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Sample records for cetyl pyridinium bromide

  1. Release of cetyl pyridinium chloride from fatty acid chelate temporary dental cement

    PubMed Central

    Hurt, Andrew; Coleman, Nichola J.; Tüzüner, Tamer; Bagis, Bora; Korkmaz, Fatih Mehmet; Nicholson, John W.

    2016-01-01

    Abstract Objective To determine whether the antimicrobial nature of a fatty acid chelate temporary dental cement can be enhanced by the addition of 5% cetyl pyridinium chloride (CPC). Materials and methods The temporary cement, Cavex Temporary was employed, and additions of CPC were made to either the base or the catalyst paste prior to mixing the cement. Release of CPC from set cement specimens was followed using reverse-phase HPLC for a period of up to 2 weeks following specimen preparation. Potential interactions between Cavex and CPC were examined by Fourier transform infrared spectroscopy (FTIR) and antimicrobial effects were determined using zone of inhibition measurements after 24 h with disc-shaped specimens in cultured Streptococcus mutans. Results FTIR showed no interaction between CPC and the components of the cement. CPC release was found to follow a diffusion mechanism for the first 6 h or so, and to equilibrate after approximately 2 weeks, with no significant differences between release profiles when the additive was incorporated into the base or the catalyst paste. Diffusion was rapid, and had a diffusion coefficient of approximately 1 × 10−9 m2 s−1 in both cases. Total release was in the range 10–12% of the CPC loading. Zones of inhibition around discs containing CPC were significantly larger than those around the control discs of CPC-free cement. Conclusions The antimicrobial character of this temporary cement can be enhanced by the addition of CPC. Such enhancement is of potential clinical value, though further in vivo work is needed to confirm this. PMID:27335898

  2. The sensitivity to chlorhexidine and cetyl pyridinium chloride of staphylococci on the hands of dental students and theatre staff exposed to these disinfectants.

    PubMed

    Millns, B; Martin, M V; Field, E A

    1994-02-01

    The aim of this investigation was to study the possible emergence of resistant isolates of the genus Staphylococcus on the hands of dental personnel who use 'Hibiscrub' (chlorhexidine-detergent preparation) and cetyl pyridinium-coated gloves. Resistance was determined by a rate-of-kill technique. In four dental student groups (first, second, third and fourth years) no microorganisms survived 30 min exposure to cetyl pyridinium chloride (CPC) or to chlorhexidine diacetate (CDA). In a theatre staff group, no microorganisms survived 30 s exposure to CPC; and only one of 23 isolates survived 30 min exposure to CDA, but was killed after 60 min exposure. It is concluded that staphylococci resistant to either of these disinfectants do not present a problem in dental students or theatre staff. PMID:7911154

  3. Investigation of pyridine/propargyl bromide reaction and strong fluorescence enhancements of the resultant poly(propargyl pyridinium bromide).

    PubMed

    Zhou, Changming; Gao, Yong; Chen, Daoyong

    2012-09-20

    Poly(propargyl pyridinium bromide), a kind of conjugated polyelectrolyte with polyacetylene as the backbone and pyridinium as side groups, was synthesized simply via reaction between pyridine and propargyl bromide under mild conditions. The resultant polymer was characterized by (1)H NMR, elemental analysis, FT-IR, and GPC-MALLS. An alkyne group was confirmed as the end group of the polymer chains by the alkyne/azide click chemistry, which reveals that the polymerization is terminated by the reaction between propargyl bromide and carbon anions. It is known that monosubstituted polyacetylenes reported have very weak fluorescence intensities, which limit their applications. As a monosubstituted polyacetylene, the freshly prepared poly(propargyl pyridinium bromide) also has a very weak fluorescence. However, we confirmed that addition of some anions to the polymer solution in DMF or DMSO leads to the fluorescence enhancements up to 25 times. Besides, heating the polymer solution at a temperature between 70 and 130 °C for longer than 0.5 h greatly enhanced the fluorescence intensity. The interaction with the anions or the heating enhances the effective exciton confinement within the conjugated backbone and thus results in the fluorescence enhancements. After the fluorescence enhancements, poly(propargyl pyridinium bromide) has relatively strong fluorescence emissions, which will make it promising in fluorescence-based applications. PMID:22928912

  4. Investigating Two-Photon-Induced Fluorescence in Rhodamine-6G in Presence of Cetyl-Trimethyl-Ammonium-Bromide.

    PubMed

    Maurya, Sandeep Kumar; Yadav, Dheerendra; Goswami, Debabrata

    2016-09-01

    We investigate the effect of cetyl-trimethyl-ammonium-bromides (CTAB) concentration on the fluorescence of Rhodamine-6G in water. This spectroscopic study of Rhodamine-6G in presence of CTAB was performed using two-photon-induced-fluorescence at 780 nm wavelength using high repetition rate femtosecond laser pulses. We report an increment of ∼10 % in the fluorescence in accordance with ∼12 % enhancement in the absorption intensity of the dye molecule around the critical micellar concentration. We discuss the possible mechanism for the enhancement in the two-photon fluorescence intensity and the importance of critical micellar concentration. PMID:27324955

  5. Crystal structure of 3-amino-1-propyl­pyridinium bromide

    PubMed Central

    Venkatesan, P.; Rajakannan, V.; Thamotharan, S.

    2014-01-01

    The title mol­ecular salt, C8H13N2 +·Br−, crystallizes with two independent 3-amino­pyridinium cations and two bromide anions in the asymmetric unit (Z′ = 2). In the pyridine ring, the N atom is alkyl­ated by a propyl group. The dihedral angle between the mean planes of the pyridinium ring and the propyl group is 84.84 (2)° in cation A, whereas the corresponding angle is 89.23 (2)° in cation B. In the crystal, the anions and cations are linked via N—H⋯Br and C—H⋯Br hydrogen bonds, forming chains propagating along [100]. PMID:25552997

  6. Effect of cetyl trimethyl ammonium bromide concentration on structure, morphology and carbon dioxide adsorption capacity of calcium hydroxide based sorbents

    NASA Astrophysics Data System (ADS)

    Hlaing, Nwe Ni; Vignesh, K.; Sreekantan, Srimala; Pung, Swee-Yong; Hinode, Hirofumi; Kurniawan, Winarto; Othman, Radzali; Thant, Aye Aye; Mohamed, Abdul Rahman; Salim, Chris

    2016-02-01

    Calcium hydroxide (Ca(OH)2) has been proposed as an important material for industrial, architectural, and environmental applications. In this study, calcium acetate was used as a precursor and cetyl trimethyl ammonium bromide (CTAB) was used as a surfactant to synthesize Ca(OH)2 based adsorbents for carbon dioxide (CO2) capture. The effect of CTAB concentration (0.2-0.8 M) on the structure, morphology and CO2 adsorption performance of Ca(OH)2 was studied in detail. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), BET surfaced area and thermogravimetry-differential thermal analysis (TG-DTA) techniques. The phase purity, crystallite size, Brunauer-Emmett-Teller (BET) surface area and CO2 adsorption performance of Ca(OH)2 precursor adsorbents were significantly increased when the concentration of CTAB was increased. XRD results showed that pure Ca(OH)2 phase was obtained at the CTAB concentration of 0.8 M. TGA results exhibited that 0.8 M of CTAB-assisted Ca(OH)2 precursor adsorbent possessed a residual carbonation conversion of ∼56% after 10 cycles.

  7. Enhanced adsorption of congo red from aqueous solutions by chitosan hydrogel beads impregnated with cetyl trimethyl ammonium bromide.

    PubMed

    Chatterjee, Sudipta; Lee, Dae S; Lee, Min W; Woo, Seung H

    2009-06-01

    The adsorption of congo red (CR) onto chitosan (CS) beads impregnated by a cationic surfactant (CTAB, cetyl trimethyl ammonium bromide) was investigated. Chitosan beads impregnated at a ratio of 1/20 of CTAB to CS (0.05% of CTAB and 1% of CS) increased the CR adsorption capacity by 2.2 times from 162.3 mg/g (0% CTAB) to 352.5 mg/g (0.05% CTAB). The CR adsorption decreased with an increase in pH of the CR solution from 4.0 to 9.0. The Sips isotherm model showed a good fit with the equilibrium experimental data and the values of the heterogeneity factor (n) indicated heterogeneous adsorption of CR onto CS/CTAB beads, as well as CS beads. The kinetic data showed better fit to the pseudo second-order rate model than to the pseudo first-order rate model. The impregnation of CS beads by cationic surfactants showed the highest adsorption capacities of CR compared to any other adsorbents and would be a good method to increase adsorption efficiency for the removal of anionic dyes in a wastewater treatment process. PMID:19208471

  8. Thermochemistry of alkyl pyridinium bromide ionic liquids: calorimetric measurements and calculations.

    PubMed

    Tong, Bo; Liu, Qing-Shan; Tan, Zhi-Cheng; Welz-Biermann, Urs

    2010-03-25

    Two ionic liquids, 1-ethylpyridinium bromide (EPBr) and 1-propylpyridinium bromide (PPBr), were prepared and the structures were characterized by 1H NMR. The thermodynamic properties of EPBr and PPBr were studied with adiabatic calorimetry (AC) and thermogravimatric analysis (TG-DTG). The heat capacity was precisely measured in the temperature range from 78 to 410 K by means of a fully automated adiabatic calorimeter. For EPBr, the melting temperature, enthalpy, and entropy of solid-liquid phase transition were determined to be 391.31 +/- 0.28 K, 12.77 +/- 0.09 kJ x mol(-1), and 32.63 +/- 0.22 J x K(-1) x mol(-1), respectively, and for PPBr they were 342.83 +/- 0.69 K, 10.97 +/- 0.05 kJ x mol(-1), and 32.00 +/- 0.10 J x K(-1) x mol(-1), respectively. The thermodynamic functions (H(T)(0) - H(298.15)(0)) and (S(T)(0) - S(298.15)(0)) were derived from the heat capacity data in the experimental temperature range with an interval of 5 K. The thermostablility of the compounds was further studied by TGA measurements. The phase change behavior and thermodynamic properties were compared and estimated in a series of alkyl pyridinium bromide ionic liquids. Results indicate that EPBr has higher melting and decomposition temperature, as well as phase transition enthalpy and entropy but lower heat capacity than PPBr due to their different molecular structures. PMID:20235601

  9. The Comparative Evaluation of Antibacterial Activity of Methacryloxydodecyl Pyridinium Bromide and Non-methacryloxydodecyl Pyridinium Bromide Dentin Bonding Systems Using Two Different Techniques: An In vitro Study

    PubMed Central

    Deshpande, Prashanth; Nainan, Mohan Thomas; Metta, Kiran Kumar; Shivanna, Vasundhara; Ravi, Ramkrishna; Prashanth, B R

    2014-01-01

    zones (P > 0.05), but the bonding resin of CPB did not produce any inhibition. When tested by the tooth cavity model technique, the application of CPB resulted in significantly less bacterial recovery than the PBNT (P < 0.05), demonstrating substantial antibacterial effects. Conclusion: The CPB that employs the antibacterial primer containing methacryloxydodecyl pyridinium bromide, was effective in inactivating the bacteria in the cavity compared to little antibacterial activity shown by PBNT. The tooth cavity mode test used in the present study is a reliable method to evaluate the antibacterial effects of dentin bonding agents simulating clinical situations. PMID:25395795

  10. Synergistic inhibition behavior between indigo carmine and cetyl trimethyl ammonium bromide on carbon steel corroded in a 0.5 M HCl solution

    NASA Astrophysics Data System (ADS)

    Zhang, Zhe; Tian, Ningchen; Li, Xiuying; Zhang, Lingzhi; Wu, Ling; Huang, Yan

    2015-12-01

    This work reports on a newly observed synergistic inhibition between indigo carmine and cetyl trimethyl ammonium bromide (CTAB) on 1045 carbon steel (CS) corroded in a 0.5 M HCl solution. The results of electrochemical measurements showed that CTAB could change indigo carmine in a manner that would accelerate corrosion and produce an effective inhibitor. The maximal protection efficiency was significantly greater than 0.985, with the concentration of the combination inhibitors reaching approximately 5 × 10-5 M. The microstructure of the CS corrosion surface demonstrated that the indigo disulfonate anions and cetyltrimethylammonium cations were adsorbed simultaneously on the CS surface to protect it from corrosion. Diffusion coefficient analysis and the surface concentration profiles of the corrosive species were used to investigate the synergistic effect of the indigo carmine/CTAB combination inhibitors, and the results demonstrate the existence of synergy.

  11. Complete dechlorination of 2,4-dichlorophenol in aqueous solution on palladium/polymeric pyrrole-cetyl trimethyl ammonium bromide/foam-nickel composite electrode.

    PubMed

    Sun, Zhirong; Wei, Xuefeng; Han, Yanbo; Tong, Shan; Hu, Xiang

    2013-01-15

    The electrochemically reductive dechlorination of 2,4-dichlorophenol (2,4-DCP) in aqueous solution on palladium/polymeric pyrrole-cetyl trimethyl ammonium bromide/foam-nickel electrode (Pd/PPy-CTAB/foam-Ni electrode) was investigated in this paper. Pd/PPy-CTAB/foam-Ni electrode was prepared and characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) adsorption and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The influences of some experimental factors such as the dechlorination current, dechlorination time and the initial pH on the removal efficiency and the current efficiency of 2,4-DCP dechlorination on Pd/PPy-CTAB/foam-Ni electrode were studied. Complete removal of 2,4-DCP was achieved and the current efficiency of 47.4% could be obtained under the conditions of the initial pH of 2.2, the dechlorination current of 5 mA and the dechlorination time of 50 min when the initial 2,4-DCP concentration was 100 mg L(-1). The analysis of high performance liquid chromatography (HPLC) identified that the intermediate products were 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP). The final products were mainly phenol. Its further reduction product cyclohexanone was also detected. The electrocatalytic dechlorination pathways of 2,4-DCP on Pd/PPy-CTAB/foam-Ni electrode were discussed. The stability of the electrode was favorable that it could keep dechlorination efficiency at 100% after having been reused 10 times. Results revealed that the stable prepared Pd/PPy-CTAB/foam-Ni electrode presented a good application prospect in dechlorination process with high effectiveness and low cost. PMID:23270952

  12. Synthesis, antibacterial and antioxidant activities of new 1-alkyl-4-(1-alkyl-4-oxo-1,4-dihydroquinolin-2-yl)pyridinium bromides.

    PubMed

    Kahriman, Nuran; Yaylı, Büşra; Aktaş, Ayça; Iskefiyeli, Zeynep; Beriş, Fatih Şaban; Yaylı, Nurettin

    2013-11-01

    New 1-alkyl-4-(1-alkyl-4-oxo-1,4-dihydroquinolin-2-yl)pyridinium bromides (3a-k) were synthesized from 1,4'-diazaflavone [2-pyridin-4-ylquinolin-4(1H)-one] and evaluated for antibacterial and antioxidant activities. A rapid one-pot preparation of 1,4'-diazaflavone (2) was done from 2'-amino substituted chalcone (1) by intramolecular Michael addition using solvent-free microwave heating. New N,N'-dialkyl substituted (C₅-C₁₅) 1,4'-diazaflavonium bromides were synthesized from compound 2 with corresponding alkyl halides. Compounds 3a-k were active against six bacteria (MIC: 7.8-500.0 μg/mL). They also showed good antioxidant activities in DPPH scavenging (SC₅₀: 45-133 μg/mL) and ferric reducing/antioxidant power (14-141 μM TEAC) tests. The biological activities decreased as alkyl chain length increased. The reason behind the obvious negative effect of alkyl chain elongation is unclear and requires investigations about the intermolecular interactions of these pyridinium salts with bioassay components. PMID:24077525

  13. Spectra, stability and labeling of 1-(5-carboxypentyl)-4-(2-(N-ethyl-carbazole-3-yl) vinyl) pyridinium bromide with a large Stokes shift.

    PubMed

    Gu, Yingchun; Lin, Dayong; Li, Ran; Tang, Yalin; Fei, Xuening; Zhou, Jianguo

    2016-03-01

    Carbazole and its derivatives have been widely utilized as a functional building block in the fabrication of the organic medicine, pesticides, materials, etc., because of their excellent solubility, stability and biological activity. In this paper, 1-(5-carboxypentyl)-4-(2-(N-ethyl-carbazole-3-yl) vinyl) pyridinium bromide with a large Stokes shift was synthesized and characterized by (1) H NMR and MS. The UV/vis absorption and fluorescence spectra in different solvents and at different pH values were investigated preliminarily. The photostability and thermostability were also studied and the results showed that the compound was stable. The compound was also used to label bovine serum albumin (BSA) and calf thymus (ct)DNA. The results showed that the fluorescence intensity is enhanced when labeling with BSA and the binding ability is stronger than ctDNA, making it may be used as a biological probe. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26249113

  14. The reaction of substituted N-phenacyl-pyridinium bromides in the pyridine ring with DABCO and DBU in water and DMSO. Kinetics and DFT studies

    NASA Astrophysics Data System (ADS)

    Szwajca, A.; Łęska, B.; Schroeder, G.; Szafran, M.

    2004-12-01

    The rate constants have been measured for deprotonation reaction of substituted N-phenacyl-pyridinium bromides, in the pyridine ring, with 1,4-diazabicyclo[2,2,2]octane in water and DMSO, and some with 1,8-diazabicyclo[5,4,0]undec-7-ene. The dependence of the rate constant, k, on p Ka of substituted pyridines is made of two distinct linear branches obtained for the salts with electron-withdrawing and electron-donating substituents, respectively. The structures of four salts have been determined by the B3LYP/6-31G(d,p) level of theory and compared with the available X-ray structure. The effect of the substituent and solvent on k values has been discussed.

  15. A novel dodine-free selective medium based on the use of cetyl trimethyl ammonium bromide (CTAB) to isolate Beauveria bassiana, Metarhizium anisopliae sensu lato and Paecilomyces lilacinus from soil.

    PubMed

    Posadas, Julieta B; Comerio, Ricardo M; Mini, Jorge I; Nussenbaum, Ana L; Lecuona, Roberto E

    2012-01-01

    This study evaluated the quaternary ammonium compound cetyl trimethyl ammonium bromide (CTAB) as an alternative to the chemically related dodecylguanidine (dodine) for the selective isolation of entomopathogenic fungi. Oatmeal agar (OA) with chloramphenicol was used as basal medium, and three concentrations of CTAB (0.5, 0.6, 0.7 g/L) were evaluated and compared against OA + 0.46 g/L dodine. Selective isolation and growth studies were performed with the entomopathogens Beauveria bassiana, Metarhizium anisopliae s.l. and Paecilomyces lilacinus and five common non-entomopathogenic non-target species. The three entomopathogenic fungi sporulated earlier on OA + 0.6 g/L CTAB than on OA + 0.46 g/L dodine, while none of the non-target fungi sporulated on OA + 0.6 g/L CTAB. All entomopathogenic fungal isolates grew on OA + 0.6 g/L CTAB, despite some intra-species variation, whereas non-target fungi showed no growth or sporulation. OA + 0.6 g/L CTAB resulted in an efficient medium to isolate B. bassiana, M. anisopliae s. l. and P. lilacinus from soil samples. Results of our study suggest that OA + 0.6 g/L CTAB is a suitable, simple and inexpensive to prepare medium to replace OA + 0.46 g/L dodine for the selective isolation of these fungi. PMID:22314588

  16. Crystal structure of 2,6-bis-(2-hy-droxy-5-methyl-phen-yl)-4-phenyl-pyridinium bromide di-chloro-methane hemisolvate hemihydrate.

    PubMed

    Mankaev, Badma N; Zaitsev, Kirill V; Karlov, Sergey S; Egorov, Mikhail P; Churakov, Andrei V

    2015-12-01

    The asymmetric unit in the structure of the title compound, C25H22NO2 (+)·Br (-)·0.5CH2Cl2·0.5H2O, comprises two pseudosymmetry-related cations, two bromide anions, a di-chloro-methane molecule and a water mol-ecule of solvation. The two independent cations are conformationally similar with the comparative dihedral angles between the central pyridine ring and the three benzene substituent rings being 3.0 (2), 36.4 (1) and 24.2 (1)°, and 3.7 (2), 36.5 (1) and 24.8 (1)°, respectively. In the crystal, the cations, anions and water mol-ecules are linked through O-H⋯O and O-H⋯Br hydrogen bonds, forming an insular unit. Within the cations there are also intra-molecular N-H⋯O hydrogen bonds. Adjacent centrosymmetrically related aggregates are linked by π-π stacking inter-actions between the pyridine ring and a benzene ring in both cations [ring-centroid separations = 3.525 (3) and 3.668 (3) Å], forming chains extending across the ac diagonal. Voids between these chains are filled by dichloromethane molecules. PMID:26870547

  17. Effect of counterion on the mesomorphic behavior and optical properties of columnar pyridinium ionic liquid crystals derived from 4-hydroxypyridine

    NASA Astrophysics Data System (ADS)

    Pană, Amalia; Badea, Florentina L.; Iliş, Monica; Staicu, Teodora; Micutz, Marin; Pasuk, Iuliana; Cîrcu, Viorel

    2015-03-01

    A series of 3,4,5-tridodecyloxybenzyl pyridinium salts derived from 4-hydroxypyridine has been designed and prepared. The liquid crystalline properties of these compounds were investigated by polarized optical microscopy, differential scanning calorimetry and powder X-ray diffraction while their thermal stability was studied by thermogravimetric analysis. The N-3,4,5-tridodecyloxybenzyl-4-pyridone intermediate shows a monotropic columnar hexagonal mesophase ranging from 56 °C down to room temperature while the corresponding bromide dodecyl O-alkylated pyridinium salt shows one enantiotropic columnar mesophase and one additional monotropic columnar phase at lower temperatures. Replacing bromide ion (Br-) with other counterions (NO3-, BF4- and PF6-) resulted in mesophase suppression. These luminescent pyridinium salts show weak emission in dichloromethane solutions at room temperature and a pronounced red-shifted emission in solid state. Photoluminescent properties of the pyridinium salts do not depend significantly on the nature of counterion employed.

  18. Crystal structure of 2,6-bis­(2-hy­droxy-5-methyl­phen­yl)-4-phenyl­pyridinium bromide di­chloro­methane hemisolvate hemihydrate

    PubMed Central

    Mankaev, Badma N.; Zaitsev, Kirill V.; Karlov, Sergey S.; Egorov, Mikhail P.; Churakov, Andrei V.

    2015-01-01

    The asymmetric unit in the structure of the title compound, C25H22NO2 +·Br −·0.5CH2Cl2·0.5H2O, comprises two pseudosymmetry-related cations, two bromide anions, a di­chloro­methane molecule and a water mol­ecule of solvation. The two independent cations are conformationally similar with the comparative dihedral angles between the central pyridine ring and the three benzene substituent rings being 3.0 (2), 36.4 (1) and 24.2 (1)°, and 3.7 (2), 36.5 (1) and 24.8 (1)°, respectively. In the crystal, the cations, anions and water mol­ecules are linked through O—H⋯O and O—H⋯Br hydrogen bonds, forming an insular unit. Within the cations there are also intra­molecular N—H⋯O hydrogen bonds. Adjacent centrosymmetrically related aggregates are linked by π–π stacking inter­actions between the pyridine ring and a benzene ring in both cations [ring-centroid separations = 3.525 (3) and 3.668 (3) Å], forming chains extending across the ac diagonal. Voids between these chains are filled by dichloromethane molecules. PMID:26870547

  19. Synthesis, characterization and comparative evaluation of phenoxy ring containing long chain gemini imidazolium and pyridinium amphiphiles.

    PubMed

    Bhadani, Avinash; Kataria, Hardeep; Singh, Sukhprit

    2011-09-01

    Two series of phenoxy ring containing long chain imidazolium and pyridinium based gemini amphiphiles have been synthesized from renewable cardanol oil having different spacers (i. e. -S-(CH(2))(n)-S-, where n is 2, 3, 4 & 6). Critical micelle concentration (cmc) of these new gemini amphiphiles has been determined by conductivity method. Further, these new cationic amphiphiles have been evaluated for their DNA binding capability by agarose gel electrophoresis, ethidium bromide exclusion experiments and transmission electron microscopy (TEM). The cytotoxicity of these new amphiphiles have been evaluated by MTT (3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay. Comparative studies of these phenoxy ring containing long chain gemini imidazolium amphiphiles and their pyridinium analogues depicted low cmc values of the later but greater DNA interaction capability and low cytotoxicity of the former series of amphiphiles. PMID:21676409

  20. Cyanogen bromide

    Integrated Risk Information System (IRIS)

    Cyanogen bromide ; CASRN 506 - 68 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  1. Vinyl bromide

    Integrated Risk Information System (IRIS)

    Vinyl bromide ; CASRN 593 - 60 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  2. Solvent-free enzymatic production of high quality cetyl esters.

    PubMed

    Serrano-Arnaldos, Mar; Máximo-Martín, María Fuensanta; Montiel-Morte, María Claudia; Ortega-Requena, Salvadora; Gómez-Gómez, Elisa; Bastida-Rodríguez, Josefa

    2016-04-01

    A solvent-free biocatalytic process for the synthesis of high quality cetyl laurate, myristate, palmitate and stearate has been optimized. This enzymatic procedure follows the fundamental principles of the Green Chemistry and lead to sustainable products, which can be labeled as natural and conform to the principal requirements for its use in high value-added goods. The four esters selected are the main components of spermaceti, a mixture of waxes very appreciated in cosmetic and pharmacy because of its physical properties and emolliency, which was formerly extracted from the head of the sperm whales. In this paper, the influence of the amount of biocatalyst, the commercially available Novozym(®) 435, and the temperature were studied in an open-air batch reactor before carrying out the synthesis in a high performance vacuum reactor with dry nitrogen input to shift the equilibrium towards product formation. Under optimal conditions, conversion was higher than 98.5 %. The characterization of the enzymatic cetyl esters puts in evidence that these are ultra-pure compounds, which have similar properties to the ones obtained through the conventional industrial processes with the extra benefit of being environmentally friendly. PMID:26801670

  3. Factors influencing the formation of polybromide monoanions in solutions of ionic liquid bromide salts.

    PubMed

    Easton, Max E; Ward, Antony J; Chan, Bun; Radom, Leo; Masters, Anthony F; Maschmeyer, Thomas

    2016-03-01

    Six different bromide salts - tetraethylammonium bromide ([N2,2,2,2]Br, Br), 1-ethyl-1-methylpiperidinium bromide ([C2MPip]Br, Br), 1-ethyl-1-methylpyrrolidinium bromide ([C2MPyrr]Br, Br), 1-ethyl-3-methylimidazolium bromide ([C2MIm]Br, Br), 1-ethylpyridinium bromide ([C2Py]Br, Br), and 1-(2-hydroxyethyl)pyridinium bromide ([C2OHPy]Br, Br) - were studied in regards to their capacity to form polybromide monoanion products on addition of molecular bromine in acetonitrile solutions. Using complementary spectroscopic and computational methods for the examination of tribromide and pentabromide anion formation, key factors influencing polybromide sequestration were identified. Here, we present criteria for the targeted synthesis of highly efficient bromine sequestration agents. PMID:26890026

  4. Supramolecular helical nanofibers assembled from a pyridinium-functionalized methyl glycyrrhetate amphiphile

    NASA Astrophysics Data System (ADS)

    Gao, Yuxia; Hao, Jie; Wu, Jindan; Zhang, Xun; Hu, Jun; Ju, Yong

    2015-08-01

    A glycyrrhetate-containing amphiphile, MGP (1-[2-(methyl glycyrrhetate)-2-oxoethyl]pyridinium bromide), has been synthesized, and found to assemble into supramolecular helical nanofibers in chloroform/aromatic solvents, which are primarily driven by π-π stacking, van der Waals forces, and hydrophobic interactions. During the assembly process, MGP stacked into J-aggregates resulting in the sequestration of the hydrophilic pyridinium cation within the interior with the concomitant projection of its hydrophobic skeleton on the outside surface. Ultimately, this protrusion generated a staggered angle due to the steric hindrance between stacked molecules. This staggered angle further led to molecular misalignments and the formation of helical fibrils, which could twist with each other to fabricate larger helical fibers. Consequently, a gel was formed by intertwining these nanofibers into three-dimensional networks. Using this strategy, we found that other triterpenoid-tailored pyridinium amphiphiles are also potential scaffolds for supramolecular helical structures. This work provides a facile approach for the fabrication of supramolecular macroscopic chiral nanostructures that originate from natural products.A glycyrrhetate-containing amphiphile, MGP (1-[2-(methyl glycyrrhetate)-2-oxoethyl]pyridinium bromide), has been synthesized, and found to assemble into supramolecular helical nanofibers in chloroform/aromatic solvents, which are primarily driven by π-π stacking, van der Waals forces, and hydrophobic interactions. During the assembly process, MGP stacked into J-aggregates resulting in the sequestration of the hydrophilic pyridinium cation within the interior with the concomitant projection of its hydrophobic skeleton on the outside surface. Ultimately, this protrusion generated a staggered angle due to the steric hindrance between stacked molecules. This staggered angle further led to molecular misalignments and the formation of helical fibrils, which could

  5. Application of pyridinium salts derived of barbituric acid in Kröhnke's reaction.

    PubMed

    Prelicz, D; Kasperek, L

    1975-01-01

    A series of pyridinium salts derived of barbituric acid (BAC) was obtained, as starting substances in Kröhnke's reaction. On the example of 3-(1',3'-dimethyl-5'-isopropylbarbituryl-5')-1-acetonylene-N-pyrifinium bromide it was stated that the corresponding nitron can be formed only when in positions 1 and 3 of barbituric ring are no hydrogen atoms able to enolization. 3-(1',3'-Dimethyl-5'-isopropylbarbituryl-5')-pyruvic aldehyde (XIII) was obtained by decomposition of nitron XII. PMID:1144211

  6. Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts.

    PubMed

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent

    2016-07-01

    The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asymmetric hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3 N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee values up to 90 %. The role of the base was elucidated with a mechanistic study involving the isolation of the various reaction intermediates and isotopic labeling experiments. Additionally, this study provided some evidence for an enantiodetermining step involving a dihydropyridine intermediate. PMID:27140832

  7. Synthesis, Biological Evaluation and Molecular Docking Study of Hydrazone-Containing Pyridinium Salts as Cholinesterase Inhibitors.

    PubMed

    Parlar, Sulunay; Bayraktar, Gulsah; Tarikogullari, Ayse Hande; Alptüzün, Vildan; Erciyas, Ercin

    2016-01-01

    A series of pyridinium salts bearing alkylphenyl groups at 1 position and hydrazone structure at 4 position of the pyridinium ring were synthesized and evaluated for the inhibition of both acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) enzymes. The cholinesterase (ChE) inhibitory activity studies were carried out by using the Ellman's colorimetric method. All compounds displayed considerable AChE and BuChE inhibitory activity and some of the compounds manifested remarkable anti-AChE activity compared to the reference compound, galantamine. Among the title compounds, the series including benzofuran aromatic ring exhibited the best inhibitory activity both on AChE and BuChE enzymes. Compound 3b, 4-[2-(1-(benzofuran-2-yl)ethylidene)hydrazinyl]-1-(3-phenylpropyl)pyridinium bromide, was the most active compound with IC50 value of 0.23 (0.24) µM against enantiomeric excess (ee)AChE (human (h)AChE) while compound 3a, 4-[2-(1-(benzofuran-2-yl)ethylidene)hydrazinyl]-1-phenethylpyridinium bromide, was the most active compound with IC50 value of 0.95 µM against BuChE. Moreover, 3a and b exhibited higher activity than the reference compound galantamine (eeAChE (hAChE) IC50 0.43 (0.52) µM; BuChE IC50 14.92 µM). Molecular docking studies were carried out on 3b having highest inhibitory activity against AChE. PMID:27581632

  8. Methyl Bromide Poisoning

    PubMed Central

    Rathus, E. M.; Landy, P. J.

    1961-01-01

    Seven cases of methyl bromide poisoning which occurred amongst workers engaged on a fumigation project are described. The methods adopted for investigation of the environmental situation are discussed and the measurement of blood bromide levels on random samples of workers is suggested as an index of the effectiveness of equipment and working methods. PMID:13739738

  9. Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

    SciTech Connect

    Krishnan,S.; Ward, R.; Hexemer, A.; Sohn, K.; Lee, K.; Angert, E.; Fischer, D.; Kramer, E.; Ober, C.

    2006-01-01

    Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

  10. Assessment of bromide-based ionic liquid toxicity toward aquatic organisms and QSAR analysis.

    PubMed

    Wang, Chao; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

    2015-05-01

    The toxicities of 24 bromide-based ionic liquids (Br-ILs) towards Vibrio fischeri (V. fischeri) and Daphnia magna (D. magna) were determined. These Br-ILs are composed of a bromide ion and a generic cation (i.e., pyrrolidinium, piperidinium, pyridinium or imidazolium) with different alkyl side chains. QSAR models with relatively high correlation coefficients, R(2), of 0.954 and 0.895 were developed for V. fischeri and D. magna. The model for V. fischeri indicated that the Br-IL toxicity towards V. fischeri was negatively correlated with the energy of the lowest unoccupied molecular orbitals (ELUMO) which reflects the electron affinities (EAs) and positively correlated with the volumes of Br-IL cations. For the D. magna model, the Br-IL toxicity was positively correlated with the dipole moment (μ) and negatively correlated with the total energy (TE) that is highly correlated with the molecular volume (V). For Br-ILs with the same cation ring, the toxicity increased as the length of the alkyl chains increased. For the same alkyl chain length, the toxicity order for V. fischeri was pyridinium>imidazolium>piperidinium>pyrrolidinium, except for those containing octyl side chains, while the toxicity ranking for D. magna was imidazolium~pyridinium>piperidinium>pyrrolidinium. PMID:25682588

  11. Preferred gauche conformation in N-(2-aminoethyl)pyridinium ions

    NASA Astrophysics Data System (ADS)

    Razenberg, Johannes A. S. J.; Nolte, Roeland J. M.; Drenth, Wiendelt; Kanters, Jan A.; Van Duijneveldt, Frans B.

    1984-01-01

    X-ray analysis of 1-[(2 S, 3 S)-2- N,N-dibenzylamino-3-methyl-1-pentyl]pyridinium p-toluenesulphonate and 1-[(2 S)-2- N,N-dibenzylamino-1-propyl]pyridinium p-toluenesulphonate reveals that in both compounds the central NCCN moiety is in the syn-clinal conformation. According to SCF-LCAO-MO calculations the syn-clinal conformation of the parent on, N-(2-aminomethyl)pyridinium is 23.4 kJ mol -1 lower in energy than the anti-periplanar conformation. The calculations suggest incipient bond formation between the amino nitrogen atom and the pyridinium ring in the syn-clinal conformation.

  12. Synthesis of indoles from pyridinium salts

    SciTech Connect

    Gromov, S.P.; Bkhaumik, M.M.; Bundel', Yu.G.

    1987-10-01

    The detailed analysis of the products of the interaction of nitropyridinium salts with ketones and alkylamines resulted in new data testifying in favor of the previously proposed scheme for the formation of indoles from pyridinium salts. The PMR spectra were taken on a Bruker WM-500 spectrometer for the compounds (IXa,b) in CDCl/sub 3/, and (IVg, i-Z) in acetone-D/sub 6/, and a Varian T-60 spectrometer for the alkylindoles (IVa,c,h) in CDCl/sub 3/, with reference to HMDS. The /sup 13/C NMR spectra were taken on a Bruker WM-250 spectrometer in CDCl/sub 3/. The mass spectra were taken on a Finnigan-4021 instrument.

  13. QSPR CORRELATION OF THE MELTING POINT FOR PYRIDINIUM BROMIDES, POTENTIAL IONIC LIQUIDS. (R828257)

    EPA Science Inventory

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

  14. [Quantitative aspects of the percutaneous uptake of wool wax alcohols (cetyl alcohol) and paraffins (octadecane) from different ointment bases].

    PubMed

    Zesch, A; Bauer, E

    1985-01-01

    Since topical vehicles are partly responsible for the effects of active agents--both the wanted and the unwanted effects--attempt was made to obtain quantitative data on the possible penetration of cetyl alcohol contained in an aqueous hydrophilie cream (DAB 8) and in a wool fat alcohol ointment (lanoline) (DAB 8). Also the behaviour of the long-chained hydrocarbon, paraffin (octadecan), in these vehicles and in petrolatum (DAB 8) was studied. We found that the emulsifying agent in a W/O emulsion was detectable in the epidermis in low concentrations after 100 min, but the same agent in O/W emulsions only after 1000 min. It is, therefore, unlikely that cetyl alcohol penetrates the intact skin in allergicologically relevant concentrations. However, with diseased skin, a marked percutaneous absorption of cetyl alcohol, but not with paraffin, must be expected. PMID:3987517

  15. The effect of cetylated fatty esters and physical therapy on myofascial pain syndrome of the neck.

    PubMed

    Sharan, Deepak; Jacob, Biju Nirmal; Ajeesh, P S; Bookout, Jack B; Barathur, Raj R

    2011-07-01

    Participants with Myofascial Pain Syndrome (MPS) of the neck were randomly assigned into 2 groups of the double-blinded study: topical cetylated fatty ester complex (CFEC) cream application plus physical therapy (CF-PT; n=37), and placebo cream application plus physical therapy (PL-PT; n=35). There were 3 visits during 4 weeks of treatment. Physical Therapy (PT), given twice/week, included Ischaemic Compression, Deep Pressure Trigger Point Massage and Myofascial Releases. Topical cream [CFEC cream (5.6%) and 1.5% menthol] or placebo cream [1.5% menthol, in a cream base] was applied twice/day. CF-PT provided the fastest and most effective study treatment modality. The addition of CFEC cream to PT resulted in statistically significant improvements, compared to PL-PT, for reduction of pain, neck disability and life quality indicators. Our results indicate that cetylated derivatives of fatty acids can effectively reduce pain and symptoms associated with neck MPS, when combined with physical therapy. PMID:21665114

  16. Lipase catalysed synthesis of cetyl oleate using ultrasound: Optimisation and kinetic studies.

    PubMed

    Khan, Nishat R; Jadhav, Sachin V; Rathod, Virendra K

    2015-11-01

    The current paper exemplifies the application of ultrasound technology to enzymatic synthesis of a cosmetic emollient ester, cetyl oleate. Fermase CALB™10000, a commercial Candida antarctica lipase B was used as a catalyst to accomplish the ultrasound supported synthesis. Multiple process parameters like reaction time, temperature, enzyme dose, alcohol to acid molar ratio, ultrasound power, frequency and speed of agitation were optimised. Maximum conversion of ∼95.96% was discerned at optimum conditions, i.e., 60°C temperature, 5% enzyme dose, 2:1 alcohol:acid ratio, 60 W ultrasound power, 25 kHz ultrasound frequency, 80% duty cycle and 80 rpm speed of agitation after purification steps. It was observed that the reaction reached equilibrium in a short duration of 30 min under the optimised conditions. This was considerably lesser than the time required for attaining equilibrium in conventional mechanical stirring method which was over 2h. Bisubstrate kinetic models like random bi-bi, ping pong bi-bi and ordered bi-bi were applied to the experimental data to determine initial rates and other kinetic parameters. Ordered bi-bi model showed the best fit with kinetic parameters, Vmax=0.029 M/min/gcatalyst, KA=0.00001 M, KB=4.8002 M, KiA=0.00014 M, KiB=3.7914 M & SSE=0.00022 for enzymatic cetyl oleate synthesis under ultrasound irradiation with inhibition by both acid and alcohol at high concentrations. PMID:25913878

  17. Copper-Catalyzed Annulation: A Method for the Systematic Synthesis of Phenanthridinium Bromide.

    PubMed

    Jhang, Yuan-Ye; Fan-Chiang, Tai-Ting; Huang, Jun-Min; Hsieh, Jen-Chieh

    2016-03-01

    A novel procedure for the Cu-catalyzed systematic synthesis of phenanthridinium bromide is reported. This transformation was achieved with direct construction of central pyridinium core by using an in situ formed biaryl imine as a substrate. Tolerance of a very wide variety of N-substituents is indicated; this has never previously been disclosed by other reports. Application of this method to synthesis of the natural alkaloid bicolorine, and its derivatives, was also carried out in only three synthetic steps from commercially available compounds. PMID:26883677

  18. Magnetochemistry of the tetrahaloferrate (III) ions. 7. Crystal structure and magnetic ordering in (pyridinium){sub 3}Fe{sub 2}Br{sub 9}

    SciTech Connect

    Lowe, C.B.; Shaviv, R.; Carlin, R.L.

    1994-07-06

    A monoclinic crystal structure was found by X-ray diffraction for bis [pyridinium tetrabromferrate(III)]-pyridinium bromide. The double salt contains two slightly distorted [FeBr{sub 4}]{sup -} tetrahedra, three pyridinium rings, and an uncoordinated halide in each asymmetric unit, as is characteristic of the A{sub 3}Fe{sub 2}X{sub 9} series of compounds. Unit cell parameters, monoclinic space group P2{sub 1}, are a = 7.656(3) {angstrom}, b = 14.237(5) {angstrom}, c = 13.725(5) {angstrom}, {beta} = 93.42(3){degrees}, and V = 1493(1) {angstrom}{sup 3}, using Mo K{alpha} radiation {lambda} = 0.710 69 {angstrom}, {rho}{sub calc} = 2.38 g cm{sup -3}, and Z = 2. The tetrahedra are aligned with their 3-fold axes parallel to the crystallographic c axis. Bond lengths (Fe-Br) range from 2.271(9) {angstrom} to 2.379(9) {angstrom} for the two different slightly distorted tetrahedral units. Magnetic susceptibility studies show that the material orders three-dimensionally at 7.4 {+-} 0.2 K. The data are compared to a HTS expansion of 1/{sub {chi}} for the S = 5/2 three-dimensional Heisenberg model antiferromagnet for a sc lattice with g = 1.98 and J/k{sub B} = -0.43 K. The specific heat measurements indicate two odd-shaped {lambda} features, at 7.3 and 8 K.

  19. Solvent-Directed Assembly of a Pyridinium-Tailored Methyl Oleanolate Amphiphile: Stepwise Growth of Microrods and Nanofibers.

    PubMed

    Gao, Yuxia; Hao, Jie; Wu, Jindan; Zhang, Xun; Hu, Jun; Ju, Yong

    2016-02-23

    Although a few architectures have been fabricated by the self-assembly of natural triterpenoids, the precise control of shape and size is rarely studied. Herein, a methyl oleanolate-bearing amphiphile, 1-[2-(methyl oleanolate)-2-oxoethyl]pyridinium bromide (MOP), has been designed and its assembly behavior was investigated. It was found that the morphologies of MOP assemblies ranged from nanoparticles to rigid microrods and flexible nanofibers in chloroform/p-xylene and methanol/water, respectively. During the assembly process, the systematical variational solvophobic/solvophilic effect resulted in the formation of spherical nanoparticles with opposite dipoles and converse bilayer structures. Moreover, such opposite molecular orientations lead to the inversion of supramolecular chirality and distinct mechanical properties. The driving forces and packing patterns of MOP in each solvent system were clearly demonstrated by the combination of NMR, UV-vis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), theoretical computation, and contact angle experiments, which revealed the roles of triterpenoids and pyridinium cations in the assembly process. This work provides a facile strategy to control the supramolecular structures in triterpenoid-based assemblies by adjusting the solvent polarity and composition. PMID:26829548

  20. Synthesis and antibacterial activity of pyridinium-tailored aromatic amphiphiles.

    PubMed

    Wang, Peiyi; Gao, Manni; Zhou, Lei; Wu, Zhibing; Hu, Deyu; Hu, Jun; Yang, Song

    2016-02-15

    In this Letter, the antibacterial activities of pyridinium-tailored aromatic amphiphiles were evaluated by turbidimeter tests in vitro. The bioassays revealed that most of the target compounds exhibit appreciable inhibition activities against the plant pathogenic bacteria Xanthomonas oryzae pv. oryzae, Ralstonia solanacearum, and Xanthomonas axonopodis pv. citri. The half-maximal effective concentrations (EC50) of 2-NP-10, 9-AP-10, and 9-AP-7 against these three bacteria were relatively high, which may be ascribed to the favourable hydrophobicity/hydrophilicity balance in these compounds. Our results suggest that pyridinium-tailored aromatic amphiphiles are promising bactericide candidates against plant bacterial diseases. PMID:26832217

  1. Bromide affecting drinking water mutagenicity.

    PubMed

    Myllykangas, T; Nissinen, T K; Mäki-Paakkanen, J; Hirvonen, A; Vartiainen, T

    2003-11-01

    The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide. PMID:13129514

  2. Action of reactive oxygen species in the antifungal mechanism of gemini-pyridinium salts against yeast.

    PubMed

    Shirai, Akihiro; Ueta, Shouko; Maseda, Hideaki; Kourai, Hiroki; Omasa, Takeshi

    2012-06-01

    We previously found that the gemini quaternary salt (gemini-QUAT) containing two pyridinium residues per molecule, 3,3'- (2,7-dioxaoctane) bis (1-decylpyridinium bromide) (3DOBP-4,10) , exerted fungicidal activity against Saccharomyces cerevisiae and caused respiration inhibition and the cytoplasmic leakage of ATP, magnesium, and potassium ions. Here, we investigated how the gemini-QUAT, 3DOBP-4,10, exerts more powerful antimicrobial activity than the mono-QUAT N-cetylpyridinium chloride (CPC) and examined the association between reactive oxygen species (ROS) and the antimicrobial mechanism. Antifungal assays showed that the activity of 3DOBP-4,10 against two yeasts, S. cerevisiae and Candida albicans, was significantly elevated under aerobic conditions, and largely reduced under anaerobic conditions (nitrogen atmosphere) . Adding radical scavengers such as superoxide dismutase, catalase and potassium iodide (KI) also decreased the fungicidal activity of 3DOBP-4,10 but negligibly affected that of CPC. We measured survival under static conditions and found that the rapid fungicidal profile of 3DOBP-4,10 was lost, whereas that of CPC was slightly affected in the presence of KI. Our results suggest that 3DOBP-4,10 exerts powerful antimicrobial activity by penetrating the cell wall and membrane, which then allows oxygen to enter the cells, where it participates in the generation of intracellular ROS. The activity could thus be attributable to a synergic antimicrobial combination of the disruption of organelle membranes by the QUAT and oxidative stress imposed by ROS. PMID:22790843

  3. Partition coefficients of organic compounds between water and imidazolium-, pyridinium-, and phosphonium-based ionic liquids.

    PubMed

    Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario

    2014-12-01

    The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions. PMID:25326892

  4. Condensed pyridines. 6. Synthesis and structure of adamantyl-, cyclopropyl- and alkyl-substituted 3-halomethyl-2,3-dihydro-8-cyanothiazolo(3,2-a)pyridinium salts and their oxazolo and selenazolo derivatives

    SciTech Connect

    Litvinov, V.P.; Sharanin, Yu.A.; Apenoeva, E.E.; Shestopalov, A.M.; Mortikov, V.Yu.; Nesterov, V.N.; Shklover, V.E.; Struchkov, Yu.T.

    1987-11-01

    The reaction of substituted 2-cyanopyridin-2(1H)-ones and their thione and selenone derivatives with allyl bromide gives the corresponding 2-allyloxy-, 2-allylmercapto-, and 2-allylseleno-3-pyridines, which upon treatment with halogens, form intramolecular quaternization products, namely, 3-halomethyl-2,3-dihydro-8-cyanooxazole(3,2-a)pyridinium salts and their thiazolo and selen-azolo analogs. X-ray diffraction structural analysis was used to determine the structure of 3-bromomethyl-2,3-dihydro-5,7-dimethyl-8-cyanothiazolo(3,2-a)pyridinium perchlorate. The IR spectra were taken in KBr pellets on a UR-20 spectrometer. The UV spectra were taken on a Specord UV-vis spectrometer in ethanol and DMF. The PMR spectra were taken on a Bruker WM-250 spectrometer at 250 MHz in CDCl/sub 3/ and DMSO-d/sub 6/ with TMS as the internal standard.

  5. Development of cetyl dimethicone based water-in-oil emulsion containing botanicals: Physical characteristics and stability.

    PubMed

    Waqas, Muhammad Khurram; Akhtar, Naveed; Shah, Pervaiz Akhtar; Danish, Muhammad Zeeshan; Shah, Arshad Ali; Braga, Valdir de Andrade; Khan, Barkat Ali

    2016-01-01

    The aim of current research was to develop a water-in-oil emulsion containing grape seed extract for application in cosmeceuticals. Finally grinded dried grape seeds powder was extracted with hydro alcoholic mixture. Emulsions consisting of different concentrations of cetyl dimethicone (Abile EM90), the nonionic emulsifier, liquid paraffin as oily phase and water as aqueous phase were developed. Color, odor, pH, viscosity, liquefaction, phase separation, centrifugation and thermal stability of the formulated emulsions were observed at various storage temperatures i.e. 8±0.5°C, 25±0.5°C, 40±0.5°C and 40°C±0.5°C with 70% RH. The stable formulation consist of 16% mineral oil, 4% of ABIL EM 90(®), 4% grape seeds extract, 1% rose oil and 75% distilled water. All the results derived from this study showed good stability over the three months study period which indicates w/o emulsion can be used as carrier of 4% grape seeds extract to enhance desired effects when applied topically. PMID:26826810

  6. High Yield of Wax Ester Synthesized from Cetyl Alcohol and Octanoic Acid by Lipozyme RMIM and Novozym 435

    PubMed Central

    Kuo, Chia-Hung; Chen, Hsin-Hung; Chen, Jiann-Hwa; Liu, Yung-Chuan; Shieh, Chwen-Jen

    2012-01-01

    Wax esters are long-chain esters that have been widely applied in premium lubricants, parting agents, antifoaming agents and cosmetics. In this study, the biocatalytic preparation of a specific wax ester, cetyl octanoate, is performed in n-hexane using two commercial immobilized lipases, i.e., Lipozyme® RMIM (Rhizomucor miehei) and Novozym® 435 (Candida antarctica). Response surface methodology (RSM) and 5-level-4-factor central composite rotatable design (CCRD) are employed to evaluate the effects of reaction time (1–5 h), reaction temperature (45–65 °C), substrate molar ratio (1–3:1), and enzyme amount (10%–50%) on the yield of cetyl octanoate. Using RSM to optimize the reaction, the maximum yields reached 94% and 98% using Lipozyme® RMIM and Novozym® 435, respectively. The optimum conditions for synthesis of cetyl octanoate by both lipases are established and compared. Novozym® 435 proves to be a more efficient biocatalyst than Lipozyme® RMIM. PMID:23109878

  7. Aqueous Zinc Bromide Waste Solidification

    SciTech Connect

    Langton, C.A.

    2002-07-23

    The goal of this study was to select one or more commercially available aqueous sorbents to solidify the zinc bromide solution stored in C-Area, identify the polymer to zinc bromide solution ratio (waste loading) for the selected sorbents, and identify processing issues that require further testing in pilot-scale testing.

  8. Tiotropium Bromide: An Update

    PubMed Central

    Heredia, Josep Lluis

    2009-01-01

    Tiotropium bromide is a once-daily inhaled anticholinergic bronchodilator. It works by blocking the muscarinic receptors in airway smooth muscle. Tiotropium has a wide therapeutic margin, due to its poor gastrointestinal absorption and its very low systemic bioavailability. The drug is mainly indicated in COPD patients. Clinically relevant outcomes such as significant improvements in spirometry, hyperinflation, dyspnea, heath status, acute exacerbations and mortality have been consistently observed in tiotropium clinical trials, and the drug has been shown to reduce the risk of mortality due to cardiac-vascular disease and respiratory failure. The main side effect reported is dryness of the mouth. Some subgroups of asthmatics also seem to respond to anticholinergic drugs: among them, those with the Arg/Arg genotype for the β2-adrenergic receptor and those with a high percentage of neutrophils in sputum. PMID:19461900

  9. N-Acetyl Cysteine (NAC)-Directed Detoxification of Methacryloxylethyl Cetyl Ammonium Chloride (DMAE-CB)

    PubMed Central

    Shan, Lequn; Wang, Yingjie; Tian, Min; Yang, Yanwei; Sun, Jinlong; Ban, Jinghao; Chen, Jihua

    2015-01-01

    Methacryloxylethyl cetyl ammonium chloride (DMAE-CB) is a polymerizable antibacterial monomer and has been proved as an effective strategy to achieve bioactive bonding with reliable bacterial inhibitory effects. However, the toxicity of DMAE-CB may hamper its wide application in clinical situations. Thus, this study was designed to investigate the toxicity of DMAE-CB and explore the possible protective effects of N-acetyl cysteine (NAC). High performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) analysis showed that chemical binding of NAC and DMAE-CB occurred in a time dependent manner. Pre-incubation of fourty-eight hours is required for adequate reaction between DMAE-CB and NAC. DMAE-CB reduced human dental pulp cells (hDPCs) viability in a dose-dependent manner. The toxic effects of DMAE-CB were accompanied by increased reactive oxygen species (ROS) level and reduced glutathione (GSH) content. NAC alleviated DMAE-CB-induced oxidative stress. Annexin V/ Propidium Iodide (PI) staining and Hoechst 33342 staining indicated that DMAE-CB induced apoptosis. Collapsed mitochondrial membrane potential (MMP) and activation of caspase-3 were also observed after DMAE-CB treatment. NAC rescued hDPCs from DMAE-CB-induced apoptosis, accompanied by lower level of MMP loss and caspase-3 activity. This study assists to elucidate the mechanism underlying the cytotoxic effects of DMAE-CB and provides theoretical supports for the searching of effective strategies to reduce toxicity of quaternary ammonium dental monomers. PMID:26274909

  10. Method for making aromatic ethers using diorganoamino pyridinium salt catalyst

    SciTech Connect

    Brunelle, D. J.; Singleton, D. A.

    1985-04-23

    A method is provided for making aromatic ethers by effecting the displacement of reactive radicals on an activated aromatic nucleus such as a phthalimide with a mono or bisalkali metal phenoxide in the presence of an organic solvent and a dialkylamino branched alkyl substituted pyridinium salt as a phase transfer catalyst. Improved yields of bis(aromatic ethers) are achieved without the production of undesirable by-products, such as alkylated phenols.

  11. Epoxy nanocomposites based on high temperature pyridinium-modified clays.

    PubMed

    Zhang, Qingxin; Naito, Kimiyoshi; Qi, Ben; Kagawa, Yutaka

    2009-01-01

    Polymer/clay nanocomposites are generally fabricated by thermal curing or melt compounding at elevated temperatures, however the thermal stability of common alkyl ammonium treated clays is poor and decomposition occurs inevitably during high temperature processing. In this study, we modified clays with an aromatic pyridinium salt. Thermogravimetric analysis (TGA) showed that the onset degradation temperature (Td(onset)) and maximum decomposition temperature (Td(max)) of the pyridinium treatment clays was up to 310 and 457 degrees C respectively implying high thermal stability. The thermal decomposition behaviour of the pyridinium modified clays was discussed. A series of epoxy/clay nanocomposites were synthesized using a diglycidyl ether of bisphenol A (DGEBA) epoxy and diethyltoluene diamine (DETDA). The morphology of epoxy/clay nanocomposites was characterized with wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM), and intercalated structures were observed. The storage modulus of epoxy was increased but glass transition temperature was decreased with clay incorporation. The effects of clays on glass transition temperature (Tg) of epoxy were also discussed. PMID:19441298

  12. Efficient and synergetic DNA delivery with pyridinium amphiphiles-gold nanoparticle composite systems having different packing parameters.

    PubMed

    Kizewski, Adrian; Ilies, Marc A

    2016-01-01

    Mixtures of highly curved pyridinium-decorated Au nanoparticles and standard pyridinium cationic lipids efficiently and synergetically transfected DNA in vitro, while displaying an excellent cytotoxic profile. PMID:26553432

  13. Investigation of the Pyridinium Ylide--Alkyne Cycloaddition as a Fluorogenic Coupling Reaction.

    PubMed

    Bonte, Simon; Ghinea, Ioana Otilia; Dinica, Rodica; Baussanne, Isabelle; Demeunynck, Martine

    2016-01-01

    The cycloaddition of pyridinium ylides with alkynes was investigated under mild conditions. A series of 13 pyridinium salts was prepared by alkylation of 4-substituted pyridines. Their reactivity with propiolic ester or amide in various reaction conditions (different temperatures, solvents, added bases) was studied, and 11 indolizines, with three points of structural variation, were, thus, isolated and characterized. The highest yields were obtained when electron-withdrawing groups were present on both the pyridinium ylide, generated in situ from the corresponding pyridinium salt, and the alkyne (X, Z = ester, amide, CN, carbonyl, etc.). Electron-withdrawing substituents, lowering the acid dissociation constant (pKa) of the pyridinium salts, allow the cycloaddition to proceed at pH 7.5 in aqueous buffers at room temperature. PMID:26978335

  14. Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

    SciTech Connect

    Hansen, Christopher S. Trevitt, Adam J.; Blanksby, Stephen J.; Chalyavi, Nahid; Bieske, Evan J.; Reimers, Jeffrey R.

    2015-01-07

    The S{sub 1}←S{sub 0} electronic transition of the N-pyridinium ion (C{sub 5}H{sub 5}NH{sup +}) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N{sub 2}-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H{sub 2}) in the photon energy range 37 000–45 000 cm{sup −1} with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculations are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum.

  15. Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

    NASA Astrophysics Data System (ADS)

    Hansen, Christopher S.; Blanksby, Stephen J.; Chalyavi, Nahid; Bieske, Evan J.; Reimers, Jeffrey R.; Trevitt, Adam J.

    2015-01-01

    The S1←S0 electronic transition of the N-pyridinium ion (C5H5NH+) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N2-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H2) in the photon energy range 37 000-45 000 cm-1 with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculations are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum.

  16. Interaction of Lucifer yellow with cetyltrimethyl ammonium bromide micelles and the consequent suppression of its non-radiative processes

    NASA Astrophysics Data System (ADS)

    Mishra, Padmaja P.; Koner, Apurba L.; Datta, Anindya

    2004-12-01

    The interaction of the fluorophore Lucifer yellow with micelles has been monitored using steady state and time resolved fluorescence techniques. Contrary to the popular belief that the fluorophore is too polar to associate with the stern layer or hydrophobic core of micelles, we have observed that it binds with the micelles of the positively charged surfactant cetyl trimethyl ammonium bromide and that such interaction causes an decrease in the rates of its non-radiative processes. This phenomenon cannot be explained solely in the light of a reduced polarity, as we have demonstrated that the photophysics of Lucifer yellow is complex and intramolecular charge transfer does not seem to be the only excited state process that is operative.

  17. Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2.

    PubMed

    Peroff, A G; Weitz, E; Van Duyne, R P

    2016-01-21

    Protonated heterocyclic amines, such as pyridinium, have been utilized as catalysts in the electrocatalytic reduction of carbon dioxide. While these represent a new and exciting class of electrocatalysts, the details of the mechanism and faradaic processes occurring in solution are unclear. We report a series of cyclic voltammetry experiments involving Pt, Ag, Au, and Cu electrodes, under both aqueous and nonaqueous conditions, directed towards gaining an improved mechanistic understanding of pyridinium electrochemistry. Surface-enhanced Raman (SER) spectroelectrochemistry was also performed on Cu film-over-nanosphere electrodes in order to identify adsorbed species. It was found that the reduction potential of pyridinium (-0.58 V vs. SCE) and its electrochemical reversibility are unique features of platinum electrodes. In contrast, the reduction potentials on Ag, Au, and Cu electrodes are ∼400 mV more negative than Pt in both the presence and the absence of CO2. SER spectroelectrochemistry of pyridinium solutions shows no evidence for a pyridinium radical or a pyridinium ion. Increased cathodic current in the presence of CO2 is only detected at scan rates less than 10 mV s(-1) in aqueous solutions. The addition of CO2 resulted in a shift in the potential for the hydrogen evolution reaction. Pyridinium electrochemistry was observed under nonaqueous conditions; however no increase in cathodic current was observed when CO2 was added to the solution. Based on this set of results it is concluded that the reduction potential of pyridinium is surface dependent, CO2 acts as a pseudo-reserve of H(+), and pyridinium and CO2 create an alternative mechanism for hydrogen evolution. PMID:26670579

  18. Two Equilibria of (N-Methyl-3-pyridinium)chlorocarbene, a Cationic Carbene.

    PubMed

    Cang, Hui; Moss, Robert A; Krogh-Jespersen, Karsten

    2016-02-11

    Equilibrium constants and the associated thermodynamic parameters are reported for the equilibria established between the cationic carbene (N-methyl-3-pyridinium)chlorocarbene tetrafluoroborate (MePyr(+)CCl BF4(-), 3) and 1,3,5-trimethoxybenzene (TMB) to form a carbene-TMB complex, as well as between carbene 3 and chloride ion to form the zwitterion, N-methyl-3-pyridinium dichloromethide (10). These equilibrium constants and thermodynamic parameters are contrasted with analogous data for several related carbenes, and the influence of the pyridinium unit in carbene 3 is thereby highlighted. Computational studies augment and elucidate the experimental results. PMID:26830199

  19. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  20. Mini review on blood-brain barrier penetration of pyridinium aldoximes.

    PubMed

    Kalász, H; Nurulain, S M; Veress, G; Antus, S; Darvas, F; Adeghate, E; Adem, A; Hashemi, F; Tekes, K

    2015-02-01

    This paper reviews the blood-brain barrier (BBB) penetration of newly developed pyridinium aldoximes. Pyridinium aldoximes are highly charged hydrophilic compounds used in the treatment of subjects exposed to organophosphonates because they are effective as acetylcholinesterase reactivators. Pyridinium aldoximes have antidotal effects against poisoning with cholinesterase inhibitors, a frequent problem affecting people working with organophosphate-based insecticides and pesticides. Toxic organophosphonate products such as sarin and tabun can be used by terrorists as chemical warfare agents. This poses a severe challenge to all innocent and peace-loving people worldwide. This review gives a brief summary of BBB transporters and description of the current in vitro and in vivo methods for the characterization of BBB penetration of established and novel pyridinium aldoximes. The authors provide a putative mechanism of penetration, outline some future ways of formulation and discuss the possible advantages and disadvantages of increasing BBB penetration. PMID:25291712

  1. 2-Amino-5-methyl-pyridinium 4-chloro-benzoate.

    PubMed

    Thanigaimani, Kaliyaperumal; Farhadikoutenaei, Abbas; Arshad, Suhana; Razak, Ibrahim Abdul

    2013-01-01

    The 4-chloro-benzoate anion of the title salt, C6H9N2(+)·C7H4ClO2(-), is nearly planar with a dihedral angle of 5.14 (16)° between the benzene ring and the carboxyl-ate group. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds with an R2(2)(8) ring motif. The ion pairs are further connected via N-H⋯O and weak C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. The crystal structure also features a π-π stacking inter-action between the pyridinium and benzene rings with a centroid-centroid distance of 3.7948 (9) Å. PMID:23476392

  2. 2-Amino-6-methyl-pyridinium 3-chloro-benzoate.

    PubMed

    Thanigaimani, Kaliyaperumal; Khalib, Nuridayanti Che; Arshad, Suhana; Razak, Ibrahim Abdul

    2013-03-01

    In the title salt, C6H9N2(+)·C7H4ClO2(-), the 3-chloro-benzoate anion shows a whole-mol-ecule disorder over two positions with a refined occupancy ratio of 0.505 (4):0.495 (4). In the crystal, the cations and anions are linked via N-H⋯O hydrogen bonds, forming a centrosymmetric 2 + 2 aggregate with R2(2)(8) and R4(2)(8) ring motifs. The crystal structure also features a π-π stacking inter-action between the pyridinium rings with a centroid-centroid distance of 3.8339 (9) Å. PMID:23476517

  3. 2-Amino-5-methyl-pyridinium 4-methyl-benzoate.

    PubMed

    Thanigaimani, Kaliyaperumal; Farhadikoutenaei, Abbas; Arshad, Suhana; Razak, Ibrahim Abdul

    2013-01-01

    The 4-methyl-benzoate anion of the title salt, C6H9N2(+)·C8H7O2(-), is nearly planar, with a dihedral angle of 6.26 (10)° between the benzene ring and the carboxyl-ate group. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds with an R2(2)(8) ring motif, forming an approximately planar ion pair with a dihedral angle of 9.63 (4)° between the pyridinium and benzene rings. The ion pairs are further connected via N-H⋯O and weak C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. PMID:23476474

  4. Reduction and alkaline hydrolysis of 5-oxoindeno(1,2-b)pyridinium salts

    SciTech Connect

    Mutsenietse, D.Kh.; Zandersons, A.Z.; Lusis, V.K.; Dubur, G.Ya.

    1987-07-01

    5,9b-dihydro derivatives of indeno(1,2-b)pyridine were obtained by the reduction of the corresponding 1,2-dimethyl-4-acryl-5-oxoindeno(1,2-b)pyridinium perchlorates. 1,2-dimethyl-3-ethoxycarbonyl-4-phenyl-5-oxoindeno(1,2-b)pyridinium perchlorate forms in alkaline medium with splitting, recyclization and deamination products.

  5. Lanthanum Bromide Detectors for Safeguards Measurements

    SciTech Connect

    Wright, J.

    2011-05-25

    Lanthanum bromide has advantages over other popular inorganic scintillator detectors. Lanthanum bromide offers superior resolution, and good efficiency when compared to sodium iodide and lanthanum chloride. It is a good alternative to high purity germanium detectors for some safeguards applications. This paper offers an initial look at lanthanum bromide detectors. Resolution of lanthanum bromide will be compared lanthanum chloride and sodium-iodide detectors through check source measurements. Relative efficiency and angular dependence will be looked at. Nuclear material spectra, to include plutonium and highly enriched uranium, will be compared between detector types.

  6. Structure and rheology of semisolid o/w creams containing cetyl alcohol/non-ionic surfactant mixed emulsifier and different polymers.

    PubMed

    Ribeiro, H M; Morais, J A; Eccleston, G M

    2004-04-01

    Oil-in-water (o/w) emulsions for cosmetic use, such as lotions and creams, are complex multiple-phase systems, which may contain a number of interacting surfactants, fatty amphiphiles, polymers and other excipients. This study investigates the influence of two synthetic cationic polymers, Polyquaternium-7 and Polyquaternium-11, and the natural anionic polymer, gum of acacia, on the rheology and microstructure of creams prepared with a non-ionic mixed emulsifier (cetyl stearyl alcohol-12EO/cetyl alcohol) using rheology (continuous shear, and viscoelastic creep and oscillation), microscopy and differential scanning calorimetry (DSC). A control cream containing no polymer was also investigated. The semisolid control cream was structured by a swollen lamellar gel network phase formed from the interaction of cetyl alcohol and the POE surfactant, in excess of that required to stabilize oil droplets, with continuous phase water. Endothermic transitions between 25 and 100 degrees C were identified as components of this phase. Incorporation of cationic polymer into the formulation caused significant loss of structure to produce a mobile semisolid containing larger oil droplets. The microscopical and thermal data implied that the cationic polymer caused the swollen lamellar gel network phase to transform into non-swollen crystals of cetyl alcohol. In contrast, incorporation of gum of acacia produced a thicker cream than the control, with smaller droplet sizes and little evidence of the gel network. Microscopical and thermal data implied that although there were also interactions between gum of acacia and both the surfactant and the swollen gel network phase, the semisolid properties were probably because of the ability of the gum of acacia to stabilize and thicken the emulsion in the absence of the swollen lamellar network. PMID:18494913

  7. Methacryloxylethyl Cetyl Ammonium Chloride Induces DNA Damage and Apoptosis in Human Dental Pulp Cells via Generation of Oxidative Stress

    PubMed Central

    Jiao, Yang; Ma, Sai; Wang, Yirong; Li, Jing; Shan, Lequn; Sun, Jinlong; Chen, Jihua

    2016-01-01

    The polymerizable antibacterial monomer methacryloxylethyl cetyl ammonium chloride (DMAE-CB) has provided an effective strategy to combat dental caries. However, the application of such material raises the question about the biological safety and the question remains open. The mechanism of this toxic action, however, is not yet clearly understood. The present study aims at providing novel insight into the possible causal link between cellular oxidative stress and DNA damage, as well as apoptosis in human dental pulp cells exposed to DMAE-CB. The enhanced formation of reactive oxygen species and depletion of glutathione, as well as differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase in DMAE-CB-treated cells indicated oxidative stress. By using substances that can alter GSH synthesis, we found that GSH was the key component in the regulation of cell response towards oxidative stress induced by DMAE-CB. The increase in oxidative stress-sensitive 8-Oxo-2'-deoxyguanosine (8-OHdG) content, formation of γ-H2AX and cell cycle G1 phase arrest indicated that DNA damage occurred as a result of the interaction between DNA base and ROS beyond the capacities of antioxidant mechanisms in cells exposed to DMAE-CB. Such oxidative DNA damage thus triggers the activation of ataxia telangiectasia-mutated (ATM) signaling, the intrinsic apoptotic pathway, and destruction of mitochondrial morphology and function. PMID:27143955

  8. Methacryloxylethyl Cetyl Ammonium Chloride Induces DNA Damage and Apoptosis in Human Dental Pulp Cells via Generation of Oxidative Stress.

    PubMed

    Jiao, Yang; Ma, Sai; Wang, Yirong; Li, Jing; Shan, Lequn; Sun, Jinlong; Chen, Jihua

    2016-01-01

    The polymerizable antibacterial monomer methacryloxylethyl cetyl ammonium chloride (DMAE-CB) has provided an effective strategy to combat dental caries. However, the application of such material raises the question about the biological safety and the question remains open. The mechanism of this toxic action, however, is not yet clearly understood. The present study aims at providing novel insight into the possible causal link between cellular oxidative stress and DNA damage, as well as apoptosis in human dental pulp cells exposed to DMAE-CB. The enhanced formation of reactive oxygen species and depletion of glutathione, as well as differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase in DMAE-CB-treated cells indicated oxidative stress. By using substances that can alter GSH synthesis, we found that GSH was the key component in the regulation of cell response towards oxidative stress induced by DMAE-CB. The increase in oxidative stress-sensitive 8-Oxo-2'-deoxyguanosine (8-OHdG) content, formation of γ-H2AX and cell cycle G1 phase arrest indicated that DNA damage occurred as a result of the interaction between DNA base and ROS beyond the capacities of antioxidant mechanisms in cells exposed to DMAE-CB. Such oxidative DNA damage thus triggers the activation of ataxia telangiectasia-mutated (ATM) signaling, the intrinsic apoptotic pathway, and destruction of mitochondrial morphology and function. PMID:27143955

  9. Immobilized Rhizopus oryzae lipase catalyzed synthesis of palm stearin and cetyl alcohol wax esters: Optimization by Response Surface Methodology

    PubMed Central

    2011-01-01

    Background Waxes are esters of long-chain fatty acids and long-chain alcohols. Their principal natural sources are animals (sperm whale oil) and vegetables (jojoba) which are expensive and not easily available. Wax esters synthesized by enzymatic transesterification, using palm stearin as raw material, can be considered as an alternative to natural ones. Results Palm stearin is a solid fraction obtained by fractionation of palm oil. Palm stearin was esterified with cetyl alcohol to produce a mixture of wax esters. A non-commercial immobilized lipase from Rhizopus oryzae was used as biocatalyst. Response surface methodology was employed to determine the effects of the temperature (30-50°C), the enzyme concentration (33.34-300 IU/mL), the alcohol/palm stearin molar ratio (3-7 mol/mol) and the substrate concentration (0.06-0.34 g/mL) on the conversion yield of palm stearin. Under optimal conditions (temperature, 30°C; enzyme concentration, 300 IU/mL; molar ratio 3 and substrate concentration 0.21 g/mL) a high conversion yield of 98.52% was reached within a reaction time of 2 h. Conclusions Response surface methodology was successfully applied to determine the optimum operational conditions for synthesis of palm stearin based wax esters. This study may provide useful tools to develop economical and efficient processes for the synthesis of wax esters. PMID:21682865

  10. Ionic Vapor Composition in Pyridinium-Based Ionic Liquids.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

    Strong electrostatic interactions in ionic compounds make vaporization a complex process. The gas phase can contain a broad range of ionic clusters, and the cluster composition can differ greatly from that in the liquid phase. Room-temperature ionic liquids (RTILs) constitute a complicated case due to their ionic nature, asymmetric structure, and a huge versatility of ions and ionic clusters. This work reports vapor-liquid equilibria and vapor compositions of butylpyridinium (BPY) RTILs formed with hexafluorophosphate (PF6), trifluoromethanesulfonate (TF), and bis(trifluoromethanesulfonyl)imide (TFSI) anions. Unlike inorganic crystals, the pyridinium-based RTILs contain significant percentages of charged clusters in the vapor phase. Ion triplets and ion quadruplets each constitute up to 10% of the vapor phase composition. Triples prevail over quadruples in [BPY][PF6] due to the size difference of the cation and the anion. The percentage of charged ionic clusters in the gas phase is in inverse proportion to the mass of the anion. The largest identified vaporized ionic cluster comprises eight ions, with a formation probability below 1%. Higher temperature fosters formation of larger clusters due to an increase of the saturated vapor density. PMID:27165866

  11. Spectroscopic Studies of Imidizolium and Pyridinium Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Booth, Ryan; Stearns, Jaime

    2015-03-01

    Ionic liquids (ILs) have been shown to be extremely useful in areas ranging from chemical synthesis to energetic materials. Furthermore, ILs are thought to be a potential replacement for hydrazine as satellite propellants because a subset are hypergolic with nitric acid. While ILs are useful, however, there is a lack of understanding of the microscopic origins for their macroscopic properties (e.g. viscosity). An example of this is that [emim+][tf2N-] is three times less viscous than its methylated counterpart [emmim+][tf2N-] and there is some discord regarding the reason. We have investigated the molecular properties of such IL pairs using UV and IR spectroscopy in the gas phase on both imidozolium and pyridinium-based ([pyr+]) ILs. UV data show that the photophysics of [emmim+][tf2N-] is different than [emim+][tf2N-] in that there is a lack of evidence for the existence of a charge transfer (CT) state (as was seen in [emim+][tf2N-]). Preliminary UV spectra for the [pyr+] ILs show at least two distinct peaks in the region from 208-270 nm, which are tentatively established as CT states between the anion and cation. IR spectra deliver structural information for both sets of ILs and should provide insight into the correlation between microscopic and macroscopic properties.

  12. Reverse Anomeric Effect in Large-Amplitude Pyridinium Amide-Containing Mannosyl [2]Rotaxane Molecular Shuttles.

    PubMed

    Riss-Yaw, Benjamin; Waelès, Philip; Coutrot, Frédéric

    2016-06-17

    The reverse anomeric effect (RAE) was investigated in different mannosyl [2]rotaxane molecular shuttle isomers that contain dibenzo-24-crown-8 (DB24C8) as the macrocycle, and anilinium and pyridinium amide as molecular stations. The switching on or off of the RAE was possible depending on both the pyridinium amide motif and the localization of the DB24C8 along the thread. The (1) C4 mannopyranosyl chair-like conformation was observed in all the non-interlocked molecules because the anomeric carbon of the mannose is linked to the positively charged nitrogen of the pyridinium unit. In the protonated rotaxanes, the (1) C4 chair conformation of the mannose end remains because the DB24C8 resides around the best anilinium station, which is located at the other end of the axle. Upon deprotonation of the anilinium, the DB24C8 shuttles with a large-amplitude motion toward the pyridinium amide stations, where it interacts in a different fashion depending on the pyridinium motif. In one molecular shuttle, the RAE could be switched on or off with control at one end of the encircled thread upon protonation/deprotonation of the other end, through shuttling of the DB24C8. PMID:27062432

  13. METHYL BROMIDE ALTERNATIVES FOR VINEYARD REPLANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation with methyl bromide is needed by grape growers in central California to control soilborne pests. However, use of methyl bromide is banned and soil fumigation with other chemicals subjects to strict regulations to protect human health and air quality. The objective was to determine,...

  14. Measuring methyl bromide emissions from fields

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.; Yates, M.V.

    1995-12-31

    Methyl bromide is used extensively for pest control. Recent evidence suggests that methyl bromide may react with stratospheric ozone and, due to the Clean Air Act, is scheduled for phase-out within the next 5 to 10 years. As indicated in a recent report from The National Agricultural Pesticide Impact Assessment Program, there will be substantial economic impact on the agricultural community if the use of methyl bromide is restricted. There are several areas of uncertainty concerning the agricultural use of methyl bromide. Foremost is the quantification of mass emitted to the atmosphere from agricultural fields. To address this, two field experiments were conducted to directly measure methyl bromide emissions. In the first experiment, methyl bromide was injected at approximately 25 cm depth and the soil was covered with 1 mil high-density polyethylene plastic. The second experiment was similar except that methyl bromide was injected at approximately 68 cm depth and the soil was not covered. From these experiments, the emission rate into the atmosphere and the subsurface transport of methyl bromide was determined. Both experiments include a field-scale mass balance to verify the accuracy of the flux-measurement methods as well as to check data consistency. The volatilization rate and mass lost was determined from estimates of the degradation and from several atmospheric and chamber flux methods.

  15. 77 FR 35295 - Methyl Bromide; Pesticide Tolerances

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-13

    ... AGENCY 40 CFR Part 180 RIN 2070-ZA16 Methyl Bromide; Pesticide Tolerances AGENCY: Environmental... methyl bromide in or on cotton, undelinted seed under the Federal Food, Drug, and Cosmetic Act (FFDCA.... Background In the Federal Register of April 6, 2012 (77 FR 20752) (FRL-9345- 1), EPA issued a proposed...

  16. Modulation of pyridinium cationic lipid-DNA complex properties by pyridinium gemini surfactants and its impact on lipoplex transfection properties.

    PubMed

    Sharma, Vishnu Dutt; Lees, Julia; Hoffman, Nicholas E; Brailoiu, Eugen; Madesh, Muniswamy; Wunder, Stephanie L; Ilies, Marc A

    2014-02-01

    The study presents the effects of blending a cationic gemini surfactant into cationic lipid bilayers and its impact on the plasmid DNA compaction and delivery process. Using nanoDSC, dynamic light scattering, zeta potential, and electrophoretic mobility measurements, together with transfection (2D- and 3D-) and viability assays, we identified the main physicochemical parameters of the lipid bilayers, liposomes, and lipoplexes that are affected by the gemini surfactant addition. We also correlated the cationic bilayer composition with the dynamics of the DNA compaction process and with transfection efficiency, cytotoxicity, and the internalization mechanism of the resultant nucleic acid complexes. We found that the blending of gemini surfactant into the cationic bilayers fluidized the supramolecular assemblies, reduced the amount of positive charge required to fully compact the plasmid DNA and, in certain cases, changed the internalization mechanism of the lipoplexes. The transfection efficiency of select ternary lipoplexes derived from cationic gemini surfactants and lipids was several times superior to the transfection efficiency of corresponding binary lipoplexes, also surpassing standard transfection systems. The overall impact of gemini surfactants into the formation and dynamic of cationic bilayers was found to depend heavily on the presence of colipids, their nature, and amount present in lipoplexes. The study confirmed the possibility of combining the specific properties of pyridinium gemini surfactants and cationic lipids synergistically to obtain efficient synthetic transfection systems with negligible cytotoxicity useful for therapeutic gene delivery. PMID:24377350

  17. Modulation of pyridinium cationic lipid-DNA complex properties by pyridinium gemini surfactants and its impact on lipoplex transfection properties

    PubMed Central

    Sharma, Vishnu Dutt; Lees, Julia; Hoffman, Nicholas E.; Brailoiu, Eugen; Madesh, Muniswamy; Wunder, Stephanie L.; Ilies, Marc A.

    2014-01-01

    The study presents the effects of blending a cationic gemini surfactant into cationic lipid bilayers and its impact towards plasmid DNA compaction and delivery process. Using nanoDSC, dynamic light scattering, zeta potential and electrophoretic mobility measurements, together with transfection (2D- and 3D-) and viability assays, we identified the main physicochemical parameters of the lipid bilayers, liposomes and lipoplexes that are affected by the gemini surfactant addition. We also correlated the cationic bilayer composition with the dynamics of the DNA compaction process, and with transfection efficiency, cytotoxicity and internalization mechanism of the resultant nucleic acid complexes. We found that blending of gemini surfactant into the cationic bilayers fluidized the supramolecular assemblies, reduced the amount of positive charge required to fully compact the plasmid DNA and, in certain cases, changed the internalization mechanism of the lipoplexes. Transfection efficiency of select ternary lipoplexes derived from cationic gemini surfactants and lipids was several times superior to transfection efficiency of corresponding binary lipoplexes, also surpassing standard transfection systems. The overall impact of gemini surfactants into the formation and dynamic of cationic bilayers was found to depend heavily on the presence of co-lipids, their nature and amount present into lipoplexes. The study confirmed the possibility of combining the specific properties of pyridinium gemini surfactants and cationic lipids synergistically for obtaining efficient synthetic transfection systems with negligible cytotoxicity useful for therapeutic gene delivery. PMID:24377350

  18. Pyridinium derivatives of histamine are potent activators of cytosolic carbonic anhydrase isoforms I, II and VII.

    PubMed

    Dave, Khyati; Scozzafava, Andrea; Vullo, Daniela; Supuran, Claudiu T; Ilies, Marc A

    2011-04-21

    A series of positively-charged derivatives has been prepared by reaction of histamine with substituted pyrylium salts. These pyridinium histamine derivatives were investigated as activators of the zinc enzyme carbonic anhydrase (CA, EC 4.2.1.1) and more precisely the human isoforms hCA I, II and VII. Activities from the subnanomolar to the micromolar range were detected for these compounds as activators of the three isoforms, confirming the validity of current and previous designs. The substitution pattern at the pyridinium ring was the main factor influencing activity, the three isoforms showing different structural requirements for good activity, related with the number of pyridinium substituting groups and their nature, among various alkyl, phenyl and para-substituted styryl moieties. We were successful in identifying nanomolar potent and selective activators for each isozyme and also activators with a relatively good activity against all isozymes tested--valuable lead compounds for physiology and pathology studies involving these isozymes. PMID:21369613

  19. Thermal decomposition and vibrational spectroscopic aspects of pyridinium hexafluorophosphate (C5H5NHPF6)

    NASA Astrophysics Data System (ADS)

    Lekgoathi, M. D. S.; Kock, L. D.

    2016-12-01

    Thermal decomposition and vibrational spectroscopic properties of pyridinium hexafluorophosphate (C5H5NHPF6) have been studied. The structure of the compound is better interpreted as having a cubic space group, based on Raman and infrared vibrational spectroscopy experiments and group theoretical correlation data between site symmetry species and the spectroscopic space group. The 13C NMR data shows three significant signals corresponding to the three chemical environments expected on the pyridinium ring i.e. γ, β and α carbons, suggesting that the position of the anion must be symmetrical with respect to the pyridinium ring's C2v symmetry. The process of thermal decomposition of the compound using TGA methods was found to follow a contracting volume model. The activation energy associated with the thermal decomposition reaction of the compound is 108.5 kJ mol-1, while the pre exponential factor is 1.51 × 109 sec-1.

  20. Structural and Formulation Factors Influencing Pyridinium Lipid-based Gene Transfer

    PubMed Central

    Zhu, Lin; Lu, Yan; Miller, Duane D.; Mahato, Ram I.

    2009-01-01

    A series of pyridinium lipids containing a heterocyclic ring and a nitrogen atom were synthesized to determine the structure-activity relationship for gene delivery. Pyrylium chloroaluminate was synthesized by monoacylation of mesityl oxide and converted into pyrylium hexafluorophosphate, which was used as the key intermediate for reaction with different primary amines, to yield hydroxyethylpyridinium hexafluorophosphate and aminoethylpyridinium hexafluorophosphate. Acylation of these pyridinium salts with different types of fatty acid chlorides afforded the final pyridinium lipids, which were mixed with a co-lipid, such as L-alpha-dioleoylphosphatidylethanolamine (DOPE) and cholesterol (Chol) to prepare cationic liposomes by sonication. These liposomes were mixed with plasmid DNA encoding enhanced green fluorescent protein (pCMS-EGFP) or luciferase (pDNA3-Luc) and transfected into Chinese Hamster Ovary (CHO) cells. Several factors including hydrophobic anchor chain length, anchor chain type, configuration of double bond, linker type, co-lipid type, cationic lipid: co-lipid molar ratio, charge ratio (N/P), and cell type had significant influence on transfection efficiency and cytotoxicity. Pyridinium lipids with amide linker showed significantly higher transfection efficiency compared to their ester counterparts. Liposomes prepared at 1:1 molar ratio of pyridinium lipid and co-lipid showed higher transfection efficiency when either DOPE or cholesterol was used as a co-lipid to prepare cationic liposomes for complex formation with plasmid DNA at 3:1(+/−) charge ratio. Pyridinium liposomes based on hydrophobic anchor chain length of 16 showed higher transfection efficiency and lower cytotoxicity. The pyridinium lipid with trans-configuration of the double bond in fatty acid chain showed higher transfection efficiency than its counterpart with cis-configuration at the same fatty acid chain length. In the presence of serum, C16:0 and Lipofectamine significantly

  1. Unexpected formation of a novel pyridinium-containing catecholate ligand and its manganese(III) complex.

    PubMed

    Sheriff, Tippu S; Watkinson, Michael; Motevalli, Majid; Lesin, Jocelyne F

    2010-01-01

    Nucleophilic aromatic substitution of tetrachloro-o-benzoquinone by pyridine and reduction of the o-quinone to the catechol by hydroxylamine forms 1,2-dihydroxy-3,5,6-trichlorobenzene-4-pyridinium chloride. This compound reacts with manganese(II) acetate in air to form chlorobis(3,5,6-trichlorobenzene 4-pyridinium catecholate)manganese(III), which represents the first complex of this ligand class to be structurally characterized by X-ray diffraction; this complex is active in the catalytic reduction of dioxygen to hydrogen peroxide under ambient conditions and turnover frequencies (TOFs) >10,000 h(-1) can be obtained. PMID:20023930

  2. High Proton Conductivity of Zinc Oxalate Coordination Polymers Mediated by a Hydrogen Bond with Pyridinium.

    PubMed

    Yamada, Teppei; Nankawa, Takuya

    2016-09-01

    A novel metal-organic framework, (Hpy)2[Zn2(ox)3]·nH2O (n = 0, 1), having a pyridinium cation, was newly synthesized, and the crystal structures were determined. The hydrated compound shows a high proton conductivity of 2.2 × 10(-3) S cm(-1) at 298 K and 98% relative humidity. Single crystal XRD analysis revealed a rotational displacement factor for the hydrated pyridinium ring and elongated water site that is thought to cause the high proton conductivity. PMID:27552647

  3. Tandem dinucleophilic cyclization of cyclohexane-1,3-diones with pyridinium salts

    PubMed Central

    Kiamehr, Mostafa; Mkrtchyan, Satenik; Semeniuchenko, Volodymyr; Supe, Linda; Villinger, Alexander

    2013-01-01

    Summary The cyclization of cyclohexane-1,3-diones with various substituted pyridinium salts afforded functionalized 8-oxa-10-aza-tricyclo[7.3.1.02,7]trideca-2(7),11-dienes. The reaction proceeds by regioselective attack of the central carbon atom of the 1,3-dicarbonyl unit to 4-position of the pyridinium salt and subsequent cyclization by base-assisted proton migration and nucleophilic addition of the oxygen atom to the 2-position, as was elucidated by DFT computations. Fairly extensive screening of bases and additives revealed that the presence of potassium cations is essential for formation of the product. PMID:23843903

  4. [pi]-Stacking and aggregation of pyridinium-substituted indolizines

    SciTech Connect

    Carter, P.W.; DiMagno, S.G. ); Porter, J.D.; Streitwieser, A. )

    1993-02-04

    The tendency for pyridinium-substituted indolizines to aggregate in aqueous and acetonitrile solution is dominated by solute-solvent interactions and by the amphiphilic nature of the cations. In solution, these compounds exhibit an unusual sequence of discrete, red-shifted fluorescence bands whose intensities are a function of concentration over the range 10[sup [minus]5]--10[sup [minus]3] M. It is proposed that [pi]-stacking of the indolizine residues results in weak electronic interactions ([beta] [approximately]0.13 eV) which are sufficient to result in the delocalization of bound excitonic states over the aggregate. Fluorescence from the aggregate occurs by radiative annihilation of the delocalized exciton. Stepwise dimerization (K[sub 2]) and trimerization (K[sub 3]) equilibrium constants for the cations calculated from the emission spectra range from about 400 to 65,000. Solution conductivity measurements indicate that cation aggregation does not require ion pairing. However, where significant ion-pairing does occur, K[sub 2] and K[sub 3] are increased by at least an order of magnitude. X-ray crystallography was used to determine the structures of cation dimers which form in the solid state, and these structures were used as working models for the geometry of the solution aggregates. Electrostatic and dispersion interactions calculated on the basis of those geometries account for some of the free energy of aggregate formation, but solvent entropic effects are believed to provide the strongest driving force for indolizine aggregation in solution. 58 refs., 8 figs., 4 tabs.

  5. Crystal structure and thermal behaviour of pyridinium styphnate

    PubMed Central

    Muthulakshmi, Selvarasu; Kalaivani, Doraisamyraja

    2015-01-01

    In the crystal structure of the title mol­ecular salt, C5H6N+·C6H2N3O8 − (systematic name: pyridinium 3-hy­droxy-2,4,6-tri­nitro­phenolate), the pyridin­ium cation and the 3-hy­droxy-2,4,6-tri­nitro­phenolate anion are linked through bifurcated N—H⋯(O,O) hydrogen bonds, forming an R 1 2(6) ring motif. The nitro group para with respect to phenolate ion forms an intra­molecular hydrogen bond with the adjacent phenolic –OH group, which results in an S(6) ring motif. The nitro group flanked by the phenolate ion and the phenolic –OH group deviates noticeably from the benzene ring, subtending a dihedral angle of 89.2 (4)°. The other two nitro groups deviate only slightly from the plane of the benzene ring, making dihedral angles of 2.8 (4) and 3.4 (3)°. In the crystal, the 3-hy­droxy-2,4,6-tri­nitro­phenolate anions are linked through O—H⋯O hydrogen bonds, forming chains along [100]. These anionic chains, to which the cations are attached, are linked via C—H⋯O hydrogen bonds, forming a three-dimensional structure. Impact friction sensitivity tests and TGA/DTA studies on the title mol­ecular salt imply that it is an insensitive high-energy-density material. PMID:25878796

  6. Neurological manifestation of methyl bromide intoxication.

    PubMed

    Suwanlaong, Kanokrat; Phanthumchinda, Kammant

    2008-03-01

    Methyl bromide is a highly toxic gas with poor olfactory warning properties. It is widely used as insecticidal fumigant for dry foodstuffs and can be toxic to central and peripheral nervous systems. Most neurological manifestations of methyl bromide intoxication occur from inhalation. Acute toxicity characterized by headache, dizziness, abdominal pain, nausea, vomiting and visual disturbances. Tremor, convulsion, unconsciousness and permanent brain damage may occur in severe poisoning. Chronic exposure can cause neuropathy, pyramidal and cerebellar dysfunction, as well as neuropsychiatric disturbances. The first case of methyl bromide intoxication in Thailand has been described. The patient was a 24-year-old man who worked in a warehouse of imported vegetables fumigated with methyl bromide. He presented with unstable gait, vertigo and paresthesia of both feet, for two weeks. He had a history of chronic exposure to methyl bromide for three years. His fourteen co-workers also developed the same symptoms but less in severity. Neurological examination revealed ataxic gait, decreased pain and vibratory sense on both feet, impaired cerebellar signs and hyperactive reflex in all extremities. The serum concentration of methyl bromide was 8.18 mg/dl. Electrophysilogical study was normal. Magnetic resonance imaging of the brain (MRI) revealed bilateral symmetrical lesion of abnormal hypersignal intensity on T2 and fluid-attenuation inversion recovery (FLAIR) sequences at bilateral dentate nuclei of cerebellum and periventricular area of the fourth ventricle. This incident stresses the need for improvement of worker education and safety precautions during all stages of methyl bromide fumigation. PMID:18575299

  7. Potassium bromide method of infrared sampling

    USGS Publications Warehouse

    Milkey, R.G.

    1958-01-01

    In the preparation of potassium bromide pressed windows for use in the infrared analysis of solids, severe grinding of the potassium bromide powder may produce strong absorption bands that could interfere seriously with the spectra of the sample. These absorption bands appear to be due to some crystal alteration of the potassium bromide as a result of the grinding process. They were less apt to occur when the coarser powder, which had received a relatively gentle grinding, was used. Window blanks prepared from the coarser powders showed smaller adsorbed water peaks and generally higher over-all transmittance readings than windows pressed from the very fine powders.

  8. 2-Alkynyl-N-propargyl pyridinium salts: pyridinium-based heterocyclic skipped aza-enediynes that cleave DNA by deoxyribosyl hydrogen-atom abstraction and guanine oxidation.

    PubMed

    Tuesuwan, Bodin; Kerwin, Sean M

    2006-06-13

    Diradical-generating cyclizations such as the enediyne Bergman cyclization and the enyne allene Myers-Saito cyclization have been exploited by nature in the mechanism of DNA cleavage by a series of potent antitumor antibiotics. Alternative diradical-generating cyclizations have been proposed in the design of selective antitumor agents; however, little information is available concerning the utility of these alternative cyclizations in radical-based DNA cleavage chemistry. One such alternative diradical-generating cyclization, the aza-Myers-Saito cyclization of aza-enyne allenes that are derived from base-promoted isomerization of skipped aza-enediynes, has been recently reported. Here, we report the synthesis and DNA cleavage chemistry of a series of pyridinium skipped aza-enediynes (2-alkynyl-N-propargyl pyridinium salts). Efficient DNA cleavage requires the presence of the skipped aza-enediyne functionality, and optimal DNA cleavage occurs at basic pH. Within this series of compounds, the analogue bearing a p-methoxyphenyl group on the pyridinium 2-alkyne substituents was found to be the most effective DNA cleavage agent, displaying significant supercoiled DNA-nicking activity at concentrations as low as 1 microM. Detailed studies of this analogue show that DNA cleavage occurs through 4'-hydrogen-atom abstraction from the DNA backbone and oxidation of guanine bases. This is the first report of enediyne-like radical-based DNA cleavage by an agent designed to undergo an alternative diradical-generating cyclization. PMID:16752915

  9. Emission of methyl bromide from biomass burning

    SciTech Connect

    Manoe, S.; Andreae, M.O. )

    1994-03-04

    Bromine is, per atom, far more efficient than chlorine in destroying stratospheric ozone, and methyl bromide is the single largest source of stratospheric bromine. The two main previously known sources of this compound are emissions from the ocean and from the compound's use as an agricultural pesticide. Laboratory biomass combustion experiments showed that methyl bromide was emitted in the smoke from various fuels tested. Methyl bromide was also found in smoke plumes from wildfires in savannas, chaparral, and boreal forest. Global emissions of methyl bromide from biomass burning are estimated to be in the range of 10 to 50 gigagrams per year, which is comparable to the amount produced by ocean emission and pesticide use and represents a major contribution ([approximately]30 percent) to the stratospheric bromine budget.

  10. Growth and characterization of lead bromide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Glicksman, M. E.; Coriell, S. R.; Santoro, G. J.; Duval, W. M. B.

    1992-01-01

    Lead(II) bromide was purified by a combination of directional freezing and zone-refining methods. Differential thermal analysis of the lead bromide showed that a destructive phase transformation occurs below the melting temperature. This transformation causes extensive cracking, making it very difficult to grow a large single crystal. Energy of phase transformation for pure lead bromide was determined to be 24.67 cal/g. To circumvent this limitation, crystals were doped by silver bromide which decreased the energy of phase transformation. The addition of silver helped in achieving the size, but enhanced the inhomogeneity in the crystal. The acoustic attenuation constant was almost identical for the pure and doped (below 3000 ppm) crystals.

  11. A Facile Oxidation of Alcohols Using Pyridinium Chlorochromate/Silica Gel

    NASA Astrophysics Data System (ADS)

    Luzzio, Frederick A.; Fitch, Richard W.; Moore, William J.; Mudd, Kelli J.

    1999-07-01

    An efficient and convenient adaptation of the pyridinium chlorochromate (PCC) oxidation for an organic chemistry student exercise is based on the employment of reagent-grade silica gel, which simplifies workup and purification of the product. The procedures include the oxidation of 4-tert-butylcyclohexanol to 4-tert-butylcyclohexanone and d,l-menthol to d,l-menthone.

  12. Aryl-triazole foldamers incorporating a pyridinium motif for halide anion binding in aqueous media.

    PubMed

    Shang, Jie; Zhao, Wei; Li, Xichen; Wang, Ying; Jiang, Hua

    2016-03-15

    Aryl-triazole oligomers incorporating a pyridinium motif have been synthesized from their pyridine precursors. Anion binding studies show that methylation of the pyridine units can significantly enhance the halide anion affinities of the folded oligomers so that the foldamers are capable of binding halide anions in aqueous solutions. PMID:26933696

  13. Pyridinium hydrobromide perbromide: a versatile catalyst for aziridination of olefins using Chloramine-T.

    PubMed

    Ali, S I; Nikalje, M D; Sudalai, A

    1999-09-01

    [reaction: see text] Pyridinium hydrobromide perbromide (Py x HBr3) catalyzes effectively the aziridination of electron-deficient as well as electron-rich olefins using Chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide) as a nitrogen source to afford the corresponding aziridines in moderate to good yields. PMID:16118868

  14. Investigation of drug interactions with pinaverium bromide.

    PubMed

    Devred, C; Godeau, P; Guerot, C; Librez, P; Mougeot, G; Orsetti, A; Segrestaa, J M

    1986-01-01

    A series of studies was carried out at 6 centres to investigate possible drug interaction between the spasmolytic, pinaverium bromide, and cardiac glycosides, anticoagulants and hypoglycaemic agents given to patients as part of the long-term treatment of their condition. The results of clinical and laboratory investigations did not show any evidence of pinaverium bromide interfering with the action or activity of any of the drugs studied. PMID:3084176

  15. Chiral Pyridinium Phosphoramide as a Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction.

    PubMed

    Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu

    2016-05-01

    Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction. PMID:27093584

  16. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  17. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  18. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  19. Analysis of mixed micellar and interfacial behavior of cationic gemini hexanediyl-1,6-bis(dimethylcetylammonium bromide) with conventional ionic and nonionic surfactants in aqueous medium.

    PubMed

    Din, Kabir-ud; Sheikh, Mohmad Shafi; Dar, Aijaz Ahmad

    2010-05-13

    The interaction between cationic gemini hexanediyl-1,6-bis(dimethylcetylammonium bromide) (16-6-16, abbreviated as G6) with conventional cationic cetylpyridinium chloride (CPC), anionic sodium bis(2-ethyl hexyl)sulfosuccinate (AOT) and nonionic polyoxyethylene 10 cetyl ether (Brij56) in aqueous medium has been investigated at 25 degrees C. Different physicochemical properties such as critical micelle concentration (cmc), surface excess concentration (Gamma(max)), minimum area per molecule (A(min)), and interaction parameters (beta(m), beta(sigma)) as well as other thermodynamic and micellar properties have been determined. The interfacial and bulk behaviors were explored using theoretical models of Clint, Rubingh, Rosen, Motomura, and Maeda for justification and comparison of results of different binary combinations with the geminis of alkanediyl-alpha,omega-bis(dimethylcetylammonium bromide) series. Synergism was observed in all the binary combinations in the micelle and at interface with lowering of packing parameter due to slight expansion of A(min). The results of the present study could be of interest for selection of surfactant mixtures for surfactant-enhanced remediation (SER) of soils and aquifers contaminated by hydrophobic organic compounds (HOCs). PMID:20397638

  20. [The clinical pharmacological profile of pinaverium bromide].

    PubMed

    Guslandi, M

    1994-04-01

    Pinaverium bromide is a locally acting spasmolytic agent of the digestive tract. Its mechanism of action relies upon inhibition of calcium ion entrance into smooth muscle cells (calcium-antagonist effect). In humans pinaverium facilitates gastric emptying and decreases intestinal transit time in patients with constipation. Pinaverium is very effective in improving symptoms of irritable bowel syndrome (abdominal pain, gas, diarrhea or constipation). In this respect the drug proved to be significantly superior to placebo, at least as effective as trimebutine and on the whole more active than otilonium and prifinium bromide, being always extremely well tolerated. PMID:8028745

  1. Effects of pinaverium bromide on Oddi's sphincter.

    PubMed

    DiSomma, C; Reboa, G; Patrone, M G; Mortola, G P; Sala, G; Ciampini, M

    1986-01-01

    Twelve to 15 days after cholecystectomy, endocholedochal pressure was measured in ten patients before and one hour after oral administration of 15 mg of pinaverium bromide (six patients) or placebo. The mean endocholedochal pressure was 7.1 +/- 0.25 mmHg before and 3.1 +/- 0.2 mmHg after pinaverium (P less than 0.01), and 7.0 +/- 0.2 and 6.8 +/- 1.2 mmHg in the placebo-treated patients. The results suggest that pinaverium bromide has a specific effect on the common bile duct and probably on Oddi's sphincter. PMID:3815457

  2. Oxygen versus nitrogen interactions in lithium dinitramidate dihydrate and pyridinium dinitramidate.

    PubMed

    Klapötke, Thomas M; Krumm, Burkhard; Scherr, Matthias

    2008-01-01

    The title compounds, diaquadinitramidatolithium(I), [Li(N3O4)(H2O)2], (I), and pyridinium dinitramidate, C5H6N+ x N3O4(-), (II), differ significantly in their cation-anion contacts. The Li+ atom of (I) is coordinated by two O atoms of the dinitramide anion in a chelate and by four additional water molecules, with the Li and central N atom of the anion on a twofold rotation axis. The pyridinium cation of (II) exhibits a contact with the dinitramide anion via an intermolecular N-H...N hydrogen bridge. These interactions are compared with those found in reported anhydrous lithium dinitramide and ammonium dinitramide salts. PMID:18216429

  3. On the viscosity of pyridinium based ionic liquids: an experimental and computational study.

    PubMed

    Bandrés, Isabel; Alcalde, Rafael; Lafuente, Carlos; Atilhan, Mert; Aparicio, Santiago

    2011-11-01

    A study on the viscosity of eight pyridinium based ionic liquids is reported for wide pressure and temperature ranges. Measurements were performed using an electromagnetic moving piston viscometer. Experimental data were fitted to a Tait-like equation demonstrating good correlations, which was used to calculate pressure/viscosity and temperature/viscosity coefficients. The effect of the involved anions and cation on the ionic liquid viscosity was analyzed from a molecular viewpoint using hole theory, quantum chemistry calculations using density functional theory, and classical molecular dynamics simulations. The analysis of the experimental and computational results shows the complex effects controlling viscosity of studied fluids, including strength of ionic pairs, molecular sizes, and mobility and effects rising from the availability and cavity sizes distributions in pyridinium-based ionic liquids. PMID:21942824

  4. Regioselective nucleophilic addition of organometallic reagents to 3-geminal bis(silyl) N-acyl pyridinium.

    PubMed

    Wu, Ya; Li, Linjie; Li, Hongze; Gao, Lu; Xie, Hengmu; Zhang, Zhigao; Su, Zhishan; Hu, Changwei; Song, Zhenlei

    2014-04-01

    A regioselective nucleophilic addition to 3-geminal bis(silyl) N-acyl pyridinium has been described. Geminal bis(silane) shows contrasting roles that lead to different regioselectivities for the addition of different nucleophiles: its steric effect dominates to favor 1,6-addition of alkyl, vinyl, and aryl organometallic reagents; its directing effect dominates to favor 1,2-addition of less sterically demanding alkynyl Grignard reagents. PMID:24666415

  5. Molecular-structural aspects of formation of spectral-luminescent properties of the arylsubstituted pyridinium cations

    SciTech Connect

    Tymyansky, Ya.P.; Knyazhansky, M.I.; Feigelman, V.M.; Kharlanov, V.A.

    1985-04-01

    Using the structure modelling method, the nature of different bands in the absorption spectra of arylsubstituted pyridinium cations has been ascertained. The nature and localization of radiative transitions from singlet and triplet states have been determined. The anomalous Stokes fluorescence shift at room temperature has been explained by adiabatic twist of 2,6-aryl substituents around C-C bond in an excited state. The general scheme of the excited state energy deactivation photophysical processes at 293 and 77 K is presented.

  6. Electronic structure and spectral-luminescent properties of 1,2,4,6-tetrasubstituted pyridinium salts

    SciTech Connect

    Korunova, A.F.; Krainov, I.P.; Protsenko, E.G.

    1985-09-01

    The structure of the electronic excitation of 1,2,4,6-tetrasubstituted pyridinium salts was studied by quantum-chemical calculations carried out by the SCF PPP CI method, using excitation-localization numbers on the atoms and fragments, and interfragmentary charge transfer numbers. The nature of the absorption bands observed in the spectra and certain structural factors causing the spectral-luminescent properties were established.

  7. Kinetics of the reduction of pyridinium ions by 2-hydroxy-2-propyl radicals in aqueous solution

    SciTech Connect

    Shimura, M.; Espenson, J.H.

    1983-01-19

    Kinetic measurements were made for the reductions of the pyridinium ions derived from pyridine, 4-methylpyridine, 3-hydroxypyridine, nicotinamide, and isonicotinamide as well as 1-methylpyridinium and 1,4-dimethylpyridinium ions by 2-hydroxy-2-propyl radicals, which were generated by the homolytic cleavage of the chromium-carbon bond in (H/sub 2/O)/sub 5/CrC(CH/sub 3/)/sub 2/OH/sup 2 +/. The rate constants (dm/sup 3/ mol/sup -1/ s/sup -1/) at 25.0/sup 0/C and an ionic strength of 1.0M (LiClO/sub 4/) are as follows: pyridinium ion, 9.6 x 10/sup 5/; 1-methylpyridinium ion, 3.7 x 10/sup 5/; 4-methylpyridinium ion, 7.3 x 10/sup 4/; 1,4-dimethylpyridinium ion, less than or equal to1 x 10/sup 4/; 3-hydroxypyridinium ion, 1.4 x 10/sup 8/; 3-(aminocarbonyl)pyridinium ion, 7.9 x 10/sup 8/; 4-(aminocarbonyl)pyridinium ion, 1.2 x 10/sup 9/. The rate constants are reasonably well correlated by the Hammett p-sigma equation with p = +8.5. The first two compounds show a second kinetic term corresponding to the rate law k'(Cr/sup 2 +/)(pyH/sup +/)(.C-(CH/sub 3/)/sub 2/OH)(H/sup +/)/sup -1/, consistent with reduction of a Cr(II)-pyridine complex by the free radical.

  8. Stereoselective Synthesis of Tetrahydroindolizines through the Catalytic Formation of Pyridinium Ylides from Diazo Compounds.

    PubMed

    Day, Jonathan; McKeever-Abbas, Ben; Dowden, James

    2016-05-01

    Commercially available iron(III) and copper(I) complexes catalyzed multicomponent cycloaddition reactions between diazo compounds, pyridines, and electrophilic alkenes to give alkaloid-inspired tetrahydroindolizidines in high yield with high diastereoselectivity. Hitherto, the catalytic formation of versatile pyridinium ylides from metal carbenes has been poorly developed; the broad utility demonstrated herein sets the stage for the invention of further multicomponent reactions in future. PMID:27059910

  9. Antithrombotic effects of pyridinium compounds formed from trigonelline upon coffee roasting.

    PubMed

    Kalaska, Bartlomiej; Piotrowski, Lukasz; Leszczynska, Agnieszka; Michalowski, Bartosz; Kramkowski, Karol; Kaminski, Tomasz; Adamus, Jan; Marcinek, Andrzej; Gebicki, Jerzy; Mogielnicki, Andrzej; Buczko, Wlodzimierz

    2014-04-01

    Coffee may exert a preventive effect on arterial thrombosis. Trigonelline is one of the most abundant compounds in coffee that undergoes pyrolysis upon roasting of coffee beans. The aim of the present study was to identify pyridinium compounds formed upon trigonelline pyrolysis and coffee roasting and to investigate the effect of three of them, i.e., 1-methylpyridine and 1,3- and 1,4-dimethylpyridine, on experimentally induced arterial thrombosis in rats. 1,3- and 1,4-dimethylpyridine but not 1-methylpyridine inhibited arterial thrombus formation. 1,3-Dimethylpyridine inhibited platelet aggregation and reduced fibrin formation in platelet-rich plasma, whereas 1,4-dimethylpyridine increased the plasma level of 6-keto-PGF1α. 1,4-Dimethylpyridine slightly increased rat tissue plasminogen activator plasma activity. In summary, we demonstrated that pyridinium compounds display mild antithrombotic properties due to stimulation by prostacyclin release (1,4-dimethylpyridine) and inhibition of platelet aggregation (1,3-dimethylpyridine). Those pyridinium compounds may, to some extent, be responsible for the beneficial effects of coffee drinking. PMID:24650005

  10. Crystal structure of 2,6-di­amino­pyridinium chloride

    PubMed Central

    Mastalir, Matthias; Schroffenegger, Martina; Stöger, Berthold; Weil, Matthias; Kirchner, Karl

    2016-01-01

    The asymmetric unit of the title salt, C5H8N3 +·Cl−, comprises one half of the 2,6-di­amino­pyridinium cation (the other half being completed by the application of mirror symmetry) and one Cl− counter-anion, also located on the mirror plane. The amino N atom shows a significant pyramidalization, with a dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di­amino­pyridinium moiety. In the crystal, the cationic mol­ecules and Cl− counter-anions are arranged in sheets parallel to (001) consisting of alternating polar and non-polar parts associated with the the Cl− anions, pyridinium and amino moieties, and the pyridine rings, respectively. N—H⋯Cl inter­actions within the polar part, as well as slipped π–π inter­actions in the non-polar part, help to establish the three-dimensional network. PMID:27006800

  11. Crystal structure of 2,6-di-amino-pyridinium chloride.

    PubMed

    Mastalir, Matthias; Schroffenegger, Martina; Stöger, Berthold; Weil, Matthias; Kirchner, Karl

    2016-03-01

    The asymmetric unit of the title salt, C5H8N3 (+)·Cl(-), comprises one half of the 2,6-di-amino-pyridinium cation (the other half being completed by the application of mirror symmetry) and one Cl(-) counter-anion, also located on the mirror plane. The amino N atom shows a significant pyramidalization, with a dihedral angle of 30.4 (14)° between the least-squares planes of the amino group and the non-H atoms of the 2,6-di-amino-pyridinium moiety. In the crystal, the cationic mol-ecules and Cl(-) counter-anions are arranged in sheets parallel to (001) consisting of alternating polar and non-polar parts associated with the the Cl(-) anions, pyridinium and amino moieties, and the pyridine rings, respectively. N-H⋯Cl inter-actions within the polar part, as well as slipped π-π inter-actions in the non-polar part, help to establish the three-dimensional network. PMID:27006800

  12. Zinc Bromide Waste Solution Treatment Options

    SciTech Connect

    Langston, C.A.

    2001-01-16

    The objective of this effort was to identify treatment options for 20,000 gallons of low-level radioactively contaminated zinc bromide solution currently stored in C-Area. These options will be relevant when the solutions are declared waste.

  13. Methyl Bromide Alternatives for Vineyard Replant

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The project is part of the USDA-ARS Pacific Area-Wide Pest Management Program for Methyl Bromide Alternatives. This is the first year of a three-year project. The research was initiated in summer 2007 with a field study planned for October 2007 at the USDA-ARS San Joaquin Valley Agricultural Scienc...

  14. METHYL BROMIDE ALTERNATIVES FOR CALIFORNIA STRAWBERRY NURSERIES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effects of methyl bromide (MB) alternative fumigants on soil pests, plant productivity in nursery and fruiting fields, as well as production costs, were evaluated in California strawberry nurseries by an interdisciplinary team. Our trials followed nursery stock through low and high elevation ph...

  15. Challenges in Weed Management Without Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemical and i...

  16. Methyl bromide emissions from tarped fields

    SciTech Connect

    Cicerone, R.J.; Williams, J.; Wang, N.Y.

    1995-12-31

    Once in the stratosphere, bromine atoms can destroy ozone effectively. Because of this potential effect, certain organobromine compounds including methyl bromide (MeBr) are being controlled or eliminated by national and international regulations. It would be valuable to determine the fraction of MeBr used in soil fumigations that subsequently enters the atmosphere to better assess the need for, and value of, strong regulations. We have designed and conducted several experiments accompanying field fumigations with MeBr/chloropicrin mixtures. In each of three field-fumigation experiments new Irvine, CA in which the fumigated field was covered immediately with plastic tarping, we have deployed static flux chambers on top of the tarping and measured escape fluxes of MeBr. After tarp removal, the same chambers were replaced on the bare soil to continue the measurements. We have also measured soil bromide contents before and after the fumigation. One experiment yielded an escape fraction of 80 to 87% (with 19% remaining as bromide) while the other two experiments yielded escape fractions of 30 to 35% (with about 70% remaining as bromide). This paper will summarize stratospheric bromine chemistry, describe the field experiments and discuss factors that influence emissions, including soil pH, moisture and organic content and injection technique. We acknowledge TriCal, Inc. for many helpful discussions and for professional field applications of MeBr.

  17. Can Georgia growers replace methyl bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The price and availability of methyl bromide is limiting its use on Georgia farms; the need for an alternative is essential for sustainable vegetable production in GA. Three alternatives were evaluated in on-farm trials in the spring 2007 in Tift, Colquitt and Echols Counties. Treatments were replic...

  18. Torque vs. induced load of A-286, and MP35N nuts and bolts with cadmium, dry film, and cetyl alcohol lubricants

    NASA Technical Reports Server (NTRS)

    Crispell, C.

    1978-01-01

    Data for specific joint design, utilizing various combinations of bolt, nut and lubricants in typical structure of the shuttle booster rocket is obtained. Requirements of the structure performance criteria were to withstand temperatures of 260 C (500 F) and to provide a nut lubricant which would be compatible with sealants used in the joint. Cadmium plating and dry film lubricant meeting the requirements of MIL-L-8937 were the lubricants specified. In a follow up effort, cadmium plating and cetyl alcohol were further specified The materials for the bolt and nut combinations were MP35N and A-286. These materials demand a lubricant to be used to prevent galling of the thread when tightened and also to help reduce the scatter of clamping load in application.

  19. A comparison of the action of otilonium bromide and pinaverium bromide: study conducted under clinical control.

    PubMed

    Defrance, P; Casini, A

    1991-11-01

    We studied 40 patients with irritable bowel syndrome (IBS) which received in a simple-blind fashion otilonium and pinaverium bromide (15 days each drug). During each 15-day period we evaluated: number of pain episodes, intensity of pain, number of bowel movements, side effects. Otilonium bromide, (OB), compared with pinaverium bromide was able to significantly (p less than 0.05) reduce the number of pain attacks, whereas no significant differences were found between the 2 groups as regards the other parameters. The occurrence of side effects was similar in the two treatment courses. We can conclude that the two types of treatment were similarly useful in IBS, although OB seems more effective than pinaverium bromide. PMID:1756286

  20. EVALUATION OF PROPARGYL BROMIDE AS A SOIL FUMIGANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The cut flower and bulb industry has relied heavily upon the use of methyl bromide as a key soil treatment for soilborne pest control. Due to the phase-out of methyl bromide it is important to develop alternatives to manage pests now managed by methyl bromide. The emphasis of this work was to eval...

  1. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  2. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  3. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  4. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  5. WEED CONTROL IN THE LIFE AFTER METHYL BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable growers are losing the soil fumigant methyl bromide. Efforts are on-going to extend the deadline for using methyl bromide until suitable alternatives are developed. Regardless of whether the deadline is extended or not, growers need to begin to study alternatives to methyl bromide and be...

  6. 75 FR 5582 - Methyl Bromide; Amendments to Terminate Uses

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... AGENCY Methyl Bromide; Amendments to Terminate Uses AGENCY: Environmental Protection Agency (EPA). ACTION... requested by the registrants and accepted by the Agency, of products containing the pesticide methyl bromide... Requests from the registrants listed in Table 2 to amend to terminate post-harvest methyl bromide uses...

  7. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Methyl bromide; tolerances for... § 180.124 Methyl bromide; tolerances for residues. (a) General. A tolerance is established for residues of the fumigant methyl bromide, including metabolites and degradates, in or on the commodity in...

  8. 7 CFR 305.6 - Methyl bromide fumigation treatment schedules.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Methyl bromide fumigation treatment schedules. 305.6..., fumigation with methyl bromide for sapote fruit fly. Regulated citrus fruits originating inside an area... equal concentrations of methyl bromide throughout the chamber, a fan should be placed near the point...

  9. A one-dimensional CdII coordination polymer constructed from 4-(dimethylamino)pyridinium-1-acetate ligands and thiocyanate coordination bridges.

    PubMed

    Wang, Hui-Ting; Zhou, Lin

    2015-07-01

    A new cadmium-thiocyanate complex, namely catena-poly[1-carboxymethyl-4-(dimethylamino)pyridinium [cadmium(II)-tri-μ-thiocyanato-κ(4)N:S;κ(2)S:N] [[[4-(dimethylamino)pyridinium-1-acetate-κ(2)O,O']cadmium(II)]-di-μ-thiocyanato-κ(2)N:S;κ(2)S:N

  10. Measurements of atmospheric methyl bromide and bromoform

    SciTech Connect

    Cicerone, R.J.; Heidt, L.E.; Pollock, W.H.

    1988-04-20

    We have measured gaseous methyl bromide (CH/sub 3/Br) and bromoform (CHBr/sub 3/) in air samples that were gathered approximately weekly from five ground-level sites: Point Barrow, Alaska; Mauna Loa Observatory and Cape Kumukahi, Hawaii; Matatula, Samoa; and Kaitorete Spit, New Zealand. Approximately 750 samples have been analyzed for CH/sub 3/Br between January 1985 and October 1987 and 990 samples have been analyzed for CHBr/sub 3/ between early 1984 and September 1987, all by gas chromatography/mass spectroscopy. Methyl bromide concentrations are typically 10--11 parts per trillion (ppt) by volume; there are no clear indications of temporal increases. Bromoform concentrations are typically 2--3 ppt, but large seasonal variations are seen at Point Barrow. copyright American Geophysical Union 1988

  11. Removal of bromide and natural organic matter by anion exchange.

    PubMed

    Hsu, Susan; Singer, Philip C

    2010-04-01

    Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 microg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC. PMID:20045170

  12. Methyl bromide: Ocean sources, ocean sinks, and climate sensitivity

    SciTech Connect

    Anbar, A.D.; Yung, Y.L.; Chavez, F.P.

    1996-03-01

    This study was performed to examine conflicting conclusions of two previously published studies which estimated the size of oceanic sources of methyl bromide. In addition, the sensitivity of atmospheric methyl bromide to climatic variations was examined. A steady state mass balance model was used to reexamine data from the previous studies. Linear scaling of methyl bromide production rates to chlorophyll content provided agreement between the two models. The results suggest that the open ocean is a small net sink for atmospheric methyl bromide, rather than a large net source. A high rate of biological production of methyl bromide in seawater is also strongly indicated. A coupled ocean-atmosphere model indicated that methyl bromide variations induced by climatic change can be larger than those resulting from 25% variations in anthropogenic sources. Quantifying marine production rates of methyl bromide is suggested as a necessary step in assessing stratospheric ozone loss. 63 refs., 10 figs., 2 tabs.

  13. [Research advances in methyl bromide in the ocean].

    PubMed

    Du, Hui-na; Xie, Wen-xia; Cui, Yu-qian; Chen, Jian-lei; Ye, Si-yuan

    2014-12-01

    Methyl bromide is an important atmospheric trace gas, which plays significant roles in the global warming and atmospheric chemistry. The ocean plays important and complex roles in the global biogeochemical cycles of methyl bromide, not only the source of atmospheric methyl bromide, but also the sink. Therefore, developing the chemical research of the soluble methyl bromide in the ocean, will not only have a certain guiding significance to the atmospheric ozone layer protection, but also provide a theoretical basis for estimating methyl bromide's contribution to the global environmental change on global scale. This paper reviewed the research advances on methyl bromide in the ocean, from the aspects of the biogeochemical cycle of methyl bromide in the ocean, the analysis and determination method, the concentration distribution, the sea-to-air flux and its sources and sinks in the atmosphere. Some deficiencies in the current studies were put forward, and the directions of the future studies were prospected. PMID:25876424

  14. Lattice vibrations in lead bromide and chloride

    NASA Astrophysics Data System (ADS)

    Carabatos-Nédelec, C.; Bréhat, F.; Wyncke, B.

    Lead bromide and lead chloride lattice dynamics studies by polarized IR reflectivity and Raman scattering are reported at room temperature and at 10 K. Reflectivity spectra from 20 to 300 cm -1 have been fitted with a model of the factorized form of the dielectric function. The lattice modes frequencies, damping factors and oscillators strengths are given, as well as the effective charges of the polar modes. The study concludes the ionic character of the compounds.

  15. Methyl bromide users search for science

    SciTech Connect

    Winegar, E.D.

    1995-01-01

    Workers, neighbors and the ozone are protected by regulation from this chemical, but those needing it complain that a solid foundation is lacking for the rules. Although not yet featured on {open_quotes}60 Minutes,{close_quotes} the pesticide methyl bromide is gaining widespread attention because of its central position in debates about worker health and safety, environmental toxics exposure and global ozone depletion.

  16. Bromate oxidized from bromide during sonolytic ozonation.

    PubMed

    Lu, Ning; Wu, Xue-Fei; Zhou, Ji-Zhi; Huang, Xin; Ding, Guo-Ji

    2015-01-01

    Sonolytic ozonation (US/O3) is an effective way to degrade many pollutants in drinking water as the elevated mass transfer rate of ozone gas and the enhanced forming of hydroxyl radicals (OH). This work investigated the formation of bromate (BrO3(-)) from bromide (Br(-)) in sonolytic ozonation. At neutral pH, the bromate conversion rate ([BrO3(-)]/[Br(-)]0) was increased to 60% by ultrasound at continuous ozone flow (0-0.2Lmin(-1)), much higher than that without ultrasound or without bubbling. This indicates that the promoting effect of sonolysis on BrO3(-) formation is mainly due to the sonolytic decomposition of ozone and the enhancement of gas-liquid transfer. The [BrO3(-)]/[Br(-)]0 was increased with increasing pH. In addition, the reduction of HOBr/OBr(-) with ultrasound demonstrates that bromate may be inhibited as the bromide was formed with the H2O2 generation under ultrasound. This suggests the competition between bromate and bromide during the US/O3 led to the inhibition of bromate formation at high ozone flow. Therefore, our result reveals that the bromate formation under ultrasound is improved remarkably in US/O3 in quick treatment with proper ozone flow (<0.2Lmin(-1)). PMID:24931426

  17. Methyl bromide volatility measurements from treated fields

    SciTech Connect

    Majewski, M.S.; Woodrow, J.E.; Seiber, J.N. |

    1995-12-31

    Methyl bromide is used as an agricultural soil fumigant and concern is growing over the role it may play in the depletion of stratospheric ozone. Methyl bromide is applied using various techniques and little is known about how much of the applied fumigant volatilizes into the atmosphere after application. The post-application volatilization losses of methyl bromide from two fields using different application practices were measured using an aerodynamic-gradient technique. One field was covered with a high-barrier plastic film tarp during application and the other was left uncovered, but the furrows made by the injection shanks were bedded over. The cumulative volatilization losses from the tarped field were 22% of the nominal application within the first 5 days of the experiment and about 32% of the nominal application within 9 days including the one day after the tarp was removed on day 8. The nontarped field lost 89%of the nominal application by volatilization in 5 days. The error associated, with each flux measurement, as well as variations in daily flux losses with differing sampling period lengths show the degree of variability inherent in this type of study.

  18. Methyl bromide fate in fumigated soils

    SciTech Connect

    Anderson, T.A.; Rice, P.J.; Cink, J.H.

    1995-12-31

    Although widespread use of methyl bromide (MeBr) as a sail and structure fumigant has previously been recognized as a potential significant source of atmospheric MeBr, losses have not been well quantified. Our research indicates that, in laboratory studies, MeBr is volatilized rapidly from fumigated soils and that volatility increases with temperature (35{degrees}C > 25{degrees}C and 15{degrees}C) and moisture (0.03 bar and 0.3 bar > 1 bar > 3 bar). Degradation of MeBr in soil, as indicated by production of bromide ion, was also directly related to temperature and moisture. Most of the soil degradation of MeBr in these studies appears to be abiotic based on the observation of toxicity (reduced microbial respiration) in fumigated soils. We also determined the transformation and movement of MeBr in undisturbed soil columns. These studies also indicated that MeBT volatilizes rapidly (> 50% in 48 h) from soil. In addition, MeBr was not detected in the leachate from the soil columns, however, bromide ion was detected at levels above background 48 h after fumigation and peaked at 5 weeks.

  19. [I(KACh) inhibitor 2-[(4-methylphenyl)sulfonylcarbamido]-1-(4-nitrobenzyl)pyridinium bromide (2-AP27) is a muscarinic M(2) receptor antagonist].

    PubMed

    Skeberdis, Vytenis Arvydas; Gendviliene, Vida; Zablockaite, Danguole; Martisiene, Irma; Stankevicius, Antanas

    2009-01-01

    Aminopyridines are known to inhibit acetylcholine-activated K(+) current (I(KACh)) in cardiac myocytes. The aim of this study was to examine the effect of 2-aminopyridine sulfonylcarbamide derivative 2-AP27 on isoprenaline-stimulated L-type Ca(2+) current (I(CaL)) and to identify whether 2-AP27 acts via blocking of muscarinic M(2)-receptors in frog cardiomyocytes. The whole-cell configuration of the patch-clamp technique was used to record I(CaL) in enzymatically isolated cardiac myocytes. Isoprenaline (0.1 microM), an agonist of beta(1)-beta(2)-adrenoreceptors, stimulated the I(CaL) up to 475+/-61% (n=4) (P<0.05) vs. control. Then, in the first series of experiments, carbachol (0.01 microM), an agonist of M(2 )muscarinic receptors, reduced the stimulatory effect of isoprenaline to 42+/-15% vs. isoprenaline alone. 2-AP27 (100 microM) alone completely abolished the inhibitory effect of carbachol on isoprenaline-stimulated I(CaL), which recovered to 95+/-5.8% of the effect of isoprenaline. In the second series of experiments, adenosine (1microM), an agonist of A(1)-adenosine receptors, reduced the stimulatory effect of isoprenaline on I(CaL) to 56+/-10% (n=3) (P<0.05). Then 2-AP27 (100 microM) applied in the presence of adenosine, had no effect on I(CaL), which remained at 51+/-7.9% (n=3) (P<0.05) of the effect of isoprenaline. These results suggest that 2-AP27, a new derivative of 2-AP, containing 4-toluolsulfonylcarbamide instead of amino group and quaternizated nitrogen by 4-nitrobenzylbromide in pyridine ring, is acting as an antagonist of muscarinic M(2) receptors in frog ventricular myocytes. PMID:19667745

  20. Pyridinium-phosphonium dications: highly electrophilic phosphorus-based Lewis acid catalysts.

    PubMed

    Bayne, Julia M; Holthausen, Michael H; Stephan, Douglas W

    2016-04-14

    Using commercially available 2-pyridyldiphenylphosphine (o-NC5H4)PPh2, a family of electrophilic phosphonium cations [(o-NC5H4)PFPh2](+) (2) and dications [(o-MeNC5H4)PRPh2](2+) (R = F (4); Me (5)) were prepared. The Lewis acidity of these pyridinium-phosphonium dications was probed in Friedel-Crafts dimerization, hydrodefluorination, hydrosilylation, dehydrocoupling and hydrodeoxygenation reactions. The influence of the counterion on the catalytic activity of the electrophilic phosphonium cations is also discussed. PMID:26666332

  1. Bis[(E)-4-(hydroxy­imino­meth­yl)pyridinium] oxalate

    PubMed Central

    Seidel, Rüdiger W.; Winter, Manuela V.; Oppel, Iris M.

    2008-01-01

    The formula unit of the title compound, 2C6H7N2O+·C2O4 2−, comprises two symmetry-equivalent 4-(hydroxy­imino­meth­yl)­pyridinium cations on general positions, linked through hydrogen bonding via an oxalate anion that resides on a crystallographic centre of symmetry. The crystal structure consists of infinite chains of cations and oxalate anions directed by O—H⋯O and multicentre N—H⋯O inter­molecular hydrogen-bonding inter­actions. PMID:21200745

  2. Bis[3-(2-carboxy­ethen­yl)pyridinium-1-acetato]dichloridozinc(II)

    PubMed Central

    Jing, Xue-Hui; Sun, Wei-Wei; Gao, En-Qing

    2009-01-01

    In the title complex, [ZnCl2(C10H9NO4)2], the ZnII ion lies on a twofold rotation axis and is four-coordinated by two carboxyl­ate O atoms from two 3-(2-carboxy­ethen­yl)pyridinium-1-acetate ligands in a monodentate mode and two Cl atoms in a distorted tetra­hedral geometry. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into a double-chain structure extending parallel to [101]. PMID:21578626

  3. Pyridinium molten salts as co-adsorbents in dye-sensitized solar cells

    SciTech Connect

    Chang, Jui-Cheng; Sun, I-Wen; Yang, Cheng-Hsien; Yang, Hao-Hsun; Hsueh, Mao-Lin; Ho, Wen-Yueh; Chang, Jia-Yaw

    2011-01-15

    The influence of using pyridinium molten salts as co-adsorbents to modify the monolayer of a TiO{sub 2} semiconductor on the performance of a dye-sensitized solar cell is studied. The current-voltage characteristics are measured under AM 1.5 (100 mW cm{sup -2}). The pyridinium molten salts significantly enhance the open-circuit photovoltage (V{sub oc}), the short circuit photocurrent density (J{sub sc}) as well as the solar energy conversion efficiency ({eta}). 1-Ethyl-3-carboxypyridinium iodide ([ECP][I]) is applied successfully to prepare an insulating molecular layer with N719, and achieve high energy conversion efficiency as high as 4.49% at 100 mW cm{sup -2} and AM 1.5. The resulting efficiency is 20% higher than that of a non-additive device. This enhancement of conversion efficiency is attributed to the negative shift of the conduction band (CB) edge and the abundant concentration of I{sup -} on the surface of the electrode when using [ECP][I] as the co-adsorbent. (author)

  4. Physical Properties of Pyridinium Fluorohydrogenate, [pyridine · H+][H2F3]-

    NASA Astrophysics Data System (ADS)

    Hulse, Ryan; Singh, Rajiv

    2008-12-01

    Ionic liquids (ILs), also referred to as molten salts, have found application as electrolytes for batteries and super-capacitors, in electroplating baths, as designer solvents, and as reaction media. A few of the desired properties of a super-capacitor electrolyte are nonflammability, thermal stability, and electrochemical stability. ILs containing aromatic cations have been shown to have low viscosity which results in a high electrochemical conductivity. There is a delicate balance between increasing the thermal stability, or decreasing the melting point, and increasing the electrochemical conductivity of the IL. This study focuses on pyridinium fluorohydrogenate, [pyridine · H+][H2F3]-. Pyridinium fluorohydrogenate has been synthesized by the reaction of pyridine and anhydrous hydrofluoric acid. This IL has a relatively high electrical conductivity (~98 mS · cm-1 at 23 °C), a wide electrochemical window, and a boiling point of 186 °C. A stable gel can also be formed by combining [pyridine · H+][H2F3]- and a super absorbent polymer such as polyacrylic acid. The gel adds mechanical stability to the matrix while not greatly affecting the conductivity of the IL.

  5. Functional Role of Pyridinium during Aqueous Electrochemical Reduction of CO2 on Pt(111).

    PubMed

    Ertem, Mehmed Z; Konezny, Steven J; Araujo, C Moyses; Batista, Victor S

    2013-03-01

    Recent breakthroughs in electrochemical studies have reported aqueous CO2 reduction to formic acid, formaldehyde, and methanol at low overpotentials (-0.58 V versus SCE), with a Pt working electrode in acidic pyridine (Pyr) solutions. We find that CO2 is reduced by H atoms bound to the Pt surface that are transferred as hydrides to CO2 in a proton-coupled hydride transfer (PCHT) mechanism activated by pyridinium (PyrH(+)), CO2 + Pt-H + PyrH(+) + e(-) → Pyr + Pt + HCO2H. The surface-bound H atoms consumed by CO2 reduction is replenished by the one-electron reduction of PyrH(+) through the proton-coupled electron transfer (PCET), PyrH(+) + Pt + e(-) → Pyr + Pt-H. Pyridinium is essential to establish a high concentration of Brønsted acid in contact with CO2 and with the Pt surface, much higher than the concentration of free protons. These findings are particularly relevant to generate fuels with a carbon-neutral footprint. PMID:26281929

  6. 2,3-Diamino­pyridinium 2-hy­droxy­benzoate

    PubMed Central

    Hemamalini, Madhukar; Goh, Jia Hao; Fun, Hoong-Kun

    2011-01-01

    In the title mol­ecular salt, C5H8N3 +·C7H5O3 −, the 2,3-diamino­pyridinium cation is essentially planar, with a maximum deviation of 0.006 (2) Å. In the crystal, adjacent cations and anions are linked by pairs of N—H⋯O hydrogen bonds, generating R 2 2(8) loops. These dimers are linked by further N—H⋯O hydrogen bonds and C—H⋯O inter­actions to form sheets lying parallel to (001). A typical intra­molecular O—H⋯O hydrogen bond is also observed in the salicylate (2-hy­droxy­benzoate) anion, which generates an S(6) ring. The crystal structure also features π–π stacking inter­actions between the pyridinium rings of the cations, with a centroid–centroid distance of 3.5896 (15) Å. PMID:22220123

  7. Using Pyridinium Styryl Dyes as the Standards of Time-Resolved Instrument Response.

    PubMed

    Li, Lei; Chang, Mengfang; Yi, Hua; Jia, Menghui; Cao, Xiaodan; Zhou, Zhongneng; Zhang, Sanjun; Pan, Haifeng; Shih, Chun-Wei; Jimenez, Ralph; Xu, Jianhua

    2016-07-01

    In this paper, two pyridinium styryl dyes, [2-(4-dimethylamino-phenyl)-vinyl]-1-methylpyridinium iodide (DASPMI), were synthesized and characterized by steady state fluorescence spectroscopy as well as picosecond and femtosecond time-resolved fluorescence spectroscopies. Both dyes exhibit large Stokes shifts and fluorescence decays equivalent to the instrument response function (IRF) standards employed in time-correlated single-photon counting. Due to their styryl and pyridinium moieties, DASPMIs have higher peak fluorescence intensity and shorter excited-state lifetimes than iodide ion-quenched fluorophores. The fluorescence lifetimes of o-DASPMI and p-DASPMI were measured to be 6.6 ps and 12.4 ps, respectively. The fluorescence transients of these DASPMIs were used as the IRFs for iterative reconvolution fitting of the time-resolved fluorescence decay profiles of Rhodamine B (RhB), sulforhodamine B (SRB), and the SRB-SRB2m RNA aptamer complex. The quality of the fits employing the DASPMI-derived IRFs are consistently equivalent to those employing IRFs obtained from light scattering. These results indicate that DASPMI-derived IRFs may be suited for a broad range of applications in time-resolved spectroscopy and fluorescence lifetime imaging microscopy (FLIM), especially in the visible emission range. PMID:27231333

  8. Evaluation of Range-Corrected Density Functionals for the Simulation of Pyridinium-Containing Molecular Crystals.

    PubMed

    Ruggiero, Michael T; Gooch, Jonathan; Zubieta, Jon; Korter, Timothy M

    2016-02-18

    The problem of nonlocal interactions in density functional theory calculations has in part been mitigated by the introduction of range-corrected functional methods. While promising solutions, the continued evaluation of range corrections in the structural simulations of complex molecular crystals is required to judge their efficacy in challenging chemical environments. Here, three pyridinium-based crystals, exhibiting a wide range of intramolecular and intermolecular interactions, are used as benchmark systems for gauging the accuracy of several range-corrected density functional techniques. The computational results are compared to low-temperature experimental single-crystal X-ray diffraction and terahertz spectroscopic measurements, enabling the direct assessment of range correction in the accurate simulation of the potential energy surface minima and curvatures. Ultimately, the simultaneous treatment of both short- and long-range effects by the ωB97-X functional was found to be central to its rank as the top performer in reproducing the complex array of forces that occur in the studied pyridinium solids. These results demonstrate that while long-range corrections are the most commonly implemented range-dependent improvements to density functionals, short-range corrections are vital for the accurate reproduction of forces that rapidly diminish with distance, such as quadrupole-quadrupole interactions. PMID:26814572

  9. Role of alkyl group in the aromatic extraction using pyridinium-based ionic liquids.

    PubMed

    Kim, Min Ji; Shin, Seung Hoon; Kim, Young Jin; Cheong, Minserk; Lee, Je Seung; Kim, Hoon Sik

    2013-11-27

    The performance of N-alkylpyridinium-based ionic liquids with a SCN anion (PyILs) was evaluated for the selective extraction of aromatics from aliphatic hydrocarbons. The aromatic extraction ability of PyILs was greatly enhanced by the presence of a methyl group on the pyridinium ring at the 3- or 4-position, whereas the solubility of the aromatics in the PyILs decreased with increasing the number of methyl groups on the benzene ring. The FT-IR studies revealed that the solubility of an aromatic compound in a PyIL is closely correlated with the degree of aromatic C-H bending frequency shift observed during the dissolution of the aromatic compound in the PyIL: the larger the shift, the higher the solubility. The computational calculations on the dispersion interactions between aromatics and PyILs demonstrated that the anion-aromatic interaction is much more important than the cation-aromatic interaction in determining the aromatic solubility in PyILs, and such anion-aromatic interaction can be enhanced by introducing a methyl group at the carbon atom of the pyridinium ring. PMID:24180561

  10. Properties of columns with several pyridinium and imidazolium ionic liquid stationary phases.

    PubMed

    Shashkov, M V; Sidelnikov, V N

    2013-09-27

    Recent advances in the development of new liquid phases (ILs) made it possible to use some classes of ILs as polar stationary liquid phases (SLP). In our days only alkylimidazolium- and alkylphosphonium-based ILs are widely used as polar SLP. In present work some other types of ILs - pyridinium and cyanopropyl/hydroxypropyl imidazolium were investigated as SLP. Columns with efficiencies 2000-2500 plates/m by high-pressure static method were prepared. Polarity and selectivity of these phases were measured. Selectivity was described in terms of intermolecular interactions by using Abraham solvatation parameter model. The set of the regularities between cation structure of ionic liquid and selectivity has been shown. The number and position of methyl groups in ionic liquid pyridinium ring were shown to have the sufficient influence on all type of molecular interactions. Finally the resolutions of test mixture for the several ionic liquid SLP were obtained. For columns with some ionic liquids the dependencies of the height equivalent to a theoretical plate (HETP) and sample loading capacity were obtained and compared with the conventional phases. It was found that the optimal efficiency for the IL columns is attained at lower carrier gas velocities in comparison with traditional phases. Nevetheless sample loading capacity of IL phases is comparable to those of conventional GC phases. PMID:23958690

  11. CuO nanostructures: optical properties and morphology control by pyridinium-based ionic liquids.

    PubMed

    Sabbaghan, Maryam; Shahvelayati, Ashraf Sadat; Madankar, Kamelia

    2015-01-25

    Copper oxide nanostructures have been synthesized by a simple reflux method in aqueous medium of pyridinium based ionic liquids. The structural and optical properties of CuO nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy (PL) and UV-visible. The morphologies of the nanostructures can be controlled by changing the amount of NaOH and ionic liquids. The results show that the use identical pyridinium based ionic liquids in ratio of 4:1 NaOH/Cu(OAc)2⋅H2O yield minor differences in morphology of CuO nanostructures. Different morphologies of CuO nanostructures were obtained by changing the ratio NaOH/Cu(OAc)2⋅H2O to 2:1. Ionic liquids play an important role on optical properties of CuO nanostructures. The results of optical measurements of the CuO nanostructures illustrate that band gaps are estimated to be 1.67-1.85 eV. PL patterns studies show that the ionic liquids can be effect on PL patterns of the samples. The reasons of these phenomena are discussed. PMID:25128679

  12. Europium-doped barium bromide iodide

    SciTech Connect

    Gundiah, Gautam; Hanrahan, Stephen M.; Hollander, Fredrick J.; Bourret-Courchesne, Edith D.

    2009-10-21

    Single crystals of Ba0.96Eu0.04BrI (barium europium bromide iodide) were grown by the Bridgman technique. The title compound adopts the ordered PbCl2 structure [Braekken (1932). Z. Kristallogr. 83, 222-282]. All atoms occupy the fourfold special positions (4c, site symmetry m) of the space group Pnma with a statistical distribution of Ba and Eu. They lie on the mirror planes, perpendicular to the b axis at y = +-0.25. Each cation is coordinated by nine anions in a tricapped trigonal prismatic arrangement.

  13. Advanced hydrogen electrode for hydrogen-bromide battery

    NASA Technical Reports Server (NTRS)

    Kosek, Jack A.; Laconti, Anthony B.

    1987-01-01

    Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

  14. Rotamerism-driven large magnitude host-guest binding change in a crown ether derivatized pyridinium-phenolate series.

    PubMed

    Ay, Emel; Hobeika, Nelly; Chaumeil, Hélène; Tschamber, Théophile; Jin, Ming; Versace, Davy-Louis; Malval, Jean-Pierre

    2016-03-17

    Two TICTOID-based pyridinium-phenolates bearing a crown ether macrocycle have been designed for the complexation of a potassium cation. The nucleophilicity of the intraannular phenolate -O(-) function can be strongly modulated by biaryl twisting. Such a structure/electronic transduction effect gives rise to a host-guest binding change by more than two orders of magnitude. PMID:26948128

  15. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  16. An Ill Wind: Methyl Bromide Use Near California Schools, 1998.

    ERIC Educational Resources Information Center

    Ross, Zev; Walker, Bill

    A California study investigates the use of the toxic pesticide methyl bromide near the state's public schools, explains why proposed safety rules have failed to protect children and others from exposure, and examines regions at particular exposure risk. Study results show an increasing exposure to methyl bromide near schools already at risk while…

  17. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  18. Interaction of methyl bromide with soil.

    PubMed

    Tao, Ting; Maciel, Gary E

    2002-02-15

    Because methyl bromide (CH3Br) is a widely used agricultural fumigant for soil disinfection, it is important to know the chemical behavior and fate of CH3Br as a result of its use for soil treatment. A solid-state 13C NMR study of 13CH3Br-treated soil and soil-component samples shows that methylation of soil organic matter may be the major pathway for degradation of CH3Br in soils. Adsorption of CH3Br on a dried clay like Ca-montmorillonite or kaolinite does not contribute directly to the degradation of CH3Br. The results are interpreted in terms of the chemical structures of separated soil fractions and the nature of the separation procedure. PMID:11878373

  19. Single ion dynamics in molten sodium bromide

    SciTech Connect

    Alcaraz, O.; Trullas, J.; Demmel, F.

    2014-12-28

    We present a study on the single ion dynamics in the molten alkali halide NaBr. Quasielastic neutron scattering was employed to extract the self-diffusion coefficient of the sodium ions at three temperatures. Molecular dynamics simulations using rigid and polarizable ion models have been performed in parallel to extract the sodium and bromide single dynamics and ionic conductivities. Two methods have been employed to derive the ion diffusion, calculating the mean squared displacements and the velocity autocorrelation functions, as well as analysing the increase of the line widths of the self-dynamic structure factors. The sodium diffusion coefficients show a remarkable good agreement between experiment and simulation utilising the polarisable potential.

  20. Degradation of methyl bromide in anaerobic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Miller, L.G.; Strohmaler, F.E.

    1994-01-01

    Methyl bromide (MeBr) was anaerobically degraded in saltmarsh sediments after reaction with sulfide. The product of this nucleophilic substitution reaction was methanethiol, which underwent further chemical and bacterial reactions to form dimethyl sulfide. These two gases appeared transiently during sediment incubations because they were metabolized by methanogenic and sulfate-reducing bacteria. A second, less significant reaction of MeBr was the exchange with chloride, forming methyl chloride, which was also susceptible to attack by sulfide. Incubation of 14C-labeled methyl iodide as an analogue of MeBr resulted in the formation of 14CH4 and 14CO2 and also indicated that sulfate-reducing bacteria as well as methanogens metabolized the methylated sulfur intermediates. These results suggest that exposed sediments with abundant free sulfide, such as coastal salt-marshes, may constitute a sink for atmospheric MeBr.

  1. Glycopyrronium bromide for the treatment of chronic obstructive pulmonary disease.

    PubMed

    Riario-Sforza, Gian Galeazzo; Ridolo, Erminia; Riario-Sforza, Edoardo; Incorvaia, Cristoforo

    2015-02-01

    Glycopyrronium bromide is a new long-acting muscarinic antagonist to be used once-daily, which is approved as a bronchodilator for the symptomatic maintenance treatment of adult patients with chronic obstructive pulmonary disease (COPD). In the Glycopyrronium bromide in chronic Obstructive pulmonary disease airWays trials, treatment with inhaled glycopyrronium bromide at 50 μg once daily achieved a significantly better lung function than placebo, as measured by the trough forced expiratory volume in 1 s in patients with moderate-to-severe COPD. The lung function improvement was maintained for up to 52 weeks. Other improved indexes were dyspnea scores, health status, exacerbation rates and time of exercise endurance. Studies comparing the efficacy of glycopyrronium versus tiotropium bromide found substantial equivalence of the two drugs. Glycopyrronium was generally well tolerated. These data add inhaled glycopyrronium bromide to the treatment of patients with moderate to severe COPD as an effective once-daily LAMA. PMID:25547422

  2. Atmosphere-plant canopy interactions of methyl bromide

    SciTech Connect

    Taylor, G.E. Jr.; Leonard, T.D.; Gustin, M.S.

    1995-12-31

    In the planetary boundary layer, parcels of air containing background and elevated concentrations of methyl bromide commonly pass through plant canopies in managed (agriculture) and natural (forests, grasslands) ecosystems. It is hypothesized that leaf surfaces are a significant sink or methyl bromide on a local and regional scale and that failure to account for this sink results in a significant overestimation of methyl bromide transport to the stratosphere. Using highly controlled environments, studies are investigating the reactivity of leaf surfaces for methyl bromide at elevated and global background concentrations. Estimates of pathway resistances are being calculated and sites of deposition determined. The results indicate that plant canopies are a significant unrecognized sink for methyl bromide in the atmosphere.

  3. Infrared and Ultraviolet Spectroscopy of Gas-Phase Imidazolium and Pyridinium Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Young, Justin W.; Booth, Ryan S.; Annesley, Christopher; Stearns, Jaime A.

    2015-06-01

    Ionic liquids (ILs) are a highly variable and potentially game-changing class of molecules for a number of Air Force applications such as satellite propulsion, but the complex nature of IL structure and intermolecular interactions makes it difficult to adequately predict structure-property relationships in order to make new IL-based technology a reality. For example, methylation of imidazolium ionic liquids leads to a substantial increase in viscosity but the underlying physical mechanism is not understood. In addition, the role of hydrogen bonding in ILs, and especially its relationship to macroscopic properties, is a matter of ongoing research. Here we describe the gas-phase spectroscopy of a series of imidazolium- and pyridinium-based ILs, using a combination of infrared spectroscopy and density functional theory to establish the intermolecular interactions present in various ILs, to assess how well they are described by theory, and to relate microscopic structure to macroscopic properties.

  4. Secondary interactions in N-(chloromethyl)pyridinium chlorides (n = 2, 3, 4).

    PubMed

    Jones, Peter G; Vancea, Fabiola; Herbst-Irmer, Regine

    2002-11-01

    In the isomeric title compounds, viz. 2-, 3- and 4-(chloromethyl)pyridinium chloride, C(6)H(7)ClN(+).Cl(-), the secondary interactions have been established as follows. Classical N-H.Cl(-) hydrogen bonds are observed in the 2- and 3-isomers, whereas the 4-isomer forms inversion-symmetric N-H(.Cl(-).)(2)H-N dimers involving three-centre hydrogen bonds. Short Cl.Cl contacts are formed in both the 2-isomer (C-Cl.Cl(-), approximately linear at the central Cl) and the 4-isomer (C-Cl.Cl-C, angles at Cl of ca 75 degrees ). Additionally, each compound displays contacts of the form C-H.Cl, mainly to the Cl(-) anion. The net effect is to create either a layer structure (3-isomer) or a three-dimensional packing with easily identifiable layer substructures (2- and 4-isomers). PMID:12415176

  5. Fluorescence upconversion properties of a class of improved pyridinium dyes induced by two-photon absorption

    NASA Astrophysics Data System (ADS)

    Xu, Guibao; Hu, Dawei; Zhao, Xian; Shao, Zongshu; Liu, Huijun; Tian, Yupeng

    2007-06-01

    We report the fluorescence upconversion properties of a class of improved pyridinium toluene- p-sulfonates having donor- π-acceptor (D- π-A) structure under two-photon excitation at 1064 nm. The experimental results show that both the two-photon excited (TPE) fluorescence lifetime and the two-photon pumped (TPP) energy upconversion efficiency were increased with the enhancement of electron-donating capability of the donor in the molecule. It is also indicated that an overlong alkyl group tends to result in a weakened molecular conjugation, leading to a decreased two-photon absorption (TPA) cross section. By choosing the donor, we can obtain a longest fluorescence lifetime of 837 ps, a highest energy upconversion efficiency of ˜6.1%, and a maximum TPA cross-section of 8.74×10 -48 cm 4 s/photon in these dyes.

  6. Antiradiation compounds. 20. 1-Methylquinolinium(and pyridinium)-2-dithioacetic acid derivatives

    SciTech Connect

    Foye, W.O.; Jones, R.W.; Ghoshal, P.K.; Almassian, B.

    1987-01-01

    A new class of radiation-protective compounds has been found in the bis(methylthio) and methylthio amino derivatives of 1-methylquinolinium- and 1-methylpyridinium-2-dithioacetic acids. The compounds gave good protection to mice vs. 1000-rad gamma-radiation in ip doses of 10 mg/kg or less, much lower than those required for the aminoalkyl thiols (approximately 150-600 mg/kg). The dithioacetic acid zwitterions were prepared from the base-catalyzed reaction of carbon disulfide with quinaldine and picoline methiodides, and the bis(methylthio) derivatives resulted from reaction with methyl iodide at room temperature. Replacement of one methylthio moiety took place readily on reaction of the bis(methylthio) derivatives with 1 molar equiv of an amine. The best protective activity was found with the methylthio piperidino derivative in both the quinolinium and pyridinium series.

  7. Structure-activity correlation in transfection promoted by pyridinium cationic lipids.

    PubMed

    Parvizi-Bahktar, P; Mendez-Campos, J; Raju, L; Khalique, N A; Jubeli, E; Larsen, H; Nicholson, D; Pungente, M D; Fyles, T M

    2016-03-21

    The efficiency of the transfection of a plasmid DNA encoding a galactosidase promoted by a series of pyridinium lipids in mixtures with other cationic lipids and neutral lipids was assessed in CHO-K1 cells. We identify key molecular parameters of the lipids in the mixture - clog P, lipid length, partial molar volume - to predict the morphology of the lipid-DNA lipoplex and then correlate these same parameters with transfection efficiency in an in vitro assay. We define a Transfection Index that provides a linear correlation with normalized transfection efficiency over a series of 90 different lipoplex compositions. We also explore the influence of the same set of molecular parameters on the cytotoxicity of the formulations. PMID:26891970

  8. Electrochemical and spectroscopic studies of sulfur in aluminum chloride-N-(n-butyl)pyridinium chloride

    SciTech Connect

    Marassi, R.; Laher, T.M.; Mamantov, G.; Trimble, D.S.

    1985-07-01

    The behavior of sulfur in aluminum chloride-N-(n-butyl)pyridinium chloride (AlCl/sub 3/-BPC) was studied using Raman spectroscopy and electrochemical techniques. In basic (BPC-rich) melts, sulfur can be reduced to sulfide, probably in the form of an AlSCl-like species. No oxidation to positive oxidation states of sulfur is observed in basic melts. In acidic (AlCl/sub 3/-rich) melts, sulfur can be oxidized to S(I) and eventually to S(IV), which is only stabl in the melt for short periods of time. No reduction to sulfide-like species or formation of low oxidation states is observed in acidic melts.

  9. Novel pyridinium based cobalt carbonyl ionic liquids: synthesis, full characterization, crystal structure and application in catalysis.

    PubMed

    Deng, Fan-Guo; Hu, Bin; Sun, Wei; Chen, Jing; Xia, Chun-Gu

    2007-10-10

    Through an optimized synthetic strategy, a series of novel alkylpyridinium cobalt tetracarbonyl salts, [C(1)Py][Co(CO)(4)] (), [C(4)Py][Co(CO)(4)] () and [C(16)Py][Co(CO)(4)] () (C(n)Py = N-C(n)H(2n+1)-pyridinium), were successfully prepared in good yields, using a water-organic biphasic system. All the three compounds melt well below 100 degrees C and could be classified as ionic liquids. The compounds were fully characterized using IR, UV-Vis, (1)H NMR, (13)C NMR, ESI-MS and elemental analysis, and was structurally characterized by X-ray single crystal analysis. Compound has been found to be an efficient and reusable catalyst for the alkoxycarbonylation of propylene oxide without the aid of a base additive. PMID:17893815

  10. Oxidative desulfurization of fuel oil by pyridinium-based ionic liquids.

    PubMed

    Zhao, Dishun; Wang, Yanan; Duan, Erhong

    2009-01-01

    In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF(4) was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF(4) has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil) /V(H(2)O(2)) = 1:1:0.4, temperature 55 degrees C, the time 30 min. The ratio of desulfurization to thiophene and DBT reached 78.5% and 84.3% respectively, which is much higher than extraction desulfurization with simple ionic liquids. Under these conditions, the effect of desulfurization on gasoline was also investigated. The used ionic liquids can be recycled up to four times after regeneration. PMID:19924069

  11. Atomistic force field for pyridinium-based ionic liquids: reliable transport properties.

    PubMed

    Voroshylova, Iuliia V; Chaban, Vitaly V

    2014-09-11

    Reliable force field (FF) is a central issue in successful prediction of physical chemical properties via computer simulations. This work introduces refined FF parameters for six popular ionic liquids (ILs) of the pyridinium family (butylpyridinium tetrafluoroborate, bis(trifluoromethanesulfonyl)imide, dicyanamide, hexafluorophosphate, triflate, chloride). We elaborate a systematic procedure, which allows accounting for specific cation-anion interactions in the liquid phase. Once these interactions are described accurately, all experimentally determined transport properties can be reproduced. We prove that three parameters per interaction site (atom diameter, depth of potential well, point electrostatic charge) provide a sufficient basis to predict thermodynamics (heat of vaporization, density), structure (radial distributions), and transport (diffusion, viscosity, conductivity) of ILs at room conditions and elevated temperature. The developed atomistic models provide a systematic refinement upon the well-known Canongia Lopes-Pádua (CL&P) FF. Together with the original CL&P parameters the present models foster a computational investigation of ionic liquids. PMID:25144141

  12. Collective ion diffusion and localized single particle dynamics in pyridinium-based ionic liquids.

    PubMed

    Burankova, Tatsiana; Hempelmann, Rolf; Wildes, Andrew; Embs, Jan P

    2014-12-11

    Quasielastic neutron scattering with polarized neutrons allows for an experimental separation of single-particle and collective processes, as contained in the incoherent and coherent scattering contributions. This technique was used to investigate the dynamical processes in the pyridinium-based ionic liquid 1-butylpyridinium bis(trifluoromethylsulfonyl)-imide. We observed two diffusion processes with different time scales. The slower diffusional process was present in both the coherent and the incoherent contribution, meaning that this process has at least a partial collective nature. The second faster localized process is only present in the incoherent scattering contribution. We conclude that it is a true single-particle process on a shorter time scale. PMID:25387035

  13. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  14. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  15. Selective oxidation of bromide in wastewater brines from hydraulic fracturing.

    PubMed

    Sun, Mei; Lowry, Gregory V; Gregory, Kelvin B

    2013-07-01

    Brines generated from oil and natural gas production, including flowback water and produced water from hydraulic fracturing of shale gas, may contain elevated concentrations of bromide (~1 g/L). Bromide is a broad concern due to the potential for forming brominated disinfection byproducts (DBPs) during drinking water treatment. Conventional treatment processes for bromide removal is costly and not specific. Selective bromide removal is technically challenging due to the presence of other ions in the brine, especially chloride as high as 30-200 g/L. This study evaluates the ability of solid graphite electrodes to selectively oxidize bromide to bromine in flowback water and produced water from a shale gas operation in Southwestern PA. The bromine can then be outgassed from the solution and recovered, as a process well understood in the bromine industry. This study revealed that bromide may be selectively and rapidly removed from oil and gas brines (~10 h(-1) m(-2) for produced water and ~60 h(-1) m(-2) for flowback water). The electrolysis occurs with a current efficiency between 60 and 90%, and the estimated energy cost is ~6 kJ/g Br. These data are similar to those for the chlor-alkali process that is commonly used for chlorine gas and sodium hydroxide production. The results demonstrate that bromide may be selectively removed from oil and gas brines to create an opportunity for environmental protection and resource recovery. PMID:23726709

  16. Theoretical study for pyridinium-based ionic liquid 1-ethylpyridinium trifluoroacetate: synthesis mechanism, electronic structure, and catalytic reactivity.

    PubMed

    Zhu, Xueying; Cui, Peng; Zhang, Dongju; Liu, Chengbu

    2011-07-28

    By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+)[CF(3)COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF(3)COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1,3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C≡N group by C≡N···H H bond to increase the polarity of the C═C double bond in acrylonitrile, while the anion CF(3)COO(-) links with the methyl group in 2-methyl-1,3-butadiene by C-H···O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids. PMID:21671599

  17. Conformation and interactions of 4-(pyridinium-1-yl)-phenolate betaine-dye and its cation in the crystalline state

    NASA Astrophysics Data System (ADS)

    Wojtas, Łukasz; Pawlica, Dariusz; Stadnicka, Katarzyna

    2006-03-01

    The crystals of 4-(pyridinium-1-yl)-phenolate dihydrate, 1-(4-hydroxyphenyl)-pyridynium chloride monohydrate, 1-(4-hydroxyphenyl)-pyridynium phosphate dihydrate were obtained to explore the molecular behaviour of the simplest pyridynium betaine-dye in various crystalline environments. 4-(Pyridinium-1-yl)-phenolate ( 1), as a push-pull chromophore showing the negative solvatochromism of ICT band, can be useful in NLO applications if the polar dipole arrangement is achieved in the solid-state. The attempt to overcome the tendency of betaine dipoles to form anti-parallel arrangements was successful to some extent. X-ray structure analysis of the crystals, obtained from aqueous solutions, revealed space groups Pnna, P212121 and P2 1/ c, respectively. For 4-(pyridinium-1-yl)-phenolate dihydrate and 1-(4-hydroxyphenyl)-pyridynium chloride monohydrate, the anti-parallel arrangements of the betaine-dye molecules/cations force a nonpolar space group. In the centrosymmetrical crystals of 1-(4-hydroxyphenyl)-pyridynium phosphate dihydrate, between the centrosymmetric layers built of phosphate anions and water molecules, there are the polar arrangement of the betaine-dye cations connected to the phosphate-hydrate layers; however, the centrosymmetricity of the layers precludes the polarity of the structure. The alteration of geometrical parameters of the cation, as compared to 4-(pyridinium-1-yl)-phenolate molecule, is observed only in the phenolate moiety due to the protonation of the oxygen atom. A twisted conformation for the betaine-dye molecule observed in the crystalline state, with the dihedral angle of 47.0(1)°, is similar to the results of computational studies for the ground state of the single molecule in an aqueous solution. The influence of crystal environment, and that of the oxygen atom protonation, on the variation of the torsion angle is small.

  18. Lithium bromide chiller technology in gas processing

    SciTech Connect

    Huey, M.A.; Leppin, D.

    1995-12-31

    Lithium Bromide (LiBr) Absorption Chillers have been in use for more than half a century, mainly in the commercial air conditioning industry. The Gas Research Institute and EnMark Natural Gas Company co-funded a field test to determine the viability of this commercial air conditioning technology in the gas industry. In 1991, a 10 MMCFC natural gas conditioning plant was constructed in Sherman, Texas. The plant was designed to use a standard, off-the-shelf chiller from Trane with a modified control scheme to maintain tight operating temperature parameters. The main objective was to obtain a 40 F dewpoint natural gas stream to meet pipeline sales specifications. Various testing performed over the past three years has proven that the chiller can be operated economically and on a continuous basis in an oilfield environment with minimal operation and maintenance costs. This paper will discuss how a LiBr absorption chiller operates, how the conditioning plant performed during testing, and what potential applications are available for LiBr chiller technology.

  19. Pyridinium quenchers of Ru(bpy)/sub 3//sup 2 +/ charge effects of the yield of electron transfer

    SciTech Connect

    Jones, G. II.; Malba, V.

    1985-12-27

    The quenching of the luminescent state of tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)/sub 3//sup 2 +/) by a series of pyridinium ions has been studied. 4-Acetyl-, 4-cyano-, 4-carbomethoxy-, or 4-carboxy-1-methylpyridinium, along with the well-known electron-transfer agent methyl viologen (MV/sup 2 +/), were employed as electron-acceptor quenchers in order to reveal the effects of charge type on the yield of photoinduced electron transfer involving the Ru(II) luminescent state as electron donor. Rates of quenching by the pyridinium ions were measured by using steady irradiation techniques and compared with expectations based on the calculated energetics of electron transfer. Electron transfer yields were obtained by measurement of the transient absorbances of photogenerated radicals (e.g., pyridinyls) using conventional flash photolysis (broad band visible excitation, pH 5, ..mu.. = 0.5). The transient photoleaching of Ru(bpy)/sub 3//sup 2 +/ by 4-carboxy-1-methylpyridinium was studied by using a Nd:YAG laser with results showing pH control of the charge type and yield of net electron transfer due to in-cage protonation of photogenerated geminate radical pairs. The electrochemical properties of the pyridinium ions were also examined by cyclic voltammetry and a Hammett correlation was made of the reduction potentials.

  20. Kinetics and Mechanism of the Chlorate-Bromide Reaction.

    PubMed

    Sant'Anna, Rafaela T P; Faria, Roberto B

    2015-11-01

    The chlorate-bromide reaction, ClO3(-) + 6Br(-) + 6H(+) → 3Br2 + Cl(-) + 3H2O, was followed at the Br3(-)/Br2 isosbestic point (446 nm). A fifth-order rate law was found: (1)/3 d[Br2]/dt = k[ClO3(-)][Br(-)][H(+)](3) (k = 5.10 × 10(-6) s(-1) L(4) mol(-4)) at 25 °C and I = 2.4 mol L(-1). At high bromide concentrations, the bromide order becomes close to zero, indicating a saturation profile on bromide concentration, similar to the chloride saturation profile observed in the chlorate-chloride reaction. A mechanism is proposed that considers the formation of the intermediate BrOClO2(2-), similar to the intermediate ClOClO2(2-) proposed in the mechanism of the chlorate-chloride reaction. PMID:26467822

  1. Health and Environmental Effects Profile for methyl bromide

    SciTech Connect

    Not Available

    1986-06-01

    The Health and Environmental Effects Profile for methyl bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life, and environmental effects. Quantitative estimates are presented provided sufficient data are available. Methyl bromide has been determined to be a systemic toxicant. An Acceptable Daily Intake (ADI), for methyl bromide is 0.0014 mg/kg/day for oral exposure. The Reportable Quantity (RQ) value for methyl bromide is 100.

  2. The oceans: A source or a sink of methyl bromide?

    SciTech Connect

    Pilinis, C.; King, D.B.; Saltzman, E.S.

    1996-04-15

    The global ocean/atmosphere flux of methyl bromide has been estimated from shipboard measurements of the saturation anomaly. When such data are extrapolated globally on the basis of constant saturation anomaly, the ocean is a net sink for methyl bromide [Lobert et al.]. The same data can also be extrapolated on the basis of steady-state production rate of methyl bromide in the water column, allowing regional and seasonal variations in temperature to affect the saturation anomaly. The authors have carried out this type of extrapolation, and they found that the oceans are a strong net source of methyl bromide to the atmosphere. The difference arises mainly due to slow degradation rates in water of higher latitudes. A reduction of the applied production rate by more than 35% is needed in order to switch the ocean from a source to a sink of methyl bromide. These results demonstrate the sensitivity of current estimates of oceanic flux to assumptions about methyl bromide production and destruction in the water column. 19 refs., 2 fig.

  3. The toxic chemistry of methyl bromide.

    PubMed

    Bulathsinghala, A T; Shaw, I C

    2014-01-01

    Methyl bromide (MeBr) is a chemically reactive compound that has found use as a fire retardant and fumigant used for wood, soil, fruits and grains. Its use is banned in many countries because of its ozone-depleting properties. Despite this ban, the use of MeBr persists in some parts of the world (e.g. New Zealand) due to its important role in maintaining strict biosecurity of exported and imported products. Its high chemical reactivity leads to a broad toxicological profile ranging from acute respiratory toxicity following inhalation exposure, through carcinogenicity to neurotoxicty. In this article, we discuss the chemistry of MeBr in the context of its mechanisms of toxicity. The chemical reactivity of MeBr clearly underlies its toxicity. Bromine (Br) is electronegative and a good leaving group; the δ+ carbon thus facilitates electrophilic methylation of biological molecules including glutathione (GSH) via its δ- sulphur atom, leading to downstream effects due to GSH depletion. DNA alkylation, either directly by MeBr or indirectly due to reduction in GSH-mediated detoxification of reactive alkylating chemical species, might explain the carcinogenicity of MeBr. The neurotoxicity of MeBr is much more difficult to understand, but we speculate that methyl phosphates formed in cells might contribute to its neurone-specific toxicity via cholinesterase inhibition. Finally, evidence reviewed shows that it is unlikely for Br⁻ liberated by the metabolism of MeBr to have any toxicological effect because the Br⁻ dose is very low. PMID:23800997

  4. Assessment of Ethidium bromide and Ethidium monoazide bromide removal from aqueous matrices by adsorption on cupric oxide nanoparticles.

    PubMed

    Fakhri, Ali

    2014-06-01

    The present study was undertaken to develop an effective adsorbent and to study the adsorption of Ethidium bromide and Ethidium monoazide bromide from aqueous solution using the CuO nanoparticles. The characteristics of CuO nanoparticles were determined and found to have a surface area 89.59m(2)/g. Operational parameters such as pH, contact time and adsorbent concentration, initial concentration and temperature were also studied. The amount of removal increases with the increase in pH from one to seven and reaches the maximum when the pH is nine. Adsorption data fitted well with the Langmuir, Freundlich and Florry-Huggins models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 0.868 and 0.662mg/g for Ethidium bromide and Ethidium monoazide bromide, respectively. The adsorption process was found to follow pseudo-second-order kinetics. The calculated thermodynamic parameters, namely ΔG, ΔH and ΔS showed that adsorption of Ethidium bromide and Ethidium monoazide bromide was spontaneous and endothermic under examined conditions. PMID:24630576

  5. Translation of in vitro to in vivo pyridinium oxime potential in tabun poisoning.

    PubMed

    Katalinić, Maja; Maček Hrvat, Nikolina; Žďárová Karasová, Jana; Misik, Jan; Kovarik, Zrinka

    2015-12-01

    Even if organophosphorus (OP) nerve agents were banned entirely, their presence would remain a problem as weapons of terror (like in Syria). Oxime antidotes currently used in medical practice still fall short of their therapeutic purpose, as they fail to fully restore the activity of cholinesterases, the main target for OPs. As orphan drugs, these antidotes are tested too seldom for anybody's benefit. Over the last few decades, search for improved reactivators has reached new levels, but the translation of data obtained in vitro to in vivo application is still a problem that hinders efficient therapy. In this study, we tested the strengths and weaknesses of extrapolating pyridinium oxime antidotes reactivation efficiency from in vitro to in vivo application. Our results show that this extrapolation is possible with well-determined kinetic constants, but that it also largely depends on oxime circulation time and its tissue-specific distribution. This suggests that pharmacokinetic studies should be planned at the early stages of antidote development. Special attention should also be given to improving oxime distribution throughout the organism to overcome this major constraint in improving overall OP therapy. PMID:26751861

  6. Poly(phenyl sulfone) anion exchange membranes with pyridinium groups for vanadium redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Zhang, Bengui; Zhang, Enlei; Wang, Guosheng; Yu, Ping; Zhao, Qiuxia; Yao, Fangbo

    2015-05-01

    To develop high performance and cost-effective membranes with low permeability of vanadium ions for vanadium redox flow battery (VRFB) application, poly(phenyl sulfone) anion exchange membranes with pyridinium groups (PyPPSU) are prepared and first investigated for VRFB application. PyPPSU membranes show much lower vanadium ions permeability (0.07 × 10-7-0.15 × 10-7 cm2 min-1) than that of Nafion 117 membrane (31.3 × 10-7 cm2 min-1). As a result, the self-discharge duration of the VRFB cell with PyPPSU membrane (418 h) is about four times longer than that of VRFB cell with Nafion 117 membrane (110 h). Furthermore, the VRFB cell with PyPPSU membrane exhibits higher battery efficiency (coulombic efficiency of 97.8% and energy efficiency of 80.2%) compare with that of VRFB cell with Nafion 117 membrane (coulombic efficiency of 96.1% and energy efficiency of 77.2%) at a high current density of 100 mA cm-2. In addition, PyPPSU membrane exhibits stable performance in 100-cycle test. The results indicate that PyPPSU membrane is high performance and low-cost alternative membrane for VRFB application.

  7. Charged tag founded in N-(1-chloroalkyl)pyridinium quaternization for quantification of fatty aldehydes.

    PubMed

    Cao, Yanjing; Guan, Qing; Sun, Tuanqi; Qi, Wanshu; Guo, Yinlong

    2016-09-21

    N-(1-chloroalkyl)pyridinium quaternization was developed for the derivatization of fatty aldehydes. Differing from common pre-charged reagents, non-charged pyridine and thionyl chloride were designed to add permanently charged tag on aldehydes. Pyridine was far less competitive than charged derivatives in ionization. Thionyl chloride in excess was quenched by deionized water, converting into less residual sulfur dioxide bubbles. Thus solutions could be tested directly by mass spectrometry without further post-treatments. Pyridine-d5 labeled fatty aldehydes were prepared as internal standards. Mixed derivatives were then analyzed by high performance liquid chromatography coupled to positive electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analytical parameters including reaction yield, stability, precision, linearity, and detection limits (LODs < 0.3 pg mL(-1)) were carefully validated. This method facilitated the analysis low content (ng mL(-1)) levels of free aliphatic aldehydes (C6C18) in human thyroid carcinoma and para-carcinoma tissue with a simple pretreatment procedure. Content of long chain nonvolatile aldehydes (C10C18) remarkably increased in thyroid carcinoma tissues (p < 0.05). PMID:27590548

  8. Full-color tunable photoluminescent ionic liquid crystals based on tripodal pyridinium, pyrimidinium, and quinolinium salts.

    PubMed

    Tanabe, Kana; Suzui, Yuko; Hasegawa, Miki; Kato, Takashi

    2012-03-28

    Color-tunable luminescent ionic liquid crystals have been designed as a new series of luminescent materials. To achieve tuning of emission colors, intramolecular charge transfer (ICT) character has been incorporated into tripodal molecules. A series of the compounds has three chromophores in each molecule, incorporated with both electron-donating moieties such as alkylaminobenzene and alkoxybenzene, and electron-accepting moieties such as pyridinium, pyrimidinium, and quinolinium parts. These C(3)-symmetrical molecules self-assemble into liquid-crystalline (LC) columnar (Col) structures over wide temperature ranges through nanosegregation between ionic moieties and nonionic aliphatic chains. Photoluminescent (PL) emissions of these tripodal molecules are observed in the visible region both in the self-assembled condensed states and in solutions. For example, a pyrimidinium salt with didodecylaminobenzene moieties exhibits yellowish orange emission (λ(em) = 586 nm in a thin film). Multicolor PL emissions are successfully achieved by simple tuning of changing electron-donating and electron-accepting moieties of the compounds, covering the visible region from blue-green to red. It has been revealed that ICT processes in the excited states and weak intermolecular interactions play important roles in the determination of the PL properties of the materials, by measurements of UV-vis absorption and emission spectra, fluorescence lifetimes, and PL quantum yields. PMID:22372372

  9. Two-stage prediction of the effects of imidazolium and pyridinium ionic liquid mixtures on luciferase.

    PubMed

    Ge, Hui-Lin; Liu, Shu-Shen; Su, Bing-Xia; Zhu, Xiang-Wei

    2014-01-01

    The predicted toxicity of mixtures of imidazolium and pyridinium ionic liquids (ILs) in the ratios of their EC50, EC10, and NOEC (no observed effect concentration) were compared to the observed toxicity of these mixtures on luciferase. The toxicities of EC50 ratio mixture can be effectively predicted by two-stage prediction (TSP) method, but were overestimated by the concentration addition (CA) model and underestimated by the independent action (IA) model. The toxicities of EC10 ratio mixtures can be basically predicted by TSP and CA, but were underestimated by IA. The toxicities of NOEC ratio mixtures can be predicted by TSP and CA in a certain concentration range, but were underestimated by IA. Our results support the use of TSP as a default approach for predicting the combined effect of different types of ILs at the molecular level. In addition, mixtures of ILs mixed at NOEC and EC10 could cause significant effects of 64.1% and 97.7%, respectively. Therefore, we should pay high attention to the combined effects in mixture risk assessment. PMID:24858273

  10. Phase equilibria and modeling of pyridinium-based ionic liquid solutions.

    PubMed

    Domańska, Urszula; Królikowski, Marek; Ramjugernath, Deresh; Letcher, Trevor M; Tumba, Kaniki

    2010-11-25

    The phase diagrams of the ionic liquid (IL) N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide ([BM(4)Py][NTf(2)]) with water, an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol), an aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), an alkane (n-hexane, n-heptane, n-octane), or cyclohexane have been measured at atmospheric pressure using a dynamic method. This work includes the characterization of the synthesized compound by water content and also by differential scanning calorimetry. Phase diagrams for the binary systems of [BM(4)Py][NTf(2)] with all solvents reveal eutectic systems with regards to (solid-liquid) phase equilibria and show immiscibility in the liquid phase region with an upper critical solution temperature (UCST) in most of the mixtures. The phase equilibria (solid, or liquid-liquid) for the binary systems containing aliphatic hydrocarbons reported here exhibit the lowest solubility and the highest immiscibility gap, a trend which has been observed for all ILs. The reduction of experimental data has been carried out using the nonrandom two-liquid (NRTL) correlation equation. The phase diagrams reported here have been compared with analogous phase diagrams reported previously for systems containing the IL N-butyl-4-methylpyridinium tosylate and other pyridinium-based ILs. The influence of the anion of the IL on the phase behavior has been discussed. PMID:20964426

  11. Experimental evidence of dual emission in a negatively solvatochromic push-pull pyridinium derivative.

    PubMed

    Carlotti, B; Cesaretti, A; Fortuna, C G; Spalletti, A; Elisei, F

    2015-01-21

    We report here experimental evidence of dual emission in a cationic push-pull system (bearing a methyl pyridinium group as an electron acceptor and a diphenylamino group as an electron donor), which shows negative solvatochromism. An intriguing blue shift and enlargement of the fluorescence band upon increasing the solvent polarity have suggested a possible contribution of an upper excited state to the stationary emission. Ultrafast transient absorption has indeed revealed the presence of an intermediate transient species in some solvents. The investigation of the fluorescence properties at low temperatures and in the rigid matrix has given a clear indication of this additional emission at shorter wavelengths. Femtosecond up-conversion measurements have shown interesting rise-decay dynamics in the kinetics and two well distinguished emission bands characterized by different deactivations. A single isoemissive point in the time-resolved area-normalized spectra has unambiguously pointed out the presence of two consecutive emissive species: the locally excited and the intramolecular charge transfer excited states. PMID:25474173

  12. Pyridinium crosslinking and collagen types in myocardium and valve are altered in copper deficient swine

    SciTech Connect

    McCormick, R.J.; Vadiamudl, R.K.; Medeiros, D.M.; Failla, M.L. Ohio State Univ., Columbus Dept. of Agriculture, Beltsville, MD )

    1991-03-15

    Weaned pigs were fed semipurified diets with either adequate or deficient Cu for 10 weeks and sacrificed at mean body wt of 49.1 and 45.8 ({minus}Cu) kg. Cu deficient pigs were characterized by decreased plasma and tissue Cu, plasma ceruloplasmin activity and hematocrit, and increased relative heart size. Collagen was extracted from left ventricle (LV) and bicuspid valves (BV) and analyzed for nonreducible collagen crosslink hydroxylsylpyridinoline (HP) by reverse phase HPLC and for type III and type I collagens by peptide mapping in SDS-PAGE after CNBr digestion. The quantity of collagen in LV and BV was not altered by Cu deficiency. However, pyridinium crosslinking was decreased in LV and in BV. Also, the proportion of type III collagen was higher in collagen extracted from LV and BV of Cu deficient pigs. These data show that dietary Cu deficiency reduced the concentration of mature crosslinks in cardiac collagen and was associated with a shift in collagen type to the form characteristic of developing tissues. Such changes in collagen may directly contribute to cardiac abnormalities associated with dietary Cu deficiency.

  13. Free energy of solvation of carbon nanotubes in pyridinium-based ionic liquids.

    PubMed

    Chaban, Vitaly V; Fileti, Eudes Eterno

    2016-07-27

    Numerous prospective applications require the availability of individual carbon nanotubes (CNTs). Pristine CNTs, strongly hydrophobic in nature, are known to be either totally insoluble or poorly dispersible. While it is unlikely to be possible to prepare a real solution of CNTs in any solvent, the ability of certain solvents to maintain dispersions of CNTs for macroscopic times constitutes great research interest. In the present work, we characterize two pyridinium-based ionic liquids (ILs), N-butylpyridinium chloride [BPY][Cl] and N-butylpyridinium bis(trifluoromethanesulfonyl)imide [BPY][TFSI], with respect to their potential to solvate CNTs of different diameters, from the CNT (10,10) to the CNT (25,25). Using a universal methodology, we found that both ILs exhibit essentially the same solvation performance. Solvation of CNTs is strongly prohibited entropically, whereas the energy penalty increases monotonically with the CNT diameter. Weak van der Waals interactions, which guide enthalpy alteration upon the CNT solvation, are unable to compensate for the large entropic penalty from the destruction of the IL-IL electrostatic interactions. The structure of ILs inside and outside CNTs is also discussed. The reported results are necessary for gaining a fundamental understanding of the CNT solvation problems, thereby inspiring the search for more suitable solvents. PMID:27400869

  14. Growth and characterization of dexterous nonlinear optical material: Dimethyl amino pyridinium 4-nitrophenolate 4-nitrophenol (DMAPNP)

    NASA Astrophysics Data System (ADS)

    Saravanan, M.

    2016-08-01

    The crystals (dimethyl amino pyridinium 4-nitrophenolate 4-nitrophenol [DMAPNP] suitable for NLO applications were grown by the slow cooling method. The solubility and metastable zone width measurement of DMAPNP specimen was studied. The material crystallizes in the orthorhombic crystal system with noncentrosymmetric space group of P212121. The ocular precision in the intact visible region was found to be good for non-linear optical claim. Quality of the grown crystal is ascertained by the HRXRD and etching studies. Laser Damage Threshold and Photoluminescence studies designate that the grown crystal contains less imperfection. The mechanical behaviour of DMAPNP sample at different temperatures was investigated to determine the hardness stability of the grown specimen. The piezoelectric temperament and the relative Second Harmonic Generation (for diverse particle sizes) of the material were also studied. The third order nonlinear optical properties of DMAPNP crystals were premeditated by Z-scan method. Birefringence and optical homogeneity of the crystal were evaluated using modified channel spectrum method. The half wave voltage of the grown crystal deliberate from the elector optic experimentation. Photoconductivity measurement specified consummate of inducing dipoles owing to brawny incident radiation and also disclose the nonlinear activities of the grown specimen.

  15. Disposition of ( UC)methyl bromide in rats after inhalation

    SciTech Connect

    Bond, J.A.; Dutcher, J.S.; Medinsky, M.A.; Henderson, R.F.; Birnbaum, L.S.

    1985-01-01

    The purpose of this investigation was to determine the disposition and metabolism of ( UC)methyl bromide in rats after inhalation. Male Fischer-344 rats were exposed nose only to a vapor concentration of 337 nmol ( UC)methyl bromide/liter air (9.0 ppm, 25C, 620 torr) for 6 hr. Urine, feces, expired air, and tissues were collected for up to 65 hr after exposure. Elimination of UC as UCO2 was the major route of excretion with about 47% (3900 nmol/rat) of the total ( UC)methyl bromide absorbed excreted by this route. CO2 excretion exhibited a biphasic elimination pattern with 85% of the UCO2 being excreted with a half-time of 3.9 +/- 0.1 hr (anti x +/- SE) and 15% excreted with a half-time of 11.4 +/- 0.2 hr. Half-times for elimination of UC in urine and feces were 9.6 +/- 0.1 and 16.1 +/- 0.1 hr, respectively. By 65 hr after exposure, about 75% of the initial radioactivity had been excreted with 25% remaining in the body. Radioactivity was widely distributed in tissues immediately following exposure with lung (250 nmol equivalents/g), adrenal (240 nmol equivalents/g), and nasal turbinates (110 nmol equivalents/g) containing the highest concentrations of UC. Radioactivity in livers immediately after exposure accounted for about 17% of the absorbed methyl bromide. Radioactivity in all other tissues examined accounted for about 10% of the absorbed methyl bromide. Elimination half-times of UC from tissues were on the order of 1.5 to 8 hr. In all tissues examined, over 90% of the UC in the tissues was methyl bromide metabolities. The data from this study indicate that after inhalation methyl bromide is rapidly metabolized in tissues and readily excreted. 22 references, 4 figures, 4 tables.

  16. Effect of cation type, alkyl chain length, adsorbate size on adsorption kinetics and isotherms of bromide ionic liquids from aqueous solutions onto microporous fabric and granulated activated carbons.

    PubMed

    Hassan, Safia; Duclaux, Laurent; Lévêque, Jean-Marc; Reinert, Laurence; Farooq, Amjad; Yasin, Tariq

    2014-11-01

    The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures. PMID:24929502

  17. UV photodissociation of methyl bromide and methyl bromide cation studied by velocity map imaging

    SciTech Connect

    Blanchet, Valerie; Samartzis, Peter C.; Wodtke, Alec M.

    2009-01-21

    We employ the velocity map imaging technique to measure kinetic energy and angular distributions of state selected CH{sub 3} (v{sub 2}=0,1,2,3) and Br ({sup 2}P{sub 3/2}, {sup 2}P{sub 1/2}) photofragments produced by methyl bromide photolysis at 215.9 nm. These results show unambiguously that the Br and Br* forming channels result in different vibrational excitations of the umbrella mode of the methyl fragment. Low energy structured features appear on the images, which arise from CH{sub 3}Br{sup +} photodissociation near 330 nm. The excess energy of the probe laser photon is channeled into CH{sub 3}{sup +} vibrational excitation, most probably in the {nu}{sub 4} degenerate bend.

  18. Effect of Bromide-Hypochlorite Bactericides on Microorganisms1

    PubMed Central

    Shere, Lewis; Kelley, Maurice J.; Richardson, J. Harold

    1962-01-01

    A new principle in compounding stable, granular bactericidal products led to unique combinations of a water-soluble inorganic bromide salt with a hypochlorite-type disinfectant of either inorganic or organic type. Microbiological results are shown for an inorganic bactericide composed of chlorinated trisodium phosphate containing 3.1% “available chlorine” and 2% potassium bromide, and for an organic bactericide formulated from sodium dichloroisocyanurate so as to contain 13.4% “available chlorine” and 8% potassium bromide. Comparison of these products with their nonbromide counterparts are reported for Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Streptococcus lactis, Aerobacter aerogenes, and Proteus vulgaris. Test methods employed were the Chambers test, the A.O.A.C. Germicidal and Detergent Sanitizer-Official test, and the Available Chlorine Germicidal Equivalent Concentration test. The minimal killing concentrations for the bromide-hypochlorite bactericides against this variety of organisms were reduced by a factor 2 to 24 times those required for similar hypochlorite-type disinfectants not containing the bromide. PMID:13977149

  19. Zinc Bromide Combustion: Implications for the Consolidated Incinerator Facility

    SciTech Connect

    Oji, L.N.

    1998-12-16

    In the nuclear industry, zinc bromide (ZnBr2) is used for radiation shielding. At Savannah River Site (SRS) zinc bromide solution, in appropriate configurations and housings, was used mainly for shielding in viewing windows in nuclear reactor and separation areas. Waste stream feeds that will be incinerated at the CIF will occasionally include zinc bromide solution/gel matrices.The CIF air pollution systems control uses a water-quench and steam atomizer scrubber that collects salts, ash and trace metals in the liquid phase. Water is re-circulated in the quench unit until a predetermined amount of suspended solids or dissolved salts are present. After reaching the threshold limit, "dirty liquid", also called "blowdown", is pumped to a storage tank in preparation for treatment and disposal. The air pollution control system is coupled to a HEPA pre-filter/filter unit, which removes particulate matter from the flue gas stream (1).The objective of this report is to review existing literature data on the stability of zinc bromide (ZnBr2) at CIF operating temperatures (>870 degrees C (1600 degrees F) and determine what the combustion products are in the presence of excess air. The partitioning of the combustion products among the quencher/scrubber solution, bottom ash and stack will also be evaluated. In this report, side reactions between zinc bromide and its combustion products with fuel oil were not taken into consideration.

  20. Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts

    PubMed Central

    Denmark, Scott E; Werner, Nathan S.

    2009-01-01

    The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 °C in DME with allylpalladium chloride dimer (2.5 mol %) to afford 7–95% yields of the allylation products. Both electron-rich and sterically-hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution product). A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 4–83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous E-silanolates gave slightly higher γ-selectivity than the pure Z-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ–π isomerization can rationalize all of the observed trends. PMID:18998687

  1. Electrophysiological study of intravenous pinaverium bromide in cardiology.

    PubMed

    Guerot, C; Khemache, A; Sebbah, J; Noel, B

    1988-01-01

    Pinaverium bromide is a musculotropic spasmolytic agent which acts by inhibiting transmembrane calcium movements, an effect similar to that of verapamil. Because of this, an investigation was carried out to see if it had any electrophysiological effects in patients with various cardiac disorders. In an open study, 10 patients received 2 mg pinaverium bromide intravenously. In a double-blind study, 10 patients received 4 mg pinaverium bromide intravenously and 10 patients placebo. Patients included those with either normal or pathological basal conduction, such as bundle-branch block and 1st degree atrioventricular block. Measurements were made of electrophysiological parameters before and 10 minutes after injection. The results showed that neither of the two doses of pinaverium bromide had any effect on atrial excitability, sino-atrial conduction, node and trunk atrioventricular conduction or on intraventricular conduction. No significant difference was seen in comparison with placebo. Pinaverium bromide had no anti-arrhythmic properties in these studies. Local, cardiac and general clinical tolerability was good in all patients. PMID:3219882

  2. Quantum-chemical study of the mechanism of formation of the pyridinium ion on an aluminosilicate surface and in the liquid phase

    SciTech Connect

    Zhanpeisov, N.U.; Pel'menshchikov, A.G.; Paukshtis, E.A.; Zhidomirov, G.M.

    1987-08-01

    The possibility of a pyridinium ion forming on the surface of an aluminosilicate is considered in terms of the cluster approximation of the MINDO/3-NV method proposed by the authors. The calculations show that in the first stage of absorption of pyridine on Broensted-acid-site (BAC) aluminosilicates, a hydrogen-bonded complex forms which then transforms to a pyridinium ion. The energy required to transfer a proton from the surface to the pyridine is offset by the formation of a number of C-O ..pi..-bonds. A comparison is drawn between the analogous process of the formation of an ion of pyridinium in the liquid phase, which was investigated using Germer's solvation model taking the interaction of pyridine with an aqueous solution of hydrochloric acid as an example.

  3. Two novel organic-inorganic hybrid materials from tetrachloridometallate(II) salts and 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium.

    PubMed

    Campos-Gaxiola, José J; Arredondo Rea, Susana P; Corral Higuera, Ramón; Höpfl, Herbert; Cruz Enríquez, Adriana

    2015-01-01

    Two organic-inorganic hybrid compounds have been prepared by the combination of the 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium cation with perhalometallate anions to give 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C12H12N2)[CoCl4], (I), and 4-[(E)-2-(pyridin-1-ium-2-yl)ethenyl]pyridinium tetrachloridozincate(II), (C12H12N2)[ZnCl4], (II). The compounds have been structurally characterized by single-crystal X-ray diffraction analysis, showing the formation of a three-dimensional network through X-H...ClnM(-) (X = C, N(+); n = 1, 2; M = Co(II), Zn(II)) hydrogen-bonding interactions and π-π stacking interactions. The title compounds were also characterized by FT-IR spectroscopy and thermogravimetric analysis (TGA). PMID:25567575

  4. Cetyltrimethyl ammonium bromide assisted hydrothermal growth of hematite hollow cubes

    SciTech Connect

    Wang, Wei-Wei; Yao, Jia-Liang

    2010-11-15

    Hematite hollow cubes have been prepared by forced hydrolysis of ferric chloride solutions under hydrothermal conditions. The effects of reaction time, reaction temperature and cetyltrimethyl ammonium bromide on the transformation process from akageneite to hematite were investigated in detail. The products were characterized by X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. It is found that cetyltrimethyl ammonium bromide was a critical factor influencing the phase transformation process of akageneite and the final morphology of the as-prepared products. With cetyltrimethyl ammonium bromide, hematite hollow cubes and porous spheres were obtained. Otherwise only dense cubes were observed even prolonging reaction time or increasing reaction temperature. The mechanism was proposed.

  5. Self-assembly of [UO2X4]2- (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Surbella, Robert G.; Andrews, Michael B.; Cahill, Christopher L.

    2016-04-01

    Room temperature self-assembly of [UO2X4]2- (X=Cl, Br) with γ substituted pyridinium cations has resulted in the formation of twelve compounds that were studied via single crystal X-ray diffraction and fluorescence spectroscopy. Systematic variation of electron donating groups on the pyridinium species is shown to influence the presence and/or strength of various supramolecular synthons, including hydrogen bonding and pi interactions. Combinations of such non-covalent interactions (NCIs) have given rise to a range of supramolecular assemblies, and are shown to influence uranyl emission by way of second sphere coordination to equatorial ligands.

  6. Organocatalyzed One-Step Synthesis of Functionalized N-Alkyl-Pyridinium Salts from Biomass Derived 5-Hydroxymethylfurfural.

    PubMed

    Sowmiah, Subbiah; Veiros, Luís F; Esperança, José M S S; Rebelo, Luís P N; Afonso, Carlos A M

    2015-11-01

    An efficient and scalable method has been developed for the synthesis of N-alkylpyridinium salts from biomass derived 5-hydroxymethylfurfural and alkyl amines using a catalytic amount of formic acid. This protocol is also extended to various diamines providing the exclusive formation of mono-N-alkylpyridinium salts. In addition, the mechanism for the formation of pyridinium salts was studied by DFT and using H2(18)O isotope labeled experiments showing no incorporation of (18)O in the product. PMID:26493742

  7. [Application of the rough sets theory to the analysis of structure-activity relationships of pyridinium antifungal compounds].

    PubMed

    Krysiński, J

    1994-04-01

    Relationships between chemical structure and antifungal activity of 72 quaternary pyridinium chlorides were analysed using the method of rough sets. In the information system the compounds are described by eight condition attributes and divided into three classes of activity. Using the rough sets approach a smallest set of four condition attributes significant for a high quality of classification and accuracy of classes has been found. The resulting decision algorithm describes relations between structure and antifungal activity in terms of significant condition attributes. It may be helpful in predicting structures of new antifungal compounds to be synthesized. PMID:8204024

  8. Syntheses of [omega]-alkynyl aldehydes and ketones via oxidation of [omega]-alkynyl alcohols with pyridinium dichromate

    SciTech Connect

    Bierer, D.E.; Kabalka, G.W. )

    1988-01-01

    Pyridinium dichromate (PDC) is an effective reagent for the oxidation of alcohols and a number of modifications of the original procedure have been reported. Interestingly, PDC has never been used to oxidize non-conjugated acetylenic alcohols. As a part of a project involving the chemical preparation of a number of unsaturated amino acids, the authors investigated the synthesis of a series of [omega]-alkynyl aldehydes. The authors now report that the PDC oxidation of [omega]-alkynyl alcohols is an effective route to the corresponding [omega]-alkynyl carbonyl compounds.

  9. Eco-Friendly Synthesis of a New Class of Pyridinium-Based Ionic Liquids with Attractive Antimicrobial Activity.

    PubMed

    Messali, Mouslim

    2015-01-01

    The present study reports a green synthesis of a new family of ionic liquids (ILs) based on functionalized 4-dimethylaminopyridinium derivatives. The structures of 23 newly synthesized ILs (2-24) were confirmed by FT-IR, (1)H-, (13)C-, (11)B-, (19)F-, and (31)P-NMR spectroscopy and mass spectrometry. The antimicrobial activity of all novel ILs was tested against a panel of bacteria and fungi. The results prove that all tested ILs are effective antibacterial and antifungal agents, especially 4-(dimethylamino)-1-(4-phenoxybutyl) pyridinium derivatives 5 and 19. PMID:26287148

  10. Oxidation of manganese(II) during chlorination: role of bromide.

    PubMed

    Allard, S; Fouche, L; Dick, J; Heitz, A; von Gunten, U

    2013-08-01

    The oxidation of dissolved manganese(II) (Mn(II)) during chlorination is a relatively slow process which may lead to residual Mn(II) in treated drinking waters. Chemical Mn(II) oxidation is autocatalytic and consists of a homogeneous and a heterogeneous process; the oxidation of Mn(II) is mainly driven by the latter process. This study demonstrates that Mn(II) oxidation during chlorination is enhanced in bromide-containing waters by the formation of reactive bromine species (e.g., HOBr, BrCl, Br2O) from the oxidation of bromide by chlorine. During oxidation of Mn(II) by chlorine in bromide-containing waters, bromide is recycled and acts as a catalyst. For a chlorine dose of 1 mg/L and a bromide level as low as 10 μg/L, the oxidation of Mn(II) by reactive bromine species becomes the main pathway. It was demonstrated that the kinetics of the reaction are dominated by the adsorbed Mn(OH)2 species for both chlorine and bromine at circumneutral pH. Reactive bromine species such as Br2O and BrCl significantly influence the rate of manganese oxidation and may even outweigh the reactivity of HOBr. Reaction orders in [HOBr]tot were found to be 1.33 (±0.15) at pH 7.8 and increased to 1.97 (±0.17) at pH 8.2 consistent with an important contribution of Br2O which is second order in [HOBr]tot. These findings highlight the need to take bromide, and the subsequent reactive bromine species formed upon chlorination, into account to assess Mn(II) removal during water treatment with chlorine. PMID:23859083

  11. Intensification of sonochemical degradation of malachite green by bromide ions.

    PubMed

    Moumeni, Ouarda; Hamdaoui, Oualid

    2012-05-01

    Sonochemical oxidation has been investigated as a viable advanced oxidation process (AOP) for the destruction of various pollutants in water. Ultrasonic irradiation generates ()OH radicals that can recombine, react with other gaseous species present in the cavity, or diffuse out of the bubble into the bulk liquid medium where they are able to react with solute molecules. The extent of degradation of an organic dye such as malachite green (MG) is limited by the quantity of hydroxyl radicals diffused from cavitation bubbles. In this work, the effect of bromide ions on sonolytic degradation of MG was investigated. The obtained results clearly demonstrated the considerable enhancement of sonochemical destruction of MG in the presence of bromide. No significant differences were observed in the presence of chloride and sulfate, excluding the salting-out effect. Positive effect of bromide ions, which increases with increasing bromide level and decreasing MG concentration, is due to the generation of dibromine radical anion (Br(2)(-)) formed by reaction of Br(-) with ()OH radicals followed by rapid complexation with another anion. The generated Br(2)(-) radicals, reactive but less than ()OH, are likely able to migrate far from the cavitation bubbles towards the solution bulk and are suitable for degradation of an organic dye such as MG. Additionally, Br(2)(-) radicals undergo radical-radical recombination at a lesser extent than hydroxyl radicals and would be more available than ()OH for substrate degradation, both at the bubble surface and in the solution bulk. This effect compensates for the lower reactivity of Br(2)(-) compared to ()OH toward organic substrate. Addition of bromide to natural and sea waters induces a slight positive effect on MG degradation. In the absence of bromide, ultrasonic treatment for the removal of MG was promoted in complex matrices such as natural and sea waters. PMID:21911308

  12. Methyl bromide emissions from a covered field: II. Volatilization

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.

    1996-01-01

    An experiment to investigate the environmental fate and transport of methyl bromide in agricultural fields is described. The methyl bromide volatilization rate was determined as a function of time for conditions where methyl bromide was applied at a rate of 843 kg in a 3.5-ha (i.e., 240 kg/ha) field covered with plastic at a depth of 25 cm. Three methods were used to estimate the methyl bromide volatilization rate, including: the aerodynamic, theoretical profile shape and integrated horizontal flux methods. The highest methyl bromide volatilization rates were at the beginning of the experiment. Within the first 24 h, approximately 36% of the applied methyl bromide mass was lost. Diurnally, the largest volatilization rates occurred during the day when temperatures were high and the atmosphere was unstable. Cooler temperatures, light winds, and neutral to stable atmospheric conditions were present at night, reducing the flux. The total emission calculated using these methods was found to be approximately 64% ({+-} 10%) of the applied mass. A mass balance was calculated using each flux estimation technique and several methods for analyzing the data. The average mass recovery using all the flux methods was 867 kg ({+-}83 kg), which was 102.8% ({+-}9.8%) of the applied (i.e., 843 kg). The range in the mass balance percent (i.e., percent of applied mass that is measured) is from 88 to 112%. The averaged mass balance percent for the aerodynamic method, which involved using the measured data directly, was approximately 100.8%. The total emission calculated using the aerodynamic method was found to be approximately 62% ({+-}11%) of the applied mass. 29 refs., 7 figs., 1 tab.

  13. Photochemistry of alkyl bromides trapped in water ice films

    NASA Astrophysics Data System (ADS)

    Schrems, O.; Okaikwei, B.; Bluszcz, Th.

    2012-04-01

    Photochemical reactions of atmospheric trace gases taking place at the surface of atmospheric ice particles and in bulk ice are important in stratospheric and tropospheric chemistry but also in polar and alpine snowpack chemistry. Consequently, the understanding of the uptake und incorporation of atmospheric trace gases in water ice as well as their interactions with water molecules is very important for the understanding of processes which occur in ice particles and at the air/ice interface. Reactive atmospheric trace gases trapped in ice are subject of photochemical reactions when irradiated with solar UV radiation. Among such compounds bromine species are highly interesting due to their potential of depleting ozone both in the stratosphere and troposphere. Organic bromine gases can carry bromine to the stratosphere. Methyl bromide (CH3Br) is the largest bromine carrier to the stratosphere. It has both natural and anthropogenic sources. In this contribution we will present the results of our laboratory studies of alkyl bromides (methyl, bromide (CH3Br), dimethyl bromide (CH2Br2), n-propyl bromide (C3H7Br), 1,2-dibromoethane C2H4Br2)), trapped in water ice. We have simulated the UV photochemistry of these brominated alkanes isolated in ice films kept at 16 K and for comparison in solid argon matrices. The photoproducts formed in the ice have been identified by means of FTIR spectroscopy. Reflection absorption infrared spectroscopy (RAIRS) is especially useful to study nascent ice surfaces, kinetics of adsorption/decomposition, and heterogeneous catalysis. Among the observed photoproducts we could identify carbon monoxide and carbon dioxide for each alkyl bromide studied. The photoproduct HBr is dissociated in the bulk ice. Based on the experimental observations possible reaction mechanisms will be discussed.

  14. Reversible phase transition of 2-carboxypyridinium perchlorate-pyridinium-2-carboxylate (1/1).

    PubMed

    Wang, Bi-Qin; Yan, Hai-Biao; Huang, Zheng-Qing; Zhang, Yun-Hua; Sun, Jing

    2015-04-01

    The title salt, C6H6NO2(+)·ClO4(-)·C6H5NO2, was crystallized from an aqueous solution of equimolar quantities of perchloric acid and pyridine-2-carboxylic acid. Differential scanning calorimetry (DSC) measurements show that the compound undergoes a reversible phase transition at about 261.7 K, with a wide heat hysteresis of 21.9 K. The lower-temperature polymorph (denoted LT; T = 223 K) crystallizes in the space group C2/c, while the higher-temperature polymorph (denoted RT; T = 296 K) crystallizes in the space group P2/c. The relationship between these two phases can be described as: 2a(RT) = a(LT); 2b(RT) = b(LT); c(RT) = c(LT). The crystal structure contains an infinite zigzag hydrogen-bonded chain network of 2-carboxypyridinium cations. The most distinct difference between the higher (RT) and lower (LT) temperature phases is the change in dihedral angle between the planes of the carboxylic acid group and the pyridinium ring, which leads to the formation of different ten-membered hydrogen-bonded rings. In the RT phase, both the perchlorate anions and the hydrogen-bonded H atom within the carboxylic acid group are disordered. The disordered H atom is located on a twofold rotation axis. In the LT phase, the asymmetric unit is composed of two 2-carboxypyridinium cations, half an ordered perchlorate anion with ideal tetrahedral geometry and a disordered perchlorate anion. The phase transition is attributable to the order-disorder transition of half of the perchlorate anions. PMID:25836279

  15. Can betaine pyridinium derivatives be used to control the photoejection of cation?

    PubMed

    Aloïse, S; Ruan, Y; Hamdi, I; Tiwari, A K; Buntinx, G; Azarias, C; Perrier, A; Leray, I

    2016-06-01

    Using a combination of advanced DFT/TDDFT calculations together with ultrafast and stationary spectroscopies we have investigated the photochemistry and cationic complexation ability of 1-pyridinio-benzimidazolate (PyB) and analogs substituted by 15-aza-5-crown (PyB-Aza) or dimethyl-amino groups (PyB-DiMe). Focusing on PyB-Aza, the first aim was to assess the competitive complexation of the imidazole bridge vs. the macrocycle. In acetonitrile, it was found by absorption and emission that the imidazole moiety binds efficiently through lateral electrostatic interaction of high charge density cations and especially Ca(2+) to form a 1 : 1, metal : ligand (M : L) complex. Modulation of the complexation toward para substitution of the phenyl ring with a donor group is reported with values ranging from log K = 3.4 to 6.8. Complexation values are properly predicted by DFT calculations. From a photochemical point of view, for the same series, the trend is parallel to the rate of the photo-release process, found to be less than 200 femtosecond (fs), the fastest photorelease characteristic time reported so far. Unlike photoinduced charge transfer molecules linked with an aza-crown group, the mechanism appears simpler with no participation of loose complexes due to the macrocavity effect. Relaxation mechanisms after cation ejection are discussed as well. Finally, even if any photoinduced translocation of cation is reported for the PyB-Aza molecule between two complexation sites, a discussion about the use of betaine pyridinium as a molecular tool for the smart manipulation of cation systems is initiated. PMID:27212223

  16. Brain levels of the neurotoxic pyridinium metabolite HPP+ and extrapyramidal symptoms in haloperidol-treated mice.

    PubMed

    Crowley, James J; Ashraf-Khorassani, Mehdi; Castagnoli, Neal; Sullivan, Patrick F

    2013-12-01

    The typical antipsychotic haloperidol is a highly effective treatment for schizophrenia but its use is limited by a number of serious, and often irreversible, motor side effects. These adverse drug reactions, termed extrapyramidal syndromes (EPS), result from an unknown pathophysiological mechanism. One theory relates to the observation that the haloperidol metabolite HPP+ (4-(4-chlorophenyl)-1-[4-(4-fluorophenyl)-4-oxobutyl]-pyridinium) is structurally similar to MPP+ (1-methyl-4-phenylpyridinium), a neurotoxin responsible for an irreversible neurodegenerative condition similar to Parkinson's disease. To determine whether HPP+ contributes to haloperidol-induced EPS, we measured brain HPP+ and haloperidol levels in strains of mice at high (C57BL/6J and NZO/HILtJ) and low (BALB/cByJ and PWK/PhJ) liability to haloperidol-induced EPS following chronic treatment (7-10 adult male mice per strain). Brain levels of HPP+ and the ratio of HPP+ to haloperidol were not significantly different between the haloperidol-sensitive and haloperidol-resistant strain groups (P=0.50). Within each group, however, strain differences were seen (P<0.01), indicating that genetic variation regulating steady-state HPP+ levels exists. Since the HPP+ levels that we observed in mouse brain overlap the range of those detected in post-mortem human brains following chronic haloperidol treatment, the findings from this study are physiologically relevant to humans. The results suggest that strain differences in steady-state HPP+ levels do not explain sensitivity to haloperidol-induced EPS in the mice we studied. PMID:24107597

  17. CATALYTIC DETOXIFICATION OF NERVE AGENT AND PESTICIDE ORGANOPHOSPHATES BY BUTYRYLCHOLINESTERASE ASSISTED WITH NON-PYRIDINIUM OXIMES

    PubMed Central

    Radić, Zoran; Dale, Trevor; Kovarik, Zrinka; Berend, Suzana; Garcia, Edzna; Zhang, Limin; Amitai, Gabriel; Green, Carol; Radić, Božica; Duggan, Brendan M.; Ajami, Dariush; Rebek, Julius; Taylor, Palmer

    2016-01-01

    SYNOPSIS We present here a comprehensive in vitro, ex vivo and in vivo study on hydrolytic detoxification of nerve agent and pesticide organophosphates (OPs) catalyzed by purified human butyrylcholinesterase (hBChE) in combination with novel non-pyridinium oxime reactivators. We identified 2-trimethylammonio-6-hydroxybenzaldehyde oxime (TAB2OH) as an efficient reactivator of OP-hBChE conjugates formed by the nerve agents, VX and cyclosarin, and the pesticide, paraoxon. It was also functional in reactivation of sarin and tabun inhibited hBChE. A three to five-fold enhancement of in vitro reactivation of VX, cyclosarin and paraoxon inhibited hBChE was observed, when compared to the commonly used N-methylpyridinium aldoxime reactivator, 2PAM. Kinetic analysis showed the enhancement resulted from improved molecular recognition of corresponding OP-hBChE conjugates by TAB2OH. The unique features of TAB2OH stem from an exocyclic quaternary nitrogen and a hydroxyl, both ortho to an oxime group on a benzene ring. pH dependences reveal participation of the hydroxyl (pKa=7.6) forming an additional ionizing nucleophile to potentiate the oxime (pKa=10) at physiological pH. The TAB2OH protective indices in therapy of sarin and paraoxon exposed mice were enhanced by 30% – 60% when they were treated with a combination of TAB2OH and sub-stoichiometric hBChE. These results establish that oxime-assisted catalysis is feasible for OP bioscavenging. PMID:23216060

  18. 2-Pyridinium propanol hydrogen squarate: Experimental and computational study of a nonlinear optical material

    NASA Astrophysics Data System (ADS)

    Korkmaz, Ufuk; Bulut, Ahmet

    2015-02-01

    The experimental and theoretical investigation of a novel organic nonlinear optical (NLO) squarate salt of 2-pyridinium propanol hydrogen squarate (1), C8H12ON+ ·C4HO4-, were reported in this study. The crystal structure of the title compound was found to crystallize in the triclinic P-1 space group. In the asymmetric unit each squaric acid molecules have donated one H atom to the pyridines N1 and N2 atoms of a 2-pyridine propanol molecule, forming the salt (1). The X-ray analysis clearly indicated that the crystal packing has shown the hydrogen bonding ring pattern of D22 (10) (α-dimer) through Nsbnd H⋯O interactions. The structural and vibrational properties of the compound were also studied by computational methods of ab initio performed on the compound at DFT/B3LYP/6-31++G(d,p) (2) and HF/6-31++G(d,p) (3) level of theory. The calculation results on the basis of two models for both the optimized molecular structure and vibrational properties for the 1 are presented and compared with the X-ray analysis result. The molecular electrostatic potential (MEP), electronic absorption spectra, frontier molecular orbitals (FMOs), conformational flexibility and non-linear optical properties (NLO) of the title compound were also studied at the 2 level and the results are reported. In order to evaluate the suitability for NLO applications thermal analysis (TG, DTA and DTG) data of 1 were also obtained.

  19. 2-Pyridinium propanol hydrogen squarate: experimental and computational study of a nonlinear optical material.

    PubMed

    Korkmaz, Ufuk; Bulut, Ahmet

    2015-02-01

    The experimental and theoretical investigation of a novel organic nonlinear optical (NLO) squarate salt of 2-pyridinium propanol hydrogen squarate (1), C8H12ON(+)·C4HO4(-), were reported in this study. The crystal structure of the title compound was found to crystallize in the triclinic P-1 space group. In the asymmetric unit each squaric acid molecules have donated one H atom to the pyridines N1 and N2 atoms of a 2-pyridine propanol molecule, forming the salt (1). The X-ray analysis clearly indicated that the crystal packing has shown the hydrogen bonding ring pattern of D2(2)(10) (α-dimer) through N-H⋯O interactions. The structural and vibrational properties of the compound were also studied by computational methods of ab initio performed on the compound at DFT/B3LYP/6-31++G(d,p) (2) and HF/6-31++G(d,p) (3) level of theory. The calculation results on the basis of two models for both the optimized molecular structure and vibrational properties for the 1 are presented and compared with the X-ray analysis result. The molecular electrostatic potential (MEP), electronic absorption spectra, frontier molecular orbitals (FMOs), conformational flexibility and non-linear optical properties (NLO) of the title compound were also studied at the 2 level and the results are reported. In order to evaluate the suitability for NLO applications thermal analysis (TG, DTA and DTG) data of 1 were also obtained. PMID:25459503

  20. Interaction of pyridinium bis-retinoid (A2E) with bilayer lipid membranes.

    PubMed

    Sokolov, V S; Sokolenko, E A; Sokolov, A V; Dontsov, A E; Chizmadzhev, Y A; Ostrovsky, M A

    2007-02-01

    The accumulation of lipofuscin granules within the retinal pigment epithelium (RPE) cells is correlated with the progression of age-related macular degeneration. One of the fluorophores contained in lipofiscin granules is pyridinium bis-retinoid (A2E). To test its membrane-toxic effect, the interaction of A2E with bilayer lipid membranes (BLM) was studied. The incorporation of charged A2E molecules into the membranes has been detected as a change of either zeta-potential of multilayer liposomes or boundary potential of BLM. It was shown that the presence of up to 25mol% of A2E did not destabilize the bilayers made of saturated phosphatidylcholine (PC). However, the destabilizing effect became very significant when BLM contained negatively charged lipids such as cardiolipin or phosphatidylserine. The electrical breakdown measurements revealed that the A2E-induced decrease of BLM stability was primarily associated with the growing probability of lipid pore formation. It was found from the measurements of boundary potential of BLM that exposure of A2E to light initiates its transformation into at least two products. One of them is epoxy-A2E, which, being hydrophilic, moves from the membrane into water solution. The other product is a non-identified hydrophobic substance. Illumination of A2E-containing BLM made from unsaturated PC by visible light caused the membrane damage presumably due to oxidation of these lipids by singlet oxygen generated by excited A2E molecules. However, this effect was very weak compared to the effect of known photosensitizers. The illumination of BLM with A2E also leads to the damage of gramicidin incorporated into the membrane, as was detected by measuring the conductance of channels formed by this peptide. PMID:17070694

  1. Investigation of possible interaction between pinaverium bromide and digoxin.

    PubMed

    Weitzel, O; Seidel, G; Engelbert, S; Berksoy, M; Eberhardt, G; Bode, R

    1983-01-01

    A single-blind study was carried out in 25 patients, who were receiving maintenance therapy for congestive heart failure with digoxin, to investigate the effect on steady-state plasma digoxin levels of concomitant administration of the spasmolytic, pinaverium bromide (50 mg 3-times daily). Patients received pinaverium bromide for 12 days followed by placebo for a further 7 days. Assessment of the results in 21 patients showed no evidence of any statistically significant variations in plasma digoxin levels during either treatment period or in the clinical observations which might indicate drug interaction. PMID:6653138

  2. Action of pinaverium bromide on calmodulin-regulated functions.

    PubMed

    Wuytack, F; De Schutter, G; Casteels, R

    1985-08-01

    Pinaverium bromide at concentrations below 10(-5) M did not inhibit calmodulin-dependent enzymes such as phosphodiesterase and the Ca transport ATPase of the plasma membrane. At higher concentrations the compound interacted with the stimulation of those enzymes by calmodulin and also inhibited the calmodulin-independent activity. A similar inhibitory action was observed for the NaK ATPase. It is concluded that the inhibitory action of pinaverium bromide on smooth muscle concentration at concentrations below 10(-5) M was due to its interaction with the voltage-dependent Ca channels and not to its interference with the calmodulin-dependent activation of the contractile proteins. PMID:2995077

  3. Versatile Route to Arylated Fluoroalkyl Bromide Building Blocks.

    PubMed

    Kaplan, Peter T; Vicic, David A

    2016-02-19

    New difunctionalized and fluoroalkylated silyl reagents have been prepared that react with silver and copper salts to afford active catalysts that can be used to synthesize arylated fluoroalkyl bromide building blocks. It has been shown that the [(phen)Ag(CF2)nBr] intermediates are capable of transferring both the phenanthroline ligand and the fluoroalkyl bromide chain to copper iodide, eliminating the need for a preligated copper salt precursor. The methodology is compatible with various chain lengths of the fluoroalkyl halide functionality. PMID:26820388

  4. Magnesium Lewis Acid Assisted Oxidative Bromoetherification Involving Bromine Transfer from Alkyl Bromides with Aldehydes by Umpolung of Bromide.

    PubMed

    Moriyama, Katsuhiko; Nishinohara, Chihiro; Togo, Hideo

    2016-08-16

    An oxidative bromoetherification involving a bromine transfer from alkyl bromides upon reacting them with aldehydes in a Grignard reaction with a concurrent oxidation of bromide was developed to provide substituted tetrahydrofurans in high yields. This reaction, which proceeds through two types of bromine transfer, was promoted by the addition of a Brønsted acid. Mechanistic studies suggested that a magnesium Lewis acid activates hypobromate, which is generated in situ from the reaction of bromide and Oxone to improve the electrophilicity of the bromonium ion (Br(+) ) for the oxidative bromoetherification of alkenyl alcohols. Furthermore, the magnesium Lewis acid catalyzed oxidative bromoetherification of an alkenyl alcohol proceeded to provide a cyclization product in 92 % yield. PMID:27304660

  5. Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Alkyl Bromides: Et3N as the Terminal Reductant.

    PubMed

    Duan, Zhengli; Li, Wu; Lei, Aiwen

    2016-08-19

    Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants. PMID:27472556

  6. Disiloxanes and Functionalized Silica Gels: One Route, Two Complementary Outcomes-Guanidinium and Pyridinium Ion-Exchangers.

    PubMed

    Tabisz, Łukasz; Tukibayeva, Ainur; Pankiewicz, Radoslaw; Dobielska, Marta; Leska, Boguslawa

    2015-01-01

    Five novel disiloxane compounds comprising guanidinium and pyridinium moieties were obtained with high yields and purity. The verified synthetic pathways were then applied for modification of pre-functionalized silica gel, producing materials with the analogous organic side-chains. These halide-containing compounds and materials were then compared as to their ion-exchange properties: two disiloxanes proved to be effective in leaching different anions (nitrate, benzoate and ascorbate) from solid to organic phase, and pyridinium-functionalized silica gels showed selectivity towards perchlorate ion, removing it from methanolic solutions with preference to other singly charged anions. The results presented demonstrate that both compounds and materials containing silicon-carbon bonds can be produced using the same methodology, but offer strikingly different application opportunities. Comparison of their properties provides additional insight into the binding mode of different anions and hints at how the transition from a flexible siloxane bridge to immobilization on solid surface influences anion-binding selectivity. Additionally, one of the siloxane dipodands was found to form a crystalline and poorly soluble nitrate salt (1.316 g/L, water), although it was miscible with a wide range of solvents as a hydrochloride. A possible explanation is given with the help of semi-empirical calculations. A simple, time- and cost-efficient automated potentiometric titration methodology was used as a viable analytical tool for studying ion-exchange processes for both compounds and materials, in addition to standard NMR, FT-IR and ESI-MS methods. PMID:26714187

  7. Structural effects of the β-vinyl linker in pyridinium porphyrins: spectroscopic studies in organic solvents and AOT reverse micelles.

    PubMed

    Vaz Serra, Vanda; Andrade, Suzana M; Silva, Eduarda M P; Silva, Artur M S; Neves, Maria G P M S; Costa, Sílvia M B

    2013-12-01

    Two isomeric β-vinylpyridinium porphyrins, 2-[2-(2-methylpyridinium)vinyl]-5,10,15,20-tetraphenylporphyrin (1, ortho isomer) and 2-[2-(4-methylpyridinium)vinyl]-5,10,15,20-tetraphenylporphyrin (2, para isomer), which have shown different photodynamic behavior were investigated in organic solvents and sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. In organic systems, the absorption spectra present a red-shifted band that is more intense in the para isomer, in addition to the usual Soret band. This new band presents interesting solvatochromic effects which obey the multiparametric Kamlet-Taft equation. In AOT reverse micelles, the ortho isomer exhibits a strong dependence with the parameter ω0 = [H2O]/[AOT] which indicates that the molecule resides at the interface toward the organic phase. By contrast, no evidence was detected for the encapsulation of para isomer 2 in AOT reverse micelles. The hypothesis of two ground state isomers with different contributions of trans and quinoid structures is advanced on the basis of the overall data collected from electronic absorption, steady-state, and transient-state fluorescence emission. A charge transfer state in which an electron is fully transferred from the porphyrin to the pyridinium moiety is associated to a quinoid structure in isomer 2. The trans/quinoid relative proportions may be accounted for by the orientation of the ortho-/para-pyridinium isomers relatively to the porphyrin core. PMID:24175940

  8. Crystal structure of bis-[4-(di-methyl-amino)-pyridinium] aqua-bis-(oxalato)oxidovanadate(IV) dihydrate.

    PubMed

    Sehimi, Hiba; Chérif, Ichraf; Zid, Mohamed Faouzi

    2016-07-01

    The title organic-inorganic hybrid salt, (C7H11N2)2[V(C2O4)2O(H2O)]·2H2O, shows a distorted octa-hedral coordination environment for the vanadium(IV) atom in the anion (point group symmetry 2), with four O atoms from two symmetry-related chelating oxalate dianions and two O atoms in trans configuration from a coordinating water mol-ecule and a terminal vanadyl O atom. In the crystal, (001) layers of cations and anions alternate along [001]. The anionic layers are built up by inter-molecular O-H⋯O hydrogen bonds involving the coordinating and solvent water mol-ecules. The cationic layers are linked to the anionic layers via N-H⋯O hydrogen bonds between the pyridinium group and the non-coordinating O atoms of the oxalate group. The 4-(di-methyl-amino)-pyridinium cations are also engaged in π-π stacking with their anti-parallel neighbours [centroid-to-centroid distance = 3.686 (2) Å]. Considering all supra-molecular features, a three-dimensional network structure is accomplished. PMID:27555950

  9. Disiloxanes and Functionalized Silica Gels: One Route, Two Complementary Outcomes—Guanidinium and Pyridinium Ion-Exchangers

    PubMed Central

    Tabisz, Łukasz

    2015-01-01

    Five novel disiloxane compounds comprising guanidinium and pyridinium moieties were obtained with high yields and purity. The verified synthetic pathways were then applied for modification of pre-functionalized silica gel, producing materials with the analogous organic side-chains. These halide-containing compounds and materials were then compared as to their ion-exchange properties: two disiloxanes proved to be effective in leaching different anions (nitrate, benzoate and ascorbate) from solid to organic phase, and pyridinium-functionalized silica gels showed selectivity towards perchlorate ion, removing it from methanolic solutions with preference to other singly charged anions. The results presented demonstrate that both compounds and materials containing silicon-carbon bonds can be produced using the same methodology, but offer strikingly different application opportunities. Comparison of their properties provides additional insight into the binding mode of different anions and hints at how the transition from a flexible siloxane bridge to immobilization on solid surface influences anion-binding selectivity. Additionally, one of the siloxane dipodands was found to form a crystalline and poorly soluble nitrate salt (1.316 g/L, water), although it was miscible with a wide range of solvents as a hydrochloride. A possible explanation is given with the help of semi-empirical calculations. A simple, time- and cost-efficient automated potentiometric titration methodology was used as a viable analytical tool for studying ion-exchange processes for both compounds and materials, in addition to standard NMR, FT-IR and ESI-MS methods. PMID:26714187

  10. Synthesis and characterization of an ionic conjugated polymer: poly[2-ethynyl-N-(2-furoyl)pyridinium chloride].

    PubMed

    Gal, Yeong-Soon; Jin, Sung-Ho; Park, Jong Wook

    2014-08-01

    A new ionic polyacetylene derivative with furoyl substituents was prepared by the uncatalyzed polymerization of 2-ethynylpyridine by using 2-furoyl chloride in high yield. The polymer structure was characterized by such instrumental methods as NMR, IR, and UV-visible spectroscopies to have a polyacetylene backbone system with the N-(2-furoyl)pyridinium chloride. The electro-optical and electrochemical properties of poly[2-ethynyl-N-(2-furoyl)pyridinium chloride [PEFPC] were studied. The photoluminescence spectrum showed that the PL peak is at 578 nm corresponding to the photon energy of 2.15 eV. The cyclovoltammograms of PEFPC exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of polymer versus the scan rates is approximately linear relationship in the range of 30 mV/sec-150 mV/sec. It was found that the kinetics of redox process is controlled by the reactant diffusion process from the oxidation current density of PEFPC versus the scan rates. PMID:25936097

  11. Distribution and quantification of pyridinium cross-links of collagen within the different maturational zones of the chick growth plate.

    PubMed

    Farquharson, C; Duncan, A; Seawright, E; Whitehead, C C; Robins, S P

    1996-08-13

    In order to assess alterations in the collagen network during endochondral ossification the pyridinium cross-links of collagen were quantified in sequential transverse sections through the chick growth plate. This was accomplished using both morphological (alkaline phosphatase (ALP) histochemistry and collagen type X immunostaining) and analytical (HPLC) analyses. In articular cartilage, pyridinoline concentrations were maximal in the deep mature zones. In contrast, the proliferating chondrocyte zone of the growth plate had approximately a 10-fold greater pyridinoline cross-link concentration than the mature hypertrophic zone. Deoxypyridinoline was first found in the prehypertrophic zone of the growth plate cartilage that reacted positively for ALP activity but before collagen type X was detected. However, deoxypyridinoline concentrations were highest in the most differentiated regions of the growth plate where it was the principal pyridinium cross-link. In tibial dyschondroplasia, where chondrocyte differentiation is arrested in the prehypertrophic zone, higher concentrations of both cross-links were found with increasing distance down the lesion. We conclude that the decrease in pyridinoline cross-link concentration down the growth plate may be an essential adaptation (via increased collagenase activity and collagen turnover) of the matrix for vascular invasion and osteoclastic resorption to occur. PMID:8765127

  12. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common dis...

  13. A COMPARISON OF BROMIDE AND NITRATE TRANSPORT IN SOILS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sandy soils (with sand content 95-98%) are used for agricultural production, which require careful management of water, chemicals, and nutrients to minimize leaching below the rooting zone. Bromide is used as an indicator of downward transport of soluble nutrients in soils. A leching column study ...

  14. HEALTH AND ENVIRONMENTAL EFFECTS PROFILE FOR METHYL BROMIDE

    EPA Science Inventory

    The Health and Environmental Effects Profile for Methyl Bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency a...

  15. Nickel-Catalyzed Reductive Amidation of Unactivated Alkyl Bromides.

    PubMed

    Serrano, Eloisa; Martin, Ruben

    2016-09-01

    A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. PMID:27357076

  16. Reactive films for mitigating methyl bromide emissions from fumigated soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Emissions of methyl bromide (MeBr) from agricultural fumigation can lead to depletion of the stratospheric ozone layer, and so its use is being phased out. However, as MeBr is still widely used under Critical Use Exemptions, strategies are still required to control such emissions. In this work, nove...

  17. Methyl Bromide Alternatives for Floriculture Production in a Problem Site

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Successful methyl bromide alternatives must manage a variety of pest problems in floriculture and vegetable production systems including weeds, plant-parasitic nematodes, and soil-borne diseases. Methods that may be successful in some situations may be challenged in sites with unusually heavy pest p...

  18. EFFECT OF BROMIDE ION ON FORMATION OF HAAS DURING CHLORINATION

    EPA Science Inventory

    loacetic acids (HAAs) during chlorination and he effects of independent variables, including pH, reaction time, and chlorine dosage. Almost all of the indpendent loaetic acids (HAAs) during chlorin...designed to statistically evaluate the influence of bromide ion on the formatio...

  19. The Fate of Alternative Soil Funigants to Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation is an important agricultural practice for the control of soil-borne pests. Since the phase–out of methyl bromide, due to its role in the depletion of stratospheric ozone, several alternatives such as 1,3-dichloropropene (1,3-D), chloropicrin (CP), and dimethyl disulfide (DMDS) are b...

  20. Status of Alternatives for Methyl Bromide in the United States

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide is a fumigant used for disinfestation of soils, commodities and structures. Listed as an ozone-depleting chemical international environmental protocols and the U.S. Clean Air Act require that its use be severely restricted. Although use of this fumigant has fallen considerably, the U....

  1. Weed Control with Methyl Bromide Alternatives: A Review.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide (MeBr) has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemica...

  2. PHYTOREMEDIATON POTENTIALS OF SELECTED TROPICAL PLANTS FOR ETHIDIUM BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Research and development has its own benefits and inconveniences. One of the inconveniences is the generation of enormous quantity of diverse toxic and hazardous wastes and its eventual contamination to soil and groundwater resources. Ethidium bromide (EtBr) is one of the commonly used substances i...

  3. Methyl bromide phase out could affect future reforestation efforts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has long been an integral component in producing healthy tree seedlings in forest nurseries of California, Idaho, Montana, Oregon and Washington. The fumigant was supposed to be completely phased out of use in the United States of America by 2005, but many forest nurseries continue to...

  4. REVIEW OF CONTROL OPTIONS FOR METHYL BROMIDE IN COMMODITY TREATMENT

    EPA Science Inventory

    The report describes recent developments in the control of methyl bromide (MeBr) and discusses technical considerations and requirements for and economic feasibility of recovery. (NOTE: MeBr, fumigant for agricultural commodities, is an ozone depleting chemical. The U.S. EPA has ...

  5. Investigation of bromide's spectra by high resolution UV-laser

    NASA Astrophysics Data System (ADS)

    Zhang, Jin; Ma, Jian-guo

    2011-12-01

    Experimental investigation has been carried out for dissociation/ionisation of methyl bromide using time of flight mass spectrometer, then, the mass signals were assigned to H+, CHm+ (m= 0-3), iBr+ (i = 79, 81), and the main processes of multi-photon ionization and dissociation of CH3Br were given.

  6. Calla lily production with methyl bromide alternatives – Year 2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cut flower and ornamental bulb industries rely heavily on a methyl bromide/chloropicrin (MB/Pic) mixture as a key pest management tool. The loss of MB will seriously affect the cut flower and bulb industry, and, in the future, will require growers to use alternative fumigants. Past experiments have...

  7. Depleting methyl bromide residues in soil by reaction with bases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the...

  8. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common disi...

  9. BROMIDE-OXIDANT INTERACTIONS AND THM (TRIHALOMETHANE) FORMATION: A LITERATURE REVIEW

    EPA Science Inventory

    The review focuses on the interactions, not only of bromide and chlorine, but also of bromide and two common oxidation alternatives to chlorine--chlorine dioxide and monochloramine. The data evaluations include discussions of reaction products, potentials for trihalomethane (THM)...

  10. T-type Ca2+ channel modulation by otilonium bromide

    PubMed Central

    Strege, Peter R.; Sha, Lei; Beyder, Arthur; Bernard, Cheryl E.; Perez-Reyes, Edward; Evangelista, Stefano; Gibbons, Simon J.; Szurszewski, Joseph H.

    2010-01-01

    Antispasmodics are used clinically to treat a variety of gastrointestinal disorders by inhibition of smooth muscle contraction. The main pathway for smooth muscle Ca2+ entry is through L-type channels; however, there is increasing evidence that T-type Ca2+ channels also play a role in regulating contractility. Otilonium bromide, an antispasmodic, has previously been shown to inhibit L-type Ca2+ channels and colonic contractile activity. The objective of this study was to determine whether otilonium bromide also inhibits T-type Ca2+ channels. Whole cell currents were recorded by patch-clamp technique from HEK293 cells transfected with cDNAs encoding the T-type Ca2+ channels, CaV3.1 (α1G), CaV3.2 (α1H), or CaV3.3 (α1I) alpha subunits. Extracellular solution was exchanged with otilonium bromide (10−8 to 10−5 M). Otilonium bromide reversibly blocked all T-type Ca2+ channels with a significantly greater affinity for CaV3.3 than CaV3.1 or CaV3.2. Additionally, the drug slowed inactivation in CaV3.1 and CaV3.3. Inhibition of T-type Ca2+ channels may contribute to inhibition of contractility by otilonium bromide. This may represent a new mechanism of action for antispasmodics and may contribute to the observed increased clinical effectiveness of antispasmodics compared with selective L-type Ca2+ channel blockers. PMID:20203058