compounds (organo-halogens) in the formation of reactive halogen species in the atmosphere during bromine explosion events. The load of organo-halogens was studied during a winter expedition to the Weddell Sea in June to August 2013. These compounds are emitted from the different compartments of the cryosphere to the atmosphere where they are photolysed to BrO and IO, which are involved in the degradation of ozone. We will present results that show the importance of organo-halogens formed during polar winter. In newly formed ice, in contrast to summer sea ice, the concentration of organo-bromine was found at levels as high as nM. These high concentrations were reflected both in frost flowers and in the sea-snow interface. Moreover, air measurements revealed high loads of organo-bromine over the sea ice. The situation was similar for iodinated compounds. Interestingly, the precursers of IO, mainly diiodomethane, could be measured in sea ice and snow, most probably due to the low light levels.

  1. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria.

    Science.gov (United States)

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-06-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas biofilter where lyophilised bacterial cultures were used as the catalyst. Four strains containing dehalogenase enzymes were tested for the hydrolysis of 1-chlorobutane. The highest removal yield was obtained using the dhaA-containing strains, the maximal reaction rate of 0.8 micromol min(-1)g(-1) being observed with Escherichia coli BL21(DE3)(dhaA). Various treatments such as cell disruption by lysozyme or alkaline gas addition in the bio-filter could stabilise the dehalogenase activity of the bacteria. A pre-treatment of the dehydrated bacterial cells by ammonia vapour improved the stability of the catalyst and a removal activity of 0.9 micromol min(-1)g(-1) was then obtained for 60h. Finally, the process was extended to a range of halogenated substrates including bromo- and chloro-substrates. It was shown that the removal capacity for long halogenated compounds (C(5)-C(6)) was greatly increased relative to traditional biological processes.

  2. Halogens, OVOC and H2O Distributions over the Eastern Pacific Ocean during TORERO

    Science.gov (United States)

    Dix, B. K.; Apel, E. C.; Baidar, S.; Zondlo, M. A.; Volkamer, R.

    2013-12-01

    As part of the Tropical Ocean tRoposphere Exchange of Reactive halogen species and Oxygenated VOC (TORERO) field project 17 research flights were conducted with the NSF/NCAR GV aircraft over the Eastern Tropical Pacific Ocean (42S to 14N Lat.; 70W to 105W Long). Equipped with a combination of chemical in-situ sensors and remote sensing instruments, a broad spectrum of reactive halogen species, oxygenated hydrocarbons, and aerosols were measured over different ocean environments. Using optical remote sensing (airborne Multi Axis DOAS), we measured iodine monoxide (IO), bromine monoxide (BrO), glyoxal (CHOCHO) and water vapor among others. A newly developed parameterization method allowed us to directly convert the measured slant column densities into mixing ratios along the whole flight track. Atmospheric reactive halogen species and organic carbon are important, because they modify HOx radical abundances, influence the reactive chemistry and lifetime of climate active gases (e.g., ozone, methane, dimethyl sulfide), modify aerosol-cloud interactions and halogen radicals can also oxidize atmospheric mercury. Here we summarize and evaluate the spatial distribution of IO, BrO and glyoxal over the TORERO study area. For select case studies we present comparisons to halogen precursors and OVOCs measured in-situ by on-line mass spectrometry (trace organic gas analyzer). The correlation of remotely observed water vapor to in-situ measurements further allows us to conclude on the homogeneity of spatial scales covered by both remote and in-situ sensors.

  3. Oceanic contributions from tropical upwelling systems to atmospheric halogens

    Science.gov (United States)

    Ziska, Franziska; Hepach, Helmke; Stemmler, Irene; Quack, Birgit; Atlas, Elliot; Fuhlbrügge, Steffen; Bracher, Astrid; Tegtmeier, Susann; Krüger, Kirstin

    2014-05-01

    Short lived halogenated substances (halocarbons) from the oceans contribute to atmospheric halogens, where they are involved in ozone depletion and aerosol formation. Oceanic regions that are characterized by high biological activity are often associated with increased halocarbon abundance of e.g. bromoform (CHBr3) and dibromomethane (CH2Br2), representing the main contributors to atmospheric organic bromine. Apart from biological production, photochemical pathways play an important role in the formation of methyl iodide (CH3I), the most abundant organoiodine in the marine atmosphere. Recently, the contribution of biogenic diiodomethane (CH2I2) and chloroiodomethane (CH2ClI) to atmospheric organic iodine has been estimated to be similarly significant as CH3I. In the tropics, rapid uplift of surface air can transport these short-lived compounds into the upper troposphere and into the stratosphere. Oceanic upwelling systems off Mauritania, Peru and in the equatorial Atlantic might therefore potentially contribute large amounts of halocarbons to the stratosphere. Concentrations and emissions of iodo- and bromocarbons from several SOPRAN campaigns in different tropical upwelling systems, the Mauritanian and the equatorial upwelling in the Atlantic, as well as the Peruvian upwelling in the Pacific, will be presented. Processes contributing to halocarbon occurrence in the water column, as well as biological and physical factors influencing their emission into the atmosphere are investigated (Fuhlbrügge, et al. 2013; Hepach et al., 2013). We will present the relative contribution of the upwelling systems to global air-sea fluxes from different modelling studies. The data based bottom-up emissions from Ziska et al. (2013) will be compared to model simulated halocarbons. The model is a global three-dimensional ocean general circulation model with an ecosystem model and halocarbon module embedded (MPIOM/HAMOCC). It resolves CH3I and CHBr3 production, degradation, and

  4. A DFT study of halogen atoms adsorbed on graphene layers

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Paulo V C; De Brito Mota, F; De Castilho, Caio M C [Grupo de Fisica de Superfcies e Materiais, Instituto de Fisica, Universidade Federal da Bahia, Campus Universitario da Federacao/Ondina, 40170-115 Salvador, Bahia (Brazil); Mascarenhas, Artur J S, E-mail: caio@ufba.br [Instituto Nacional de Ciencia e Tecnologia em Energia e Ambiente-INCT-E and A, Universidade Federal da Bahia, 40170-280 Salvador, Bahia (Brazil)

    2010-12-03

    In this work, ab initio density functional theory calculations were performed in order to study the structural and electronic properties of halogens (X = fluorine, chlorine, bromine or iodine) that were deposited on both sides of graphene single layers (X-graphene). The adsorption of these atoms on only one side of the layer with hydrogen atoms adsorbed on the other was also considered (H,X-graphene). The results indicate that the F-C bond in the F-graphene system causes an sp{sup 2} to sp{sup 3} transition of the carbon orbitals, and similar effects seem to occur in the H,X-graphene systems. For the other cases, two configurations are found: bonded (B) and non-bonded (NB). For the B configuration, the structural arrangement of the atoms was similar to F-graphene and H-graphene (graphane), although the electronic structures present some differences. In the NB configuration, the interaction between the adsorbed atoms and the graphene layer seems to be essentially of the van der Waals type. In these cases, the original shape of the graphene layer presents only small deviations from the pristine form and the adsorbed atoms reach equilibrium far from the sheet. The F-graphene structure has a direct bandgap of approximately 3.16 eV at the {Gamma} point, which is a value that is close to the value of 3.50 eV that was found for graphane. The Cl-graphene (B configuration), H,F-graphene and H,Cl-graphene systems have smaller bandgap values. All of the other systems present metallic behaviours. Energy calculations indicate the possible stability of these X-graphene layers, although some considerations about the possibility of spontaneous formation have to be taken into account.

  5. Environmental Factors Influencing Arctic Halogen Chemistry During Late Spring

    Science.gov (United States)

    Burd, J.; Nghiem, S. V.; Simpson, W. R.

    2015-12-01

    Reactive halogen radicals (e.g. Br, Cl atoms and their oxides, BrO, ClO) are important oxidizers in the troposphere that decrease atmospheric pollutants and deplete tropospheric ozone, affecting the abundance of other oxidizers such as the hydroxyl radical. During Arctic springtime, the heterogeneous chemical cycles (often called the "bromine explosion") produce high levels of bromine monoxide (BrO), through reactions on saline snow, ice, and/or aerosol surfaces. Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) measured BrO at Barrow, AK, from 2008-2009 and 2012-2015, as well at various locations above the frozen Arctic Ocean with O-Buoys in 2008 and 2011-2015. Observed BrO levels drop suddenly during late spring (May-June) and generally do not recover, which indicates the bromine explosion cycle can no longer produce significant amounts of BrO. We have established, through an objective algorithm, the local day of year of this drop in BrO as the "seasonal end." Additionally, in about half of the years, "recurrence" events were observed where BrO levels recover for at least a day. This study investigates the environmental factors influencing seasonal end and recurrence events including: temperature, relative humidity, precipitation and snowmelt. Analysis of BrO and air temperature revealed the temperature reaches 0°C within five days of the seasonal end event; however, temperatures drop below freezing during a recurrence event. In addition, there are periods where the temperature remains below freezing, but no recurrence event is observed. This BrO and temperature analysis indicates above-freezing air temperature prevents reactive bromine release; however, it is not the only environmental factor influencing this heterogeneous recycling. Further analysis of additional environmental influences on the bromine explosion cycle could help to better understand and model bromine chemistry in the Arctic.

  6. Global distribution of halogenated dimethyl bipyrroles in marine mammal blubber.

    Science.gov (United States)

    Tittlemier, S; Borrell, A; Duffe, J; Duignan, P J; Fair, P; Hall, A; Hoekstra, P; Kovacs, K M; Krahn, M M; Lebeuf, M; Lydersen, C; Muir, D; O'Hara, T; Olsson, M; Pranschke, J; Ross, P; Siebert, U; Stern, G; Tanabe, S; Norstrom, R

    2002-08-01

    Four halogenated dimethyl bipyrroles (HDBPs), hypothesized to be naturally produced, were quantitated in marine mammal blubber from a number of species obtained from various locations worldwide. HDBPs were found in samples from all locations studied. Concentrations of total HDBPs (SigmaHDBPs) ranged from 0.4 ng/g lipid weight in ringed seals (Phoca hispida) from the White Sea to 2,540 ng/g lipid weight in Dall's porpoise (Phocoenoides dalli) from the northwestern North Pacific Ocean. At their highest levels, SigmaHDBPs made up 11% of the total quantitated organohalogen body burden of adult male Dall's porpoises. In two beluga (Delphinapterus leucas) data subsets, it was found that males contained significantly higher concentrations of SigmaHDBPs than females. No significant effects of age or sex on SigmaHDBPs were observed in harbor seal (Phoca vitulina) and bowhead whale (Balaena mysticetus) data subsets. The geographical distribution of concentrations did not resemble that of the ubiquitous anthropogenic organohalogen, polychlorinated biphenyl congener CB-153. Higher concentrations of HDBPs and different patterns of congeners were observed in samples from Pacific as opposed to non-Pacific Ocean influenced environments. Concentrations of HDBPs in beluga from the Arctic and St. Lawrence River were similar. Their high abundance in north Pacific Ocean biota and widespread occurrence suggest that HDBPs undergo extensive transport from a source located primarily in the Pacific Ocean. Evidence from HDBP congener patterns indicates that both ocean currents and atmospheric transport likely play a role in the movement of HDBPs. These results imply that HDBPs and anthropogenic organohalogens have different sources and support the natural production hypothesis.

  7. Halogenated Phenazines that Potently Eradicate Biofilms, MRSA Persister Cells in Non-Biofilm Cultures, and Mycobacterium tuberculosis.

    Science.gov (United States)

    Garrison, Aaron T; Abouelhassan, Yasmeen; Kallifidas, Dimitris; Bai, Fang; Ukhanova, Maria; Mai, Volker; Jin, Shouguang; Luesch, Hendrik; Huigens, Robert W

    2015-12-01

    Conventional antibiotics are ineffective against non-replicating bacteria (for example, bacteria within biofilms). We report a series of halogenated phenazines (HP), inspired by marine antibiotic 1, that targets persistent bacteria. HP 14 demonstrated the most potent biofilm eradication activities to date against MRSA, MRSE, and VRE biofilms (MBEC = 0.2-12.5 μM), as well as the effective killing of MRSA persister cells in non-biofilm cultures. Frontline MRSA treatments, vancomycin and daptomycin, were unable to eradicate MRSA biofilms or non-biofilm persisters alongside 14. HP 13 displayed potent antibacterial activity against slow-growing M. tuberculosis (MIC = 3.13 μM), the leading cause of death by bacterial infection around the world. HP analogues effectively target persistent bacteria through a mechanism that is non-toxic to mammalian cells and could have a significant impact on treatments for chronic bacterial infections.

  8. Research on the Reaction of 5-Alkyloxy-3,4-dihalo-2(5H)-furanones with Aliphatic Amines%5-烷氧基-3,4-二卤-2(5H)-呋喃酮与脂肪胺类的反应研究

    Institute of Scientific and Technical Information of China (English)

    傅建花; 汪朝阳; 霍景沛; 谭越河; 曾荣华

    2012-01-01

    Using KF as catalyst and tetrahydrofuran as solvent, 5-alkyloxy-3,4-dihalo-2(5H)-furanones was reacted with several aliphatic amines. The chemical structures and absolute configurations of the products were confirmed via rotation, UV-Vis, IR, 1H NMR, 13C NMR, MS techniques, elemental analysis and X-ray single crystal diffraction. Thirteen new normal products β-amino-2(5H)-furanones were obtained via the tandem Michael addition-elimination reaction as anticipated in most cases. However, the reaction between the larger steric dicyclohexyl amine and 5-alkyloxy-3,4-dihalo-2(5H)-furanones yielded four new abnormal products, (E)-alkyl 2-halo-4-dicyclohexylamino-4-oxobut-2-enoate. The possible mechanism for the formation of 2(5H)-furanone ring-opening products involving in the rearrangement reaction was proposed.%在氟化钾作催化剂和四氢呋喃作溶剂的条件下,研究了系列脂肪胺亲核试剂与5-烷氧基-3,4-二卤-2(5H)-呋喃酮发生的反应,通过旋光度,UV-Vis,IR,1H NMR,13C NMR,MS,元素分析和X射线单晶衍射等表征方法对产物进行结构表征,发现通常情况下发生预期的串联迈克尔加成-消除反应,合成了13个新的β-胺基-2(5H)-呋喃酮.但是,空间位阻较大的二环己基胺与5-烷氧基-3,4-二卤-2(5H)-呋喃酮反应时,却得到了4个异常的2(5H)-呋喃酮开环产物,其可能是经开环重排反应的机理得到的.

  9. Correlating Precisely Defined Primary Structure with Crystalline Properties in Halogen Containing Polyolefins

    Science.gov (United States)

    Boz, Emine; Alamo, Rufina G.; Wagener, Kenneth B.

    Polyethylene (PE) and poly(vinyl chloride) (PVC) are among the most important polymers produced in industry, although other halogen-containing derivatives of PE, such as poly(tetrafluorethylene) (PTFE) have also found wides pread use. A related class of polymers is the ethylene-co-vinyl-halide family. Such copolymers are expected to show distinct properties relative to their better known industrial analogues. For example, much interest has focused on ethylene vinyl chloride (EVC) polymers based on their potential for improved thermal stability relative to PVC. Various techniques have been used to synthesize these ethylene vinyl halide (EVH) copolymers and the simplest approach is halogenation of PE, which results in an irregular distribution of halogens along the polymer backbone and poorly defined materials.

  10. Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts.

    Science.gov (United States)

    Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

    2015-10-01

    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.

  11. Halogen- and hydrogen-bonding catenanes for halide-anion recognition.

    Science.gov (United States)

    Gilday, Lydia C; Beer, Paul D

    2014-07-01

    Halogen-bonding (XB) interactions were exploited in the solution-phase assembly of anion-templated pseudorotaxanes between an isophthalamide-containing macrocycle and bromo- or iodo-functionalised pyridinium threading components. (1)H NMR spectroscopic titration investigations demonstrated that such XB interpenetrated assemblies are more stable than analogous hydrogen bonding (HB) pseudorotaxanes. The stability of the anion-templated halogen-bonded pseudorotaxane architectures was exploited in the preparation of new halogen-bonding interlocked catenane species through a Grubbs' ring-closing metathesis (RCM) clipping methodology. The catenanes' anion recognition properties in the competitive CDCl(3)/CD(3) OD 1:1 solvent mixture revealed selectivity for the heavier halides iodide and bromide over chloride and acetate.

  12. 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.

  13. 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.

  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. Halogenated and isosteric cytisine derivatives with increased affinity and functional activity at nicotinic acetylcholine receptors.

    Science.gov (United States)

    Fitch, Richard W; Kaneko, Yumika; Klaperski, Paul; Daly, John W; Seitz, Gunther; Gündisch, Daniela

    2005-02-15

    A series of pyridone ring-modified derivatives of (7R,9S)-(-)-cytisine were evaluated for affinity and functional activity at neuromuscular alpha1beta1gammadelta, ganglionic alpha3beta4, and central neuronal alpha4beta2 subtypes of nicotinic receptors. Halogenation at the 3-position improved affinity and functional activity, while substitution at the 5-position led to modest decreases in both, and disubstitution led to near abolition of functional activities and could be correlated with the electron-withdrawing ability of the halogen. Subtype selectivities of the halogenated derivatives were altered relative to cytisine in a substitution-dependent manner. Caulophylline methiodide was less potent than cytisine, but retained significant activity. Thiocytisine was relatively weak in potency and efficacy, but was significantly selective for the alpha4beta2 subtype.

  16. AutoDock VinaXB: implementation of XBSF, new empirical halogen bond scoring function, into AutoDock Vina.

    Science.gov (United States)

    Koebel, Mathew R; Schmadeke, Grant; Posner, Richard G; Sirimulla, Suman

    2016-01-01

    Halogen bonding has recently come to play as a target for lead optimization in rational drug design. However, most docking program don't account for halogen bonding in their scoring functions and are not able to utilize this new approach. In this study a new and improved halogen bonding scoring function (XBSF) is presented along with its implementation in the AutoDock Vina molecular docking software. This new improved program is termed as AutoDock VinaXB, where XB stands for the halogen bonding parameters that were added. XBSF scoring function is derived based on the X···A distance and C-X···A angle of interacting atoms. The distance term was further corrected to account for the polar flattening effect of halogens. A total of 106 protein-halogenated ligand complexes were tested and compared in terms of binding affinity and docking poses using Vina and VinaXB. VinaXB performed superior to Vina in the majority of instances. VinaXB was closer to native pose both above and below 2 Å deviation categories almost twice as frequently as Vina. Implementation of XBSF into AutoDock Vina has been shown to improve the accuracy of the docking result with regards to halogenated ligands. AutoDock VinaXB addresses the issues of halogen bonds that were previously being scored unfavorably due to repulsion factors, thus effectively lowering the output RMSD values.

  17. Stability and Characteristics of the Halogen Bonding Interaction in an Anion-Anion Complex: A Computational Chemistry Study.

    Science.gov (United States)

    Wang, Guimin; Chen, Zhaoqiang; Xu, Zhijian; Wang, Jinan; Yang, Yang; Cai, Tingting; Shi, Jiye; Zhu, Weiliang

    2016-02-04

    Halogen bonding is the noncovalent interaction between the positively charged σ-hole of organohalogens and nucleophiles. In reality, both the organohalogen and nucleophile could be deprotonated to form anions, which may lead to the vanishing of the σ-hole and possible repulsion between the two anions. However, our database survey in this study revealed that there are halogen bonding-like interactions between two anions. Quantum mechanics calculations with small model complexes composed of halobenzoates and propiolate indicated that the anion-anion halogen bonding is unstable in vacuum but attractive in solvents. Impressively, the QM optimized halogen bonding distance between the two anions is shorter than that in a neutral system, indicating a possibly stronger halogen bonding interaction, which is verified by the calculated binding energies. Furthermore, natural bond orbital and quantum theory of atoms in molecule analyses also suggested stronger anion-anion halogen bonding than that of the neutral one. Energy decomposition by symmetry adapted perturbation theory revealed that the strong binding might be attributed to large induction energy. The calculations on 4 protein-ligand complexes from PDB by the QM/MM method demonstrated that the anion-anion halogen bonding could contribute to the ligands' binding affinity up to ∼3 kcal/mol. Therefore, anion-anion halogen bonding is stable and applicable in reality.

  18. Unstable, metastable, or stable halogen bonding interaction involving negatively charged donors? A statistical and computational chemistry study.

    Science.gov (United States)

    Yang, Zhuo; Xu, Zhijian; Liu, Yingtao; Wang, Jinan; Shi, Jiye; Chen, Kaixian; Zhu, Weiliang

    2014-12-11

    The noncovalent halogen bonding could be attributed to the attraction between the positively charged σ-hole and a nucleophile. Quantum mechanics (QM) calculation indicated that the negatively charged organohalogens have no positively charged σ-hole on their molecular surface, leading to a postulation of repulsion between negatively charged organohalogens and nucleophiles in vacuum. However, PDB survey revealed that 24% of the ligands with halogen bonding geometry could be negatively charged. Moreover, 36% of ionizable drugs in CMC (Comprehensive Medicinal Chemistry) are possibly negatively charged at pH 7.0. QM energy scan showed that the negatively charged halogen bonding is probably metastable in vacuum. However, the QM calculated bonding energy turned negative in various solvents, suggesting that halogen bonding with negatively charged donors should be stable in reality. Indeed, QM/MM calculation on three crystal structures with negatively charged ligands revealed that the negatively charged halogen bonding was stable. Hence, we concluded that halogen bonding with negatively charged donors is unstable or metastable in vacuum but stable in protein environment, and possesses similar geometric and energetic characteristics as conventional halogen bonding. Therefore, negatively charged organohalogens are still effective halogen bonding donors for medicinal chemistry and other applications.

  19. 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

    retrieve additional halogenated source gases from FTIR spectra will also be evoked. Our trend results will be critically discussed and compared with measurements performed in the northern hemisphere by the in situ networks. Acknowledgments The University of Liège contribution to the present work has primarily been supported by the AGACC-II project of the SSD program funded by the Belgian Federal Science Policy Office (BELSPO), Brussels. E. Mahieu is Research Associate with the F.R.S. - FNRS. Laboratory developments and mission expenses at the Jungfraujoch station were funded by the F.R.S. - FNRS and the Fédération Wallonie-Bruxelles, respectively. We thank the International Foundation High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG, Bern) for supporting the facilities needed to perform the observations. We further acknowledge the vital contribution from all the Belgian colleagues in performing the Jungfraujoch observations used here. References Mahieu, E., S. O'Doherty, S. Reimann, et al., First retrievals of HCFC-142b from ground-based high-resolution FTIR solar observations: application to high-altitude Jungfraujoch spectra, poster presentation at the 'EGU 2013 General Assembly', 07-12 April 2013, Vienna, Austria, 2013. [http://hdl.handle.net/2268/144709] Mahieu, E., M.P. Chipperfield, J. Notholt, et al., Recent Northern Hemisphere stratospheric HCl increase due to atmospheric circulation changes, Nature, 515, 104-107, doi:10.1038/nature13857, 2014a. Mahieu, E., R. Zander, G.C. Toon, et al., Spectrometric monitoring of atmospheric carbon tetrafluoride (CF4) above the Jungfraujoch station since 1989: evidence of continued increase but at a slowing rate, Atmos. Meas. Tech., 7, 333-344, 2014b. [http://hdl.handle.net/2268/154767] Montzka, S.A., S. Reimann, A. Engel, et al., Ozone-Depleting Substances (ODSs) and Related Chemicals, Chapter 1 in Scientific Assessment of Ozone Depletion: 2010, Global Ozone Research and Monitoring Project-Report No. 52, 516

  20. Competition between hydrogen and halogen bonding in the structures of 5,10-dihydroxy-5,10-dihydroboranthrenes.

    Science.gov (United States)

    Durka, Krzysztof; Luliński, Sergiusz; Jarzembska, Katarzyna N; Smętek, Jaromir; Serwatowski, Janusz; Woźniak, Krzysztof

    2014-02-01

    X-ray crystallographic and computational studies are reported for a series of boranthrenes, substituted with halogen atoms. The role of competitive hydrogen (O-H...O, O-H...F, C-H...O) and halogen (Cl...Cl, O...Br, F...F) bonding interactions on the molecular arrangement in the crystal structures is discussed. The structural analysis and calculations reveal that the O-H...O hydrogen bond in the unsubstituted derivative 5,10-dihydroxy-5,10-dihydroboranthrene, C12H10B2O2, is of moderate strength (ca -20 kJ mol(-1)), but weaker than that in the related thiophene derivative 4,8-dihydro-4,8-dihydroxy-p-diborino[2,3-b:5,6-b]dithiophene, C8H6B2O2S2 (ca -40 kJ mol(-1)). This is due to shielding of the OH group by the H atoms in the β-position of the boranthrene unit. Structural diversity derived from the flexibility of the O-H...O hydrogen bond facilitates the occurrence of other competitive interactions. For instance, in the 1,6-difluoro derivative, C12H8B2F2O2, the crystal packing results from O-H...F and F...F interactions. In turn, the 1,6-dibromo derivative, C12H8B2Br2O2, is dominated by Br...O halogen-bond interactions. In the most interesting case, the 1,6-dichloro derivative, C12H8B2Cl2O2, molecular disorder leads to the formation of two different supramolecular arrangements co-existing in the crystal lattice, one based on the Cl...Cl and C-H...O bonds, and the other stabilized by O-H...O hydrogen bonds. Calculations performed with density-functional theory (DFT; CRYSTAL09) and PIXEL methodologies show that both lattices are characterized by similar energy values (ca -100 kJ mol(-1)). A mixed arrangement with random or short-range-ordered molecular orientations can also be expected.

  1. Efficiency of light-emitting diode and halogen units in reducing residual monomers

    Science.gov (United States)

    de Assis Ribeiro Carvalho, Felipe; Almeida, Rhita C.; Almeida, Marco Antonio; Cevidanes, Lucia H. S.; Leite, Marcia C. Amorim M.

    2011-01-01

    Introduction In this in-vitro study, we aimed to compare the residual monomers in composites beneath brackets bonded to enamel, using a light-emitting diode (LED) or a halogen unit, and to compare the residual monomers in the central to the peripheral areas of the composite. Methods Twenty bovine teeth preserved in 0.1% thymol were used in this study. Ten teeth were used to standardize the thickness of the composite film, since different thicknesses would cause different absorbance of light. Brackets were bonded to 10 bovine incisors, with the halogen light (n = 5) and the LED (n = 5). The brackets were debonded, and the remaining composite on the enamel surface was sectioned in 2 regions: peripheral (0.8 mm) and central, resulting in 2 subgroups per group: central halogen (n = 5), peripheral halogen (n = 5), central LED (n = 5), and peripheral LED (n = 5). The spectrometric analysis in the infrared region was used to measure the free monomers with the attenuated total reflectance method. Results Normal distribution was tested by using the Kolmogorov-Smirnov test. Data were compared by 2-way analysis of variance (ANOVA) at P <0.05. The LED group showed fewer residual monomers than did the halogen group (P = 0.014). No differences were found among the regions (P = 0.354), and there were no interactions between light type and region (P = 0.368). Conclusions LED leaves less residual monomer than does the halogen light, even with half of the irradiation time; there were no differences between the central and peripheral regions, and no interaction between light type and region. PMID:21055603

  2. 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 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.

  3. Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem

    Science.gov (United States)

    Sherwen, Tomás; Schmidt, Johan A.; Evans, Mat J.; Carpenter, Lucy J.; Großmann, Katja; Eastham, Sebastian D.; Jacob, Daniel J.; Dix, Barbara; Koenig, Theodore K.; Sinreich, Roman; Ortega, Ivan; Volkamer, Rainer; Saiz-Lopez, Alfonso; Prados-Roman, Cristina; Mahajan, Anoop S.; Ordóñez, Carlos

    2016-09-01

    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.

  5. 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.

  6. Investigations of the tropospheric halogen chemistry around Ross Island, Antarctica, during austral spring 2012

    Science.gov (United States)

    Zielcke, Johannes; Pöhler, Denis; Frieß, Udo; Hay, Tim; Kreher, Karin; Kalnajs, Lars; Platt, Ulrich

    2013-04-01

    A unique feature of the polar troposphere is the strong impact of halogen photochemistry, in which reactive halogen species (RHS) are responsible for ozone depletion as well as the oxidation of elemental mercury and dimethyl sulphide. The source, however, as well as release and recycling mechanisms of these halogen species are far from being completely understood, especially the role of chlorine and iodine compounds. Reactive chlorine, bromine and iodine compounds are thought to be released from sea salt particles or produced by the photolysis of halocarbons and I2 emitted by the ocean. Here we present observations of halogen oxides, ozone and nitrogen dioxide conducted for three months during austral spring 2012 on Ross Island, Antarctica. Measurements were performed with a suite of remote sensing instruments. An active long-path differential optical absorption spectroscopy (LP-DOAS) system was set up, measuring several species (BrO, O3, NO2, OBrO, IO, OIO, I2, ClO, OClO, CHOCHO, HCHO, HONO) continuously for the whole period, with two light paths over first year sea ice. In addition, a passive MAX-DOAS as well as a new Cavity-Enhanced (CE)-DOAS system were used for mobile halogen oxide measurements on a variety of locations around Ross Island (sea ice, shelf ice, snow, coastal, etc.), with top surface layer pH measurements performed at the different measurement sites. First results show highly variable ozone concentrations including partial Ozone Depletion Events (ODEs), as well as concentrations of BrO up to 16ppt and NO2 up to 15ppb. Suprisingly, a high variation of ozone was observed without significant amounts of BrO, indicating already depleted air masses transported to the measurement site and/or NOx chemistry inhibiting halogen radical reactions.

  7. New Insecticidal Agents from Halogenation/Acylation of the Furyl-Ring of Fraxinellone

    Science.gov (United States)

    Guo, Yong; Yang, Ruige; Xu, Hui

    2016-10-01

    Introduction of the halogen atom or the acyl group at the C-ring of fraxinellone was investigated. Some unexpected halogenation products were obtained with the different chlorination/bromination reagents, and their possible reaction mechanisms were also proposed. Seven key steric structures of 2a’, 2b, 2b’, 2c’, 3a, 3b, and one isomer (5’α-Cl) of 2a were further confirmed by single-crystal X-ray diffraction. Especially compounds 2a, 2a’, 3a and 3c exhibited more potent insecticidal activity than toosendanin. Some structure-activity relationships of tested compounds were also described.

  8. Chlorine dioxide as phenol and H2S scavenger - formation of halogenated phenols and subsequent environmental risk

    Energy Technology Data Exchange (ETDEWEB)

    Melbye, Alf G.; Faksness, Liv-Guri; Knudsen, Boerre Leif

    2006-03-15

    Formation of halogenated phenols as side products from treatment of produced water with aqueous chlorine dioxide has been investigated. The literature describes formation of halogenated hydrocarbons in effluent treatment using chlorine, hypochlorite and chlorine dioxide. A new chlorine dioxide product, originally intended as a H2S scavenger in the oil and gas industry, has been tested both as a phenol scavenger and H2S-scavenger for produced water applications. The concern about the possible formation of halogenated by-products initiated laboratory testing of chlorine dioxide as phenol and H2S scavenger for produced water applications. The tests also included synthetic matrixes containing phenols, and the tests show that halogenated phenols, mainly brominated species, are found in produced water after treatment with chlorine dioxide. Due to potential environmental risk from halogenated organic contaminants, the use of chlorine dioxide as phenol and H2S scavenger is not recommended. (Author)

  9. Halogenated organic species over the tropical South American rainforest

    Directory of Open Access Journals (Sweden)

    S. Gebhardt

    2008-06-01

    Full Text Available Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and about 1000 km of pristine tropical rainforest in Suriname and French Guyana (3–6° N, 51–59° W in October 2005. In the boundary layer (0–1.4 km, maritime air masses, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4–1.0 years in comparison to the advection times from the coast (1–2 days, emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of time the air spent over land and the respective relationship used to determine net fluxes from the rainforest for one week within the long dry season.

    Net fluxes from the rainforest ecosystem have been calculated for methyl chloride and chloroform as 9.5 (±3.8 2σ and 0.35 (±0.15 2σμg m-2 h−1, respectively. No significant flux was observed for methyl bromide within the limits of these measurements.

    The global budget of methyl chloride contains large uncertainties, in particular with regard to a possible source from tropical vegetation. Our measurements are used in a large-scale approach to determine the net flux from a tropical ecosystem to the planetary boundary layer. The obtained global net flux of 1.5 (±0.6 2σ Tg yr-1 for methyl chloride is at the lower end of current estimates for tropical vegetation sources, which helps to constrain the range of tropical sources and sinks (0.82 to 8.2 Tg yr-1 from tropical plants, 0.03 to 2.5 Tg yr-1 from senescent/dead leaves and a sink of 0.1 to 1.6 Tg yr-1 by soil uptake. Nevertheless, these results show that the contribution of the rainforest ecosystem is the major source in the

  10. Field Emission Electron Microprobe Analysis of Halogens in Apatite

    Science.gov (United States)

    Tacker, R. C.

    2011-12-01

    counts increase as expected from 10 to 20 kV, but the loss of chlorine is more strongly controlled by crystal orientation. With electron beam parallel to the c-axis, chlorine counts are very low, pointing to the chlorine loss during analysis. Hence fluorine and chlorine are fractionated during analysis as a complicated function of beam energies and crystal orientation. Routine analyses of halogens in apatite are unlikely to yield a quantitative analysis, and OH calculated by the difference in a normalized analysis is less likely to be meaningful. Further, the use of 15-20 kV secondary electron or backscatter electron imaging prior to analysis should be reconsidered. Stormer et al., 1993, Am. Min., 78, 641. Fialin and Chopin, 2006, Am. Min. 91, 503.

  11. Halogens in pore water of peat bogs – the role of peat decomposition and dissolved organic matter

    Directory of Open Access Journals (Sweden)

    H. Biester

    2006-01-01

    Full Text Available Halogens are strongly enriched in peat and peatlands and such they are one of their largest active terrestrial reservoir. The enrichment of halogens in peat is mainly attributed to the formation of organohalogens and climatically controlled humification processes. However, little is known about release of halogens from the peat substrate and the distribution of halogens in the peat pore water. In this study we have investigated the distribution of chlorine, bromine and iodine in pore water of three pristine peat bogs located in the Magellanic Moorlands, southern Chile. Peat pore waters were collected using a sipping technique, which allows in situ sampling down to a depth greater than 6m. Halogens and halogen species in pore water were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in pore water are 15–30 times higher than in rainwater. Mean concentrations of chlorine, bromine and iodine in pore water were 7–15 mg l−1, 56–123 μg l−1, and 10–20 μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organobromine and organoiodine were the predominant species in pore waters, whereas chlorine in pore water was mostly chloride. Advection and diffusion of halogens were found to be generally low and halogen concentrations appear to reflect release from the peat substrate. Release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. It has been concluded that the release of halogenated dissolved organic matter (DOM is the predominant mechanism of iodine and bromine release from peat.

  12. Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

    OpenAIRE

    Anon Namin; Chaya Jivacate; Dhirayut Chenvidhya; Krissanapong Kirtikara; Jutturit Thongpron

    2012-01-01

    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 charac...

  13. Blue emitting halogen-phenoxy substituted 1,8-naphthalimides for potential organic light emitting diode applications

    Science.gov (United States)

    Ulla, Hidayath; Raveendra Kiran, M.; Garudachari, B.; Satyanarayan, M. N.; Umesh, G.; Isloor, A. M.

    2014-11-01

    In this paper, we report the synthesis and characterization of six 1,8-naphthalimides [4a-4c and 5a-5c] obtained by the substitution of electron donating halogen-phenoxy groups at the C-4 position. The derivatives were characterized using 1H NMR, 13C NMR, mass spectra, FT-IR, single crystal XRD; photo-physical, thermal, surface morphological and electrochemical properties were also investigated. The derivatives exhibit deep blue photoluminescence in the range 414-423 nm (in CHCl3) and 457-466 nm (in thin film state) on UV excitation with high Stokes' shifts and good chromaticity. The TGA and DSC analysis showed that the derivatives possess good thermal stability (271-284 °C) and melting points (138-201 °C). The HOMO and LUMO energy levels estimated by cyclic voltammetry are in the range 6.21-6.34 eV and 3.31-3.41 eV respectively corresponding to energy band gaps of 2.98-3.15 eV. These energy values are relatively higher than the commonly used electron transporting materials. The optical and electronic properties of the derivatives were tuned by the introduction of different electron donating halogen-phenoxy groups through C-4 position of the naphthalimide moiety. The emissive and electron-transporting properties of the naphthalimide derivative 4a were studied by fabricating a bi-layer and tri-layer devices. Further a phosphorescent device with 4a as electron transport layer (ETL) exhibited superior performance than the device without any ETL and was comparable with the device using standard Alq3 as ETL. These results indicate that the synthesized naphthalimide derivatives could play an important role in the development of OLEDs.

  14. Review of Rate Constants and Exploration of Correlations of the Halogen Transfer Reaction of Tri-substituted Carbon-centered Radicals with Molecular Halogens

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL

    2012-01-01

    Rate constants for the reaction (R 3C + X2 R 3CX + X ; X = F, Cl, Br, and I) are reviewed. Because of curved Arrhenius plots and negative EX values, empirical structure-reactivity correlations are sought for log kX,298 rather than EX. The well-known poor correlation with measures of reaction enthalpy is demonstrated. The best quantitative predictor for R 3C is p, the sum of the Hammett p constants for the three substituents, R . Electronegative substituents with lone pairs, such as halogen or oxygen, thus appear to destabilize the formation of a polarized pre-reaction complex and/or TS ( +R---X---X -) by -inductive/field electron withdrawal while simultaneously stabilizing them by -resonance electron donation. The best quantitative predictor of the reactivity order of the halogens, I2 > Br2 >> Cl2 F2, is the polarizability of the halogen, (X-X). For the data set of 60 rate constants which span 6.5 orders of magnitude, a modestly successful correlation of log kX,298 is achieved with only two parameters, p and (X-X), with a mean unsigned deviation of 0.59 log units. How much of this residual variance is the result of inaccuracies in the data compared with over-simplification of the correlation approach remains to be seen.

  15. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Science.gov (United States)

    Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

    2015-06-01

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  16. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing, E-mail: rayinyin@nwu.edu.cn [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Bai, Hongcun [Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)

    2015-06-15

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  17. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Directory of Open Access Journals (Sweden)

    Jin-Feng Li

    2015-06-01

    Full Text Available The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN5]−1 (M =  Ca, Be clusters. At CCSD(T level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE. The largest one is 9.70 eV for [Ca2(CN5]−1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T, outer valence Green’s function (OVGF method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  18. Modified Toepler pump for small-scale halogen-deuterium exchange reactions

    Energy Technology Data Exchange (ETDEWEB)

    Bindal, R.D.

    1987-04-06

    A modified version of the Toepler pump/microhydrogenator apparatus for the preparation of tritium labelled oestrogenic compounds using deuterium gas for halogen-tritium exchange, is described. The modifications allow the transferred gas to maintain atmospheric pressure during the course of the reaction and it allows small volumes of gas uptake to be followed. (U.K.).

  19. Preparation of an Ester-Containing Grignard Reagent by Halogen-Metal Exchange

    Science.gov (United States)

    Snider, Barry B.

    2015-01-01

    In this experiment, students carry out a halogen-metal exchange reaction of methyl 2-iodobenzoate with isopropylmagnesium chloride in THF at 0°C to afford 2-carbomethoxyphenylmagnesium chloride, which is treated with "p"-methoxybenzaldehyde to give a lactone (phthalide) product. This reaction introduces students to the modern method of…

  20. Stability, defect and electronic properties of graphane-like carbon-halogen compounds

    Institute of Scientific and Technical Information of China (English)

    Lu Di; Yang Yu-Rong; Xiao Yang; Zhang Xiao-Yu

    2011-01-01

    We perform first-principles total energy calculations to investigate the stabilities and the electronic structures of graphane-like structures of carbon-halogen compounds,where the hydrogen atoms in the graphane are substituted by halogen atoms.Three halogen elements,fluorine (F),chlorine (Cl) and bromine (Br),are considered,and the graphanelike structures are named as CF,CCl and CBr,respectively.It is found that for the single-atom adsorption,only the F adatom can be chemically adsorbed on the graphene.However,the stable graphane-like structures of CF,CCl and CBr can form due to the interaction between the halogen atoms.The carbon atoms in the stable CF,CCl and CBr compounds are in the sp3 hybridization,forming a hexagonal network similar to the graphane.The electronic band calculations show that CF and CCl are semiconductors with band gaps of 3.28 eV and 1.66 eV,respectively,while CBr is a metal.Moreover,the molecular dynamics simulation is employed to clarify the stabilities of CF and CCl.Those two compounds are stable at room temperature.A high temperature (≥ 1200 K) is needed to damage CF,while CCl is destroyed at 700 K.Furthermore,the effects of a vacancy on the structure and the electronic property of CF are discussed.

  1. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad

    2017-02-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  2. Halogen chemistry reduces tropospheric O3 radiative forcing

    DEFF Research Database (Denmark)

    Sherwen, Tomás; Evans, Mat J.; Carpenter, Lucy J.

    2017-01-01

    Tropospheric ozone (O3) is a global warming gas, but the lack of a firm observational record since the preindustrial period means that estimates of its radiative forcing (RFTO3) rely on model calculations. Recent observational evidence shows that halogens are pervasive in the troposphere and need...

  3. Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride

    Science.gov (United States)

    Kononevich, Yuriy N.; Surin, Nikolay M.; Sazhnikov, Viacheslav A.; Svidchenko, Evgeniya A.; Aristarkhov, Vladimir M.; Safonov, Andrei A.; Bagaturyants, Alexander A.; Alfimov, Mikhail V.; Muzafarov, Aziz M.

    2017-03-01

    A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2-10 nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem = 433 and 445 nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction.

  4. Tropospheric Chemistry and Climate Impacts of VSL Halogens: Pre-Industrial to Present day

    Science.gov (United States)

    Kinnison, Douglas; Saiz-Lopez, Alfonso; Lamarque, Jean-Francois; Ordoñez, Carlos; Fernandez, Rafael; Tilmes, Simone

    2013-04-01

    Ozone in the troposphere is one of the most important short-lived gases contributing to greenhouse radiative forcing (IPCC, 2007) and is of central importance to the chemistry of this region of the atmosphere. Tropospheric ozone is produced by photochemical oxidation of carbon monoxide, methane and non-methane volatile organic compounds in the presence of nitrogen oxide. A large fraction of the tropospheric ozone loss occurs within the tropical marine boundary layer via photolysis to excited oxygen atoms followed by reaction with water vapor, reactions with odd hydrogen radical, and surface deposition. In addition, inorganic halogens (i.e., chlorine, bromine, and iodine species) are known to destroy ozone through efficient catalytic reaction cycles. In this study, we use the NCAR 3D chemistry climate model (CAM-CHEM). The model has a full representation of tropospheric and stratospheric chemistry. Its scope has been extended to include halogen sources, reactive halogen chemistry, and related atmospheric processes (Ordonez et al. 2012; Saiz-Lopez et al. 2012). The purpose of this work is to contrast the pre-industrial importance of tropospheric halogen driven ozone loss to present day conditions; specifically the importance of iodine chemistry.

  5. Chemistry of Very Short Lived Halogens in the Troposphere: Pre-Industrial to Present day

    Science.gov (United States)

    Kinnison, Douglas; Saiz-Lopez, Alfonso; Fernandez, Rafael; Lamarque, Jean-Francois; Tilmes, Simone

    2014-05-01

    Ozone in the troposphere is one of the most important short-lived gases contributing to greenhouse radiative forcing (IPCC, 2007) and is of central importance to the chemistry of this region of the atmosphere. Tropospheric ozone is produced by photochemical oxidation of carbon monoxide, methane and other non-methane volatile organic compounds in the presence of nitrogen oxide. A large fraction of the tropospheric ozone loss occurs within the tropical marine boundary layer via photolysis to excited oxygen atoms followed by reaction with water vapor, reactions with odd hydrogen radical, and surface deposition. In addition, inorganic halogens (i.e., chlorine, bromine, and iodine species) are known to destroy ozone through efficient catalytic reaction cycles. In this study, we use the NCAR 3D chemistry climate model (CAM-Chem), including a detailed representation of tropospheric and stratospheric chemistry. Its scope has been extended to include halogen sources, reactive halogen chemistry, and related atmospheric processes (Ordonez et al., ACP, 2012; Saiz-Lopez et al., ACP,. 2012). The purpose of this work is to contrast the pre-industrial importance of tropospheric halogen driven ozone loss to present day conditions, specifically the importance of iodine and bromine chemistry. The sensitivity to inorganic nitrogen abundance will be shown. The model results compared to the pre-industrial surface ozone measurements at Montsouris (Volz and Kley, 1988) will also be discussed.

  6. [Degradation of halogenated compounds by haloalkane dehalogenase DadA from Alcanivorax dieselolei B-5 ].

    Science.gov (United States)

    Li, Anzhang; Shao, Zongze

    2014-09-04

    [OBJECTIVE] Alcanivorax dieselolei B-5 is an important oil-degrading bacterium. We studied its substrate range and degradation of halogenated compounds. [METHODS] Growth capability of B-5 was examined with different halogenated substrates as sole carbon source. A putative haloalkane dehalogenase (HLD) gene named dadA was found from the genome of strain B-5 and analyzed by sequence alignment, phylogenetic analysis and homologous modeling. After heterologous expression in Escherichia coli and purification, the activity of DadA towards 46 substrates was determined. [RESULTS] Strain B-5 was capable of utilizing various halogenated compounds (C3-C,8) as the sole carbon source. DadA had typical catalytic pentad residues of HLD-II subfamily, but it was independent from other members of this subfamily according to phylogenetic analysis. Activity assay showed that DadA has higher specificity and narrower substrate range than other characterized HLDs and it only showed activity toward 1,2,3-tribromopropane, 1,2-dibromo-3-chloropropane and 2,3-dichloroprop-1-ene among 46 tested substrates. [CONCLUSIONS] Strain B-5 and its HLD DadA can degrade halogenated aliphatic pollutants although.

  7. Rapid and reliable determination of the halogenating peroxidase activity in blood samples.

    Science.gov (United States)

    Flemmig, Jörg; Schwarz, Pauline; Bäcker, Ingo; Leichsenring, Anna; Lange, Franziska; Arnhold, Jürgen

    2014-12-15

    By combining easy and fast leukocyte enrichment with aminophenyl-fluorescein (APF) staining we developed a method to quickly and specifically address the halogenating activity of the immunological relevant blood heme peroxidases myeloperoxidase and eosinophil peroxidase, respectively. For leukocyte enrichment a two-fold hypotonic lysis procedure of the blood with Millipore water was chosen which represents a cheap, fast and reliable method to diminish the amount of erythrocytes in the samples. This procedure is shown to be suitable both to human and murine blood micro-samples, making it also applicable to small animal experiments with recurring blood sampling. As all types of leukocytes are kept in the sample during the preparation, they can be analysed separately after discrimination during the flow cytometry analysis. This also holds for all heme peroxidase-containing cells, namely neutrophils, eosinophils and monocytes. Moreover additional parameters (e.g. antibody staining) can be combined with the heme peroxidase activity determination to gain additional information about the different immune cell types. Based on previous results we applied APF for specifically addressing the halogenating activity of leukocyte peroxidases in blood samples. This dye is selectively oxidized by the MPO and EPO halogenation products hypochlorous and hypobromous acid. This approach may provide a suitable tool to gain more insights into the immune-physiological role of the halogenating activity of heme peroxidases.

  8. Polydiphenylamine/Zeolite Y composites and electrical conductivity responses toward halogenated hydrocarbons

    Directory of Open Access Journals (Sweden)

    Tharaporn Permpool

    2013-01-01

    Full Text Available Composites of polydiphenylamine (D-PDPA and zeolite Y with H+ as the cation (Y_H+ have been fabricated to be used as a sensing material towards non-halogenated and halogenated solvents (hexane, dichloromethane, 1, 2-dichloroethane, chloroform. These composites are toxic towards human and environment and are widely used as solvents in various industries. Polydiphenylamine, zeolite Y, and their composites are characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, particle size analysis, surface area, and pore size analysis. The effects of the Si/Al ratio, zeolite content, and vapor concentrations are investigated. The electrical conductivity sensitivity of the composites towards the solvents is higher than the pristine D-PDPA by ~1 order of magnitude. The composites can discriminate a non-halogenated solvent from halogenated solvents. They possess maximum electrical conductivity sensitivity values towards dichloromethane, but the composites do not respond to hexane. Generally, the sensitivity of the composites increases with increasing zeolite content and vapor concentration. The interactions between the composites and the vapors are investigated by FT-IR spectroscopy and UV-Vis spectroscopy. A mechanism for the interaction between the composites and the solvents is proposed.

  9. 21 CFR 700.15 - Use of certain halogenated salicylanilides as ingredients in cosmetic products.

    Science.gov (United States)

    2010-04-01

    ... ingredients in cosmetic products. 700.15 Section 700.15 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.15 Use of certain halogenated salicylanilides as ingredients in cosmetic products....

  10. Protecting-group-free amination of halogenated nitrobenzaldehyde with palladium catalyst

    Institute of Scientific and Technical Information of China (English)

    Jing Cao; Jun Xiang Feng; Yong Xiang Wu; Ya Ya Tuo

    2010-01-01

    One-step method for the synthesis of secondary aliphatic amine substituted nitrobenzaldehyde was developed.In the presence of Pd catalyst,halogenated nitrobenzaldehyde could be smoothly coupled with secondary aliphatic amine to give the target product in hexamethylphosphamide (HMPT) media without the protection of aldehyde groups.

  11. Request for Correction 11001 Toxicological Review of Halogenated Platinum Salts and Platinum Compounds

    Science.gov (United States)

    Request for Correction by the International Platinum Group Metals Association seeking the correction of information disseminated in the draft EPA document Toxicological Review of Halogenated Platinum Salts and Platinum Compounds: In Support of Summary Information on the Integrated Risk Information System (IRIS).

  12. Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, A.H.; Cook, J.A.; Goffman, T. (National Cancer Inst., Bethesda, MD (United States)); Glatstein, E. (Texas Univ., Dallas, TX (United States). Southwestern Medical Center)

    1993-02-01

    The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.).

  13. Free Radical Halogenation, Selectivity, and Thermodynamics: The Polanyi Principle and Hammond's Postulate

    Science.gov (United States)

    Scala, Alfred A.

    2004-01-01

    The underlying ideas of the Polanyi principle and Hammond's postulate in relation to the simple free halogenation reactions and their selectivity and thermodynamics is presented. The results indicate that the chlorine atom exhibits a slightly less selectivity in the liquid phase as compared to in the gas phase.

  14. Halogen-free ionic liquids and their utilization as cellulose solvents

    Science.gov (United States)

    Gräsvik, John; Eliasson, Bertil; Mikkola, Jyri-Pekka

    2012-11-01

    This work demonstrates a novel synthesis route to halogen-free ionic liquids. A one-pot synthetic reaction route avoiding the use of toxic and high-energetic alkyl halides was developed to reduce the environmental impact of the synthesis process of ionic liquids. However, the elimination of halogens and alkyl halides in the preparation of ionic liquids is not just an environmental issue: the aforementioned species are also among the most common and persistent contaminants in today's Ionic Liquids (ILs). Thus, this paper introduces a range of quaternized nitrogen based ionic liquids, including both aromatic and non-aromatic components, all prepared without alkyl halides in any step of the process. Moreover, bio-renewable precursors such as (bio-)alcohols and carboxylic acids were employed as anion sources and alkylation media, thus avoiding halogen contamination or halogen-containing anions. The IL's prepared were designed to dissolve cellulose, some of which was included in a cellulose dissolution study using a sulphite cellulose from the company Domsjö.

  15. Effects of Halogen Ions on Phase Equilibrium of Methane Hydrate in Porous Media

    Science.gov (United States)

    Yang, Mingjun; Song, Yongchen; Liu, Yu; Lam, Wei-Haur; Li, Qingping; Yu, Xichong

    2012-05-01

    The influences of halogen ions extracted from sodium fluoride, sodium chloride, sodium bromide, and sodium iodide and their concentrations on methane hydrate phase equilibrium conditions in porous media were investigated experimentally using an orthogonal test method at a pressure of 8 MPa. The experimental results showed that the equilibrium temperature of methane hydrate decreased when halogen ions were added. The equilibrium temperature decreased with the increase of halogen ion concentrations. The influence of the sources of the halogens ion to the methane hydrate equilibrium temperature were insensitive according to variance analysis, which could be explained by about the same mean ionic activity coefficient (a dimensionless coefficient relates the activity to a measured concentration) of sodium fluoride, sodium chloride, sodium bromide, and sodium iodide. The experimental measurements were also in close agreement with the thermodynamic model of Song et al. (J. Nat. Gas Chem. 19, 241 (2010)), in which the mechanical equilibrium of force between the interfaces in a hydrate-liquid-vapor system was considered.

  16. The direct asymmetric vinylogous aldol reaction of furanones with α-ketoesters: Access to chiral γ-Butenolides and glycerol derivatives

    KAUST Repository

    Luo, Jie

    2011-01-11

    Twice as good: The title reaction using the tryptophan-derived bifunctional organic catalyst 1 has been developed. The reported method led to the synthesis of chiral γ-substituted butenolides in excellent yields, with high diastereo- and enantioselectivities. Facile synthesis of chiral glycerol derivatives containing a tertiary hydroxy group has also been demonstrated. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study

    Science.gov (United States)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  18. Extending Halogen-based Medicinal Chemistry to Proteins: IODO-INSULIN AS A CASE STUDY.

    Science.gov (United States)

    El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B; Smith, Brian J; Menting, John G; Whittaker, Jonathan; Lawrence, Michael C; Meuwly, Markus; Weiss, Michael A

    2016-12-30

    Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (Tyr(B26)) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-Tyr(B26)]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (Tyr(B16), Phe(B24), Phe(B25), 3-I-Tyr(B26), and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-Tyr(B26)]insulin analog (determined as an R6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-Tyr(B26) in a receptor complex must differ from that in the free hormone. Based on the recent structure of a "micro-receptor" complex, we predict that 3-I-Tyr(B26) engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such "halogen engineering" promises to extend principles of medicinal chemistry to proteins.

  19. Comparison of halogen light and vibroacoustic stimulation on nonreactive fetal heart rate pattern.

    Science.gov (United States)

    Rahimikian, Fatemeh; Rahiminia, Tahereh; Modarres, Maryam; Mehran, Abbas

    2013-03-01

    One of the first-line assessment tools for fetal surveillance is nonstress test (NST), although it is limited by a high rate of false-nonreactive results. This study was performed to investigate if external stimulation from vibroacoustic and halogen light could help in provoking fetal responsiveness and altering NST results. This is a clinical trial. Sampling was done from April to July 2010. One hundred pregnant women with nonreactive NST for 20 min were allocated in two groups: Vibroacoustic stimulated NST (VNST, n = 50) who received vibration from a standard fetal vibratory stimulator and halogen light stimulated NST (LNST, n = 50) who received a halogen light source for 3 and 10 sec, respectively. Results were compared together and then compared to biophysical profile (BPP) scores as a backup test. We used Mann-Whitney U test, Chi-square test, and Fisher's exact test to compare the variables in the two groups through SPSS version 14. P stimulations, 68% nonreactive subjects in halogen light stimulation group and 62% in vibroacoustic stimulation group changed to reactive patterns. Time to onset of the first acceleration (VNST: 2.17 min; LNST: 2.27 min) and the test duration (VNST: 4.91 min; LNST: 5.26 min) were the same in the two groups. In VNST 89.5% and in LNST 87.5% of nonreactivity followed by score 8 in BPP. There was no significant relation between stimulus NSTs and BPPs. Vibroacoustic and light stimulation offer benefits by decreasing the incidence of nonreactive results and reducing the test time. Both halogen light stimulation and vibroacoustic stimulation are safe and efficient in fetal well-being assessment services.

  20. Do marine natural products interfere with prokaryotic AHL regulatory systems?

    DEFF Research Database (Denmark)

    Kjelleberg, S.; Steinberg, P.; Givskov, Michael Christian

    1997-01-01

    signalling system. We demonstrate that halogenated furanones, a class of secondary metabolites produced by the Australian subtidal red alga DeLisea pulchra, interfere with the acylated homoserine lactone (AHL) regulatory system in several Gram-negative bacteria. Furanones were found to interfere with the AHL...

  1. Theoretical study on O$\\cdots$Br and O$\\cdots$Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    Damanjit Kaur; Rajinder Kaur

    2014-11-01

    Halogen bonding interactions of type X$\\cdots$O=C are important in various fields including biological systems. In this work, theoretical calculations were carried out using B3LYP/6-31++G∗∗, MP2/6-31++G∗∗ and MP2/aug-cc-pVDZ methods on a series of O$\\cdots$X halogen bonds between CH2O andCH3CHO as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2 H, CFH2, CN, CCH, CCCN) as halogen bond donors. The strength of interaction energy for O$\\cdots$Br halogen-bonded complexes varies from −2.16 to −5.26 kcal/mol while for O$\\cdots$Cl complexes, it is between −1.65 to −3.67 kcal/mol, which indicate the O$\\cdots$Br bond to be stronger in comparison to O$\\cdots$Cl bond. SAPT analysis suggests that the strength of halogen bonding arises from the electrostatic and induction forces while dispersion is playing a comparatively smaller role. The halogen-bonded interaction energies were found to correlate well with positive electrostatic potential VS,max, halogen bonded distances, and the change in s-character of C-X bond. The halogen-bonded interaction energies were also evaluated for O$\\cdots$I bonded complexes and thus these complexes were found to be stronger than O$\\cdots$Br and O$\\cdots$Cl bonded complexes.

  2. Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

    2016-02-28

    Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  3. Nontraditional π Gelators Based on β-Iminoenolate and Their Difluoroboron Complexes: Effect of Halogens on Gelation and Their Fluorescent Sensory Properties Towards Acids.

    Science.gov (United States)

    Wu, Zhu; Sun, Jingbo; Zhang, Zhenqi; Yang, Hao; Xue, Pengchong; Lu, Ran

    2017-02-03

    We have synthesized a series of new β-iminoenolates and their corresponding difluoroboron complexes without any traditional gelation moieties, and some of them were able to gelatinize organic solvents. It was found that the presence of halogen atoms as substituents had a significant effect on gelation ability. In particular, bromo-containing compounds 4 A and 4 B exhibited excellent gelation abilities compared with other halogen-substituted gelators. By analyses of the single-crystal structure, the PXRD pattern of the xerogel, and electronic spectral changes during gelation, we deemed that π-π, C-H⋅⋅⋅F, and C-H⋅⋅⋅Br interactions were the driving forces for the gelation of 4 B. Interestingly, (Z)-1-(4-bromophenyl)-2-(3-methylpyrazin-2-yl)ethen-1-ol (8 A), prepared in this work, is the lowest-molecular-weight organogelator to have been reported. It should be noted that although β-iminoenolates 3 A-5 A are nonemissive in solution, they emit strong yellow light in organogels, which suggests aggregation-induced emissive activity, whereas the difluoroboron complexes 3 B-5 B show strong fluorescence in solutions, organogels, and xerogel-based films. Moreover, we found that the emission of 4 B in a nanofiber-based film could be quenched significantly upon exposure to gaseous trifluoroacetic acid and that the decay time and detection limit were 0.5 s and 0.17 ppm, respectively. Thus, through this work we have provided a new strategy for the design of nontraditional π gelators by introducing halogen atoms into π-conjugated systems with moderate polarities.

  4. Monomer conversion of composite dental resins photoactivated by a halogen lamp and a LED: a FT-Raman spectroscopy study

    Directory of Open Access Journals (Sweden)

    Luís Eduardo Silva Soares

    2005-03-01

    Full Text Available Eighteen circular blocks of resins cured either by a LED or a halogen lamp (20, 40 and 60 s, had their top (T and bottom (B surfaces studied using a FT-Raman spectrometer. Systematic changes in the intensity of the methacrylate C=C stretching mode at 1638 cm-1 as a function of exposure duration were observed. The calculated degree of conversion (DC ranged from 45.0% (B to 52.0% (T and from 49.0% (B to 55.0% (T for the LED and halogen lamp, respectively. LED and halogen light produced similar DC values with 40 and 60 s of irradiation.

  5. Modeling the reactive halogen plume from Ambrym volcano and its impact on the troposphere with the CCATT-BRAMS mesoscale model

    Directory of Open Access Journals (Sweden)

    L. Jourdain

    2015-12-01

    Full Text Available Ambrym volcano (Vanuatu, Southwest Pacific is one of the largest sources of continuous volcanic emissions worldwide. As well as releasing SO2 that is oxidized to sulfate, volcanic plumes in the troposphere are shown to undergo reactive halogen chemistry whose atmospheric impacts have been little explored to date. Here, two-way nested simulations were performed with the regional scale model CCATT-BRAMS to test our understanding of the volcano plume chemical processing and to assess the impact of Ambrym on atmospheric chemistry at local and regional scales. We focus on an episode of extreme passive degassing that occurred in early 2005 and for which airborne DOAS measurements of SO2 and BrO columns, in the near downwind plume, have been reported. The model was developed to include reactive halogen chemistry and a volcanic emission source specific to this extreme degassing event. SO2 simulated columns show very good quantitative agreement with the DOAS observations as well as with OMI data, suggesting that the plume direction as well as its dilution are well represented. Simulations are presented with and without a high-temperature initialization that includes radicals formed by high temperature partial oxidation of magmatic gases by ambient air. When included high-temperature chemistry initialization, the model is able to capture the observed BrO/SO2 trend with distance from the vent in the near downwind plume. However, the maximum of BrO columns enhancement is still underestimated by a factor 3. The model identifies total in-plume depletion of ozone (15 ppbv as a limiting factor to the partitioning of reactive bromine into BrO, of particular importance in this very strong plume at low background ozone conditions. Impacts of Ambrym in the Southwest Pacific region were also evaluated. As the plume disperses regionally, reactive halogen chemistry continues on sulfate aerosols produced by SO2 oxidation and promotes BrCl formation. Ozone depletion is

  6. Spectroscopical Determination of ground-level concentrations of Reactive Halogen Species (RHS) above salt lakes, salt pans and other areas with high halogen emissions

    Science.gov (United States)

    Holla, Robert; Landwehr, Sebastian; Platt, Ulrich; Kotte, Karsten; Lisitsyna, Linda V.; Mulder, Ines; Emmerich, Maren; Huber, Stefan; Heidak, Markus

    2010-05-01

    Reactive Halogen Species (RHS), especially BrO and IO, are crucial for the photo chemistry of ozone, the oxidation capacity of the troposphere and have an impact on the equilibria of many atmospheric reaction cycles. This also induces a potential influence on the earth's climate. Beside polar regions, volcanoes and the marine boundary layer salt lakes are an important source for reactive halogen species. At the Dead Sea BrO mixing ratios of up to 176 ppt were measured in summer 2001 [Matveev et al., 2001] and IO was identified with maximal mixing ratios of more than 10 ppt by [Zingler and Platt, 2005]. The Salar de Uyuni in Bolivia showed the presence of up to 20 ppt BrO [Hönninger et al., 2004]. Salt pans and salt deserts may be important halogen sources as well. Saline soils cover 2.5% of the land surface of the earth and might increase in the near future due to desertification as one aspect of the global climate change. Within the scope of the DFG research group HALOPROC a measurement campaign in Southern Russia was performed in August 2009. The ground-level concentrations of BrO, IO, Ozone and other trace gases above the salt lakes El'Ton, Baskuntschak and other local areas were measured using the Multi-AXis-DOAS technique. A further campaign was performed in Mauritania in November/December 2009 in cooperation with the BMBF project SOPRAN. In addition to the above-mentioned measurements the Long-Path DOAS technique was used in order to measure the ground-level concentrations at two different sites: 1. the salt pan Sebkha N'Dramcha and 2. close to a sea weed field at Poste Iwik in a coastal area. We present results from both campaigns concerning the concentrations of bromine oxide (BrO), iodine oxide (IO), ozone (O3)and formaldehyde (HCHO) and give an outlook on possible further campaigns in the future.

  7. Unexpected autumnal halogen activity in the lower troposphere at Neumayer III/Antarctica

    Science.gov (United States)

    Nasse, Jan-Marcus; Frieß, Udo; Pöhler, Denis; Schmitt, Stefan; Weller, Rolf; Schaefer, Thomas; Platt, Ulrich

    2017-04-01

    The influence of Reactive Halogen Species (RHS, like IO, BrO, ClO, etc.) on the lower polar troposphere has been subject of intense research for several decades. Ozone Depletion Events (ODEs) caused by the catalytic reaction of tropospheric ozone with inorganic halogen species or the oxidation of gaseous elemental mercury are well observed phenomena that occur during the respective springtime in both Arctic and Antarctica. Chlorine atoms also react more efficiently with hydrocarbons than e.g. OH radicals and all reactive halogen species can furthermore influence the atmospheric sulphur or nitrate cycles. While an autocatalytic release mechanism from salty surfaces, the so called bromine explosion, has been identified to rapidly increase inorganic bromine mixing ratios many aspects of atmospheric halogen chemistry in polar regions remains unclear. Since January 2016, we are operating an active Long Path DOAS instrument at Neumayer III on the Antarctic Ekström shelf ice designed for autonomous measurements. This instrument is able to detect a wide range of trace gases absorbing in the UV/Vis including ClO, BrO, OClO, IO, I2, OIO, ozone, NO2, H2O, O4, and SO2 at a temporal resolution of 5-30 minutes. The analysis of the first year of observations shows several surprising findings which give new insights into polar halogen chemistry. E.g. we observe surprisingly strong bromine activity in late summer and autumn (in addition to well-known springtime events) with mixing ratios often higher than 20 pptv. We could even observe peak mixing ratios of 110 pptv. The observed BrO levels could be the result of local/regional chemistry rather than long-range transport and modulated by the stability of the boundary layer. Also, there are hints for NOx - driven halogen activation. Furthermore, chlorine monoxide (ClO) and OClO mixing ratios of several ten pptv could be detected on a number of days, however the source mechanism for reactive chlorine remains unclear. We will give an

  8. Importance of reactive halogens in the tropical marine atmosphere using WRF-chem

    Science.gov (United States)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; Apel, Eric; Saiz-Lopez, Alfonso; von Glasow, Roland

    2017-04-01

    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens participate in catalytic reaction cycles that efficiently destroy O3, change the HOX and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. Up to 34% of O3 loss in the tropical East Pacific is due to I and Br combined. Recent studies have highlighted the key role that heterogeneous chemistry plays in explaining observations of BrO and IO abundances in the tropical troposphere. The main objective of this study is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. Our reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. Heterogeneous recycling reactions involving sea-salt aerosol and other particles have been included into the model, along with oceanic emissions of important OVOCs and halocarbons. Sea surface emissions of inorganic iodine are calculated using the parameterisation of Carpenter et al., 2013. Focusing on TORERO observations from the ships and a selected number of flights we present the tropospheric impacts of halogens (BrO, IO) in the tropospheric chemistry of relevant species (O3, OH and OVOCS). Sensitivity runs are made in order to study the impact of heterogeneous chemistry in the iodine and bromine species partitioning. A comparison between the online calculation of Very Short Lived Halocarbons (VSLH) oceanic emissions with prescribed oceanic emissions is

  9. Organic halogenated contaminants in mother-fetus pairs of harbor seals (Phoca vitulina richardii) from Alaska, 2000-2002

    Science.gov (United States)

    Environmental stressors may interfere with foraging, survival and reproduction of marine mammals resulting in marine mammal population decline. In this study, organic halogenated pollutants [OHs, including organochlorine pesticides, polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCN...

  10. Investigations into the nature of halogen- and hydrogen-bonding interactions of some heteroaromatic rings with dichlorine monoxide.

    Science.gov (United States)

    Wu, Junyong

    2014-09-01

    We have studied the structures, properties, and nature of halogen- and hydrogen-bonding interactions between some heteroaromatic rings (C(5)H(5)N, C(4)H(4)O, and C(4)H(4)S) with Cl(2)O at the MP2/aug-cc-pVTZ level. We also considered the solvent effect on the halogen bonds and hydrogen bonds in the C(5)H(5)N-Cl(2)O complexes and found that the solvent has a weakening effect on the π-type halogen bond and hydrogen bond but a prominent enhancing effect on σ-type halogen bond. The complexes have also been analyzed with symmetry adapted perturbation theory method (SAPT).

  11. Stability of mutagenic tautomers of uracil and its halogen derivatives: the results of quantum-mechanical investigation

    OpenAIRE

    Hovorun D. M.; Brovarets’ O. O.

    2010-01-01

    Aim. To investigate using the quantum-mechanical methods uracil (Ura) intramolecular tautomerisation and the effect of the thymine (Thy) methyl (Me) group substitution by the halogen on that process. Methods. Non-empirical quantum mechanic, analysis of the electron density by means of Bader’s atom in molecules (AIM) theory and physicochemical kinetics were used. Results. For the first time it has been established that the substitution of thymine Me-group for the halogen (Br, F, Cl) has practi...

  12. Syntheses of halogen derivatives of L-tryptophan, L-tyrosine and L-phenylalanine labeled with hydrogen isotopes.

    Science.gov (United States)

    Pająk, Małgorzata; Pałka, Katarzyna; Winnicka, Elżbieta; Kańska, Marianna

    2016-01-01

    Halogenated, labeled with tritium and doubly with deuterium and tritium, derivatives of L-tryptophan, i.e. 5'-bromo-[2-(3)H]-, 5'-bromo-[2-(2)H/(3)H]-, 5'-fluoro-[2-(3)H]-5'-fluoro-[2-(2)H/(3)H]-, 6'-fluoro-[2-(3)H]-, 6'-fluoro-[2-(2)H/(3)H]-L-tryptophan, as well as, L-tyrosine, i.e. 3'-fluoro-[2-(3)H]-, 3'-fluoro-[2-(2)H/(3)H]-, 3'-chloro-[2-(3)H]-, and 3'-chloro-[2-(2)H/(3)H]-L-tyrosine, and also L-phenylalanine, i.e. 2'-fluoro-[(3S)-(3)H]-, 2'-fluoro-[(3S)-(2)H/(3) H]-, 2'-chloro-[(3S)-(3)H]-, 2'-chloro-[(3S)-(2)H/(3)H]-, 4'-chloro-[(3S)-(3)H]-, and 4'-chloro-[(3S)-(2)H/(3)H]-L-phenylalanine were synthesized using enzymatic methods. Isotopomers of L-tryptophan were synthesized by coupling of halogenated indoles with S-methyl-L-cysteine carried out in deuteriated or tritiated incubation media. Labeled halogenated derivatives of L-tyrosine were obtained by the enzymatically supported exchange between halogenated L-tyrosine and isotopic water. Labeled halogenated isotopologues of L-Phe were synthesized by the enzymatic addition of ammonia to halogenated cinnamic acid. As a source of hydrogen tritiated water (HTO) and heavy water (D2O) with addition of HTO were used.

  13. Brønsted Acidic Ionic Liquid Accelerated Halogenation of Organic Compounds with N-Halosuccinimides (NXS

    Directory of Open Access Journals (Sweden)

    Stojan Stavber

    2012-12-01

    Full Text Available The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutylimidazolium triflate [BMIM(SO3H][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H][OTf] ionic liquid (IL-A was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

  14. Brønsted acidic ionic liquid accelerated halogenation of organic compounds with N-Halosuccinimides (NXS).

    Science.gov (United States)

    Vražič, Dejan; Jereb, Marjan; Laali, Kenneth K; Stavber, Stojan

    2012-12-21

    The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium triflate [BMIM(SO(3)H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO(3)H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

  15. Effect of phenol and halogenated phenols on energy transfer reactions of rat liver mitochondria.

    Directory of Open Access Journals (Sweden)

    Izushi,Fumio

    1988-02-01

    Full Text Available The in vitro effects of phenol and p-halogenated phenols on mitochondrial energy transfer reactions were examined using isolated rat liver mitochondria. The relationship between physiochemical properties of phenolic compounds and their effects on mitochondria were studied. Phenol and p-halogenated phenols induced the release of K+ ions from mitochondria, suggesting a change in permeability to K+ ions. A decrease in the respiratory control index, an increase in K+ release and stimulation of latent ATPase activity were observed with these compounds in the descending order of p-iodophenol, p-bromophenol, p-chlorophenol, p-fluorophenol and phenol. The concentrations of the phenolic compounds resulting in fifty percent inhibition of the respiratory control index and those resulting in fifty percent release of K+ ions significantly correlated with Hammett's substituent constant (sigma and the hydrophobic binding constant (pi of the compounds.

  16. Harnessing the Potential of Halogenated Natural Product Biosynthesis by Mangrove-Derived Actinomycetes

    Directory of Open Access Journals (Sweden)

    Xiang Xiao

    2013-10-01

    Full Text Available Mangrove-derived actinomycetes are promising sources of bioactive natural products. In this study, using homologous screening of the biosynthetic genes and anti-microorganism/tumor assaying, 163 strains of actinomycetes isolated from mangrove sediments were investigated for their potential to produce halogenated metabolites. The FADH2-dependent halogenase genes, identified in PCR-screening, were clustered in distinct clades in the phylogenetic analysis. The coexistence of either polyketide synthase (PKS or nonribosomal peptide synthetase (NRPS as the backbone synthetases in the strains harboring the halogenase indicated that these strains had the potential to produce structurally diversified antibiotics. As a validation, a new enduracidin producer, Streptomyces atrovirens MGR140, was identified and confirmed by gene disruption and HPLC analysis. Moreover, a putative ansamycin biosynthesis gene cluster was detected in Streptomyces albogriseolus MGR072. Our results highlight that combined genome mining is an efficient technique to tap promising sources of halogenated natural products synthesized by mangrove-derived actinomycetes.

  17. Comparative computational study of model halogen-bonded complexes of FKrCl.

    Science.gov (United States)

    Joseph, Jerelle A; McDowell, Sean A C

    2015-03-19

    Quantum chemical calculations for the FKrCl molecule at various levels of theory were performed and suggest that this molecule is metastable and may be amenable to experimental synthesis under cryogenic conditions. The FKrCl molecule forms weak halogen-bonded complexes FKrCl···Y with small molecules like FH and H2O and its computed properties were compared with those for analogous complexes of its precursor, FCl, and its rare gas hydride counterpart, FKrH. The cooperative effect of additional noncovalent interactions introduced at the F atom in the FKrCl···Y dimer (to give Z···FKrCl···Y trimers) showed a general strengthening of the intermolecular interactions in the order halogen bond < hydrogen bond < beryllium bond < lithium bond.

  18. Experimental and theoretical studies on a novel helical architecture driven by hydrogen and halogen bonding interactions

    Indian Academy of Sciences (India)

    QING ZHU LIU; SHAN SHAN WANG; TENG FEI WANG; JIAN GUO LIN; XUE HAI JU; LING QIU

    2016-12-01

    A novel two-dimensional (2D), layered, helical supramolecular architecture constructed via cooperative hydrogen bond and halogen bonds was synthesized and characterized: [(BMBA)₂(TPB)]n (1) [BMBA= 3-bromo-2-methylbenzoic acid, TPB = 1,2,3,4-tetra-(4-pyridyl)-butane]. Density functional theory (DFT) calculations were carried out to investigate the nature of intermolecular interactions between BMBA and TPB. The cooperation between hydrogen bond and halogen bond in building up the open organic architecture was demonstrated elaborately. Complex 1 exhibits strong photoluminescence and high thermal stability. The nature of electronic transitions in the photoluminescent process was investigated by means of time-dependent DFT (TDDFT) calculations and molecular orbital analyses, revealing that the luminescent property of the helical supramolecular architecture of 1 was ligand-based. Periodic DFT calculations show that 1 is an electrical insulator with a band gap of 3.29 eV.

  19. Structure-activity relationship of dopaminergic halogenated 1-benzyl-tetrahydroisoquinoline derivatives.

    Science.gov (United States)

    El Aouad, Noureddine; Berenguer, Inmaculada; Romero, Vanessa; Marín, Paloma; Serrano, Angel; Andujar, Sebastián; Suvire, Fernando; Bermejo, Almudena; Ivorra, M Dolores; Enriz, Ricardo D; Cabedo, Nuria; Cortes, Diego

    2009-11-01

    Two series of halogenated 1-benzyl-7-chloro-6-hydroxy-tetrahydroisoquinolines were prepared to explore the influence of each series on the affinity for dopamine receptors. All the compounds displayed a high affinity for D(1)-like and/or D(2)-like dopamine receptors in striatal membranes, although they were unable to inhibit [(3)H]-dopamine uptake in striatal synaptosomes. The halogen placed on the benzylic ring in 1-benzyl-THIQs, compounds of the series 1, 2'-bromobenzyl derivatives with K(i) values into the nanomolar range, and the series 2, 2',4'-dichlorobenzyl-THIQ homologues, proves to be an important factor to modulate affinity at dopamine receptor.

  20. 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...... spectra recorded at different temperatures, the complexation enthalpies and entropies for the complexes were determined to be −2.9(1) kJ mol−1 and −19.1(2) J K−1 mol−1 for the 2-C3F7I⋅toluene-d8 complex and −2.7(1) kJ mol−1 and −16.0(4) K−1 mol−1 for the 1-C3F7I⋅toluene-d8 complex. The experimental...

  1. Conformational equilibrium of phenylacetic acid and its halogenated analogues through theoretical studies, NMR and IR spectroscopy

    Science.gov (United States)

    Levandowski, Mariana N.; Rozada, Thiago C.; Melo, Ulisses Z.; Basso, Ernani A.; Fiorin, Barbara C.

    2017-03-01

    This paper presents a study on the conformational preferences of phenylacetic acid (PA) and its halogenated analogues (FPA, CPA, BPA). To clarify the effects that rule these molecules' behaviour, theoretical calculations were used, for both the isolated phase and solution, combined with nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. Most conformations of phenylacetic acid and its halogenated derivatives are stabilized through the hyperconjugative effect, which rules the conformational preference. NMR analyses showed that even with the variation in medium polarity, there was no significant change in the conformation population. Infrared spectroscopy showed similar results for all compounds under study. In most spectra, two bands were found through the carbonyl deconvolution, which is in accordance with the theoretical data. It was possible to prove that variation in the nature of the substituent in the ortho position had no significant influence on the conformational equilibrium.

  2. Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic

    Directory of Open Access Journals (Sweden)

    P. B. Shepson

    2008-03-01

    Full Text Available Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack to correctly simulate the VOC chemistry of the Arctic, and further evidence that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events is presented.

  3. Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic

    Directory of Open Access Journals (Sweden)

    A. E. Cavender

    2007-08-01

    Full Text Available Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack to correctly simulate the VOC chemistry of the Arctic, and that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events.

  4. Halogen bonded supramolecular capsules: a challenging test case for quantum chemical methods.

    Science.gov (United States)

    Sure, Rebecca; Grimme, Stefan

    2016-08-02

    Recently, Diederich et al. synthesized the first supramolecular capsule with a well-defined four-point halogen bonding interaction [Angew. Chem., Int. Ed., 2015, 54, 12339]. This interesting system comprising about 400 atoms represents a challenging test case for accurate quantum chemical methods. We investigate it with our new density functional based composite method for structures and noncovalent interactions (PBEh-3c) as well as our standard protocol for supramolecular thermochemistry and give predictions for chemical modifications to improve the binding strength.

  5. Determination of absolute configuration using heavy atom based co-crystallization method: Halogen atom effects

    Science.gov (United States)

    Wang, Jian-Rong; Fan, Xiaowu; Ding, Qiaoce; Mei, Xuefeng

    2016-09-01

    Heavy atom (chloride, bromide, and iodide) based co-crystals for determination of absolute configuration (AC) for chiral molecules were synthesized and evaluated. Co-crystals of cholestanol and L-ascorbic acid were analysed and the effects and potential benefits of varying the heavy atom are discussed. Changing the halogen atoms (chloride, bromide, or iodide) affects the co-crystal formation, X-ray absorption, and anomalous dispersion, and hence the ability to determine AC.

  6. Cascade anionotropy of the halogen in 3-acetoxy-4-bromo(chloro)-2-methyl-1-butanes

    Energy Technology Data Exchange (ETDEWEB)

    Gevorkyan, A.A.; Kazaryan, P.I.; Avakyan, S.V.

    1987-10-20

    The authors determined that the title compounds, which contain the halogen at the homoallylic position, undergo anionotropy without skeletal isomerization when heated or under the influence of acidic catalysts. Temperature ranges for the bromine and chlorine variants of the compounds were established. Gas-liquid chromatography was used along with IR and NMR spectroscopy to identify the compounds. Chemical shifts and spin-spin coupling constants were analyzed.

  7. 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......-normalized concentrations were found in brown trout. Salmon and brown trout were similar in their PHC pattern suggesting similar food sources. Variation in PHC patterns among trophic levels was not smaller than that among geographically distinct locations, confirming the importance of comparable trophic levels...

  8. Preparation of functionalized cyclic enol phosphates by halogen-magnesium exchange and directed deprotonation reactions.

    Science.gov (United States)

    Piller, Fabian M; Bresser, Tomke; Fischer, Markus K R; Knochel, Paul

    2010-07-02

    Cyclic enol phosphates were magnesiated by a halogen/magnesium exchange reaction or deprotonation using TMP-derived magnesium amide bases. The resulting magnesium reagents react readily with a wide range of electrophiles like allyl bromides and acid chlorides or can be used in Pd-catalyzed cross-coupling reactions. Several optically pure enol phosphates were prepared starting from readily available d-(+)-camphor derivatives.

  9. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III ? gas phase reactions of inorganic halogens

    OpenAIRE

    Atkinson, R.; Baulch, D. L.; Cox, R A; J. N. Crowley; Hampson, R. F.; Hynes, R. G.; Jenkin, M. E.; M. J. Rossi; Troe, J.

    2007-01-01

    International audience; This article, the third in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of inorganic halogen species, which were last published in J. Phys. Chem. Ref. Data, in 2000 (Atkinson et al., 2000), were updated on the IUPAC website in 2003 and are updated again in the present evaluation. The article consists of a summary sheet...

  10. Halogenation of a capsaicin analogue leads to novel vanilloid TRPV1 receptor antagonists

    Science.gov (United States)

    Appendino, Giovanni; Harrison, Selena; De Petrocellis, Luciano; Daddario, Nives; Bianchi, Federica; Schiano Moriello, Aniello; Trevisani, Marcello; Benvenuti, Francesca; Geppetti, Pierangelo; Di Marzo, Vincenzo

    2003-01-01

    The C-5 halogenation of the vanillyl moiety of resiniferatoxin, an ultrapotent agonist of vanilloid TRPV1 receptors, results in a potent antagonist for these receptors. Here, we have synthesized a series of halogenated derivatives of ‘synthetic capsaicin' (nonanoyl vanillamide=nordihydrocapsaicin) differing for the nature (iodine, bromine–chlorine) and the regiochemistry (C-5, C-6) of the halogenation.The activity of these compounds was investigated on recombinant human TRPV1 receptors overexpressed in HEK-293 cells. None of the six compounds exerted any significant agonist activity, as assessed by measuring their effect on TRPV1-mediated calcium mobilization. Instead, all compounds antagonized, to various extents, the effect of capsaicin in this assay.All 6-halo-nordihydrocapsaicins behaved as competitive antagonists against human TRPV1 according to the corresponding Schild's plots, and were more potent than the corresponding 5-halogenated analogues. The iodo-derivatives were more potent than the bromo- and chloro-derivatives.Using human recombinant TRPV1, 6-iodo-nordihydrocapsaicin (IC50=10 nM against 100 nM capsaicin) was about four times more potent than the prototypical TRPV1 antagonist, capsazepine, and was tested against capsaicin also on native TRPV1 in: (i) rat dorsal root ganglion neurons in culture; (ii) guinea-pig urinary bladder; and (iii) guinea-pig bronchi. In all cases, except for the guinea-pig bronchi, the compound was significantly more potent than capsazepine as a TRPV1 antagonist.In conclusion, 6-iodo-nordihydrocapsaicin, a stable and easily prepared compound, is a potent TRPV1 antagonist and a convenient replacement for capsazepine in most of the in vitro preparations currently used to assess the activity of putative vanilloid receptor agonists. PMID:12922928

  11. Enthalpy-entropy compensation in biomolecular halogen bonds measured in DNA junctions.

    Science.gov (United States)

    Carter, Megan; Voth, Andrea Regier; Scholfield, Matthew R; Rummel, Brittany; Sowers, Lawrence C; Ho, P Shing

    2013-07-23

    Interest in noncovalent interactions involving halogens, particularly halogen bonds (X-bonds), has grown dramatically in the past decade, propelled by the use of X-bonding in molecular engineering and drug design. However, it is clear that a complete analysis of the structure-energy relationship must be established in biological systems to fully exploit X-bonds for biomolecular engineering. We present here the first comprehensive experimental study to correlate geometries with their stabilizing potentials for fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) X-bonds in a biological context. For these studies, we determine the single-crystal structures of DNA Holliday junctions containing halogenated uracil bases that compete X-bonds against classic hydrogen bonds (H-bonds), estimate the enthalpic energies of the competing interactions in the crystal system through crystallographic titrations, and compare the enthalpic and entropic energies of bromine and iodine X-bonds in solution by differential scanning calorimetry. The culmination of these studies demonstrates that enthalpic stabilization of X-bonds increases with increasing polarizability from F to Cl to Br to I, which is consistent with the σ-hole theory of X-bonding. Furthermore, an increase in the X-bonding potential is seen to direct the interaction toward a more ideal geometry. However, the entropic contributions to the total free energies must also be considered to determine how each halogen potentially contributes to the overall stability of the interaction. We find that bromine has the optimal balance between enthalpic and entropic energy components, resulting in the lowest free energy for X-bonding in this DNA system. The X-bond formed by iodine is more enthalpically stable, but this comes with an entropic cost, which we attribute to crowding effects. Thus, the overall free energy of an X-bonding interaction balances the stabilizing electrostatic effects of the σ-hole against the competing

  12. Directional emission of nonthermal halogen atoms by electron bombardment of alkali halides

    Energy Technology Data Exchange (ETDEWEB)

    Postawa, Z.; Szymonski, M.

    1989-06-15

    We present the first experimental results on angle-resolved kinetic-energydistributions of halogen atoms desorbed from single crystals of alkali halidesbecause of electron bombardment. We found that the ejection of nonthermal Bratoms from the (100) surface of KBr is strongly forward peaked along thenormal. We suggest that this effect is caused by a thin damaged layer on thesurface due to a strong nonstoichiometry of the erosion process itself.

  13. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-07-13

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO2(2+) ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. "Textbook" adsorption at "nontextbook" adsorption sites: Halogen atoms on alkali halide surfaces

    OpenAIRE

    Li, B.; Michaelides, A.; Scheffler, M.

    2006-01-01

    Density-functional theory (DFT) and second order Møller-Plesset perturbation theory calculations indicate that halogen atoms bond preferentially to halide substrate atoms on a series of alkali halide surfaces, rather than to the alkali atoms as might be anticipated. An analysis of the electronic structures in each system reveals that this novel adsorption mode is stabilized by the formation of textbook two-center three-electron covalent bonds. The implications of these findings to, for exampl...

  15. Biodehalogenation: The kinetics and rates of the microbial cleavage of carbon-halogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Castro, C.E. (Univ. of California, Riverside, CA (United States). Nematology Dept.)

    1993-09-01

    Specific rate constants associated with defined molecular paths of carbon-halogen bond cleavage from a variety of alkyl halide substrates by six soil organisms are presented. Five aerobes (three pseudomonads, one methylotroph, and one flavobacterium) and one anaerobe (a methanogen) are compared. The rate constants were obtained with resting cells in phosphate buffer at pH 7.4 in the absence of nutrients or other substances. The observed general rate law is d(X[sup [minus

  16. Synthesis, Characterization, and Multimillion-Atom Simulation of Halogen-Based Energetic Materials for Agent Defeat

    Science.gov (United States)

    2013-04-01

    Kolesnikov NIST: Liu New Discoveries, Inventions, or Patent Disclosures K. O. Christe and G. Drake, “Energetic Ionic Liquids ,” US Patent 7,771,549, Aug...DTRA-TR-13-23 Synthesis, Characterization, and Multimillion-Atom Simulation of Halogen -Based Energetic Materials for Agent Defeat Approved for...second foot foot-pound-force gallon (U.S. liquid ) inch jerk joule/kilogram (J/kg) radiation dose absorbed kilotons kip (1000 lbf) kip/inch 2

  17. Determination of the Halogenated Skeleton Constituents of the Marine Demosponge Ianthella basta.

    Science.gov (United States)

    Ueberlein, Susanne; Machill, Susanne; Schupp, Peter J; Brunner, Eike

    2017-02-10

    Demosponges of the order Verongida such as Ianthella basta exhibit skeletons containing spongin, a collagenous protein, and chitin. Moreover, Verongida sponges are well known to produce bioactive brominated tyrosine derivatives. We recently demonstrated that brominated compounds do not only occur in the cellular matrix but also in the skeletons of the marine sponges Aplysina cavernicola and I. basta. Further investigations revealed the amino acid composition of the skeletons of A. cavernicola including the presence of several halogenated amino acids. In the present work, we investigated the skeletal amino acid composition of the demosponge I. basta, which belongs to the Ianthellidae family, and compared it with that of A. cavernicola from the Aplysinidae family. Seventeen proteinogenic and five non-proteinogenic amino acids were detected in I. basta. Abundantly occurring amino acids like glycine and hydroxyproline show the similarity of I. basta and A. cavernicola and confirm the collagenous nature of their sponging fibers. We also detected nine halogenated tyrosines as an integral part of I. basta skeletons. Since both sponges contain a broad variety of halogenated amino acids, this seems to be characteristic for Verongida sponges. The observed differences of the amino acid composition confirm that spongin exhibits a certain degree of variability even among the members of the order Verongida.

  18. Prediction of Infinite Dilution Activity Coefficients of Halogenated Hydrocarbons in Water

    Institute of Scientific and Technical Information of China (English)

    XU Hui-Ying; MIN Jian-Qing

    2008-01-01

    Geometrical optimization and electrostatic potential calculations have been performed for a series of halogenated hydrocarbons at the HF/Gen-6d level. A number of electrostatic potentials and the statistically based structural descriptors derived from these electrostatic potentials have been obtained. Multiple linear regression analysis and artificial neural network are employed simultaneously in this paper. The result shows that the parameters derived from electrostatic potentials σ2tot, Vs and ΣVs+, together with the molecular volume (Vmc) can be used to express the quantitative structure-infinite dilution activity coefficients (γ∞) relationship of halogenated hydrocarbons in water. The result also demonstrates that the model obtained by using BFGS quasi-Newton neural network method has much better predictive capability than that from multiple linear regression. The goodness of the model has been validated through exploring the predictive power for the external test set. The model obtained via neural network may be applied to predict γ∞ of other halogenated hydrocarbons not present in the data set.

  19. Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

    KAUST Repository

    Fu, Boyi

    2015-04-01

    The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

  20. Evaluation of wear rate of dental composites polymerized by halogen or LED light curing units

    Directory of Open Access Journals (Sweden)

    Alaghehmand H.

    2006-08-01

    Full Text Available Background and Aim: Sufficient polymerization is a critical factor to obtain optimum physical properties and clinical efficacy of resin restorations. The aim of this study was to evaluate wear rates of composite resins polymerized by two different systems Light Emitting Diodes (LED to and Halogen lamps. Materials and Methods: In this laboratory study, 20 specimens of A3 Tetric Ceram composite were placed in brass molds of 2*10*10 mm dimensions and cured for 40 seconds with 1 mm distance from surface. 10 specimens were cured with LED and the other 10 were cured with Halogen unit. A device with the ability to apply force was developed in order to test the wear of composites. After storage in distilled water for 10 days, the specimens were placed in the wear testing machine. A chrome cobalt stylus with 1.12 mm diameter was applied against the specimens surfaces with a load of 2 kg. The weight of each samples before and after 5000, 10000, 20000, 40000, 80000 and 120000 cycles was measured using an electronic balance with precision of 10-4 grams. Data were analyzed using t test and paired t test. P0.05. Conclusion: Based on the results of this study, LED and halogen light curing units resulted in a similar wear rate in composite resin restorations.

  1. Estimating the climate significance of halogen-driven ozone loss in the tropical marine troposphere

    Directory of Open Access Journals (Sweden)

    A. Saiz-Lopez

    2012-05-01

    Full Text Available We have integrated observations of tropospheric ozone, very short-lived (VSL halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.

  2. Synthesis of deuterium-labelled halogen derivatives of L-tryptophan catalysed by tryptophanase.

    Science.gov (United States)

    Winnicka, Elżbieta; Szymańska, Jolanta; Kańska, Marianna

    2016-06-01

    The isotopomers of halogen derivatives of l-tryptophan (l-Trp) (4'-F-, 7'-F-, 5'-Cl- and 7'-Br-l-Trp), specifically labelled with deuterium in α-position of the side chain, were obtained by enzymatic coupling of the corresponding halogenated derivatives of indole with S-methyl-l-cysteine in (2)H2O, catalysed by enzyme tryptophanase (EC 4.1.99.1). The positional deuterium enrichment of the resulting tryptophan derivatives was controlled using (1)H NMR. In accordance with the mechanism of the lyase reaction, a 100% deuterium labelling was observed in the α-position; the chemical yields were between 23 and 51%. Furthermore, β-F-l-alanine, synthesized from β-F-pyruvic acid by the l-alanine dehydrogenase reaction, has been tested as a coupling agent to obtain the halogenated deuterium-labelled derivatives of l-Trp. The chemical yield (∼30%) corresponded to that as observed with S-methyl-l-cysteine but the deuterium label was only 63%, probably due to the use of a not completely deuterated incubation medium.

  3. Dansylglycine, a fluorescent probe for specific determination of halogenating activity of myeloperoxidase and eosinophil peroxidase.

    Science.gov (United States)

    Bertozo, Luiza de Carvalho; Zeraik, Maria Luiza; Ximenes, Valdecir Farias

    2017-09-01

    Myeloperoxidase (MPO) and eosinophil peroxidase (EPO) are enzymes present in neutrophil and eosinophil leukocytes, respectively. Here, we present the development of a sensitive and specific assay for determination of the halogenating enzymatic activity of MPO and EPO based on the electrophilic attack of HOCl and HOBr on aromatic ring of dansylglycine (DG). We found that the intrinsic fluorescence of DG was promptly depleted by the action of these acids. In the presence of the enzymes, the fluorescence bleaching was dependent of chloride (Cl(-)) and bromide (Br(-)), which makes the assay able to distinguish the halogenating from the peroxidase activity. A linear correlation was obtained between the hydrogen peroxide (H2O2) concentration and the fluorescent decay. Similarly, the enzyme activity was measured by keeping constant H2O2. The method was applied for studding MPO/EPO specific inhibitors as 5-fluortryptamine (reversible inhibitor) and 4-hydroxybenzhydrazide (irreversible inhibitor). Differently of the taurine chloramine/3,3',5,5'-tetramethylbenzidine assay, which is among the most used technique, the dansylglycine assay was able to differentiate these inhibitors based on their kinetic behavior. In conclusion, this assay can differentiate the peroxidase and halogenating activity of MPO and EPO. Moreover, the method is adequate for real-time measurement of the production of HOCl and HOBr. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Determination of halogens and sulfur in high-purity polyimide by IC after digestion by MIC.

    Science.gov (United States)

    Krzyzaniak, Sindy R; Santos, Rafael F; Dalla Nora, Flavia M; Cruz, Sandra M; Flores, Erico M M; Mello, Paola A

    2016-09-01

    In this work, a method for sample preparation of high-purity polyimide was proposed for halogens and sulfur determination by ion chromatography (IC) with conductivity detection and, alternatively, by inductively coupled plasma mass spectrometry (ICP-MS). A relatively high polyimide mass (600mg) was completely digested by microwave-induced combustion (MIC) using 20bar of O2 and 50mmolL(-1) NH4OH as absorbing solution. These conditions allowed final solutions with low carbon content (IC and ICP-MS. The accuracy was evaluated using a certified reference material of polymer for Cl, Br and S and spike recovery experiments for all analytes. No statistical difference (t-test, 95% of confidence level) was observed between the results obtained for Cl, Br and S by IC after MIC and the certified values. In addition, spike recoveries obtained for F, Cl, Br, I and S ranged from 94% to 101%. The proposed method was suitable for polyimide decomposition for further determination of halogens and sulfur by IC and by ICP-MS (Br and I only). Taking into account the lack of methods and the difficulty of bringing this material into solution, MIC can be considered as a suitable alternative for the decomposition of polyimide for routine quality control of halogens and sulfur using IC or ICP-MS.

  5. C3-halogenation of cytisine generates potent and efficacious nicotinic receptor agonists.

    Science.gov (United States)

    Abin-Carriquiry, J Andrés; Voutilainen, Merja H; Barik, Jacques; Cassels, Bruce K; Iturriaga-Vásquez, Patricio; Bermudez, Isabel; Durand, Claudia; Dajas, Federico; Wonnacott, Susan

    2006-04-24

    Neuronal nicotinic acetylcholine receptors subserve predominantly modulatory roles in the brain, making them attractive therapeutic targets. Natural products provide key leads in the quest for nicotinic receptor subtype-selective compounds. Cytisine, found in Leguminosae spp., binds with high affinity to alpha4beta2* nicotinic receptors. We have compared the effect of C3 and C5 halogenation of cytisine and methylcytisine (MCy) on their interaction with native rat nicotinic receptors. 3-Bromocytisine (3-BrCy) and 3-iodocytisine (3-ICy) exhibited increased binding affinity (especially at alpha7 nicotinic receptors; Ki approximately 0.1 microM) and functional potency, whereas C5-halogenation was detrimental. 3-BrCy and 3-ICy were more potent than cytisine at evoking [3H]dopamine release from striatal slices (EC50 approximately 11 nM), [3H]noradrenaline release from hippocampal slices (EC50 approximately 250 nM), increases in intracellular Ca2+ in PC12 cells and inward currents in Xenopus oocytes expressing human alpha3beta4 nicotinic receptor (EC50 approximately 2 microM). These compounds were also more efficacious than cytisine. C3-halogenation of cytisine is proposed to stabilize the open conformation of the nicotinic receptor but does not enhance subtype selectivity.

  6. The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

    Directory of Open Access Journals (Sweden)

    Stéphane La Barre

    2010-03-01

    Full Text Available Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology.

  7. Halogen-directed drug design for Alzheimer's disease: a combined density functional and molecular docking study.

    Science.gov (United States)

    Rahman, Adhip; Ali, Mohammad Tuhin; Shawan, Mohammad Mahfuz Ali Khan; Sarwar, Mohammed Golam; Khan, Mohammad A K; Halim, Mohammad A

    2016-01-01

    A series of halogen-directed donepezil drugs has been designed to inhibit acetyl cholinesterase (AChE). Density Functional theory (DFT) has been employed to optimize the chair as well as boat conformers of the parent drug and modified ligands at B3LYP/MidiX and B3LYP/6-311G + (d,p) level of theories. Charge distribution, dipole moment, enthalpy, free energy and molecular orbitals of these ligands are also investigated to understand how the halogen-directed modifications impact the ligand structure and govern the non-bonding interactions with the receptors. Molecular docking calculation has been performed to understand the similarities and differences between the binding modes of unmodified and halogenated chair-formed ligands. Molecular docking indicated donepezil and modified ligands had non-covalent interactions with hydrophobic gorges and anionic subsites of AChE. The -CF3-directed ligand possessed the most negative binding affinity. Non-covalent interactions within the ligand-receptor systems were found to be mostly hydrophobic and π- stacking type. F, Cl and -CF3 containing ligands emerge as effective and selective AChE inhibitors, which can strongly interact with the two active sites of AChE. In addition, we have also investigated selected pharmacokinetic parameters of the parent and modified ligands.

  8. Self-assembly of iodine in superfluid helium droplets. Halogen bonds and nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    He, Yunteng; Zhang, Jie; Lei, Lei; Kong, Wei [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

    2017-03-20

    We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Aa, much closer to the value of 3.5 Aa in iodine crystals than to the van der Waals distance of 4.3 Aa. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi-layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Electrostatically enhanced FF interactions through hydrogen bonding, halogen bonding and metal coordination: an ab initio study.

    Science.gov (United States)

    Bauzá, Antonio; Frontera, Antonio

    2016-07-27

    In this manuscript the ability of hydrogen and halogen bonding interactions, as well as metal coordination to enhance FF interactions involving fluorine substituted aromatic rings has been studied at the RI-MP2/def2-TZVPD level of theory. We have used 4-fluoropyridine, 4-fluorobenzonitrile, 3-(4-fluorophenyl)propiolonitrile and their respective meta derivatives as aromatic compounds. In addition, we have used HF and IF as hydrogen and halogen bond donors, respectively, and Ag(i) as the coordination metal. Furthermore, we have also used HF as an electron rich fluorine donor entity, thus establishing FF interactions with the above mentioned aromatic systems. Moreover, a CSD (Cambridge Structural Database) search has been carried out and some interesting examples have been found, highlighting the impact of FF interactions involving aromatic fluorine atoms in solid state chemistry. Finally, cooperativity effects between FF interactions and both hydrogen and halogen bonding interactions have been analyzed and compared. We have also used Bader's theory of "atoms in molecules" to further describe the cooperative effects.

  10. 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.)

  11. Determination of the Halogenated Skeleton Constituents of the Marine Demosponge Ianthella basta

    Directory of Open Access Journals (Sweden)

    Susanne Ueberlein

    2017-02-01

    Full Text Available Demosponges of the order Verongida such as Ianthella basta exhibit skeletons containing spongin, a collagenous protein, and chitin. Moreover, Verongida sponges are well known to produce bioactive brominated tyrosine derivatives. We recently demonstrated that brominated compounds do not only occur in the cellular matrix but also in the skeletons of the marine sponges Aplysina cavernicola and I. basta. Further investigations revealed the amino acid composition of the skeletons of A. cavernicola including the presence of several halogenated amino acids. In the present work, we investigated the skeletal amino acid composition of the demosponge I. basta, which belongs to the Ianthellidae family, and compared it with that of A. cavernicola from the Aplysinidae family. Seventeen proteinogenic and five non-proteinogenic amino acids were detected in I. basta. Abundantly occurring amino acids like glycine and hydroxyproline show the similarity of I. basta and A. cavernicola and confirm the collagenous nature of their sponging fibers. We also detected nine halogenated tyrosines as an integral part of I. basta skeletons. Since both sponges contain a broad variety of halogenated amino acids, this seems to be characteristic for Verongida sponges. The observed differences of the amino acid composition confirm that spongin exhibits a certain degree of variability even among the members of the order Verongida.

  12. Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations.

    Science.gov (United States)

    Redondo, Pilar; Largo, Antonio; Rayón, Víctor Manuel; Molpeceres, Germán; Sordo, José Ángel; Barrientos, Carmen

    2014-08-14

    The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in molecules.

  13. Superior anticancer activity of halogenated chalcones and flavonols over the natural flavonol quercetin.

    Science.gov (United States)

    Dias, Tatiana A; Duarte, Cecília L; Lima, Cristovao F; Proença, M Fernanda; Pereira-Wilson, Cristina

    2013-07-01

    A series of chalcone and flavonol derivatives were synthesized in good yield by an eco-friendly approach. A pharmacological evaluation was performed with the human colorectal carcinoma cell line HCT116 and revealed that the anticancer activity of flavonols was higher when compared with that of the respective chalcone precursors. The antiproliferative activity of halogenated derivatives increases as the substituent in the 3- or 4-positon of the B-ring goes from F to Cl and to Br. In addition, halogens in position 3 enhance anticancer activity in chalcones whereas for flavonol derivatives the best performance was registered for the 4-substituted derivatives. Flow cytometry analysis showed that compounds 3p and 4o induced cell cycle arrest and apoptosis as demonstrated by increased S, G2/M and sub-G1 phases. These data were corroborated by western blot and fluorescence microscopy analysis. In summary, halogenated chalcones and flavonols were successfully prepared and presented high anticancer activity as shown by their cell growth and cell cycle inhibitory potential against HCT116 cells, superior to that of quercetin, used as a positive control.

  14. Halogen Bonding or Hydrogen Bonding between 2,2,6,6-Tetramethyl-piperidine-noxyl Radical and Trihalomethanes CHX3 (X=Cl, Br, I)

    Institute of Scientific and Technical Information of China (English)

    Xiao-ran Zhao; Xue Pang; Xiao-qing Yan; Wei-jun Jin

    2013-01-01

    The halogen and hydrogen bonding complexes between 2,2,6,6-tetramethylpiperidine-noxyl and trihalomethanes (CHX3,X=Cl,Br,I) are simulated by computational quantum chemistry.The molecular electrostatic potentials,geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained.The results indicate that both halogen and hydrogen bonding interactions obey the order Cl<Br<I,and hydrogen bonding is stronger than the corresponding halogen bond ing.So,hydrogen bonding complexes should be dominant in trihalomethanes.However,it is possible that halogen bonding complex is competitive,even preponderant,in triiodomethane due to the similar interaction energy.This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.

  15. Technology for radiation efficiency measurement of high-power halogen tungsten lamp used in calibration of high-energy laser energy meter.

    Science.gov (United States)

    Wei, Ji Feng; Hu, Xiao Yang; Sun, Li Qun; Zhang, Kai; Chang, Yan

    2015-03-20

    The calibration method using a high-power halogen tungsten lamp as a calibration source has many advantages such as strong equivalence and high power, so it is very fit for the calibration of high-energy laser energy meters. However, high-power halogen tungsten lamps after power-off still reserve much residual energy and continually radiate energy, which is difficult to be measured. Two measuring systems were found to solve the problems. One system is composed of an integrating sphere and two optical spectrometers, which can accurately characterize the radiative spectra and power-time variation of the halogen tungsten lamp. This measuring system was then calibrated using a normal halogen tungsten lamp made of the same material as the high-power halogen tungsten lamp. In this way, the radiation efficiency of the halogen tungsten lamp after power-off can be quantitatively measured. In the other measuring system, a wide-spectrum power meter was installed far away from the halogen tungsten lamp; thus, the lamp can be regarded as a point light source. The radiation efficiency of residual energy from the halogen tungsten lamp was computed on the basis of geometrical relations. The results show that the halogen tungsten lamp's radiation efficiency was improved with power-on time but did not change under constant power-on time/energy. All the tested halogen tungsten lamps reached 89.3% of radiation efficiency at 50 s after power-on. After power-off, the residual energy in the halogen tungsten lamp gradually dropped to less than 10% of the initial radiation power, and the radiation efficiency changed with time. The final total radiation energy was decided by the halogen tungsten lamp's radiation efficiency, the radiation efficiency of residual energy, and the total power consumption. The measuring uncertainty of total radiation energy was 2.4% (here, the confidence factor is two).

  16. Model study of multiphase DMS oxidation with a focus on halogens

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2004-01-01

    Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

  17. A physico-chemical study of some areas of fundamental significance to biophysics. Annual report, 1991--1992

    Energy Technology Data Exchange (ETDEWEB)

    McGlynn, S.P.; Kumar, D.

    1992-04-30

    This report discusses the following topics: Radiation signatures; photoelectron spectroscopy of biologically active molecules; laser optogalvanic effect; magnetic circular dichroism; photochemistry of halogenated molecules; and density effects on high-n rydbergs.

  18. Slab-derived halogens and noble gases illuminate closed system processes controlling volatile element transport into the mantle wedge

    Science.gov (United States)

    Kobayashi, Masahiro; Sumino, Hirochika; Nagao, Keisuke; Ishimaru, Satoko; Arai, Shoji; Yoshikawa, Masako; Kawamoto, Tatsuhiko; Kumagai, Yoshitaka; Kobayashi, Tetsuo; Burgess, Ray; Ballentine, Chris J.

    2017-01-01

    Halogen and noble gas systematics are powerful tracers of volatile recycling in subduction zones. We present halogen and noble gas compositions of mantle peridotites containing H2O-rich fluid inclusions collected at volcanic fronts from two contrasting subduction zones (the Avacha volcano of Kamchatka arc and the Pinatubo volcano of Luzon arcs) and orogenic peridotites from a peridotite massif (the Horoman massif, Hokkaido, Japan) which represents an exhumed portion of the mantle wedge. The aims are to determine how volatiles are carried into the mantle wedge and how the subducted fluids modify halogen and noble gas compositions in the mantle. The halogen and noble gas signatures in the H2O-rich fluids are similar to those of marine sedimentary pore fluids and forearc and seafloor serpentinites. This suggests that marine pore fluids in deep-sea sediments are carried by serpentine and supplied to the mantle wedge, preserving their original halogen and noble gas compositions. We suggest that the sedimentary pore fluid-derived water is incorporated into serpentine through hydration in a closed system along faults at the outer rise of the oceanic, preserving Cl/H2O and 36Ar/H2O values of sedimentary pore fluids. Dehydration-hydration process within the oceanic lithospheric mantle maintains the closed system until the final stage of serpentine dehydration. The sedimentary pore fluid-like halogen and noble gas signatures in fluids released at the final stage of serpentine dehydration are preserved due to highly channelized flow, whereas the original Cl/H2O and 36Ar/H2O ratios are fractionated by the higher incompatibility of halogens and noble gases in hydrous minerals.

  19. 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 (ClO2) 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 ClO2-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 ClO2-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 ClO2 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.

  20. Nanopipe formation as a result of boron impurity segregation in gallium nitride grown by halogen-free vapor phase epitaxy

    Science.gov (United States)

    Kimura, Taishi; Aoki, Yuko; Horibuchi, Kayo; Nakamura, Daisuke

    2016-12-01

    The work reported herein demonstrated that nanopipes can be formed via a surfactant effect, in which boron impurities preferentially migrate to semipolar and nonpolar facets. Approximately 3 μm-thick GaN layers were grown using halogen-free vapor phase epitaxy. All layers grown in pyrolytic boron nitride (pBN) crucibles were found to contain a high density of nanopipes in the range of 1010 to 1011 cm-2. The structural properties of these nanopipes were analyzed by X-ray rocking curve measurements, transmission electron microscopy, and three-dimensional atom probe (3DAP) tomography. The resulting 3DAP maps showed nanopipe-sized regions of boron segregation, and these nanopipes were not associated with the presence of dislocations. A mechanism for nanopipe formation was developed based on the role of boron as a surfactant and considering energy minima. A drastic reduction in the nanopipe density was achieved upon replacing the pBN crucibles with tantalum carbide-coated carbon crucibles. Consequently, we have confirmed that nanopipes can be formed solely due to surface energy changes induced by boron impurity surface segregation. For this reason, these results also indicate that nanopipes should be formed by other surfactant impurities such as Mg and Si.

  1. SYNTHESIS AND ANTIMICROBIAL STUDIES OF SOME NEW HALOGENATED ISOXAZOLINE DERIVATIVES

    Directory of Open Access Journals (Sweden)

    M.M. Kendre, Shahid Shaikh, N.N. Shah and M.A. Baseer*

    2013-03-01

    Full Text Available ABSTRACT: A series of some new Isoxazoline derivatives derived from 3-(4’-dimethylamino-phenyl-1-(2-hydroxyphenyl-Propenone(chalcone derivatives using hydroxylamine hydrochloride is reported. These newly synthesized compounds were screened for their antimicrobial potencies which reflect moderate to good activity against different strains of bacteria and fungi employed. The promising feature of this reaction is mild reaction condition and excellent yield with high purity of compounds synthesized. All the synthesized compounds were confirmed by IR, 1HNMR and Mass.

  2. Crystal structures of four δ-keto esters and a Cambridge Structural Database analysis of cyano-halogen interactions.

    Science.gov (United States)

    Kamal, Kulsoom; Maurya, Hardesh K; Gupta, Atul; Vasudev, Prema G

    2015-10-01

    The revived interest in halogen bonding as a tool in pharmaceutical cocrystals and drug design has indicated that cyano-halogen interactions could play an important role. The crystal structures of four closely related δ-keto esters, which differ only in the substitution at a single C atom (by H, OMe, Cl and Br), are compared, namely ethyl 2-cyano-5-oxo-5-phenyl-3-(piperidin-1-yl)pent-2-enoate, C19H22N2O3, (1), ethyl 2-cyano-5-(4-methoxyphenyl)-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C20H24N2O4, (2), ethyl 5-(4-chlorophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21ClN2O3, (3), and the previously published ethyl 5-(4-bromophenyl)-2-cyano-5-oxo-3-(piperidin-1-yl)pent-2-enoate, C19H21BrN2O3, (4) [Maurya, Vasudev & Gupta (2013). RSC Adv. 3, 12955-12962]. The molecular conformations are very similar, while there are differences in the molecular assemblies. Intermolecular C-H...O hydrogen bonds are found to be the primary interactions in the crystal packing and are present in all four structures. The halogenated derivatives have additional aromatic-aromatic interactions and cyano-halogen interactions, further stabilizing the molecular packing. A database analysis of cyano-halogen interactions using the Cambridge Structural Database [CSD; Groom & Allen (2014). Angew. Chem. Int. Ed. 53, 662-671] revealed that about 13% of the organic molecular crystals containing both cyano and halogen groups have cyano-halogen interactions in their packing. Three geometric parameters for the C-X...N[triple-bond]C interaction (X = F, Cl, Br or I), viz. the N...X distance and the C-X...N and C-N...X angles, were analysed. The results indicate that all the short cyano-halogen contacts in the CSD can be classified as halogen bonds, which are directional noncovalent interactions.

  3. Halogens behaviours in Magma Degassing: Insights into Eruptive Dynamics, Hydrothermal Systems and Atmospheric Impact of Andesitic Volcanism

    Science.gov (United States)

    Villemant, B.; Balcone, H.; Mouatt, J.; Michel, A.; Komorowski, J.; Boudon, G.

    2007-12-01

    Shallow degassing of H2O in andesitic magmas determines the eruptive styles of volcanic eruptions and contributes to the hydrothermal systems developed around active volcanoes. Halogens behaviour during magma degassing primarily depends on their incompatible behaviour in the melts and on water solubility. Thus, residual contents of halogens in volcanic juvenile vitric clasts may be used as tracers of H2O degassing processes during explosive and effusive eruptions. Because of the large range of water-melt partition coefficients of halogens and their relatively low diffusion coefficients, a comparison of F, Cl, Br and I contents in volcanic clasts in function of their vesicularity and micro-cristallinity allows to precisely model the main degassing processes and to establish constraints on pre-eruptive conditions. Halogens acids (HCl, HBr and HI) extracted in the vapour phase have much more complex behaviours because of their high solubility in low temperature thermal waters, their variable condensation temperatures and their very high reactivity when mixed with low temperature and oxidizing atmospheric gases. A comparison of model compositions of high temperature gases with the composition of thermal waters, and gases from fumaroles or plumes of active volcanoes allows to characterise the shallow volcanic system and its evolutionary states. Variable halogen behaviours are discussed for a variety of eruption types (plinian, vulcanian and dome-forming) and active volcanic systems from the Lesser Antilles (Montagne Pelee, Soufrière of Guadeloupe, Soufriere Hills of Montserrat).

  4. Determination of gaseous semi-and low-volatile organic halogen compounds by barrier-discharge atomic emission spectrometry

    Institute of Scientific and Technical Information of China (English)

    Yifei Sun; Nobuhisa Watanabe; Wei Wang; Tianle Zhu

    2013-01-01

    A group parameter approach using "total organic halogen" is effective for monitoring gaseous organic halogen compounds,including fluorine,chlorine,and bromine compounds,generated from combustion.We described the use of barrier-discharge radiofrequencyhelium-plasma/atomic emission spectrometry,for the detection of semi-and low-volatile organic halogen compounds (SLVOXs),which can be collected by CarbotrapTM adsorbents and analyzed using thermal desorption.The optimal carrier gas flow rates at the injection and desorption lines were established to be 100 mL/min.The detection range for SLVOXs in the gaseous samples was from 10 ng to tens of micrograms.Measuring F was more diflicult than measuring Cl or Br,because the wavelength ofF is dose to that of air.The barrierdischarge radiofrequency-helium-plasma/atomic emission spectrometry measured from 85% to 103% of the SLVOXs in the gas sample.It has been found that Carbotrap B is appropriate for high-boiling-point compounds,and Carbotrap C is suitable for the determination of organic halogen compounds with lower boiling points,in the range 200-230℃.Under optimal analysis conditions,a chlorinecontaining plastic was destroyed using different oxygen concentrations.Lower oxygen concentrations resulted in the production of lower amounts of organic halogen compounds.

  5. Halogen poisoning effect of Pt-TiO2 for formaldehyde catalytic oxidation performance at room temperature

    Science.gov (United States)

    Zhu, Xiaofeng; Cheng, Bei; Yu, Jiaguo; Ho, Wingkei

    2016-02-01

    Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO2 (Pt-P25) catalysts with and without adsorbed halogen ions (including F-, Cl-, Br-, and I-) were prepared through impregnation and ion modification. Pt-TiO2 samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO2 sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO2. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  6. Fast and Specific Assessment of the Halogenating Peroxidase Activity in Leukocyte-enriched Blood Samples.

    Science.gov (United States)

    Flemmig, Jörg; Schwarz, Pauline; Bäcker, Ingo; Leichsenring, Anna; Lange, Franziska; Arnhold, Jürgen

    2016-07-28

    In this paper a protocol for the quick and standardized enrichment of leukocytes from small whole blood samples is described. This procedure is based on the hypotonic lysis of erythrocytes and can be applied to human samples as well as to blood of non-human origin. The small initial sample volume of about 50 to 100 µl makes this method applicable to recurrent blood sampling from small laboratory animals. Moreover, leukocyte enrichment is achieved within minutes and with low material efforts regarding chemicals and instrumentation, making this method applicable in multiple laboratory environments. Standardized purification of leukocytes is combined with a highly selective staining method to evaluate halogenating peroxidase activity of the heme peroxidases, myeloperoxidase (MPO) and eosinophil peroxidase (EPO), i.e., the formation of hypochlorous and hypobromous acid (HOCl and HOBr). While MPO is strongly expressed in neutrophils, the most abundant immune cell type in human blood as well as in monocytes, the related enzyme EPO is exclusively expressed in eosinophils. The halogenating activity of these enzymes is addressed by using the almost HOCl- and HOBr-specific dye aminophenyl fluorescein (APF) and the primary peroxidase substrate hydrogen peroxide. Upon subsequent flow cytometry analysis all peroxidase-positive cells (neutrophils, monocytes, eosinophils) are distinguishable and their halogenating peroxidase activity can be quantified. Since APF staining may be combined with the application of cell surface markers, this protocol can be extended to specifically address leukocyte sub-fractions. The method is applicable to detect HOCl and HOBr production both in human and in rodent leukocytes. Given the widely and diversely discussed immunological role of these enzymatic products in chronic inflammatory diseases, this protocol may contribute to a better understanding of the immunological relevance of leukocyte-derived heme peroxidases.

  7. Side-polished multimode fiber biosensor based on surface plasmon resonance with halogen light

    Science.gov (United States)

    Lin, Hong-Yu; Tsai, Woo-Hu; Tsao, Yu-Chia; Sheu, Bor-Chiou

    2007-02-01

    A side-polished multimode fiber sensor based on surface plasmon resonance (SPR) as the transducing element with a halogen light source is proposed. The SPR fiber sensor is side polished until half the core is closed and coated with a 37 nm gold thin film by dc sputtering. The SPR curve on the optical spectrum is described by an optical spectrum analyzer and can sense a range of widths in wavelengths of SPR effects. The measurement system using the halogen light source is constructed for several real-time detections that are carried out for the measurement of the index liquid detections for the sensitivity analysis. The sensing fiber is demonstrated with a series of refractive index (RI) liquids and set for several experiments, including the stability, repeatability, and resolution calibration. The results for the halogen light source with the resolution of the measurement based on wavelength interrogation were 3×10-6 refractive index units (RIUs). The SPR dip shifted in wavelength is used as a measure of the RI change at a surface, and this RI change varies directly with the number of biomolecules at the surface. The SPR dip shift in wavelength, which was hybridized at 0.1 μM of the target DNA to the probe DNA, was 8.66 nm. The all-fiber multimode SPR sensor, which has the advantages of being low cost, being disposable, having high stability and linearity, being free of labeling, and having potential for real-time detection, permit the sensor and system to be used in biochemical sensing and environmental monitoring.

  8. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    Science.gov (United States)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine J.

    2017-10-01

    Gas-phase clustering of nonionizable iodylbenzene (PhIO2) is attributed to supramolecular halogen bonding. Electrospray ionization results in the formation of ions of proton-charged and preferably sodium-charged clusters assignable to [H(PhIO2) n ]+, n = 1-7; [Na(PhIO2) n ]+, n = 1-6; [Na2(PhIO2) n ]2+, n = 7-20; [HNa(PhIO2) n ]2+, n = 6-19; [HNa2(PhIO2) n ]3+, n = 15-30; and [Na3(PhIO2) n ]3+, n = 14-30. The largest cluster detected has a supramolecular mass of 7147 Da. Electronic structure calculations using the M06-2X functional with the 6-311++G(d,p) basis set for C, H, and O, and LANL2DZ basis set for I and Na predict 298 K binding enthalpies for the protonated and sodiated iodylbenzene dimers and trimers are greater than 180 kJ/mol. This is exceptionally high in comparison with other protonated and sodiated clusters with well-established binding enthalpies. Strongly halogen-bonded motifs found in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations. [Figure not available: see fulltext.

  9. Influence of the Halogen Activation on the Ozone Layer in XXIst Century

    Science.gov (United States)

    Larin, Igor; Aloyan, Artash; Yermakov, Alexandr

    2016-04-01

    The aim of the work is to evaluate a possible effect of heterophase chemical reactions (HCR) with participation of reservoir gases (ClONO2, HCl) and sulfate particles of the Junge layer on the ozone layer at mid-latitudes in the XXI century, which could be relevant for more accurate predicting a recovery of the ozone layer, taking into account that just these processes were the main cause of the ozone depletion at the end of XXth century. Required for calculating the dynamics of GHR data on the specific volume/surface of the sulfate aerosols in the lower stratosphere were taken from the data of field experiments. Their physico-chemical properties (chemical composition, density, water activity and free protons activity et al.) have been obtained with help of thermodynamic calculations (Atmospheric Inorganic Model, AIM). Altitude concentration profiles of individual gas components, as well as temperature and relative humidity (RH) at a given geographic location and season have been calculated using a two-dimensional model SOCRATES. The calculations have been made for the conditions of June 1995, 2040 and 2080 at 15 km altitude and 50° N latitude. It has been shown that the rate of ozone depletion as a result of processes involving halogen activation for the given conditions in 2040, 2080 is about 35% lower than a corresponding value in 1995 (a year of maximum effect of halogen activation). From this we can conclude that in the XXI century, despite the natural decline of ozone-depleting chlorofluorocarbons. processes of halogen activation of the ozone depletion with participation of sulfate aerosols should be taken into account in the calculations of the recovery of the ozone layer at mid-latitudes.

  10. 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.

  11. Comparative toxicity of halogenated hydrocarbons: Molecular aspects. Final report, 1 January-31 December 1992

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, G.G.

    1993-07-13

    The comparative hepatotoxicities of perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA) and the tri-and tetra-oligomers of chloro-trifluoro ethylene (CTFE) have been investigated in the rat and guinea pig. All compounds have been identified as causing hepatomegaly, peroxisome proliferation and cytochrome P4504A1 induction in the rat. The guinea pig is non-responsive to these compounds and the observed liver changes appear to be specific to lower rodent species. The implications of this study are that the above compounds do not represent a health hazard to man.

  12. In vitro and in vivo studies of the effects of halogenated histidine analogs on Plasmodium falciparum.

    OpenAIRE

    Panton, L J; Rossan, R N; Escajadillo, A; Matsumoto, Y; Lee, A.T.; Labroo, V M; Kirk, K L; Cohen, L. A.; Aikawa, M.; Howard, R J

    1988-01-01

    The effects of four halogenated analogs of histidine on in vitro growth of Plasmodium falciparum malaria parasites were monitored by measurement of the incorporation of 3H-labeled amino acids into parasite proteins and by light and electron microscopy. The uptake of [3H]isoleucine was reduced to 50% of the control value by addition of 70 microM 2-fluoro-L-histidine (2-F-HIS) or 420 microM 2-iodo-L-histidine (2-I-HIS). [3H]histidine uptake into acid-insoluble material was affected equally by t...

  13. Protein ligand interactions 7 halogenated pyridinium salts as inhibitors of acetylcholinesterase from Electrophorus electricus.

    Science.gov (United States)

    Whiteley, C G; Ngwenya, D S

    1995-08-01

    The interaction of halo-quaternary pyridinium hydrochloride salts on acetylcholinesterase (AChE, E.C.3.1.1.7) has been investigated. Kinetic analysis has shown that they reflect a non-competitive inhibition with Ki values in the range 8-13 microM and 5-34 microM for chloro- and bromo-substituted salts respectively. Spectrophotometry was used to study the binding of the ligands with the enzyme and Scatchard analysis used to calculate the respective dissociation constants (Kd) and the number of binding sites. The substitution position of the halogen on the pyridine ring also influenced the binding capacity and the Ki values.

  14. Oxidative dechlorination of halogenated phenols catalyzed by two distinct enzymes: Horseradish peroxidase and dehaloperoxidase.

    Science.gov (United States)

    Szatkowski, Lukasz; Thompson, Matthew K; Kaminski, Rafal; Franzen, Stefan; Dybala-Defratyka, Agnieszka

    2011-01-01

    The mechanism of the dehalogenation step catalyzed by dehaloperoxidase (DHP) from Amphitrite ornata, an unusual heme-containing protein with a globin fold and peroxidase activity, has remarkable similarity with that of the classical heme peroxidase, horseradish peroxidase (HRP). Based on quantum mechanical/molecular mechanical (QM/MM) modeling and experimentally determined chlorine kinetic isotope effects, we have concluded that two sequential one electron oxidations of the halogenated phenol substrate leads to a cationic intermediate that strongly resembles a Meisenheimer intermediate - a commonly formed reactive complex during nucleophilic aromatic substitution reactions especially in the case of arenes carrying electron withdrawing groups.

  15. Did the Siberian Traps eruptions emit enough halogens to have an impact on ozone geochemistry?

    Science.gov (United States)

    Sibik, Svetlana; Edmonds, Marie; Villemant, Benoit; Thierry, Pauline; Polozov, Alexander

    2015-04-01

    The Siberian Traps Large Igneous Province is thought to have formed over 1 Ma at the end of the Permian, synchronous with the largest mass extinction in Earth's history. There remains much controversy as to the exact mechanism of the mass extinction, but all hypotheses revolve around the emission of volatiles in various forms. The research to date has tended to focus on sulfur and carbon rather than halogen degassing, despite this being probably critical in terms of environmental impact as they might have been played a crucial role in ozone layer depletion and therefore promote mass extinction. Current study aims to look at the behaviour of chlorine, bromine, iodine and fluorine to evaluate the halogen budget contribution from heterogeneous mantle source and from evaporates, which dominate in the south (Cambrian evaporites) and north (Devonian evaporites) of Siberian platform. For this study we use basaltic sills and lava flows emplaced in the area with no volatile-rich sediments south-east from Norilsk (Dyupkin lake and Lower Tunguska river regions) and a sill intruded into evaporates in Nepa location in the south of the platform, originally aimed at prospecting for potassium salts. Borehole samples of basalts intruded into evaporites might have been penetrated by salts and anhydrite. In order to eliminate this effect and ensure that we analyse halogen contents in pure basalts prior to any further analysis the samples were specifically treated so that penetrated material was removed as leachates. Whole rock fine powders of basalts were analysed for halogens, major and trace elements. The solutions obtained by basalt pyrohydrolysis extraction, leachates of basaltic powders and dissolved evaporites were analysed by ion chromatography for chlorine and fluorine and by ICP-MS for bromine and iodine. Basalts intruded into evaporites demonstrate predicted pronounced chlorine, bromine and iodine enrichments associated with salt assimilation. The results show that bromine

  16. Theoretical Study of the Iodine-catalyzed Nucleophilic Addition by Halogen Bond

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The iodine-catalyzed nucleophilic addition of pyrrole to acetone has been studied by density functional theory at the level of Lanl2DZ*. It has been shown that the first iodine molecule appears to have a remarkable catalytic effect on this reaction by halogen bond between carbonyl oxygen and iodine molecule, but the second one does not improve the reaction largely. In general, the nucleophilic addition at the C(2) site of pyrrole is more favorable than that at the C(3)site;however, this trend is not prominent or even changed in acetronitrile solvent for the indole system, which is consistent with the experimental result by Bandgar.

  17. Destruction of halogen-containing pesticides by means of detonation combustion

    OpenAIRE

    Biegańska, Jolanta

    2012-01-01

    Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine—2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine—herbicide; (2) bromophos—O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate—insecticide; (3) chloridazon—5-amino-4-chloro-2-phenylopyridazin-3(2H)-one—herbicide; (4) linuron—3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea—herbicide; (5) metoxychlor—1,1,1-trichloro-2,2-bis(4-meto...

  18. Application of the Langley plot for calibration of sun sensors for the Halogen Occultation Experiment (HALOE)

    Science.gov (United States)

    Moore, Alvah S., Jr.; Mauldin, L. ED, III; Stump, Charles W.; Reagan, John A.; Fabert, Milton G.

    1989-01-01

    The calibration of the Halogen Occultation Experiment (HALOE) sun sensor is described. This system consists of two energy-balancing silicon detectors which provide coarse azimuth and elevation control signals and a silicon photodiode array which provides top and bottom solar edge data for fine elevation control. All three detectors were calibrated on a mountaintop near Tucson, Ariz., using the Langley plot technique. The conventional Langley plot technique was modified to allow calibration of the two coarse detectors, which operate wideband. A brief description of the test setup is given. The HALOE instrument is a gas correlation radiometer that is now being developed for the Upper Atmospheric Research Satellite.

  19. A New Halogenated Biindole and A New Apo-carotenone from Green Alga Chaetomorpha basiretorsa Setchell

    Institute of Scientific and Technical Information of China (English)

    Da Yong SHI; Li Jun HAN; Jie SUN; Shuai LI; Su Juan WANG; Yong Chun YANG; Xiao FAN; Jian Gong SHI

    2005-01-01

    A new halogenated biindole and a new apo-carotenone have been isolated from the ethanolic extract of the green alga Chaetomorpha basiretorsa Sethcell. On the basis of chemical and spectroscopic methods including 2D NMR technique, their structures have been elucidated as 4,4′-dichloro-5,5′-dibromo-7,7′-dimethoxy-2,2′-bi- 1H-indole and l ′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien-2-one, respectively.

  20. "Textbook" adsorption at "nontextbook" adsorption sites: halogen atoms on alkali halide surfaces.

    Science.gov (United States)

    Li, Bo; Michaelides, Angelos; Scheffler, Matthias

    2006-07-28

    Density-functional theory and second order Møller-Plesset perturbation theory calculations indicate that halogen atoms bond preferentially to halide substrate atoms on a series of alkali halide surfaces, rather than to the alkali atoms as might be anticipated. An analysis of the electronic structures in each system reveals that this novel adsorption mode is stabilized by the formation of textbook two-center three-electron covalent bonds. The implications of these findings to, for example, nanostructure crystal growth, are briefly discussed.

  1. Atomic forces between noble gas atoms, alkali ions, and halogen ions for surface interactions

    Science.gov (United States)

    Wilson, J. W.; Outlaw, R. A.; Heinbockel, J. H.

    1988-01-01

    The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  2. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wu, Jiang [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, The University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon (Portugal); Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  3. Strong and Selective Halide Anion Binding by Neutral Halogen-Bonding [2]Rotaxanes in Wet Organic Solvents.

    Science.gov (United States)

    Lim, Jason Y C; Bunchuay, Thanthapatra; Beer, Paul D

    2017-04-03

    The design and construction of neutral interlocked host molecules for anion recognition are rare. Using an active-metal template approach, the preparation of a family of neutral halogen bonding (XB) rotaxanes containing two, three and four iodotriazole groups integrated into the macrocycle and axle components is achieved. In spite of the interlocked hosts' neutrality, such rotaxane systems are capable of binding halide anions strongly and selectively in wet organic solvent mixtures. Importantly, halide-binding strength and selectivity can be modulated by varying the number and position of the halogen bond donor iodotriazole groups within the interlocked cavity; the rotaxane containing the largest number of halogen bond donor groups exhibits the highest halide anion-binding affinities. By varying the percentage of water content in the solvent, neutral XB donor-mediated anion-binding strength is also demonstrated to be highly sensitive to solvent polarity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Process for simultaneously processing of used metal and/or metal scrap and scrap containing halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Dapper, G.; Kirchner, W.; Sloterdijk, W.; Verbraak, C.A.

    1982-03-02

    A process is presened for reducing environmental pollution resulting from disposal of waste containing halogenated hydrocarbons by simultaneous treatment with used metal and/or metal scrap at elevated temperatures. The halogenated hydrocarbons are pyrolyzed and the resulting hydrogen halide containing gas is brought into contact with the used metal and/or metal scrap at elevated temperatures so as to form metal halogenides that are volatile under the conditions applied. The volatile metal halogenides are largely separated from the gaseous mixture formed, and at least part of the remaining gaseous mixture and/or hydrocarbon residue is used as fuel to maintain the required temperature. The waste feed compositions and process conditions can be chosen to effect separation between various metals by selective halogenation and condensation, and substantially all of the hydrogen halide can be tied up and recovered as metal halogenides.

  5. Composes inter-halogenes sous pression: etude des transformations structurales dans le monobromure d'iode sous forme dense

    Science.gov (United States)

    Bouchard, Alexandre

    La famille des composes halogenes et inter-halogenes representent des solides moleculaires adoptant des phases denses communes avec des solides moleculaires diatomiques comme l'azote et l'hydrogene. Parmi les transformations structurales et electroniques induites sous haute pression et observees dans ces solides, on note, entre autres, la dissociation moleculaire et la metallisation. De plus, l'etude des phases denses de l'iode a permis recemment l'observation d'une structure cristalline possedant une modulation dite incommensurable, c'est-a-dire une modulation possedant une periodicite differente de celle de la structure cristalline, jetant ainsi une lumiere nouvelle sur le processus de dissociation moleculaire dans les solides halogenes. Dans ce memoire, on propose d'etudier les changements structuraux dans monobromure d'iode (IBr), un compose inter-halogene possedant des proprietes structurales semblables a celles de deux composes halogenes, soit l'iode (I 2) et le brome (Br2) sous leur forme solide. Des experiences de diffraction des rayons X de poudres en utilisant un rayonnement synchrotron ont ete realisees a temperature ambiante sur l'IBr en variant la pression jusqu'aux environs de 60 GPa. La nature chimique particuliere du compose IBr a necessite la mise au point de techniques de chargement d'echantillon destinees a preserver l'integrite chimique de la substance utilisee. On rapporte egalement l'observation d'une phase de l'IBr presentant une modulation incommensurable. Les phases observees dans l'IBr permettent d'etablir des paralleles avec les phases denses rapportees dans I2 et Br2 par le biais d'un modele phenomenologique decrivant la sequence structurale des solides halogenes sous forme condensee.

  6. Interactions between volatile organic compounds and reactive halogen in the tropical marine atmosphere using WRF-Chem

    Science.gov (United States)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; von Glasow, Roland

    2016-04-01

    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens cause ozone (O3) destruction, change the HOx and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. There are indications that the chemistry of reactive halogens and oxygenated VOCs (OVOCs) in the tropics are inter-related. Moreover, the presence of aldehydes, such as glyoxal (CHOCHO), has a potential impact on radical cycling and secondary organic aerosol (SOA) formation in the MBL and free troposphere (FT). Model calculations suggest aldehydes to be an important sink for bromine atoms and hence competition for their reaction with O3 forming BrO and so illustrating a link between the cycles of halogens and OVOCs in the marine atmosphere. The main objective of this contribution is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens and OVOCs and their links using the latest version of the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. WRF-Chem is a highly flexible community model for atmospheric research where aerosol-radiation-cloud feedback processes are taken into account. Our current reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. The MOZART mechanism includes detailed gas-phase chemistry of CHOCHO formation as well as state-of-the-science pathways to form SOA. Oceanic emissions of aldehydes, including CHOCHO, and of organic halogens based on measurements from the TORERO campaign have been added into the model. Sea

  7. Heavy Rydberg behaviour in high vibrational levels of some ion-pair states of the halogens and inter-halogens

    Energy Technology Data Exchange (ETDEWEB)

    Donovan, Robert J., E-mail: R.Donovan@ed.ac.uk, E-mail: tr01@staffmail.ed.ac.uk; Lawley, Kenneth P., E-mail: k.p.lawley@ed.ac.uk; Ridley, Trevor, E-mail: R.Donovan@ed.ac.uk, E-mail: tr01@staffmail.ed.ac.uk [School of Chemistry, University of Edinburgh, Joseph Black Building, Edinburgh EH9 3FJ (United Kingdom)

    2015-05-28

    We report the identification of heavy Rydberg resonances in the ion-pair spectra of I{sub 2}, Cl{sub 2}, ICl, and IBr. Extensive vibrational progressions are analysed in terms of the energy dependence of the quantum defect δ(E{sub b}) rather than as Dunham expansions. This is shown to define the heavy Rydberg region, providing a more revealing fit to the data with fewer coefficients and leads just as easily to numbering data sets separated by gaps in the observed vibrational progressions. Interaction of heavy Rydberg states with electronic Rydberg states at avoided crossings on the inner wall of the ion-pair potential is shown to produce distinctive changes in the energy dependence of δ(E{sub b}), with weak and strong interactions readily distinguished. Heavy Rydberg behaviour is found to extend well below near-dissociation states, down to vibrational levels ∼18 000-20 000 cm{sup −1} below dissociation. The rapid semi-classical calculation of δ(E{sub b}) for heavy Rydberg states is emphasised and shows their absolute magnitude to be essentially the volume of phase space excluded from the vibrational motion by avoiding core-core penetration of the ions.

  8. Ground-based observations of Halogen Oxides in the Antarctic Boundary Layer

    Science.gov (United States)

    Prados-Roman, Cristina; Gómez, Laura; Puentedura, Olga; Navarro-Comas, Mónica; Ochoa, Héctor; Yela, Margarita

    2017-04-01

    Being involved in ozone destruction cycles, the halogen oxides (containing Br, Cl or I) are relevant reactants not only in the stratosphere but also in the troposphere. In order to characterize the presence of halogen oxides in the Antarctic boundary layer (BL), two MAX-DOAS instruments developed by INTA were installed at two different Antarctic sites: Marambio (64° S) and Belgrano (78° S). Note that, although both stations sit on pristine and remote locations, the surroundings of each station is unique and so is the atmospheric chemistry. Here we present the results of the measurements of BrO and IO performed in the sunlit atmosphere of both stations during 2015. We will focus on the activation of reactive bromine, its sources and sinks and its vertical distribution in the troposphere. We will also address the differences found regarding the bromine content of the BL in the two Antarctic sites. Moreover, we will investigate the presence of IO in the Antarctic BL.

  9. NanoSIMS50 - a powerful tool to elucidate cellular localization of halogenated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gutleb, Arno C.; Hoffmann, Lucien [Centre de Recherche Public - Gabriel Lippmann, Department Environment and Agro-biotechnologies (EVA), Belvaux (Luxembourg); Freitas, Jaime [Wageningen University, Toxicology Section, Wageningen (Netherlands); Murk, Albertinka J. [Wageningen University, Toxicology Section, Wageningen (Netherlands); Wageningen IMARES, P.O. Box 68, IJmuiden (Netherlands); Verhaegen, Steven; Ropstad, Erik [Norwegian School of Veterinary Science, Oslo (Norway); Udelhoven, Thomas [Centre de Recherche Public - Gabriel Lippmann, Department Environment and Agro-biotechnologies (EVA), Belvaux (Luxembourg); Trier University, Remote Sensing and Geoinformatics Department, Trier (Germany); Audinot, Jean-Nicolas [Centre de Recherche Public - Gabriel Lippmann, Departement Science et Analyse des Materiaux (SAM), Belvaux (Luxembourg)

    2012-11-15

    Persistent organic pollutants are widely distributed in the environment and lots of toxicological data are available. However, little is known on the intracellular fate of such compounds. Here a method applying secondary ion mass spectrometry is described that can be used to visualize cellular localization of halogenated compounds and to semi-quantitatively calculate concentrations of such compounds. Of the model compounds tested, TBBPA was homogenously distributed in the cell membrane of the H295R cells while PFOS accumulated in very distinct locations in the cell membrane. Relative intracellular concentrations of 4-OH-BDE69 and 4-OH-BDE121 in GH3.TRE were 61 % and 18 %, respectively, compared to the parent compounds. These differences may partly explain that observed effect concentrations for 4-OH-BDEs in in vitro experiments are usually lower than what would be expected based on receptor binding studies. NanoSIMS50 proved to be a powerful tool to describe the cellular distribution of halogenated compounds. The semi-quantitative data that can be obtained may help to further explain results from in vitro or in vivo experiments. (orig.)

  10. 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.

  11. The photodynamic therapy on Streptococcus mutans biofilms using erythrosine and dental halogen curing unit.

    Science.gov (United States)

    Lee, Young-Ho; Park, Ho-Won; Lee, Ju-Hyun; Seo, Hyun-Woo; Lee, Si-Young

    2012-12-01

    The purpose of our study was to evaluate the effect of photodynamic therapy (PDT), using erythrosine as a photosensitizing agent and a dental halogen curing unit as a light source, on Streptococcus mutans in a biofilm phase. The S. mutans biofilms were formed in a 24-well cell culture cluster. Test groups consisted of biofilms divided into four groups: group 1: no photosensitizer or light irradiation treatment (control group); group 2: photosensitizer treatment alone; group 3: light irradiation alone; group 4: photosensitizer treatment and light irradiation. After treatments, the numbers of colony-forming unit (CFU) were counted and samples were examined by confocal laser scanning fluorescence microscopy (CLSM). Only group 4 (combined treatment) resulted in significant increases in cell death, with rates of 75% and 55% after 8 h of incubation, and 74% and 42% at 12 h, for biofilms formed in brain-heart infusion (BHI) broth supplemented with 0% or 0.1% sucrose, respectively. Therefore, PDT of S. mutans biofilms using a combination of erythrosine and a dental halogen curing unit, both widely used in dental clinics, resulted in a significant increase in cell death. The PDT effects are decreased in biofilms that form in the presence of sucrose.

  12. Conformation stability, halogen and solvent effects on CO stretching of 4-chloro-3-halogenobenzaldehydes.

    Science.gov (United States)

    Tursun, Mahir; Parlak, Cemal

    2015-04-15

    The effects of halogen and solvent on the conformation and carbonyl stretching of 4-chloro-3-halogenobenzaldehydes [C7H4ClXO; X=F (CFB), Cl (CCB) or Br (CBB)] were investigated using the density functional theory (DFT) method. The B3LYP functional was used by the 6-311+G(3df,p) basis set in combination with the polarizable continuum model (PCM). Computations were focused on the cis and trans isomers of the compounds in 18 different polar or non-polar organic solvents. The theoretical frequencies of the solvent-induced CO stretching vibrations were correlated with the empirical solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, the solvent acceptor number (AN), Swain parameters and the linear solvation energy relationships (LSER). The present work explores the effect of both the halogen and medium on the conformational preference and CO vibrational frequency. The findings of this work can be useful to those systems involving changes in the conformations analogous to the compounds studied.

  13. Effect of halogen light in fetal stimulation for fetal well-being assessment.

    Science.gov (United States)

    Thanaboonyawat, Isarin; Wataganara, Tuangsit; Boriboonhiransarn, Dittakarn; Viboonchart, Sommai; Tontisirin, Pornpen

    2006-09-01

    To evaluate the shortening of the time of nonstress test (NST) by using transabdominal fetal stimulation with halogen light. Experimental research. The authors enrolled 176 pregnant women between 32 and 42 weeks of gestation indicated for NST at the Division of Maternal Fetal Medicine, Siriraj Hospital, Mahidol University. They were randomly assigned to receive either NST (control) or halogen light stimulation test (LST). The stimulation was performed at the beginning of the test and repeated every 10 minutes until reassuring fetal heart rate (FHR) acceleration was achieved, or up to 3 times. All tracings were interpreted blindly by one investigator at the end of the tests. The mean (+/- SD) duration from starting the test to the first FHR acceleration was not significantly different between the control group and the LST group (5.6 +/- 7.2 and 5.4 +/- 5.2 minutes, respectively). The average testing time (+/- SD) to achieved reactivity was 10.5 +/- 8.8 minutes in the controls and 9.6 +/- 6.7 minutes in the LST group. This was not statistically different. The incidence of nonreactive tests was not significantly different between the LST and the controls (15.9% and 11.4%, respectively). Among the LST subjects, term fetuses and women with BMI stimulation did not shorten the duration of NST in the presented population. However, the presented data suggests that the fetus at term could respond to visual stimulation, especially when the gestational age is more advanced.

  14. 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.

  15. Alkoxy substituted halogenated closo-dodecaborates as anions for ionic liquids.

    Science.gov (United States)

    Jenne, Carsten; Kirsch, Christoph

    2015-08-07

    Halogenated and alkoxylated closo-dodecaborates [B12X11OR](2-) (X = Cl, Br; R = propyl, octyl, dodecyl) have been synthesized by halogenation of the known [B12H11OH](2-) anion followed by alkylation in the superbasic medium DMSO/KOH. The obtained sodium salts were transformed by simple metathesis reactions in aqueous solution to the tetrabutylammonium ([NBu4](+)) and 1-hexyl-3-methylimidazolium ([C6mim](+)) salts. All compounds were fully characterized by heteronuclear NMR, IR and Raman spectroscopy, ESI mass spectrometry, and thermal analytical measurements. Selected anions were also structurally characterized as their [Ph4P](+) salts by single crystal X-ray diffraction. The [C6mim](+) salts are thermally stable up to more than 300 °C and show clear melting points. Surprisingly, the compound [C6mim]2[B12Cl11O-propyl] having the short propyl group bound to the boron cluster shows the lowest melting point (96 °C) of all the investigated compounds. Thus this compound is a rare member of the class of ionic liquids consisting of dianions.

  16. New halogenated disinfection byproducts in swimming pool water and their permeability across skin.

    Science.gov (United States)

    Xiao, Feng; Zhang, Xiangru; Zhai, Hongyan; Lo, Irene M C; Tipoe, George L; Yang, Mengting; Pan, Yang; Chen, Guanghao

    2012-07-01

    Chlorine is widely used for disinfecting public swimming pool water. The disinfectant chlorine, protecting swimmers from pathogenic infection in swimming, may be responsible for some adverse effects on swimmers' skin and health. In this study, numerous new halogenated disinfection byproducts (DBPs) in chlorinated pool water were detected with a powerful precursor ion scan method using electrospray ionization triple quadrupole mass spectrometry, with or without preseparation with ultra performance liquid chromatography. These new pool DBPs were demonstrated to be mainly halo(nitro)phenols, resulting from chlorination of human body substances (such as urine) in the presence of bromide. Among these new DBPs, 2,4-dibromophenol, 2,4-dichlorophenol, 2-bromophenol, 2,6-dibromo-4-nitrophenol, 2-bromo-6-chloro-4-nitrophenol, and 2,6-dichloro-4-nitrophenol were fully identified or confirmed. For 2,4-dibromophenol, 2,4-dichlorophenol and 2-bromophenol with pure standard compounds available, their permeability values across human skin were measured to be 0.031, 0.021, and 0.023 cm/h, respectively. The effects of chlorine on human skin were also investigated. The interaction of chlorine with epidermis was found to generate many new halogenated DBPs as well as common DBPs; the corneous layer was observed to become rough and even form larger pores after chlorine interaction. It is recommended that swimmers should avoid urinating in pools, and avoid prolonged swimming to reduce chlorine contact and prevent accelerated permeation of DBPs across skin.

  17. Role of intermolecular interaction in crystal packing: A competition between halogen bond and electrostatic interaction

    Science.gov (United States)

    Chen, Peng-Yuan; Zhang, Lin; Zhu, Shun-Guan; Cheng, Guang-Bin

    2017-03-01

    To investigate the competition between halogen bond and electrostatic interaction and their influence on the crystal packing, four novel solvates of 1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB) and 1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB) were synthesized while the intermolecular forces and the contribution of each interaction were analyzed quantitatively. The electrostatic interaction is the main link between TCTNB, TBTNB and 1,4-dioxane respectively, while π-π interaction dominates in these two solvates of TCTNB/1,4-dimethylbenzene (PX) and TCTNB/mesitylene. The solvate interaction changes and varieties were illuminated by Hirshfeld surface analysis, and the group contributions were illustrated respectively. Molecular electrostatic potential surface (MEPs) with density functional theory (DFT) calculation was performed to compare the relative strength of electrostatic interaction and halogen bond. The result shows that MEPs can be used as a descriptor for determining the most possible intermolecular interaction under certain circumstances. The study presented here may provide the guidance for the design and synthesis of the complex with desired properties.

  18. Measurements of reactive halogen species as oxidants of mercury over the Gulf of Mexico

    Science.gov (United States)

    Volkamer, R.; Coburn, S.; Dix, B. K.; Sinreich, R.; Terschure, A. F.; Edgerton, E. S.; Wu, Y.; Nair, U. S.

    2011-12-01

    The gas-phase reaction of bromine and chlorine radicals with gaseous elemental mercury (GEM) is a source for gaseous oxidized mercury (GOM). It has been established that oxidation by bromine is relevant at high latitudes, and can also occur in mid-latitude regions (Peleg et al. 2007), or in the free troposphere. A subject of ongoing debate concerns the role of free tropospheric bromine vs boundary layer bromine in oxidizing mercury. Here we present measurements of reactive halogen species bromine oxide (BrO) and iodine oxide (IO) along with gaseous oxidized mercury (GOM), gaseous elemental mercury (GEM), and particulate mercury (Hgp) at a coastal location in Gulf Breeze, Fl. The University of Colorado has deployed a research grade Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument to measure BrO, IO, as well as formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and oxygen dimers (O4). Here we present the compilation of the data collected by this instrument over the time period from May 2009 to January 2011, which include the first measurements of BrO, IO, and CHOCHO over the Gulf of Mexico. We also present several case studies for days where significant amounts of reactive halogens were measured, explore the sources and back trajectories of the air masses carrying these compounds, and relate our observations to mercury data collected at a nearby SEARCH network site.

  19. Molecular, vibrational and electronic structure of 4-bromo-2-halogenobenzaldehydes: Halogen and solvent effects

    Science.gov (United States)

    Fernández, David; Parlak, Cemal; Bilge, Metin; Kaya, Mehmet Fatih; Tursun, Mahir; Keşan, Gürkan; Rhyman, Lydia; Ramasami, Ponnadurai; Şenyel, Mustafa

    2017-09-01

    The halogen and solvent effects on the structure of 4-bromo-2-halogenobenzaldehydes [C7H4BrXO; X = F (BFB), Cl (BCB) or Br (BBB)] were investigated by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The B3LYP functional and HF and MP2 levels of theory were used with the 6-311+G(3df,p) or aug-cc-pVDZ basis sets. Computations were focused on the cis and trans conformers of the investigated compounds in the gas phase and solutions of 18 different polar or non-polar organic solvents. The computed frequencies of the C=O stretching vibration of the compounds were correlated with some empirical solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, solvent acceptor number (AN), Swain parameters and linear solvation energy relationships (LSERs). The electronic properties of the compounds were also examined. The present work explores the effects of the medium and halogen on the conformation, geometrical parameters, dipole moment, ν(C=O) vibration, UV data, frontier orbitals and density-of-states diagram of the compounds. The findings of this research can be useful for studies on benzaldehydes.

  20. Halogen content in Lesser Antilles arc volcanic rocks : exploring subduction recycling

    Science.gov (United States)

    Thierry, Pauline; Villemant, Benoit; Caron, Benoit

    2016-04-01

    Halogens (F, Cl, Br and I) are strongly reactive volatile elements which can be used as tracers of igneous processes, through mantle melting, magma differentiation and degassing or crustal material recycling into mantle at subduction zones. Cl, Br and I are higly incompatible during partial melting or fractional cristallization and strongly depleted in melts by H2O degassing, which means that no Cl-Br-I fractionation is expected through magmatic differenciation [current thesis]. Thus, Cl/Br/I ratios in lavas reflect the halogen content of their mantle sources. Whereas these ratios seemed quite constant (e.g. Cl/Br =300 as seawater), recent works suggest significant variations in arc volcanism [1,2]. In this work we provide high-precision halogen measurements in volcanic rocks from the recent activity of the Lesser Antilles arc (Montserrat, Martinique, Guadeloupe, Dominique). Halogen contents of powdered samples were determined through extraction in solution by pyrohydrolysis and analysed by Ion Chromatography for F and Cl and high performance ICP-MS (Agilent 8800 Tripe Quad) for Cl, Br and I [3,4]. We show that lavas - and mantle sources - display significant vraiations in Cl/Br/I ratios along the Lesser Antilles arc. These variations are compared with Pb, Nd and Sr isotopes and fluid-mobile elements (Ba, U, Sr, Pb etc.) compositions which vary along the arc from a nothern ordinary arc compositions to a southern 'crustal-like' composition [5,6]. These characteristics are attributed to subducted sediments recycling into the mantle wedge, whose contribution vary along the arc from north to south [7,8]. The proportion of added sediments is also related to the distance to the trench as sediment melting and slab dehydration may occur depending on the slab depth [9]. Further Cl-Br-I in situ measurements by LA-ICP-MS in Lesser Antilles arc lavas melt inclusions will be performed, in order to provide better constraints on the deep halogen recycling cycle from crust to

  1. Reactive Halogens in the Marine Boundary Layer (RHaMBLe: the tropical North Atlantic experiments

    Directory of Open Access Journals (Sweden)

    J. D. Lee

    2009-10-01

    Full Text Available The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period.

    This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental. Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv. Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of

  2. Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments

    Science.gov (United States)

    Lee, J. D.; McFiggans, G.; Allan, J. D.; Baker, A. R.; Ball, S. M.; Benton, A. K.; Carpenter, L. J.; Commane, R.; Finley, B. D.; Evans, M.; Fuentes, E.; Furneaux, K.; Goddard, A.; Good, N.; Hamilton, J. F.; Heard, D. E.; Herrmann, H.; Hollingsworth, A.; Hopkins, J. R.; Ingham, T.; Irwin, M.; Jones, C. E.; Jones, R. L.; Keene, W. C.; Lawler, M. J.; Lehmann, S.; Lewis, A. C.; Long, M. S.; Mahajan, A.; Methven, J.; Moller, S. J.; Müller, K.; Müller, T.; Niedermeier, N.; O'Doherty, S.; Oetjen, H.; Plane, J. M. C.; Pszenny, A. A. P.; Read, K. A.; Saiz-Lopez, A.; Saltzman, E. S.; Sander, R.; von Glasow, R.; Whalley, L.; Wiedensohler, A.; Young, D.

    2010-02-01

    The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol-1 and nmol mol-1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of

  3. Kinetic and product studies of Criegee intermediate reactions with halogenated and non-halogenated carboxylic acids and their implications in the troposphere

    Science.gov (United States)

    Chhantyal-Pun, Rabi; Rotavera, Brandon; Eskola, Arkke; Taatjes, Craig; Percival, Carl; Shallcross, Dudley; Orr-Ewing, Andrew

    2016-04-01

    Criegee intermediates are important species formed during the ozonolysis of alkenes. Direct measurement and modelling studies have shown that reactions of stabilized Criegee intermediates with species like SO2 and NO2 may have a significant effect in tropospheric chemistry.[1, 2] Reaction rates of Criegee intermediates with simple carboxylic acids like HCOOH and CH3COOH have been shown to be near the collision limit and may be a significant sink for these otherwise stable species in the atmosphere.[3, 4] Results obtained from our time-resolved Cavity Ring-Down Spectroscopy (CRDS) apparatus[5] for reactions of the Criegee intermediates, CH2OO and (CH3)2COO with various halogenated (CF3COOH, CF3CF2COOH, CClF2COOH and CHCl2COOH) and non-halogenated (HCOOH and CH3COOH) carboxylic acids will be presented, together with Structure Activity Relationship (SAR) based on these observations. Structure characterization of the products from these reactions using the Multiplexed PhotoIonization Mass Spectrometry (MPIMS) apparatus[1,3] as well as implications for Secondary Organic Aerosol (SOA) formation, assessed using the global atmospheric model STOCHEM, will also be discussed. Bibliography 1. O. Welz, J. D. Savee, D. L. Osborn, S. S. Vasu, C. J. Percival, D. E. Shallcross and C. A. Taatjes, Science, 2012, 335, 204-207. 2. C. J. Percival, O. Welz, A. J. Eskola, J. D. Savee, D. L. Osborn, D. O. Topping, D. Lowe, S. R. Utembe, A. Bacak, G. McFiggans, M. C. Cooke, P. Xiao, A. T. Archibald, M. E. Jenkin, R. G. Derwent, I. Riipinen, D. W. K. Mok, E. P. F. Lee, J. M. Dyke, C. A. Taatjes and D. E. Shallcross, Faraday Discuss., 2013, 165, 45-73. 3. O. Welz, A. J. Eskola, L. Sheps, B. Rotavera, J. D. Savee, A. M. Scheer, D. L. Osborn, D. Lowe, A. M. Booth, P. Xiao, M. A. H. Khan, C. J. Percival, D. E. Shallcross and C. A. Taatjes, Angew. Chem. Int. Ed., 2014, 53, 4547-4550. 4. M. D. Hurley, M. P. S. Andersen, T. J. Wallington, D. A. Ellis, J. W. Martin and S. A. Mabury, J. Phys. Chem. A

  4. Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals.

    Science.gov (United States)

    Carletta, Andrea; Spinelli, Floriana; d'Agostino, Simone; Ventura, Barbara; Chierotti, Michele R; Gobetto, Roberto; Wouters, Johan; Grepioni, Fabrizia

    2017-02-27

    N-Salicilideneanilines are among the most studied thermo- and photochromic systems in the solid state. Although thermochromism is a general property of crystalline N-salicilideneanilines, photochromism is known in a limited number of cases. As a method for the construction of thermo- and photo-responsive molecular architectures, the co-crystallisation of 1,2,4,5-tetrafluoro-3,6-diiodobenzene (I2F4) with three selected imines of o-vanillin, named 1, 2 and 3, obtained through a condensation reaction with 3-aminopyridine, 4-bromoaniline and 4-iodoaniline, respectively, is reported herein. All crystals and co-crystals have been characterised by means of solid-state complementary techniques (X-ray diffraction, solid-state NMR spectroscopy, absorption and emission spectroscopy). The role of halogen bonding and crystal packing in the optical and chromic properties of all solid materials is discussed. All solids exhibit thermochromic behaviour, and three of them (2, 22 ⋅I2F4 and 32 ⋅I2F4) are also photochromic. Imine derivative 3 crystallises in two different polymorphic forms (3 A and 3 B) and a solvate (3Solv ). The bromo and iodo derivatives, 2 and 3 B, are isomorphous and form isomorphous co-crystals with I2F4, but behave differently when exposed to UV light because only crystalline 2 is photochromic. Interestingly, the replacement of bromine with iodine seems to turn off the photochromism because crystalline 3 A and 3Solv , and even the 20.7 30.3 solid solution, do not manifest photochromic behaviour.

  5. Dramatic effects of halogen substitution and solvent on the rates and mechanisms of nucleophilic substitution reactions of aziridines.

    Science.gov (United States)

    Banks, Harold D

    2008-04-04

    In a previous study we reported that fluorine substitution at the carbon positions of aziridine results in profound enhancements of the rate of reaction with ammonia, a typical nucleophile, in the gas phase. In this study the investigation is extended to include chloro- and bromoaziridines. Because syntheses are largely performed in the condensed phase, the present computational investigation [(MP2(Full)/6-311++G(d,p)//MP2(Full)/6-31+G(d) level] was conducted with three typical solvents that cover a wide range of polarity: THF, CH3CN, and H2O. Nucleophiles can react with haloaziridines 1 by displacing a substituted amide ion by means of an SN2 mechanism (pathway a), producing 1,2-diaminohaloethanes (from the initially formed dipolar species 2). Alternatively, a rearrangement mechanism involving rate-determining departure of a halide ion (pathway b) to form an imidoyl halide, 3, is possible. Transition-state theory was used to compute relative reaction rates of these mechanistic possibilities and to assess the role of the halogen substituents and the reaction solvent. Gas-phase results provided the basis of mechanistic insights that were more apparent in the absence of intermolecular interactions. Fluoroaziridines were found to react at accelerated rates relative to aziridine exclusively by means of the a Menshutkin-type mechanism (SN2) in each solvent tested, while the reactions of the chloro- and bromoaziridines could be directed toward 2 in the highly nonpolar solvent, cyclohexane, or toward 3 in the more polar solvents. An assessment is made of the feasibility of using this chemistry of the haloazirdines in the synthetic laboratory.

  6. Cumulative health risk assessment of halogenated and parent polycyclic aromatic hydrocarbons associated with particulate matters in urban air.

    Science.gov (United States)

    Sun, Jian-Lin; Jing, Xin; Chang, Wen-Jing; Chen, Zheng-Xia; Zeng, Hui

    2015-03-01

    Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur widely in urban air. Nevertheless, knowledge about the human health risk associated with inhalation exposure to HPAHs is scarce so far. In the present study, nine HPAHs and 16 PAHs were determined in atmospheric particulate matter (PM) collected from Shenzhen, China to address this issue. Concentrations of Σ9HPAHs varied from 0.1 to 1.5 ng/m(3) and from 0.09 to 0.4 ng/m(3) in PM10 and PM2.5 samples, respectively. As for individuals, 9-bromoanthracene, 7-bromobenz(a)anthracene, and 9,10-dibromoanthracene were the dominant congeners. Levels of Σ16PAHs in PM10 and PM2.5 samples ranged from 3.2 to 81 ng/m(3) and from 2.8 to 85 ng/m(3), respectively. Among individual PAHs, chrysene, benzo[b]fluoranthene, and indeno[1,2,3-c,d]pyrene were the main congeners. According to the season, concentrations of HPAHs and PAHs in atmospheric PM10/PM2.5 samples show a similar decreasing trend with an order: winter>autumn>spring>summer. The daily intake (DI) of PM10/PM2.5-bound HPAHs and PAHs were estimated. Our results indicated that children have the highest DI levels via inhalation exposure. The incremental lifetime cancer risk (ILCR) induced by PM10/PM2.5-bound HPAHs and PAHs were calculated. The ILCR values showed a similar decreasing trend with an order: adults>children>seniors>adolescent. Overall, the ILCR values induced by HPAHs and PAHs were far below the priority risk level (10(-4)), indicating no obvious cancer risk. To our knowledge, this is the first study to investigate the human health risk associated with inhalation exposure to PM10/PM2.5-bound HPAHs.

  7. The halogen (F, Cl, Br, I) and H2O systematics of Samoan lavas: Assimilated-seawater, EM2 and high-3He/4He components

    Science.gov (United States)

    Kendrick, Mark A.; Jackson, Matthew G.; Hauri, Erik H.; Phillips, David

    2015-01-01

    The Samoan mantle plume samples two or more mantle components including an extreme EM2 composition with 87Sr/86Sr > 0.720 and a primitive component with high 3He/4He. The high 87Sr/86Sr melts have a unique potential to constrain the composition of the EM2 mantle end-member that is commonly attributed to subduction recycling. However, a previous study of H2O, CO2, S, F and Cl in Samoan glasses was hampered by the presence of unresolved assimilated sea water. The current study builds on the earlier work by extending the volatile database to include the trace halogens Br and I, and reporting new volatile data for additional glasses with 87Sr/86Sr up to 0.7125 and 3He/4He up to 15 Ra (Ra is the atmospheric 3He/4He ratio of 1.39 ×10-6). The selected glasses with MgO of 4.0 to 6.5 wt.% have CO2 concentrations of 4 to 200 ppm that reflect degassing of CO2 on the seafloor. The glasses contain 0.7-1.9 wt.% H2O, 880-1870 ppm F, 490-1790 ppm Cl, 1.9-7.2 ppm Br, 19-130 ppb I and 0.6-1.7 wt.% K. Correlations between the concentrations of these elements suggest the melts retain H2O concentrations close to pre-degassing values and demonstrate the melts have been variably affected by assimilation of seawater-derived brines. The brines are indicated to have had salinities of 55 ± 15 wt.% salt, F/Cl ratios close to seawater (e.g. calculated the melts assimilated brine fractions of 0 to 0.45 wt.%, which contributed up to ∼30% of the total H2O and up to ∼70% of the total Cl in the melts. After accounting for the effects of brine assimilation, the Samoan melts are suggested to have a fairly constant magmatic Cl/K of 0.05 ± 0.2, which is lower than the median MORB value. Assimilation-corrected H2O/Ce values are not correlated with 87Sr/86Sr, but the sample with the highest 87Sr/86Sr of 0.7125 has an assimilation-corrected H2O/Ce of 83 ± 3, that is significantly lower than typical MORB values of 150-300. These data confirm that the Samoan EM2 source is depleted in H2O, and

  8. Headspace GC-MS Analysis of Halogenated Volatile Organic Compounds in Aqueous Samples: An Experiment for General Chemistry Laboratory

    Science.gov (United States)

    Keller, John W.; Fabbri, Cindy E.

    2012-01-01

    Analysis of halogenated volatile organic compounds (HVOCs) by GC-MS demonstrates the use of instrumentation in the environmental analysis of pollutant molecules and enhances student understanding of stable isotopes in nature. In this experiment, students separated and identified several HVOCs that have been implicated as industrial groundwater…

  9. A new halogen-free chemical oscillator: the reaction between permanganate ion and ninhydrin in a continuously stirred tank reactor

    Science.gov (United States)

    Treindl, Ľudovít; Nagy, Arpád

    1987-07-01

    The reaction between permanganate ion and ninhydrin in the presence of phosphoric acid in aqueous solution shows sustained oscillations in a continuously stirred tank reactor (CSTR). It exhibits a kinetic bistability between an oscillatory and a stationary state. Our new oscillating system seems to be a second permanganate chemical oscillator, thus broadening the small group of non-halogen-based chemical oscillators.

  10. A study of the hydration of deoxydinucleoside monophosphates containing thymine, uracil and its 5-halogen derivatives: Monte Carlo simulation.

    Science.gov (United States)

    Alderfer, J L; Danilov, V I; Poltev, V I; Slyusarchuk, O N

    1999-04-01

    An extensive Monte Carlo simulation of hydration of various conformations of the dinucleoside monophosphates (DNP), containing thymine, uracil and its 5-halogen derivatives has been performed. An anti-anti conformation is the most energetically stable one for each of the DNPs. In the majority of cases the energy preference is determined by water-water interaction. For other dimers conformational energy is the most important factor, or both the factors are of nearly equal importance. The introduction of the methyl group into the 5-position of uracil ring most noticeably influences the conformational energy and leads to the decrease of its stabilizing contribution to the total interaction energy. The introduction of halogen atoms increases the relative content of anti-syn and syn-anti conformations of DNPs as compared to the parent ones due to the formation of an energetically more favorable water structure around these conformations. A correlation is observed between the Monte Carlo results for the halogenated DNPs and their experimental photoproduct distribution. The data obtained demonstrates a sequence dependence in the photochemistry of the halogenated dinucleoside monophosphates.

  11. Large area inkjet printing for organic photovoltaics and organic light emitting diodes using non-halogenated ink formulations

    NARCIS (Netherlands)

    Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, M.W.L.; Groen, W.A.

    2014-01-01

    The transfer of laboratory scale solution processing of organic electronics to large area roll-to-roll production requires the use of up-scalable deposition techniques. Furthermore, industrial production demands the omission of halogenated and other harmful solvents. Here, the authors discuss large

  12. Performance of the wet oxidation unit of the HPLC isotope ratio mass spectrometry system for halogenated compounds.

    Science.gov (United States)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2014-08-05

    The performance of liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ(13)C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ(13)C(EA/LC-IRMS) = 8.8‰, TFA Δδ(13)C(EA/LC-IRMS) = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ(13)C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment.

  13. Halogen-bonding for visual chloride ion sensing: a case study using supramolecular poly(aryl ether) dendritic organogel systems.

    Science.gov (United States)

    Liu, Zhi-Xiong; Sun, Yihua; Feng, Yu; Chen, Hui; He, Yan-Mei; Fan, Qing-Hua

    2016-02-07

    A convenient and straightforward method for the visual recognition of chloride ion has been established through a chloride-responsive dendritic organogel. The specificity was largely attributed to the higher binding affinity of the dendritic gelator for chloride compared with other anions through halogen bonding interactions.

  14. Influence of halogen irradiance on short- and long-term wear resistance of resin-based composite materials.

    LENUS (Irish Health Repository)

    Bhamra, Gurcharn S

    2009-02-01

    The Oregon Health Science University (OHSU) four-chamber oral wear simulator was used to examine the impact of halogen irradiance on the short- and long-term wear behavior of four-methacrylate resin-based composites (RBCs). The hypothesis proposed was that exacerbated wear would occur following the long-term wear of RBCs irradiated under non-optimized irradiance conditions.

  15. Intermolecular charge flux as the origin of infrared intensity enhancement upon halogen-bond formation of the peptide group

    Science.gov (United States)

    Torii, Hajime

    2010-07-01

    The changes in the vibrational properties of the peptide group upon formation of O⋯X and N⋯X halogen bonds are studied theoretically. Calculations are carried out for complexes of N-methylacetamide (NMA), a well known model molecule of the peptide group, with halogen-containing molecules. For comparison, calculations are also carried out for some NMA-water hydrogen-bonding complexes. It is shown that the infrared (IR) intensity of the amide I mode of the peptide group is enhanced significantly (up to about 520 km mol-1 or 2.6 times) upon CO⋯X halogen-bond formation, in spite of rather modest magnitudes of the intermolecular electric field and of the changes in the CO bond length and in the amide I vibrational frequency as compared with the cases of the CO⋯H(D) hydrogen bonding. From the analysis of the changes in the dipole derivative and in the electronic structure, it is shown that this IR intensity enhancement arises from the intermolecular charge flux. For the N⋯X halogen bonding complexes, some characteristic changes in the vibrational properties are seen, among which the IR intensity enhancement of the ND out-of-plane wagging mode is most notable. The reason why such large IR intensity enhancements are seen for these particular vibrational modes is examined.

  16. Comparative efficiency of plasma and halogen light sources on composite micro-hardness in different curing conditions

    OpenAIRE

    Dietschi, Didier; Marret, N; Krejci, Ivo

    2003-01-01

    Recent developments have led to the introduction of high power curing lights, which are claimed to greatly reduce the total curing time. This study evaluated the effectiveness of a plasma-curing device (Apollo 95 E) and a halogen device (Heliolux DLX), in different curing conditions.

  17. Halogen bonding from a hard and soft acids and bases perspective: investigation by using density functional theory reactivity indices.

    Science.gov (United States)

    Pinter, Balazs; Nagels, Nick; Herrebout, Wouter A; De Proft, Frank

    2013-01-07

    Halogen bonds between the trifluoromethyl halides CF(3)Cl, CF(3)Br and CF(3)I, and dimethyl ether, dimethyl sulfide, trimethylamine and trimethyl phosphine were investigated using Pearson's hard and soft acids and bases (HSAB) concept with conceptual DFT reactivity indices, the Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework and the non-covalent interaction (NCI) index. It is found that the relative importance of electrostatic and orbital (charge transfer) interactions varies as a function of both the donor and acceptor molecules. Hard and soft interactions were distinguished and characterised by atomic charges, electrophilicity and local softness indices. Dual-descriptor plots indicate an orbital σ hole on the halogen similar to the electrostatic σ hole manifested in the molecular electrostatic potential. The predicted high halogen-bond-acceptor affinity of N-heterocyclic carbenes was evidenced in the highest complexation energy for the hitherto unknown CF(3) I·NHC complex. The dominant NOCV orbital represents an electron-density deformation according to a n→σ*-type interaction. The characteristic signal found in the reduced density gradient versus electron-density diagram corresponds to the non-covalent interaction between contact atoms in the NCI plots, which is the manifestation of halogen bonding within the NCI theory. The unexpected C-X bond strengthening observed in several cases was rationalised within the molecular orbital framework. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Large area inkjet printing for organic photovoltaics and organic light emitting diodes using non-halogenated ink formulations

    NARCIS (Netherlands)

    Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, M.W.L.; Groen, W.A.

    2014-01-01

    The transfer of laboratory scale solution processing of organic electronics to large area roll-to-roll production requires the use of up-scalable deposition techniques. Furthermore, industrial production demands the omission of halogenated and other harmful solvents. Here, the authors discuss large

  19. 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

  20. Study of the Halogen Bonding between Pyridine and Perfluoroalkyl Iodide in Solution Phase Using the Combination of FTIR and 19F NMR

    Directory of Open Access Journals (Sweden)

    Briauna Hawthorne

    2013-01-01

    Full Text Available Halogen bonding between pyridine and heptafluoro-2-iodopropane (iso-C3F7I/heptafluoro-1-iodopropane (1-C3F7I was studied using a combination of FTIR and 19F NMR. The ring breathing vibration of pyridine underwent a blue shift upon the formation of halogen bonds with both iso-C3F7I and 1-C3F7I. The magnitudes of the shifts and the equilibrium constants for the halogen-bonded complex formation were found to depend not only on the structure of the halocarbon, but also on the solvent. The halogen bond also affected the Cα-F (C-F bond on the center carbon bending and stretching vibrations in iso-C3F7I. These spectroscopic effects show some solvent dependence, but more importantly, they suggest the possibility of intermolecular halogen bonding among iso-C3F7I molecules. The systems were also examined by 19F NMR in various solvents (cyclohexane, hexane, chloroform, acetone, and acetonitrile. NMR dilution experiments support the existence of the intermolecular self-halogen bonding in both iso-C3F7I and 1-C3F7I. The binding constants for the pyridine/perfluoroalkyl iodide halogen bonding complexes formed in various solvents were obtained through NMR titration experiments. Quantum chemical calculations were used to support the FTIR and 19F NMR observations.

  1. Halogenated MOF-5 variants show new configuration, tunable band gaps and enhanced optical response in the visible and near infrared.

    Science.gov (United States)

    Yang, Li-Ming; Fang, Guo-Yong; Ma, Jing; Pushpa, Raghani; Ganz, Eric

    2016-11-30

    Inspired by recent experimental fabrication of mono-halogenated versions of Metal-Organic Framework MOF-5 (i.e., X-MOF-5, X = F to I) and some experimentally known fully halogenated MOF compounds, we systematically studied frameworks incorporating full halogenation of the BDC linkers of the prototypical Iso-Reticular Metal-Organic Framework (IRMOF) series, exemplified by MOF-5. Using quantum chemistry calculations, we find that halogenation leads to a 90° rotation of the aryl group, which is mainly ascribed to overcrowding between halogen atoms and the carboxyl and benzene ring and strong repulsion among in-plane atoms/groups. The 90° configuration decreases the repulsion, and maximizes the stabilization energy, and is therefore more stable than 0° configuration. We find that the band gap can be tuned from 4.1 to 1.5 eV as we go from F, Cl, Br, to I. This extends the optical response of these experimentally accessible materials through the visible and infrared region. We have also considered a broader range of new materials that substitute various metals for Zn. Totally, 70 materials were systematically examined computationally including (M4O)(BDC-Z4)3 (M = Zn, Cd, Be, Mg, Ca, Sr, Ba; Z = H, F, Cl, Br, I). For the full range of materials, we calculate band gaps of 4.2 to 1.0 eV, corresponding to a threshold of absorption of 290-1240 nm. Four selected materials were tested for stability using short 5 ps molecular dynamics simulations up to 600 K. The new materials with the smallest band gaps could potentially be used in near-infrared (NIR) light-emitting devices. Other properties, e.g., bulk moduli, formation energy, chemical bonding, and optical properties, were also investigated. The present results may provide new materials for use as novel photocatalysts, photoactive materials for photovoltaic cells, or functional devices in nanoelectronics and optoelectronics.

  2. 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.

  3. Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Mó, Otilia; Yáñez, Manuel; Del Bene, Janet E

    2015-01-21

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the structures, binding energies, and bonding characteristics of binary complexes HFBe:FCl, R2Be:FCl, and FCl:N-base, and of ternary complexes HFBe:FCl:N-base and R2Be:FCl:N-base for R = H, F, Cl; N-base = NH3, NHCH2, NCH. Dramatic synergistic cooperative effects have been found between the Be···F beryllium bonds and the Cl···N halogen bonds in ternary complexes. The Cl···N traditional halogen bonds and the Be···F beryllium bonds in binary complexes become significantly stronger in ternary complexes, while the F-Cl bond weakens. Charge-transfer from F to the empty p(σ) orbital of Be leads to a bending of the XYBe molecule and a change in the hybridization of Be, which in the limit becomes sp(2). As a function of the intrinsic basicity of the nitrogen base and the intrinsic acidity of the Be derivative, the halogen-bond type evolves from traditional to chlorine-shared to ion-pair bonds. The mechanism by which an ion-pair complex is formed is similar to that involved in the dissociative proton attachment process. EOM-CCSD spin-spin coupling constants (1X)J(Cl-N) across the halogen bond in these complexes also provide evidence of the same evolution of the halogen-bond type.

  4. 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

  5. Xenon and halogenated alkanes track putative substrate binding cavities in the soluble methane monooxygenase hydroxylase.

    Science.gov (United States)

    Whittington, D A; Rosenzweig, A C; Frederick, C A; Lippard, S J

    2001-03-27

    To investigate the role of protein cavities in facilitating movement of the substrates, methane and dioxygen, in the soluble methane monooxygenase hydroxylase (MMOH), we determined the X-ray structures of MMOH from Methylococcus capsulatus (Bath) cocrystallized with dibromomethane or iodoethane, or by using crystals pressurized with xenon gas. The halogenated alkanes bind in two cavities within the alpha-subunit that extend from one surface of the protein to the buried dinuclear iron active site. Two additional binding sites were located in the beta-subunit. Pressurization of two crystal forms of MMOH with xenon resulted in the identification of six binding sites located exclusively in the alpha-subunit. These results indicate that hydrophobic species bind preferentially in preexisting cavities in MMOH and support the hypothesis that such cavities may play a functional role in sequestering and enhancing the availability of the physiological substrates for reaction at the active site.

  6. Highly interpenetrated supramolecular networks supported by N...I halogen bonding.

    Science.gov (United States)

    Metrangolo, Pierangelo; Meyer, Franck; Pilati, Tullio; Proserpio, Davide M; Resnati, Giuseppe

    2007-01-01

    Halogen bonding (XB) has been used to assemble tetrakis(4-pyridyl)pentaerythritol (tetradentate XB acceptor) with different alpha,omega-diiodoperfluoroalkanes (bidentate XB donors) or tetrakis(4-iodotetrafluorophenyl)pentaerythritol (tetradentate XB donor). The remarkable linearity of the XB formed, the rodlike character of alpha,omega-diiodoperfluoroalkanes and the mutual complementarities of pentaerythritol partners, translate the three-dimensional character of the XB acceptor into open primary networks, which interpenetrate to avoid the presence of voids and to ensure segregation of the modules. Two-dimensional (2D) square 4(4) layers (sql) with fourfold and fivefold interpenetration, as well as an eightfold diamondoid network (dia) of class Ia and a remarkable tenfold dia network of class IIIa, have been obtained.

  7. Synthesis and Application of a Novel Polyamide Charring Agent for Halogen-Free Flame Retardant Polypropylene

    Directory of Open Access Journals (Sweden)

    Jie Liu

    2013-01-01

    Full Text Available A novel charring agent, poly(p-ethylene terephthalamide (PETA, for halogen-free flame retardant polypropylene was synthesized by using p-phthaloyl chloride (TPC and ethylenediamine through solution polycondensation at low temperature, and the effects of PETA on flame retardance of polypropylene (PP/IFR systems were studied. The experimental results showed that PETA could considerably enhance the fire retardant performance as proved by evidence of the increase of limiting oxygen index (LOI values, the results of UL-94 tests, and cone calorimeter tests (CCT. Fourier transform infrared spectroscopy (FTIR and scanning electron microscope (SEM demonstrated that an appropriate amount of PETA could react with PP/IFR system to form cross-link network; a more compact char layer could be formed which was responsible for the improved thermal and flame retardant properties of PP/IFR systems. However, the superfluous amount of PETA would play the negative role.

  8. Halogenated Sesquiterpenoids from the Red Alga Laurencia tristicha Collected in Taiwan.

    Science.gov (United States)

    Chen, Jia-Yu; Huang, Chiung-Yao; Lin, Yun-Sheng; Hwang, Tsong-Long; Wang, Wei-Lung; Chiou, Shu-Fen; Sheu, Jyh-Horng

    2016-09-23

    Chemical investigation of the red alga Laurencia tristicha led to the discovery of eight new halogenated chamigrane-type sesquiterpenoids (1-8) and one new bromocuparane-type sesquiterpene (9), along with nine known related metabolites (10-18). Their structures were elucidated on the basis of extensive spectroscopic analyses, and the absolute configurations of 1-8 were proposed by comparison to the biosynthetically related known compound 12. Cytotoxicity, antibacterial, and anti-inflammatory activities of these isolates were also investigated. The results showed that compound 11 exhibited good antibacterial activity against Serratia marcescens compared to the positive control ampicillin at a dosage of 100 μg/disk. Compound 17 showed strong inhibition toward elastase release generation at 10 μM.

  9. Investigations of Buffer-Gases Role in Xenon and Halogen Excimer Mixtures

    Science.gov (United States)

    Ciobotaru, L. C.; Porosnicu, C.

    2010-10-01

    Excimer- is an acronym in use for the excited dimmer, molecule which does not exist in the ground state but only in an excited state. This paper presents the role of the buffer-gas atoms (Ar, Ne, He), in the (Cl2/I2 Xe) excimer radiation emission mechanisms. The same buffer-gas produced a different effect on the excimer emission intensity: the neon and argon addition to xenon/chlorine/iodine had a negative effect while the helium and neon addition had a positive effect. The Penning reactions play an important role in the excimer radiation generation in connection with the gas-buffer addition and the halogen ionization potential value. The measurements are performed using a dielectric barrier discharge (DBD) at moderate pressure in a panel, respectively classic coaxial geometry.

  10. 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...... process of the compounds was pseudo-firstorder. Transformation rate constants, referring to the water phase and normalized to 1 m2 iron surface/mL, of up to 1100 mL m-2 h-1 (batch) and 200 mL m-2 h-1 (flowthrough) were found. The transformation was strongly dependent on pH and the presence of oxygen....... 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....

  11. Halogen effect on structure and 13C NMR chemical shift of 3,6-disubstituted-N-alkyl carbazoles

    DEFF Research Database (Denmark)

    Radula-Janik, Klaudia; Kupka, Teobald; Ejsmont, Krzysztof

    2013-01-01

    Structures of selected 3,6-dihalogeno-N-alkyl carbazole derivatives were calculated at the B3LYP/6-311++G(3df,2pd) level of theory and their 13C NMR isotropic nuclear shieldings were predicted using density functional theory (DFT). The model compounds contained 9H-, N-methyl and N-ethyl derivatives......). The decreasing electronegativity of the halogen substituent (F, Cl, Br and I) was reflected in both nonrelativistic and relativistic NMR results as decreased values of chemical shifts of carbon atoms attached to halogen (C3 and C6) leading to a strong sensitivity to halogen atom type at 3 and 6 positions...

  12. Effects of halogenated dibenzo-p-dioxins on the growth of grassy plants: Determination of hazards in mammals fed with contaminated biomass

    Energy Technology Data Exchange (ETDEWEB)

    Kuntsevich, A.D.; Golovkov, V.F.; Chernov, S.A. [Center for Ecotoximetry, Moscow (Russian Federation)] [and others

    1995-03-01

    Halogenated dibenzo-p-dioxins are known to be constant factors of environmental pollution. They are polytropic cell venoms capable of accumulating in the organic matter of the biosphere and being redistributed along food chains. This work was designed to study the dynamics of plant growth in the presence of halogenated dibenzo-p-dioxins and to evaluate the risk incurred by mammals feeding on the contaminated photomass. Our data suggest that halogenate dibenzo-p-dioxins can act as systemic regulators of plant growth. The compound can be transferred by the plant vascular system, a process that makes them toxic and hazardous to mammals. 3 refs., 1 fig., 1 tab.

  13. Co-existing Intermolecular Halogen Bonding and Hydrogen Bonding in the Compound Trans-5,10-bis(1-bromodifluoroacetyl-1-ethoxycarbonyl-methylidene)thianthrene

    Institute of Scientific and Technical Information of China (English)

    ZHU Shi-Fa祝诗发; ZHU Shi-Zheng朱士正; LIAO Yuan-Xi廖远熹; HUANG Chao-Feng黄超峰; LI Zhan-Ting黎占亭

    2004-01-01

    Trans-5,10-bis(1-bromodifluoroacetyl-1-ethoxycarbonyl-methylidene)thianthrene (1b) was prepared from the reaction of BrCF2COC(N2)CO2Et with thianthrene. X-ray single crystal diffraction analysis showed that the intermolecular halogen bonding and hydrogen bonding coexisted in this compound. The bromine atom acted as an electron acceptor in the halogen bond and an electron donor in the hydrogen bond. It is the first example that the bromine atom acted as such a dual role in the hydrogen and halogen bond.

  14. Mutation of ras Genes Induced by 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H] - furanone in Human Fetal Hepatocytes%3-氯-4-二氯甲基-5-羟基-2(5氢)-呋喃酮诱导人胚胎肝细胞ras基因突变

    Institute of Scientific and Technical Information of China (English)

    周利红; 刘爱林; 鲁文清

    2006-01-01

    背景与目的: 研究饮水氯化消毒副产物 3-氯 -4-二氯甲基 -5-羟基 -2(5氢 )-呋喃酮 (3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone, MX)对体外培养的人胚胎肝细胞 (L-02细胞 )ras基因突变的诱导. 材料与方法: MX染毒剂量为 300μ mol/L,以二甲基亚砜 (DMSO)做溶剂对照,将 L-02细胞连续染毒培养12d后,收获细胞提取基因组 DNA,应用 PCR-克隆测序法检测 ras基因 (K-ras、 H-ras、 N-ras) 12、13、61密码子是否存在突变. 结果: MX染毒组 H-ras基因 57密码子的 GAT置换成 GGT,未检测到K-ras、N-ras及H-ras12、13、61密码子突变,DMSO溶剂对照组相应的 ras基因目的片段均未检测到突变.结论:MX可能诱导L-02细胞ras基因突变.

  15. In vitro and in vivo studies of the effects of halogenated histidine analogs on Plasmodium falciparum.

    Science.gov (United States)

    Panton, L J; Rossan, R N; Escajadillo, A; Matsumoto, Y; Lee, A T; Labroo, V M; Kirk, K L; Cohen, L A; Aikawa, M; Howard, R J

    1988-11-01

    The effects of four halogenated analogs of histidine on in vitro growth of Plasmodium falciparum malaria parasites were monitored by measurement of the incorporation of 3H-labeled amino acids into parasite proteins and by light and electron microscopy. The uptake of [3H]isoleucine was reduced to 50% of the control value by addition of 70 microM 2-fluoro-L-histidine (2-F-HIS) or 420 microM 2-iodo-L-histidine (2-I-HIS). [3H]histidine uptake into acid-insoluble material was affected equally by these two compounds, 50% inhibition resulting at 200 microM concentration. Morphological analysis of parasite development proved a sensitive assay, since development of mature trophozoites was inhibited 50% by 25 microM 2-F-HIS or 100 2-I-HIS. Electron microscopy studies suggested different mechanisms of action of 2-F-HIS and 2-I-HIS on P. falciparum. 2-F-HIS produced a decrease in knob number at the erythrocyte surface and accumulation of electron-dense material under the parasite membrane. 2-I-HIS had no obvious effect on knobs or electron-dense material but affected parasite morphology. Surprisingly, 2-chloro-L-histidine and 2-bromo-L-histidine did not inhibit P. falciparum in vitro, even though their halogen atom substituents are intermediate in size between F and I atoms. 2-F-HIS and 2-I-HIS were tested in vivo against P. falciparum in owl monkeys (Aotus sp.) but were ineffective at doses that were nontoxic.

  16. Halogen species record Antarctic sea ice extent over glacial–interglacial periods

    Directory of Open Access Journals (Sweden)

    A. Spolaor

    2013-07-01

    Full Text Available Sea ice is an integral part of the earth's climate system because it affects planetary albedo, sea-surface salinity, and the atmosphere–ocean exchange of reactive gases and aerosols. Bromine and iodine chemistry is active at polar sea ice margins with the occurrence of bromine explosions and the biological production of organoiodine from sea ice algae. Satellite measurements demonstrate that concentrations of bromine oxide (BrO and iodine oxide (IO decrease over sea ice toward the Antarctic interior. Here we present speciation measurements of bromine and iodine in the TALDICE (TALos Dome Ice CorE ice core (159°11' E, 72°49' S; 2315 m a.s.l. spanning the last 215 ky. The Talos Dome ice core is located 250 km inland and is sensitive to marine air masses intruding onto the Antarctic Plateau. Talos Dome bromide (Br− is positively correlated with temperature and negatively correlated with sodium (Na. Based on the Br−/Na seawater ratio, bromide is depleted in the ice during glacial periods and enriched during interglacial periods. Total iodine, consisting of iodide (I− and iodate (IO3−, peaks during glacials with lower values during interglacial periods. Although IO3− is considered the most stable iodine species in the atmosphere it was only observed in the TALDICE record during glacial maxima. Sea ice dynamics are arguably the primary driver of halogen fluxes over glacial–interglacial timescales, by altering the distance between the sea ice edge and the Antarctic plateau and by altering the surface area of sea ice available to algal colonization. Based on our results we propose the use of both halogens for examining Antarctic variability of past sea ice extent.

  17. Biogenic halocarbons from coastal oceanic upwelling regions as tropospheric halogen source

    Science.gov (United States)

    Krüger, Kirstin; Fuhlbrügge, Steffen; Hepach, Helmke; Fiehn, Alina; Atlas, Elliot; Quack, Birgit

    2016-04-01

    Halogenated very short lived substances (VSLS) are naturally produced in the ocean and emitted to the atmosphere. Recently, oceanic upwelling regions in the tropical East Atlantic were identified as strong sources of brominated halocarbons to the troposphere. During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian Upwelling for the first time. This study presents novel observations of the three VSLS bromoform, dibromomethane and methyl iodide together with high resolution meteorological measurements and Lagrangian transport modelling. Although relatively low oceanic emissions were observed, except for methyl iodide, surface atmospheric abundances were elevated. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting both as strong barriers for convection and trace gas transport in this region. Significant correlations between observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height were found. We used a simple source-loss estimate to identify the contribution of oceanic emissions to observed atmospheric concentrations which revealed that the observed marine VSLS abundances were dominated by horizontal advection below the trade inversion. The observed VSLS variations can be explained by the low emissions and their accumulation under different MABL and trade inversion conditions. Finally, observations from a second Peruvian Upwelling cruise with R/V SONNE during El Nino in October 2015 will be compared to highlight the role of different El Nino Southern Oscillation conditions. This study confirms the importance of coastal oceanic upwelling and trade wind systems on creating effective transport barriers in the lowermost atmosphere controlling the distribution of VSLS abundances above coastal ocean upwelling

  18. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS: THE NEW X-WAND HVOC SCREENING DEVICE

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Susan S. Sorini; Joseph F. Rovani Jr

    2006-03-01

    Western Research Institute (WRI) has developed new methodology and a test kit to screen soil or water samples for halogenated volatile organic compounds (HVOCs) in the field. The technology has been designated the X-Wand{trademark} screening tool. The new device uses a heated diode sensor that is commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. This sensor is selective to halogens. It does not respond to volatile aromatic hydrocarbons, such as those in gasoline, and it is not affected by high humidity. In the current work, the heated diode leak detectors were modified further to provide units with rapid response and enhanced sensitivity. The limit of detection for trichloroethylene TCE in air is 0.1 mg/m{sup 3} (S/N = 2). The response to other HVOCS relative to TCE is similar. Variability between sensors and changes in a particular sensor over time can be compensated for by normalizing sensor readings to a maximum sensor reading at 1,000 mg/m{sup 3} TCE. The soil TCE screening method was expanded to include application to water samples. Assuming complete vaporization, the detection limit for TCE in soil is about 1 ug/kg (ppb) for a 25-g sample in an 8-oz jar. The detection limit for TCE in water is about 1 ug/L (ppb) for a 25-mL sample in an 8-oz jar. This is comparable to quantitation limits of EPA GC/MS laboratory methods. A draft ASTM method for screening TCE contaminated soils using a heated diode sensor was successfully submitted for concurrent main committee and subcommittee balloting in ASTM Committee D 34 on Waste Management. The method was approved as ASTM D 7203-05, Standard Test Method for Screening Trichloroethylene (TCE)-Contaminated Soil Using a Heated Diode Sensor.

  19. Inhibition of thyroid hormone sulfotransferase activity by brominated flame retardants and halogenated phenolics.

    Science.gov (United States)

    Butt, Craig M; Stapleton, Heather M

    2013-11-18

    Many halogenated organic contaminants (HOCs) are considered endocrine disruptors and affect the hypothalamic-pituitary-thyroid axis, often by interfering with circulating levels of thyroid hormones (THs). We investigated one potential mechanism for TH disruption, inhibition of sulfotransferase activity. One of the primary roles of TH sulfation is to support the regulation of biologically active T3 through the formation of inactive THs. We investigated TH sulfotransferase inhibition by 14 hydroxylated polybrominated diphenyl ethers (OH BDEs), BDE 47, triclosan, and fluorinated, chlorinated, brominated, and iodinated analogues of 2,4,6-trihalogenated phenol and bisphenol A (BPA). A new mass spectrometry-based method was also developed to measure the formation rates of 3,3'-T2 sulfate (3,3'-T2S). Using pooled human liver cytosol, we investigated the influence of these HOCs on the sulfation of 3,3'-T2, a major substrate for TH sulfation. For the formation of 3,3'-T2S, the Michaelis constant (Km) was 1070 ± 120 nM and the Vmax was 153 ± 6.6 pmol min(-1) (mg of protein)(-1). All chemicals investigated inhibited sulfotransferase activity with the exception of BDE 47. The 2,4,6-trihalogenated phenols were the most potent inhibitors followed by the OH BDEs and then halogenated BPAs. The IC50 values for the OH BDEs were primarily in the low nanomolar range, which may be environmentally relevant. In silico molecular modeling techniques were also used to simulate the binding of OH BDE to SULT1A1. This study suggests that some HOCs, including antimicrobial chemicals and metabolites of flame retardants, may interfere with TH regulation through inhibition of sulfotransferase activity.

  20. OH and HO2 chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake

    Directory of Open Access Journals (Sweden)

    R. Sommariva

    2006-01-01

    Full Text Available Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM, have been used to study the chemistry of OH and HO2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland in summer 2002. The base models, which were constrained to measured CO, CH4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO2] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone, highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO2] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HOx was dependant on the uptake coefficients used for HOI, HOBr and HO2. Better agreement, within the combined uncertainties of the measurements and of the model, was achieved when using high uptake coefficients for HO2 and HOI (γHO2=1, γHOI=0.6. A rate of production and destruction analysis of the models allowed a detailed study of OH and HO2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br as co-reactants for OH and HO2 and of HOX photolysis as a source for OH.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-12-01

    New developments in molecular-level {sup 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 {sup 14}C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals ({sup 14}C-free) and natural compounds should have 'modern' or 'contemporary' {sup 14}C levels. As a baseline study, we measured, for the first time, the {sup 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 {sup 14}C-free except for the pesticide toxaphene, which had a modern {sup 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 {sup 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.

  2. LED and Halogen Light Transmission through a CAD/CAM Lithium Disilicate Glass-Ceramic.

    Science.gov (United States)

    Pereira, Carolina Nemesio de Barros; De Magalhães, Cláudia Silami; Daleprane, Bruno; Peixoto, Rogéli Tibúrcio Ribeiro da Cunha; Ferreira, Raquel da Conceição; Cury, Luiz Alberto; Moreira, Allyson Nogueira

    2015-01-01

    The effect of thickness, shade and translucency of CAD/CAM lithium disilicate glass-ceramic on light transmission of light-emitting diode (LED) and quartz-tungsten-halogen units (QTH) were evaluated. Ceramic IPS e.max CAD shades A1, A2, A3, A3.5, high (HT) and low (LT) translucency were cut (1, 2, 3, 4 and 5 mm). Light sources emission spectra were determined. Light intensity incident and transmitted through each ceramic sample was measured to determine light transmission percentage (TP). Statistical analysis used a linear regression model. There was significant interaction between light source and ceramic translucency (p=0.008) and strong negative correlation (R=-0.845, pceramic thickness and TP. Increasing one unit in thickness led to 3.17 reduction in TP. There was no significant difference in TP (p=0.124) between shades A1 (ß1=0) and A2 (ß1=-0.45) but significant reduction occurred for A3 (ß1=-0.83) and A3.5 (ß1=-2.18). The interaction QTH/HT provided higher TP (ß1=0) than LED/HT (ß1=-2.92), QTH/LT (ß1=-3.75) and LED/LT (ß1=-5.58). Light transmission was more effective using halogen source and high-translucency ceramics, decreased as the ceramic thickness increased and was higher for the lighter shades, A1 and A2. From the regression model (R2=0.85), an equation was obtained to estimate TP value using each variable ß1 found. A maximum TP of 25% for QTH and 20% for LED was found, suggesting that ceramic light attenuation could compromise light cured and dual cure resin cements polymerization.

  3. Chemical mediation of bacterial surface colonisation by secondary metabolites from the red alga Delisea pulchra

    DEFF Research Database (Denmark)

    Maximilien, Ria; de Nys, Rocky; Holmström, Carola

    1998-01-01

    We investigated the effects of halogenated furanones from the red alga Delisea pulchra on colonisation of surfaces by marine bacteria. Bacterial abundance on the surface of D. pulchra, assessed using scanning electron microscopy (SEM), was significantly lower than on the surfaces of 3 co...... experimentally investigated inhibition of marine bacteria by furanones, initially testing the effects of crude extract of D. pulchra (about 50 % of which is furanones) on the growth of 144 strains of bacteria isolated from the surfaces of D. pulchra, nearby rocks, or a co-occurring alga (Sasgassum vestitum......, suggesting that swarming may be ecologically important in these systems. Overall, we found that the effects of furanones on bacteria varied among (1) furanones, (2) bacterial phenotypes, (3) different isolates and (4) different sources of isolation (e.g. rocks or algae). This differential inhibition...

  4. Chemical mediation of bacterial surface colonisation by secondary metabolites from the red alga Delisea pulchra

    DEFF Research Database (Denmark)

    Maximilien, Ria; de Nys, Rocky; Holmström, Carola

    1998-01-01

    We investigated the effects of halogenated furanones from the red alga Delisea pulchra on colonisation of surfaces by marine bacteria. Bacterial abundance on the surface of D. pulchra, assessed using scanning electron microscopy (SEM), was significantly lower than on the surfaces of 3 co...... experimentally investigated inhibition of marine bacteria by furanones, initially testing the effects of crude extract of D. pulchra (about 50 % of which is furanones) on the growth of 144 strains of bacteria isolated from the surfaces of D. pulchra, nearby rocks, or a co-occurring alga (Sasgassum vestitum....... pulchra, in contrast to the pattern for growth inhibition. We also tested individual furanones against swimming and swarming of the same 6 bacterial isolates (3 from rocks, 3 from D. pulchra) used in the attachment assays. At least some furanones inhibited swarming or swimming at non...

  5. Direct evidence of reactive ion etching induced damages in Ge{sub 2}Sb{sub 2}Te{sub 5} based on different halogen plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Li, Juntao [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Microsystem Technology Laboratory, Microsystem & Terahertz Research Center, Sichuan Province 610200 (China); Xia, Yangyang [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100080 (China); Liu, Bo, E-mail: liubo@mail.sim.ac.cn [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Feng, Gaoming [United Lab, Semiconductor Manufacturing International Corporation, Shanghai 201203 (China); Song, Zhitang [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Gao, Dan; Xu, Zhen; Wang, Weiwei [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100080 (China); Chan, Yipeng [United Lab, Semiconductor Manufacturing International Corporation, Shanghai 201203 (China); Feng, Songlin [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)

    2016-08-15

    Highlights: • The results of SEM and AFM directly showed that the surface of Cl2 etched samples were roughest with a Ge deficient damaged layer. • The XPS of Te 3d revealed the electrons were transferred from chalcogenide to halogen and the highest halogenation was observed on CF4 etching GST films. • The sidewall of HBr etching GST is nearly vertical compared with others. • HBr is promising gas for GST etching in the fabrication of high-density memory devices. - Abstract: Chalcogenide glasses based on Ge-Te-Sb are processed using reactive ion etching (RIE) in the fabrication of phase change memory (PCM). These materials are known to be halogenated easily and apt to be damaged when exposed to halogen gas based plasmas which can cause severe halogenation-induced degradation. In this paper, we investigate the RIE induced damage of popular phase change material Ge{sub 2}Sb{sub 2}Te{sub 5} (GST) in different halogen based plasmas (CF{sub 4}, Cl{sub 2} and HBr) highly diluted by argon. After blanket etching, results of scanning electron microscopy and atomic force microscopy directly showed that the surface of Cl{sub 2} etched samples were roughest with a Ge deficient damaged layer. X-ray photoelectron spectroscopy was performed to investigate the chemical shift of constituent elements. Selected scans over the valence band peaks of Te 3d revealed that electrons were transferred from chalcogenide to halogen and the highest halogenation was observed on the GST etched by CF{sub 4}. The GST films masked with patterned TiN were also etched. High-resolution transmission electron microscopy and surface scan directly showed the line profile and the damaged layer. Almost vertical and smooth sidewall without damaged layer makes HBr a promising gas for GST etch in the fabrication of high-density memory devices.

  6. Potent Methyl Oxidation of 5-Methyl-2′-deoxycytidine by Halogenated Quinoid Carcinogens and Hydrogen Peroxide via a Metal-independent Mechanism

    OpenAIRE

    Shao, Jie; Huang, Chun-Hua; Kalyanaraman, Balaraman; Zhu, Ben-Zhan

    2013-01-01

    Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection byproducts in drinking water. We found recently that the highly reactive and biologically important hydroxyl radical (•OH) can be produced by halogenated quinones and H2O2 independent of transition metal ions. However, it is not clear whether these quinoid carcinogens and H2O2 can oxidize the nucleoside 5-methyl-2′-deoxycytidine (5mdC) to its methyl oxidation prod...

  7. On-Surface Synthesis of Two-Dimensional Covalent Organic Structures versus Halogen-Bonded Self-Assembly: Competing Formation of Organic Nanoarchitectures.

    Science.gov (United States)

    Peyrot, David; Silly, Fabien

    2016-05-24

    The competition between the on-surface synthesis of covalent nanoarchitectures and the self-assembly of star-shaped 1,3,5-Tris(4-iodophenyl)benzene molecules on Au(111) in vacuum is investigated using scanning tunneling microscopy above room temperature. The molecules form covalent polygonal nanoachitectures at the gold surface step edges and at the elbows of the gold reconstruction at low coverage. With coverage increasing two-dimensional halogen-bonded structures appear and grow on the surface terraces. Two different halogen-bonded nanoarchitectures are coexisting on the surface and hybrid covalent-halogen bonded structures are locally observed. At high coverage covalent nanoarchitectures are squeezed at the domain boundary of the halogen-bonded structures. The competitive growth between the covalent and halogen-bonded nanoarchitectures leads to formation of a two-layer film above one monolayer deposition. For this coverage, the covalent nanoarchitectures are propelled on top of the halogen-bonded first layer. These observations open up new opportunities for decoupling covalent nanoarchitectures from catalytically active and metal surfaces in vacuum.

  8. Estimating the parameters of a positive column of the halogen-containing glow discharge at moderate pressures

    Directory of Open Access Journals (Sweden)

    Alexander P. Golovitskii

    2015-03-01

    Full Text Available The methodical recommendations for estimating the plasma parameters of an electronegative glow discharge containing halogens at moderate pressures (up to 40 Torr with the use of simple analytic formulae and without numerical modeling are given. The initial data are easily measureable discharge parameters such as a discharge current, a voltage and a gas mixture pressure and composition as well. It is shown how one can easily consider such important plasma features as non-Maxwellian electron energy distribution function and halogen molecules dissociation by electron impact. As a result, such plasma parameters as the absolute degree of electronegativity, the value of border coordinate between ion–ion and electron–ion plasmas, and the forms of transversal profiles of electron and negative ion concentrations can be evaluated. The comparison of the results with the ones given by a global numerical model shows the suitability of said analytic approach to estimate plasma parameters of real discharges.

  9. Bond Alternation in Halogen Substituted Polyacetylene ---Possibility of C-F Bond Length Alternation in (CF)x---

    Science.gov (United States)

    Abdelaty, S. M.; Sasai, M.; Fukutome, H.

    1985-08-01

    Using the Hückel model, we study the π electronic and lattice structures of the ground state of halogen substituted polyacetylene (CX)x where X is F, Cl, Br or I. The halogen substitution always makes the C-C bond length alternation in the main chain and the corresponding band gap smaller than those in unsubstituted polyacetylene (CH)x. (CCl)x, (CBr)x and (CI)x have only the bond alternation in the main chain. (CF)x may take one of the three lattice structures depending on the value of the C-F σ bond force constant; the structure with the bond alternation in the main chain, the one with the bond length alternation in the C-F bonds and the one with coexistence of the two kinds of bond alternation. The structure with the C-F bond length alternation is ferroelectric.

  10. Halogen-free PCB quality and performance%无卤PCB质量和性能的研究

    Institute of Scientific and Technical Information of China (English)

    赵良

    2011-01-01

    通过对当前市面上的无卤PCB产品和有卤PCB产品的相关物理、化学性能测试结果进行对比,分析了无卤PCB产品目前所能达到的质量和性能水平,总结无卤PCB产品相对较差的性能指标,并提出改善方向。%Through the comparison test of physic and chemical property with normal PCB,this paper analyzed the quality and performance level of halogen-free PCB,and then summarized the defect of halogen-free PCB and put forward the improving direction.

  11. Synthesis and characterization of lead-free tin silver nanosolders and their application to halogen free nanosolder pastes

    Science.gov (United States)

    Wernicki, Evan

    Solder paste is a key material used in attaching electronic components to printed circuit boards (PCBs). Commonly used lead-based solders, such as eutectic Sn/37Pb, are currently being replaced by lead-free alloy materials due to health and environmental concerns associated with lead. Many solder pastes, both lead-containing and lead-free, contain halogens which act as activators to remove surface oxide and enhance surface wetting, posing further environmental concern from the halogen species. Difficulties in obtaining reliable joints can occur since lead-free solder material candidates have higher melting temperatures (30-50 °C) than that of lead-based solders. Differences in material properties between the numerous materials used in assembly and packaging processes can lead to component damage during manufacturing. Furthermore, designs that include more electrical interconnects in smaller areas give rise for the need for new materials to allow this trend to continue. A surfactant-assisted chemical reduction method was used to synthesize Sn/Ag alloy nanoparticles with a target composition range of 3.5-5 wt% Ag that served as the lead-free solder material within a nanosolder paste. Structure and size characterization via SEM and TEM showed Sn-Ag nanosolders size average approximately 19 nm. Differential scanning calorimetry (DSC) measurements of the nanosolder samples containing 4.5 wt% Ag showed an endothermic peak at 222.5 °C and an onset of 219.2 °C, indicating up to 17.5 °C melting temperature depression when compared to the bulk liquidus value of 240 °C. Composition of the nanosolder material was confirmed using energy dispersive x-ray spectroscopy (EDS) and structures formed were analyzed via x-ray diffraction (XRD). Both halogen-free and halogen-containing flux materials were combined with the nanosolder material, respectively, with varying preparation parameters to form a design of experiments (DoE) for nanosolder paste preparation. Solder pastes

  12. Periodic density-functional calculations on work-function change induced by adsorption of halogens on Cu(111).

    Science.gov (United States)

    Roman, Tanglaw; Groß, Axel

    2013-04-12

    Using periodic density-functional theory calculations, we address the work-function change induced by the adsorption of chlorine and iodine on Cu(111) which are shown to change the work function in opposite ways, contrary to what one may expect for these two electron acceptors. In contrast to previous studies, we demonstrate that substrate effects play only a minor role in work-function changes brought about by halogen adsorption on metals. Instead, polarization on the adsorbate not only explains the sign of the work-function change as a contributor to a positive surface dipole moment, but it is also the decisive factor in the dependence of adsorption-induced work-function changes on the coverage of halogens on metal surfaces.

  13. The pnicogen bond: its relation to hydrogen, halogen, and other noncovalent bonds.

    Science.gov (United States)

    Scheiner, Steve

    2013-02-19

    Among a wide range of noncovalent interactions, hydrogen (H) bonds are well known for their specific roles in various chemical and biological phenomena. When describing conventional hydrogen bonding, researchers use the notation AH···D (where A refers to the electron acceptor and D to the donor). However, the AH molecule engaged in a AH···D H-bond can also be pivoted around by roughly 180°, resulting in a HA···D arrangement. Even without the H atom in a bridging position, this arrangement can be attractive, as explained in this Account. The electron density donated by D transfers into a AH σ* antibonding orbital in either case: the lobe of the σ* orbital near the H atom in the H-bonding AH···D geometry, or the lobe proximate to the A atom in the HA···D case. A favorable electrostatic interaction energy between the two molecules supplements this charge transfer. When A belongs to the pnictide family of elements, which include phosphorus, arsenic, antimony, and bismuth, this type of interaction is called a pnicogen bond. This bonding interaction is somewhat analogous to the chalcogen and halogen bonds that arise when A is an element in group 16 or 17, respectively, of the periodic table. Electronegative substitutions, such as a F for a H atom opposite the electron donor atom, strengthen the pnicogen bond. For example, the binding energy in FH(2)P···NH(3) greatly exceeds that of the paradigmatic H-bonding water dimer. Surprisingly, di- or tri-halogenation does not produce any additional stabilization, in marked contrast to H-bonds. Chalcogen and halogen bonds show similar strength to the pnicogen bond for a given electron-withdrawing substituent. This insensitivity to the electron-acceptor atom distinguishes these interactions from H-bonds, in which energy depends strongly upon the identity of the proton-donor atom. As with H-bonds, pnicogen bonds can extract electron density from the lone pairs of atoms on the partner molecule, such as N, O, and

  14. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV ? gas phase reactions of organic halogen species

    OpenAIRE

    2007-01-01

    International audience; This article, the fourth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of organic halogen species, which were last published in 1997, and were updated on the IUPAC website in 2006. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and four appen...

  15. I2-Mediated 2H-indazole synthesis via halogen-bond-assisted benzyl C-H functionalization.

    Science.gov (United States)

    Yi, Xiangli; Jiao, Lei; Xi, Chanjuan

    2016-10-18

    I2-Mediated benzyl C-H functionalization has been developed for the synthesis of 2H-indazoles, which features high efficiency, simple conditions and no need for metals. Mechanistic experiments and DFT calculations have revealed halogen bond assistance and a radical chain process for this reaction. The azo group and the bound iodine cooperate in the hydrogen abstraction step, which circumvents the thermodynamic disfavor of direct hydrogen abstraction by a simple iodine radical.

  16. Development and application of a sampling method for the determination of reactive halogen species in volcanic gas emissions

    Science.gov (United States)

    Rüdiger, Julian; Bobrowski, Nicole; Liotta, Marcello; Hoffmann, Thorsten

    2017-04-01

    Volcanoes are a potential large source of several reactive atmospheric trace gases including sulfur and halogen containing species. Besides the importance for atmospheric chemistry, the detailed knowledge of halogen chemistry in volcanic plumes can help to get insights into subsurface processes. In this study a gas diffusion denuder sampling method, using a 1,3,5-trimethoxybenzene (1,3,5-TMB) coating for the derivatization of reactive halogen species (RHS), was characterized by dilution chamber experiments. The coating proved to be suitable to collect selectively gaseous bromine species with oxidation states (OS) of +1 or 0 (such as Br2, BrCl, BrO(H) and BrONO2), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with reactive bromine species gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography mass spectrometry gives detection limits of 10 ng or less for Br2, Cl2, and I2. In 2015 the method was applied on volcanic gas plumes at Mt. Etna (Italy) giving reactive bromine mixing ratios from 0.8 ppbv to 7.0 ppbv. Total bromine mixing ratios of 4.7 ppbv to 27.5 ppbv were obtained by simultaneous alkaline trap sampling (by a Raschig-tube) followed by analysis with ion chromatography and inductively coupled plasma mass spectrometry. This leads to the first results of in-situ measured reactive bromine to total bromine ratios, spanning a range between 12±1 % and 36±2 %. Our finding is in an agreement with previous model studies, which imply values < 44 % for plume ages < 1 minute, which is consistent with the assumed plume age at the sampling sites.

  17. From charge transfer to electron transfer in halogen-bonded complexes of electrophilic bromocarbons with halide anions.

    Science.gov (United States)

    Rosokha, Sergiy V; Traversa, Alfredo

    2015-02-21

    Experimental and computational studies of the halogen-bonded complexes, [R-Br, X(-)], of bromosubstituted electrophiles, R-Br, and halide anions, X(-), revealed that decrease of a gap between the frontier orbitals of interacting species led to reduction of the energy of the optical charge-transfer transition and to increase in the ground-state charge transfer (X(-) → R-Br) in their associates. These variations were accompanied by weakening of the intramolecular, C-Br, and strengthening of the intermolecular, BrX(-), bonds. In the limit of the strongest electron donor-acceptor pairs, formation of the halogen-bonded complexes was followed by the oxidation of iodide to triiodide, which took place despite the fact that the I(-) → R-Br electron-transfer step was highly endergonic and the calculated outer-sphere rate constant was negligibly small. However, the calculated barrier for the inner-sphere electron transfer accompanied by the halogen transfer, R-BrI(-) → R˙Br-I(-)˙, was nearly 24 kcal mol(-1) lower as compared to that calculated for the outer-sphere process and the rate constant of such reaction was consistent with the experimental kinetics. A dramatic decrease of the electron-transfer barriers (leading to 18-orders of magnitude increase of the rate constant) was related to the strong electronic coupling of the donor and acceptor within the halogen-bonded precursor complex, as well as to the lower solvent reorganization energy and the successor-complex stabilization.

  18. Weakly coordinating anions: crystallographic and NQR studies of halogen-metal bonding in silver, thallium, sodium, and potassium halomethanesulfonates.

    Science.gov (United States)

    Wulfsberg, Gary; Parks, Katherine D; Rutherford, Richard; Jackson, Debra Jones; Jones, Frank E; Derrick, Dana; Ilsley, William; Strauss, Steven H; Miller, Susie M; Anderson, Oren P; Babushkina, T A; Gushchin, S I; Kravchenko, E A; Morgunov, V G

    2002-04-22

    35Cl, (79,81)Br, and (127)I NQR (nuclear quadrupole resonance) spectroscopy in conjunction with X-ray crystallography is potentially one of the best ways of characterizing secondary bonding of metal cations such as Ag(+) to halogen donor atoms on the surfaces of very weakly coordinating anions. We have determined the X-ray crystal structure of Ag(O(3)SCH(2)Cl) (a = 13.241(3) A; b = 7.544(2) A; c = 4.925(2) A; orthorhombic; space group Pnma; Z = 4) and compared it with the known structure of Ag(O(3)SCH(2)Br) (Charbonnier, F.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B 1978, 34, 3598-3601). The halogen atom in each is apical (three-coordinate), being weakly coordinated to two silver ions. (127)I NQR studies on Ag(O(3)SCH(2)I) show the expected NQR consequences of three-coordination of iodine: substantially reduced NQR frequencies nu(1) and nu(2) and a fairly small NQR asymmetry parameter eta. The reduction of the halogen NQR frequency of the coordinating halogen atom in Ag(O(3)SCH(2)X) becomes more substantial in the series X = Cl < Br < I, indicating that the coordination to Ag(+) strengthens in this series, as expected from hard-soft acid-base principles. The numbers of electrons donated by the organic iodine atom to Ag(+) have been estimated; these indicate that the bonding to the cation is weak but not insignificant. We have not found any evidence for the bonding of these organohalogen atoms to another soft-acid metal ion, thallium. A scheme for recycling of thallium halide wastes is included.

  19. Halogenated phenolic contaminants inhibit the in vitro activity of the thyroid-regulating deiodinases in human liver.

    Science.gov (United States)

    Butt, Craig M; Wang, Dongli; Stapleton, Heather M

    2011-12-01

    Halogenated contaminants, particularly brominated flame retardants, disrupt circulating levels of thyroid hormones (THs), potentially affecting growth and development. Disruption may be mediated by impacts on deiodinase (DI) activity, which regulate the levels of active hormones available to bind to nuclear receptors. The goal of this study was to develop a mass spectrometry-based method for measuring the activity of DIs in human liver microsomes and to examine the effect of halogenated phenolic contaminants on DI activity. Thyroxine (T4) and reverse triiodothyronine (rT3) deiodination kinetics were measured by incubating pooled human liver microsomes with T4 or rT3 and monitoring the production of T3, rT3, 3,3'-diiodothyronine, and 3-monoiodothyronine by liquid chromatography tandem mass spectrometry. Using this method, we examined the effects of several halogenated contaminants, including 2,2',4,4',5-pentabromodiphenyl ether (BDE 99), several hydroxylated polybrominated diphenyl ethers (OH-BDEs), tribromophenol, tetrabromobisphenol A, and triclosan, on DI activity. The Michaelis constants (K(M)) of rT3 and T4 deiodination were determined to be 3.2 ± 0.7 and 17.3 ± 2.3μM. The V(max) was 160 ± 5.8 and 2.8 ± 0.10 pmol/min.mg protein, respectively. All studied contaminants inhibited DI activity in a dose-response manner, with the exception of BDE 99 and two OH-BDEs. 5'-Hydroxy 2,2',4,4',5-pentabromodiphenyl ether was found to be the most potent inhibitor of DI activity, and phenolic structures containing iodine were generally more potent inhibitors of DI activity relative to brominated, chlorinated, and fluorinated analogues. This study suggests that some halogenated phenolics, including current use compounds such as plastic monomers, flame retardants, and their metabolites, may disrupt TH homeostasis through the inhibition of DI activity in vivo.

  20. Product screening for sources of halogenated flame retardants in Canadian house and office dust

    Energy Technology Data Exchange (ETDEWEB)

    Abbasi, Golnoush [Department of Geography, University of Toronto, 100 St. George St., Toronto M5S 3G3 (Canada); Saini, Amandeep [Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto M1C 1A4 (Canada); Goosey, Emma [Department of Earth Sciences, University of Toronto, 22 Russell Street, Toronto M5S 3B1 (Canada); Diamond, Miriam L., E-mail: miriam.diamond@utoronto.ca [Department of Earth Sciences, University of Toronto, 22 Russell Street, Toronto M5S 3B1 (Canada); Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail, Toronto M1C 1A4 (Canada)

    2016-03-01

    Human exposure to halogenated flame retardants (HFRs) such as polybrominated diphenyl ethers (PBDEs) and their replacements, can be related to exposure to indoor dust and direct contact with HFR-containing products. This study aimed to identify electronic products that contributed to HFRs measured in indoor dust and to develop a screening method for identifying HFRs in hard polymer products. Concentrations of 10 PBDEs and 12 halogenated replacements in dust and surface wipe samples of hard polymer casings of electronic products plus Br in the surfaces of those casing measured using X-ray fluorescence (XRF) were analyzed from 35 homes and 10 offices in Toronto (ON, Canada). HFR concentrations in dust and product wipes were positively correlated. Thus, we hypothesize that electronic products with the highest HFR concentrations contribute the most to concentrations in dust, regardless of the volatility of the HFR. Abundant HFRs in dust and product wipes were PBDEs (BDE-47, 99, 100, 153, 154, 183, 209), TDCPP, DBDPE, EH-TBB and BEHTBP. Older CRT TVs had the highest concentration of BDE-209 of all products tested. This was followed by higher concentrations of HFRs in PCs, Audio/Video (A/V) devices, small household appliances (HHAs) and flat screen TVs. The removal of HFRs from polymer surfaces using wipes supports concerns that HFRs could be transferred from these surfaces to hands as a result of direct contact with HFR-containing products. Surface wipe testing shows promise for screening additive HFRs. In comparison, the Br-content obtained using a handheld XRF analyzer did not correspond to concentrations obtained from surface wipe testing. - Highlights: • Concentrations of flame retardants in dust correlated with product surface wipes • Most abundant FRs in electronics were PBDEs, TDCPP, DBDPE, EH-TBB and BEHTBP. • Descending order of FRs in CRTs, TVs, PCs, A-V devices, and small household appliances • Product wipe testing, but not XRF, useful for non

  1. Improving the Solubility of Halogenated 1-Ammonio-closo-dodecaborate Anions.

    Science.gov (United States)

    Bertocco, Philipp; Derendorf, Janis; Jenne, Carsten; Kirsch, Christoph

    2017-03-20

    The partly halogenated and N-alkylated closo-dodecaborates [B12Cl6H5N(propyl)3](-) and [B12Br6H5NR3](-) (R = ethyl-pentyl) were prepared by alkylation of [B12H11NH3](-) and subsequent halogenation with elemental chlorine or N-bromosuccinimide. Simple metathesis reactions yielded the [HNMe3](+), [C6mim](+), [NBu4](+), and Na(+) salts, which were characterized by heteronuclear NMR and IR spectroscopy as well as electrospray ionization mass spectrometry. The crystal structures of the salts [HNMe3][B12Br6H5N(ethyl)3]·CH3CN, [HNMe3][B12Br6H5N(propyl)3], Na[B12Br6H5N(butyl)3], and [HNMe3][B12Cl7H4N(propyl)3]·CH3CN were determined by single-crystal X-ray diffraction. The [C6mim](+) salts are thermally stable to temperatures higher than 300 °C. The melting points are between 57 and 80 °C, which classify the [C6mim](+) salts of [B12Cl6H5N(propyl)3](-) and [B12Br6H5NR3](-) (R = propyl-pentyl) as ionic liquids. The anions are oxidized only at potentials higher than 2 V versus Fc(0/+) as determined by cyclic voltammetry. The solubility of the sodium salts in CH2Cl2 solution was determined by NMR spectroscopy. With the increasing length of the alkyl chain attached to the ammonio group the solubility is significantly enhanced. A solubility up to 125 mmol/L for Na[B12Br6H5N(pentyl)3] in dichloromethane was determined. In addition, the trialkylation of the perchlorinated anion [B12Cl11NH3](-) was investigated in detail. A Hofmann elimination was observed to occur at higher temperatures, when alkyl groups with β-hydrogen atoms were introduced. Organic substituents without β-hydrogen atoms gave more stable compounds; however, trialkylation proved to be difficult presumably due to steric hindrance. The crystal structure of the byproduct [PPh4]2[B12Cl11N(propargyl)2] was determined.

  2. 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.

  3. Kinetic method for assaying the halogenating activity of myeloperoxidase based on reaction of celestine blue B with taurine halogenamines.

    Science.gov (United States)

    Sokolov, A V; Kostevich, V A; Kozlov, S O; Donskyi, I S; Vlasova, I I; Rudenko, A O; Zakharova, E T; Vasilyev, V B; Panasenko, O M

    2015-06-01

    Myeloperoxidase (MPO) is a challenging molecular target which, if put under control, may allow regulating the development of inflammatory reactions associated with oxidative/halogenative stress. In this paper, a new kinetic method for assaying the halogenating activity of MPO is described. The method is based on measuring the rate of iodide-catalyzed oxidation of celestine blue B (CB) by oxygen and taurine N-chloramine (bromamine). The latter is produced in a reaction of taurine with HOCl (HOBr). CB is not a substrate for the peroxidase activity of MPO and does not react with hydrogen peroxide and superoxide anion radical. Taurine N-chloramine (bromamine) reacts with CB in molar ratio of 1:2. Using the new method, we studied the dependence of MPO activity on concentration of substrates and inhibitors. The specificity of MPO inhibition by non-proteolyzed ceruloplasmin is characterized. The inhibition of taurine N-chloramine production by neutrophils and HL-60 cells in the presence of MPO-affecting substances is demonstrated. The new method allows determining the kinetic parameters of MPO halogenating activity and studying its inhibition by various substances, as well as screening for potential inhibitors of the enzyme.

  4. Molecular docking and structural analysis of non-opioid analgesic drug acemetacin with halogen substitution: A DFT approach

    Science.gov (United States)

    Leenaraj, D. R.; Manimaran, D.; Joe, I. Hubert

    2016-11-01

    Acemetacin is a non-opioid analgesic which belongs to the class, the non-steroidal anti-inflammatory drug. The bioactive conformer was identified through potential energy surface scan studies. Spectral features of acemetacin have been probed by the techniques of Fourier transform infrared, Raman and Nuclear magnetic resonance combined with density functional theory calculations at the B3LYP level with 6-311 + G(d,p) basis set. The detailed interpretation of vibrational spectral assignments has been carried out on the basis of potential energy distribution method. Geometrical parameters reveal that the carbonyl substitution in between chlorophenyl and indole ring leads to a significant loss of planarity. The red-shifted Cdbnd O stretching wavenumber describe the conjugation between N and O atoms. The shifted Csbnd H stretching wavenumbers of Osbnd CH3 and Osbnd CH2 groups depict the back-donation and induction effects. The substitution of halogen atoms on the title molecule influences the charge distribution and the geometrical parameters. Drug activity and binding affinity of halogen substitution in title molecule with target protein were undertaken by molecular docking study. This study enlightens the effects of bioefficiency due to the halogen substitution in the molecule.

  5. The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts

    Directory of Open Access Journals (Sweden)

    Kari Raatikainen

    2010-01-01

    Full Text Available The series of haloanilinium and halopyridinium salts: 4-IPhNH3Cl (1, 4-IPhNH3Br (5, 4-IPhNH3H2PO4 (6, 4-ClPhNH3H2PO4 (8, 3-IPyBnCl (9, 3-IPyHCl (10 and 3-IPyH-5NIPA (3-iodopyridinium 5-nitroisophthalate, 13, where hydrogen or/and halogen bonding represents the most relevant non-covalent interactions, has been prepared and characterized by single crystal X-ray diffraction. This series was further complemented by extracting some relevant crystal structures: 4-BrPhNH3Cl (2, CCDC ref. code TAWRAL, 4-ClPhNH3Cl (3, CURGOL, 4-FPhNH3Cl (4, ANLCLA, 4-BrPhNH3H2PO4, (7, UGISEI, 3-BrPyHCl, (11, CIHBAX and 3-ClPyHCl, (12, VOQMUJ from Cambridge Structural Database for sake of comparison. Based on the X-ray data it was possible to highlight the balance between non-covalent forces acting in these systems, where the relative strength of the halogen bonding C–X···A− (X = I, Br or Cl and the ratio between the halogen and hydrogen bonds [C–X···A− : D–H···A−] varied across the series.

  6. The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts.

    Science.gov (United States)

    Raatikainen, Kari; Cametti, Massimo; Rissanen, Kari

    2010-01-15

    THE SERIES OF HALOANILINIUM AND HALOPYRIDINIUM SALTS: 4-IPhNH₃Cl (1), 4-IPhNH₃Br (5), 4-IPhNH₃H₂PO₄ (6), 4-ClPhNH₃H₂PO₄ (8), 3-IPyBnCl (9), 3-IPyHCl (10) and 3-IPyH-5NIPA (3-iodopyridinium 5-nitroisophthalate, 13), where hydrogen or/and halogen bonding represents the most relevant non-covalent interactions, has been prepared and characterized by single crystal X-ray diffraction. This series was further complemented by extracting some relevant crystal structures: 4-BrPhNH₃Cl (2, CCDC ref. code TAWRAL), 4-ClPhNH₃Cl (3, CURGOL), 4-FPhNH₃Cl (4, ANLCLA), 4-BrPhNH₃H₂PO₄, (7, UGISEI), 3-BrPyHCl, (11, CIHBAX) and 3-ClPyHCl, (12, VOQMUJ) from Cambridge Structural Database for sake of comparison. Based on the X-ray data it was possible to highlight the balance between non-covalent forces acting in these systems, where the relative strength of the halogen bonding C-X...A⁻ (X = I, Br or Cl) and the ratio between the halogen and hydrogen bonds [C-X...A⁻ : D-H...A⁻] varied across the series.

  7. Stability of mutagenic tautomers of uracil and its halogen derivatives: the results of quantum-mechanical investigation

    Directory of Open Access Journals (Sweden)

    Hovorun D.M.

    2010-07-01

    Full Text Available Aim. To investigate using the quantum-mechanical methods uracil (Ura intramolecular tautomerisation and the effect of the thymine (Thy methyl (Me group substitution by the halogen on that process. Methods. Non-empirical quantum mechanic, analysis of the electron density by means of Bader’s atom in molecules (AIM theory and physicochemical kinetics were used. Results. For the first time it has been established that the substitution of thymine Me-group for the halogen (Br, F, Cl has practically no effect on the main physico-chemical characteristics of intramolecular tautomerisation. At the same time, the energy of Ura tautomerisation increases for 3,08 kcal/mol in comparison with corresponding value for Thy under standard conditions. Conclusions. So, Thy, unlike Ura, is obviously able, as a canonical DNA nucleotide base, to provide together with Ade, Gua and Cyt an acceptable mutability degree of the genome from the point of view of its adaptation reserve. Mutagenic action of the Ura halogen derivatives is not directly associated with their tautomerisation.

  8. 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.

  9. Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide.

    Science.gov (United States)

    Zhao, Quan; Shang, Chii; Zhang, Xiangru; Ding, Guoyu; Yang, Xin

    2011-12-01

    When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination.

  10. Legacy and new halogenated persistent organic pollutants in polar bears from a contamination hotspot in the Arctic, Hudson Bay Canada.

    Science.gov (United States)

    Letcher, R J; Morris, A D; Dyck, M; Sverko, E; Reiner, E J; Blair, D A D; Chu, S G; Shen, L

    2017-08-10

    A large and complex suite of 295 legacy and new halogenated persistent organic pollutants (POPs) were investigated in fat or liver tissue samples of polar bears collected in 2013-2014 from Southern (SHB) and Western (WHB) subpopulations of the Canadian Arctic contaminants hotspot of Hudson Bay. A total of 210 POPs were detected and/or quantifiable with some frequency in all fat or liver samples. POP profile and concentration differences were investigated both within (e.g. age and sex) and between the two subpopulations. Two time-point comparisons were made relative to POPs reported for Hudson Bay polar bears harvested in 2007-2008. ΣPolychlorinated biphenyl (PCB) concentrations at both time points were the most concentrated of the POP groups, and were spatially uniform with no detectable influence of sex or age, as were concentrations of the dominant congener CB153. ΣChlordanes (ΣCHLs, 74-79% oxychlordane) and the Σperfluoroalkyl substances (ΣPFASs, ≈60% perfluorooctane sulfonate (PFOS)) had the second greatest POP group concentrations in SHB and WHB respectively, with ΣPFASs and ΣCHLs being significantly influenced by age and/or sex. ΣCHLs were spatially uniform but ΣPFASs were greater in the SHB bears, as were e.g. some flame retardants, due to e.g. local contamination and/or changes in bear behavior and diet. Endosulfans and hexabromocyclododecane were detectable in samples from 2007-2008 but not from 2013-2014, which is consistent with their global POP regulations. ΣPolychlorinated naphthalenes (ΣPCNs) were consistently detected at relatively high concentrations compared to other arctic wildlife, however these concentrations were low relative to legacy POPs. ΣShort-chain chlorinated paraffins (ΣSCCPs) were major contributors to the overall POPs burden with concentrations comparable to other legacy POPs, though there was no significant difference between or within subpopulations for PCNs or SCCPs. Except for octachlorostyrene, POPs concentrations

  11. Halogen and trace element geochemistry in Mid-Ocean Ridge basalts from the Australian-Antarctic Ridge (AAR)

    Science.gov (United States)

    Yang, Y. S.; Seo, J. H.; Park, S. H.; Kim, T.

    2015-12-01

    Australian-Antarctic Ridge (AAR) is an extension of easternmost SE Indian Mid-Ocean Ridge (MOR).We collected volcanic glasses from the "in-axis" of the KR1 and KR2 MOR, and the overlapping zones of the KR1 MOR and the nearby seamounts ("KR1 mixing"). We determined trace and halogen elements in the glasses. Halogen concentrations and its ratios in the glasses are important to understand the mantle metasomatism and volatile recycling. 52 of the collected glasses are "primitive" (higher than 6 wt% MgO), while 3 of them have rather "evolved" composition (MgO wt% of 1.72, 2.95 and 4.15). K2O concentrations and Th/Sc ratios in the glasses show a negative correlation with its MgO concentration. Incompatible element ratios such as La/Sm are rather immobile during a magma differentiation so the ratios are important to understand mantle composition (Hofmann et al. 2003). La/Sm ratios in the glasses are 0.95 ~ 3.28 suggesting that the AAR basalts can be classified into T-MORB and E-MORB (Schilling et al., 1983). La/Sm ratios are well-correlated with incompatible elements such as U, Ba, Nb, and negatively correlated with compatible elements such as Sc, Eu2+, Mg. The AAR glasses contain detectable halogen elements. The "KR1 mixing" glasses in halogen elements are more abundant than "in-axis" the glasses. Cl is the least variable element compared to the other halogens such as Br and I in the AAR. The "KR1 mixing" glasses have the largest variations of Br/Cl ratios compared to the "in-axis" glasses. The Cl/Br and Th/Sc ratios in the "in-axis" glasses and in the "KR1 mixing" glasses show positive and negative correlations, respectively. The Br-rich glasses in the "KR1 mixing" zone might be explained by a recycled Br-rich oceanic slab of paleo-subduction or by a hydrothermal alteration in the AAR. I composition in the glasses does not show a correlation other trace elements. The K/Cl and K/Ti ratios in the AAR glasses are similar to the basalts from the Galapagos Spreading Center

  12. 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)

  13. Determination of heavy metals and halogens in plastics from electric and electronic waste.

    Science.gov (United States)

    Dimitrakakis, Emmanouil; Janz, Alexander; Bilitewski, Bernd; Gidarakos, Evangelos

    2009-10-01

    The presence of hazardous substances and preparations in small waste electrical and electronic equipment (sWEEE) found in the residual household waste stream of the city of Dresden, Germany has been investigated. The content of sWEEE plastics in heavy metals and halogens is determined using handheld X-ray fluorescence analysis (HXRF), elemental analysis by means of atomic absorption spectrometry (AAS) and ion exchange chromatography (IEC). Mean value of results for heavy metals in samples (n=51) by AAS are 17.4 mg/kg for Pb, 5.7 mg/kg for Cd, 8.4 mg/kg for Cr. The mass fraction of an additive as shown by HXRF (n=161) can vary over a wide range. Precise deductions as regards sWEEE plastics content in hazardous substances and preparations cannot be made. Additional research would be expedient regarding the influence of hazardous substances to recycling processes, in particular regarding the contamination of clean fractions in the exit streams of a WEEE treatment plant. Suitable standards for calibrating HXRF for use on EEE plastics or complex electr(on)ic components do not exist and should be developed.

  14. Transformation of halogen-, alkyl-, and alkoxy-substituted anilines by a lactase of Trametes versicolor

    Energy Technology Data Exchange (ETDEWEB)

    Hoff, T.; Liu, S.Y.; Bollag, J.M.

    1985-05-01

    The lactase of the fungus Trametes versicolor was able to polymerize various halogen-, alkyl-, and alkoxy-substituted anilines, showing substrate specificity similar to that of horseradish peroxidase, whereas the lactase of Rhizoctonia praticola was active only with p-methoxyaniline. The substrate specificities of the enzymes were determined by using gas chromatography to measure the decrease in substrate concentration during incubation. With p-chloroaniline as the substrate, the peroxidase and the Trametes lactase showed maximum activity near pH 4.2. The transformation of this substrate gave rise to a number of oligomers, ranging from dimers to pentamers, as determined by mass spectrometry. The product profiles obtained by high-pressure liquid chromatography were similar for the two enzymes. A chemical reaction was observed between p-chloroaniline and an enzymatically formed dimer, resulting in the formation of a trimer. All three enzymes oxidized p-methoxyaniline to 2-amino-5-p-anisidinobenzoquinone di-p-methoxyphenylimine, but only the T. versicolor lactase and the peroxidase caused the formation of a pentamer (2,5-di-p-anisidinobenzoquinone di-p-methoxyphenylimine). These results demonstrate that in addition to horseradish peroxidase, a T. versicolor lactase can also polymerize aniline derivatives.

  15. Channel-resolved photo- and Auger-electron spectroscopy of halogenated hydrocarbons

    Science.gov (United States)

    Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Kushawaha, R.; Rudenko, A.; Rolles, D.; Xiong, H.; Berrah, N.; Bomme, C.; Savelyev, E.; Kilcoyne, D.

    2016-05-01

    Inner-shell photoelectron and Auger electron spectra of polyatomic molecules such as halogenated hydrocarbons are typically hard to interpret and assign due to many overlapping states that form broad bands even in high-resolution measurements. With the help of electron-ion-ion coincidence measurements performed using the velocity map imaging technique, we are able to detect high-energy (ionic fragmentation channels. Such channel-resolved measurements allow disentangling the overlapping electronic structures and help assigning individual components of the electron spectra to specific potential surfaces and final states. In this work, we present measurements on CH3 I, CH2 IBr, and CH2 ICl molecules in the gas-phase using soft x-ray light provided by the Advanced Light Source at LBNL. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

  16. Tunable magnetic states on the zigzag edges of hydrogenated and halogenated group-IV nanoribbons

    Science.gov (United States)

    Wang, Tzu-Cheng; Hsu, Chia-Hsiu; Huang, Zhi-Quan; Chuang, Feng-Chuan; Su, Wan-Sheng; Guo, Guang-Yu

    2016-12-01

    The magnetic and electronic properties of hydrogenated and halogenated group-IV zigzag nanoribbons (ZNRs) are investigated by first-principles density functional calculations. Fascinatingly, we find that all the ZNRs have magnetic edges with a rich variety of electronic and magnetic properties tunable by selecting the parent and passivating elements as well as controlling the magnetization direction and external strain. In particular, the electric property of the edge band structure can be tuned from the conducting to insulating with a band gap up to 0.7 eV. The last controllability would allow us to develop magnetic on-off nano-switches. Furthermore, ZNRs such as SiI, Ge, GeI and SnH, have fully spin-polarized metallic edge states and thus are promising materials for spintronics. The calculated magnetocrystalline anisotropy energy can be as large as ~9 meV/edge-site, being 2×103 time greater than that of bulk Ni and Fe (~5 μeV/atom), and thus has great potential for high density magneto-electric data-storage devices. Finally, the calculated exchange coupling strength and thus magnetic transition temperature increases as the applied strain goes from ‑5% to 5%. Our findings thus show that these ZNRs would have exciting applications in next-generation electronic and spintronic nano-devices.

  17. Halogen-Bonding-Assisted Iodosylbenzene Activation by a Homogenous Iron Catalyst

    DEFF Research Database (Denmark)

    de Sousa, David P.; Wegeberg, Christina; Vad, Mads Sørensen;

    2016-01-01

    The iron(III) complex of hexadentate N,N,N′-tris(2-pyridylmethyl)ethylendiamine-N′-acetate (tpena−) is a more effective homogenous catalyst for selective sulfoxidation and epoxidation with insoluble iodosylbenzene, [PhIO]n, compared with soluble methyl-morpholine-N-oxide (NMO). We propose that two...... molecules of [Fe(tpena)]2+ cooperate to solubilize PhIO, extracting two equivalents to form the halogen-bonded dimeric {[Fe(tpena)OIPh]2}4+. The closest intradimeric I⋅⋅⋅O distance, 2.56 Å, is nearly 1 Å less than the sum of the van de Waals radii of these atoms. A correlation of the rates of the reaction...... of {[Fe(tpena)OIPh]2}4+ with para-substituted thioanisoles indicate that this species is a direct metal-based oxidant rather than a derived ferryl or perferryl complex. A study of gas-phase reactions indicate that an ion at m/z=231.06100 originates from solution-state {[Fe(tpena)OIPh]2}4+ and is ascribed...

  18. A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Xiu-Liang [Beijing Univ. of Technology (China). College of Environmental and Energy Engineering, Beijing Key Lab. for Green Catalysis and Separation, and Dept. of Chemistry and Chemical Engineering; Wang, Kecheng [Texas A& M Univ., College Station, TX (United States). Dept. of Chemistry; Wang, Bin [Beijing Univ. of Technology (China). College of Environmental and Energy Engineering, Beijing Key Lab. for Green Catalysis and Separation, and Dept. of Chemistry and Chemical Engineering; Su, Jie [Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Dept. of Materials and; Zou, Xiaodong [Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Dept. of Materials and Environmental Chemistry; Xie, Yabo [Beijing Univ. of Technology (China). College of Environmental and Energy Engineering, Beijing Key Lab. for Green Catalysis and Separation, and Dept. of Chemistry and Chemical Engineering; Li, Jian-Rong [Beijing Univ. of Technology (China). College of Environmental and Energy Engineering, Beijing Key Lab. for Green Catalysis and Separation, and Dept. of Chemistry and Chemical Engineering; Zhou, Hong-Cai [Texas A& M Univ., College Station, TX (United States). Dept. of Chemistry

    2017-01-11

    A base-resistant porphyrin metal–organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni8(OH)4(H2O)2Pz12] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetrakis(4-(pyrazolate-4-yl)phenyl)porphyrin under the guidance of the reticular synthesis strategy. Besides its robustness in hydroxide solution, PCN-602 also shows excellent stability in aqueous solutions of F, CO32–, and PO43– ions. Interestingly, the Mn3+-porphyrinic PCN-602, as a recyclable MOF catalyst, presents high catalytic activity for the C–H bond halogenation reaction in a basic system, significantly outperforming its homogeneous counterpart. For the first time, a porphyrinic MOF was thus used as an efficient catalyst in a basic solution with coordinating anions, to the best of our knowledge.

  19. Oxidation of carbon tetrachloride, bromotrichloromethane, and carbon tetrabromide by rat liver microsomes to electrophilic halogens

    Energy Technology Data Exchange (ETDEWEB)

    Mico, B.A. (National Inst. of General Medical Sciences, Bethesda, MD); Branchflower, R.V.; Pohl, L.R.; Pudzianowski, A.T.; Loew, G.H.

    1982-01-11

    In order to determine whether CCl/sub 4/, CBrCl/sub 3/, CBr/sub 4/ or CHCl/sub 3/ undergo oxidative metabolism to electrophilic halogens by liver microsomes, they were incubated with liver microsomes from phenobarbital pretreated rats in the presence of NADPH and 2,6-dimethylphenol. The analysis of the reaction mixtures by capillary gas chromatography mass spectrometry revealed that 4-chloro-2,6-dimethylphenol was a metabolite of CCl/sub 4/ and CBrCl/sub 3/ whereas 4-bromo-2,6-dimethylphenol was a metabolite of CBr/sub 4/. The formation of the metabolites was significantly decreased when the reactions were conducted with heat denatured microsomes, in the absence of NADPH or under an atmosphere of N/sub 2/. These results indicate that the chlorines of CBrCl/sub 3/ and CCl/sub 4/ and the bromines of CBr/sub 4/ are oxidatively metabolized by rat liver microsomes to electrophilic and potentially toxic metabolites.

  20. Etching of organosilicate glass low-k dielectric films in halogen plasmas

    CERN Document Server

    Vitale, S A

    2002-01-01

    The chemistry and kinetics of alternative etching chemistries for low-k dielectric materials are explored to improve the anisotropy of the etching process and to reduce the problems associated with postetch clean-up. Etching rates, selectivities, and etching yields of Black Diamond and Coral organosilicate glasses (OSGs) have been measured. Black Diamond and Coral are etched rapidly in F sub 2 , Cl sub 2 , and HBr high density plasmas, and Cl sub 2 +HBr plasmas have been identified as a viable process chemistry with several advantages over traditional fluorocarbon plasmas. The OSG films are not spontaneously etched by F sub 2 , Cl sub 2 , HBr molecules, Cl, or Br atoms, however, F atoms etch the OSGs spontaneously. F, Cl, and H atoms extract a substantial amount of carbon from the films, but Cl and H do not attack the OSG oxide matrix. The Coral films are more strongly depleted of carbon after halogen plasma etching than the Black Diamond. In addition, oxygen atoms extract nearly all of the carbon and nitroge...