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Sample records for kappa-bedt-ttfsub 2cuncnsub 2br

  1. Cd4As2Br3

    Directory of Open Access Journals (Sweden)

    Mohammed Kars

    2014-03-01

    Full Text Available Single crystals of Cd4As2Br3 (tetracadmium biarsenide tribromide were grown by a chemical transport reaction. The structure is isotypic with the members of the cadmium and mercury pnictidohalides family with general formula M4A2X3 (M = Cd, Hg; A = P, As, Sb; X = Cl, Br, I and contains two independent As atoms on special positions with site symmetry -3 and two independent Cd atoms, of which one is on a special position with site symmetry -3. The Cd4As2Br3 structure consists of AsCd4 tetrahedra sharing vertices with isolated As2Cd6 octahedra that contain As–As dumbbells in the centre of the octahedron. The Br atoms are located in the voids of this three-dimensional arrangement and bridge the different polyhedra through Cd...Br contacts.

  2. CsPb2Br5 Single Crystals: Synthesis and Characterization

    KAUST Repository

    Dursun, Ibrahim

    2017-08-02

    CsPb2Br5 is a ternary halogen-plumbate material with close characteristics to well-reported halide perovskites. Due to its unconventional two-dimensional structure, CsPb2Br5 is being looked at broadly for potential applications in optoelectronics. CsPb2Br5 investigations are currently limited to nanostructures and powder forms of the material, which present unclear and conflicting optical properties. In this study, we present the synthesis and characterization of CsPb2Br5 bulk single crystals, which enabled us to finally clarify the material\\'s optical features. Our CsPb2Br5 crystal has a two-dimensional structure with Pb2Br5- layers spaced by Cs+ cations, and exhibits a ~3.1 eV indirect bandgap with no emission in the visible spectrum.

  3. Data of evolutionary structure change: 1MRUA-2BR1A [Confc[Archive

    Lifescience Database Archive (English)

    Full Text Available 1MRUA-2BR1A 1MRU 2BR1 A A TPSHLSDRYELGEILGFGGMSEVHLARDLRLHRDVAVKV... HHHHHHHHHH HHHH - HHHGGG- HHHH 0 1MRU... A 1MRUA EPPFT--GDSPV ARG CA 259 ARG CA 219 GLU CA 163 1MRU... A 1MRUA IVAVYDTG

  4. A2BR adenosine receptor modulates sweet taste in circumvallate taste buds.

    Directory of Open Access Journals (Sweden)

    Shinji Kataoka

    Full Text Available In response to taste stimulation, taste buds release ATP, which activates ionotropic ATP receptors (P2X2/P2X3 on taste nerves as well as metabotropic (P2Y purinergic receptors on taste bud cells. The action of the extracellular ATP is terminated by ectonucleotidases, ultimately generating adenosine, which itself can activate one or more G-protein coupled adenosine receptors: A1, A2A, A2B, and A3. Here we investigated the expression of adenosine receptors in mouse taste buds at both the nucleotide and protein expression levels. Of the adenosine receptors, only A2B receptor (A2BR is expressed specifically in taste epithelia. Further, A2BR is expressed abundantly only in a subset of taste bud cells of posterior (circumvallate, foliate, but not anterior (fungiform, palate taste fields in mice. Analysis of double-labeled tissue indicates that A2BR occurs on Type II taste bud cells that also express Gα14, which is present only in sweet-sensitive taste cells of the foliate and circumvallate papillae. Glossopharyngeal nerve recordings from A2BR knockout mice show significantly reduced responses to both sucrose and synthetic sweeteners, but normal responses to tastants representing other qualities. Thus, our study identified a novel regulator of sweet taste, the A2BR, which functions to potentiate sweet responses in posterior lingual taste fields.

  5. Electronic structure and optical properties of RbPb2Br5

    Science.gov (United States)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Denysyuk, N. M.; Shkumat, P. N.; Tarasova, A. Y.; Isaenko, L. I.; Khyzhun, O. Y.

    2016-04-01

    We report on density functional theory (DFT) calculations of the total and partial densities of states of rubidium dilead pentabromide, RbPb2Br5, employing the augmented plane wave+local orbitals (APW+lo) method as incorporated in the WIEN2k package. The calculations indicate that the Pb 6s and Br 4p states are the dominant contributors to the valence band: their main contributions are found to occur at the bottom and at the top of the band, respectively. Our calculations reveal that the bottom of the conduction band is formed predominantly from contributions of the unoccupied Pb 6p states. Data of total DOS derived in the present DFT calculations are found to be in agreement with the experimental X-ray photoelectron valence-band spectrum of this compound. The predominant contributions of the Br 4p states at the top of the valence band of rubidium dilead pentabromide are confirmed by comparison on a common energy scale of the X-ray emission band representing the energy distribution of the valence Br p states and the X-ray photoelectron valence-band spectrum of the RbPb2Br5 single crystal. Main optical characteristics of RbPb2Br5, such as dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity are explored for RbPb2Br5 by the DFT calculations.

  6. Matrix-isolated infrared absorption spectrum of CH2BrOO radical

    Science.gov (United States)

    Zhang, Xu; Sander, Stanley P.; Cheng, Lan; Thimmakondu, Venkatesan S.; Stanton, John F.

    2016-07-01

    The bromomethylperoxy radical, CH2BrOO, has been generated in cryogenic matrices. Six fundamental bands for CH2BrOO have been observed in an argon matrix at 5 K. The experimental frequencies (cm-1) are: ν4 = 1274.3, ν5 = 1229.4, ν6 = 1086.7, ν7 = 961.8, ν8 = 879.9, and ν10 = 515.4, two of which are detected for the first time. Ab initio calculations have been performed employing coupled-cluster methods. The experimental frequencies are shown to be in good agreement with the computation as well as the four bands (ν4, ν6, ν7 and ν8) observed by Huang and Lee in the gas phase.

  7. Analysis of the excitation profiles of Raman bands of linear-chain mixed-valence complexes. The geometry of [Pt(en) 2][Pt(en) 2Br 2]Br 4 in the intervalence state

    Science.gov (United States)

    Clark, Robin J. H.; Dines, Trevor J.

    1991-10-01

    Calculations of the resonance Raman excitation profiles for the ν 1 band and its overtones have been performed for the linear- chain mixed-valence platinum complex [Pt(en) 2Br 2]Br 4. It is found that the Pt IV length increases by 0.075 Å in the intervalence state. A satisfactory fit to the excitation profiles requires the inclusion of a second excited state at 16500 cm -1, which we have assigned to Br→Pt IV charge transfer.

  8. Rate constant for the reaction SO + BrO yields SO2 + Br

    Science.gov (United States)

    Brunning, J.; Stief, L.

    1986-01-01

    The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

  9. Infrared absorption and fluorescence properties of Ho-doped KPb2Br5

    Science.gov (United States)

    Brown, Ei E.; Hömmerich, Uwe; Hyater-Adams, Simone; Oyebola, Olusola; Bluiett, Althea; Trivedi, Sudhir

    2014-03-01

    Spectroscopic properties of the 2 μm infrared (IR) emission (5I7 --> 5I8) from trivalent holmium (Ho3+) doped potassium lead bromide (KPb2Br5) are presented. The investigated Ho3+ doped KPb2Br5 (KPB) material was synthesized through purification of starting materials including multi-pass zone-refinement, bromination, and subsequently grown using horizontal Bridgman technique. The bromination process was critical for removing oxidic impurities and enhancing the quality of the crystal. Judd-Ofelt intensity parameters, radiative rates, branching ratios, and emission lifetimes were calculated and compared with results reported for Ho3+ doped KPb2Cl5 (KPC). Under resonant pumping (~1.907 μm), Ho: KPB showed a broad IR emission centered at ~2 μm with an exponential decay time of 7.1 ms at room temperature. The nearly temperature independent emission lifetime is consistent with a negligibly small non-radiative decay rate for the 5I7 excited state of Ho3+, as predicted by the multiphonon energy gap law. The optical absorption, emission and gain cross-sections of Ho: KPB were determined for the 2 μm transition. The Ho: KPB crystal was also evaluated as a potential solid-state material for laser cooling applications.

  10. Spin-current injection and detection in κ-(BEDT-TTF2Cu[N(CN2]Br

    Directory of Open Access Journals (Sweden)

    Z. Qiu

    2015-05-01

    Full Text Available Spin-current injection into an organic semiconductor κ-(BEDT-TTF2Cu[N(CN2]Br film induced by the spin pumping from an yttrium iron garnet (YIG film. When magnetization dynamics in the YIG film is excited by ferromagnetic or spin-wave resonance, a voltage signal was found to appear in the κ-(BEDT-TTF2Cu[N(CN2]Br film. Magnetic-field-angle dependence measurements indicate that the voltage signal is governed by the inverse spin Hall effect in κ-(BEDT-TTF2Cu[N(CN2]Br. We found that the voltage signal in the κ-(BEDT-TTF2Cu[N(CN2]Br/YIG system is critically suppressed around 80 K, around which magnetic and/or glass transitions occur, implying that the efficiency of the spin-current injection is suppressed by fluctuations which critically enhanced near the transitions.

  11. [(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids.

    Science.gov (United States)

    Wolff, Michael; Okrut, Alexander; Feldmann, Claus

    2011-11-21

    The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.

  12. Infrared absorption of gaseous CH2BrOO detected with a step-scan Fourier-transform absorption spectrometer.

    Science.gov (United States)

    Huang, Yu-Hsuan; Lee, Yuan-Pern

    2014-10-28

    CH2BrOO radicals were produced upon irradiation, with an excimer laser at 248 nm, of a flowing mixture of CH2Br2 and O2. A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to record temporally resolved infrared (IR) absorption spectra of reaction intermediates. Transient absorption with origins at 1276.1, 1088.3, 961.0, and 884.9 cm(-1) are assigned to ν4 (CH2-wagging), ν6 (O-O stretching), ν7 (CH2-rocking mixed with C-O stretching), and ν8 (C-O stretching mixed with CH2-rocking) modes of syn-CH2BrOO, respectively. The assignments were made according to the expected photochemistry and a comparison of observed vibrational wavenumbers, relative IR intensities, and rotational contours with those predicted with the B3LYP/aug-cc-pVTZ method. The rotational contours of ν7 and ν8 indicate that hot bands involving the torsional (ν12) mode are also present, with transitions 7(0)(1)12(v)(v) and 8(0)(1)12(v)(v), v = 1-10. The most intense band (ν4) of anti-CH2BrOO near 1277 cm(-1) might have a small contribution to the observed spectra. Our work provides information for directly probing gaseous CH2BrOO with IR spectroscopy, in either the atmosphere or laboratory experiments.

  13. Infrared absorption of gaseous CH2BrOO detected with a step-scan Fourier-transform absorption spectrometer

    Science.gov (United States)

    Huang, Yu-Hsuan; Lee, Yuan-Pern

    2014-10-01

    CH2BrOO radicals were produced upon irradiation, with an excimer laser at 248 nm, of a flowing mixture of CH2Br2 and O2. A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to record temporally resolved infrared (IR) absorption spectra of reaction intermediates. Transient absorption with origins at 1276.1, 1088.3, 961.0, and 884.9 cm-1 are assigned to ν4 (CH2-wagging), ν6 (O-O stretching), ν7 (CH2-rocking mixed with C-O stretching), and ν8 (C-O stretching mixed with CH2-rocking) modes of syn-CH2BrOO, respectively. The assignments were made according to the expected photochemistry and a comparison of observed vibrational wavenumbers, relative IR intensities, and rotational contours with those predicted with the B3LYP/aug-cc-pVTZ method. The rotational contours of ν7 and ν8 indicate that hot bands involving the torsional (ν12) mode are also present, with transitions 7_0^1 12_v^v and 8_0^1 12_v^v, v = 1-10. The most intense band (ν4) of anti-CH2BrOO near 1277 cm-1 might have a small contribution to the observed spectra. Our work provides information for directly probing gaseous CH2BrOO with IR spectroscopy, in either the atmosphere or laboratory experiments.

  14. Electronic parameters and top surface chemical stability of RbPb{sub 2}Br{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Atuchin, V.V., E-mail: atuchin@thermo.isp.nsc.ru [Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 90, 630090 (Russian Federation); Isaenko, L.I. [Laboratory of Crystal Growth, Institute of Geology and Mineralogy, SB RAS, Novosibirsk 90, 630090 (Russian Federation); Kesler, V.G. [Laboratory of Physical Principles for Integrated Microelectronics, Institute of Semiconductor Physics, SB RAS, Novosibirsk 90, 630090 (Russian Federation); Pokrovsky, L.D. [Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 90, 630090 (Russian Federation); Tarasova, A.Yu. [Laboratory of Crystal Growth, Institute of Geology and Mineralogy, SB RAS, Novosibirsk 90, 630090 (Russian Federation)

    2012-01-16

    Highlights: Black-Right-Pointing-Pointer Bridgman growth of RbPb{sub 2}Br{sub 5} crystal. Black-Right-Pointing-Pointer Electronic structure measurements with XPS. Black-Right-Pointing-Pointer Optical crystalline surface fabrication. - Abstract: The RbPb{sub 2}Br{sub 5} crystal has been grown by Bridgman method. The electronic structure of RbPb{sub 2}Br{sub 5} has been measured with XPS for a powder sample. High chemical stability of RbPb{sub 2}Br{sub 5} surface is verified by weak intensity of O 1s core level recorded by XPS and structural RHEED measurements. Chemical bonding effects have been observed by the comparative analysis of element core levels and crystal structure of RbPb{sub 2}Br{sub 5} and several rubidium- and lead-containing bromides using binding energy difference parameters {Delta}{sub Rb} = (BE Rb 3d - BE Br 3d) and {Delta}{sub Pb} = (BE Pb 4f{sub 7/2} - BE Br 3d).

  15. Photocatalytic degradation of organic dyes on visible-light responsive photocatalyst PbBiO 2Br

    Science.gov (United States)

    Shan, Zhichao; Wang, Wendeng; Lin, Xinping; Ding, Hanming; Huang, Fuqiang

    2008-06-01

    The layered compound of lead bismuth oxybromide PbBiO 2Br, prepared by conventional solid-state reaction method, has an optical band gap of 2.3 eV, and possesses a good visible-light-response ability. The references, PbBi 2Nb 2O 9, TiO 2-xN x, BiOBr and BiOI 0.8Cl 0.2, which are excellent visible-light-response photocatalysts, were applied to comparatively understand the activity of PbBiO 2Br. Degradation of methyl orange and methylene blue was used to evaluate photocatalytic activity. The results show that PbBiO 2Br is more photocatalytically active than PbBi 2Nb 2O 9, TiO 2-xN x and BiOBr under visible light.

  16. High temporal resolution Br2, BrCl and BrO observations in coastal Antarctica

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2013-02-01

    Full Text Available There are few observations of speciated inorganic bromine in polar regions against which to test current theory. Here we report the first high temporal resolution measurements of Br2, BrCl and BrO in coastal Antarctica, made at Halley during spring 2007 using a Chemical Ionisation Mass Spectrometer (CIMS. We find indications for an artefact in daytime BrCl measurements arising from conversion of HOBr, similar to that already identified for observations of Br2 made using a similar CIMS method. Using the MISTRA model, we estimate that the artefact represents a conversion of HOBr to Br2 of the order of several tens of percent, while that for HOBr to BrCl is less but non-negligible. If the artefact is indeed due to HOBr conversion, then nighttime observations were unaffected. It also appears that all daytime BrO observations were artefact-free. Mixing ratios of BrO, Br2 and BrCl ranged from instrumental detection limits to 13 pptv (daytime, 45 pptv (nighttime, and 6 pptv (nighttime, respectively. We see considerable variability in the Br2 and BrCl observations over the measurement period which is strongly linked to the prevailing meteorology, and thus air mass origin. Higher mixing ratios of these species were generally observed when air had passed over the sea-ice zone prior to arrival at Halley, than from over the continent. Variation in the diurnal structure of BrO is linked to previous model work where differences in the photolysis spectra of Br2 and O3 is suggested to lead to a BrO maximum at sunrise and sunset, rather than a noon-time maxima. This suite of Antarctic data provides the first analogue to similar measurements made in the Arctic, and of note is that our maximum measured BrCl (nighttime is less than half of the maximum measured during a similar period (spring-time in the Arctic (also nighttime. This difference in maximum measured BrCl may also be the cause of a difference in the Br2 : BrCl ratio between the Arctic and Antarctic. An

  17. NMR Study of κ-(ET)2 Cu [ N(CN)2 ] Br

    Science.gov (United States)

    Lui, Tak-Kei; Gezo, J. C.; Giannetta, R. W.; Slichter, C. P.; Schlueter, J. A.

    2011-03-01

    We report measurements of the 13C spin-lattice relaxation rate, (T1 T)-1 of κ - (ET)2 Cu [ N (CN)2 ] Br , an organic superconductor with TC = 11.9 K . The shape of the (T1 T)-1 versus T graph suggests the existence of a finite spin singlet-triplet gap: A Los Alamos Symposium, pp. 427-479, ed. K.S. Bedell et al., Addison-Wesley (1994)}. Knight shifts were measured to search for a two-component electronic system. We also report measurements using an ``S-shape'' pulse sequence that inverts half of the absorption line, permitting one to study slow motions and spin density waves. Work at UIUC supported by NSF DMR 10-05708, and Center for Emergent Superconductivity USDOE Award No. DE-AC02-98CH10886, Work at Argonne supported by UChicago Argonne, LLC, Operator of Argonne National Laboratory, DOE Contract No. DE-AC02-06CH11357.

  18. New results on two synthetic conductors (TMTSF)2BrO4 and (BEDT-TTF)2I3

    DEFF Research Database (Denmark)

    Mortensen, Kell; Jacobsen, C. S.; Bechgaard, K.;

    1985-01-01

    The authors present experimental studies of transport properties of (TMTSF)2BrO4 and (BEDT-TTF)2I3 . The behaviour of the TMTSF salt suggests transport via variable-range hopping among localized states. The BEDT-TTF-salt exhibits thermopower which indicates almost isotropic metallic behaviour in ...

  19. Spin-current injection and detection in κ-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Z., E-mail: qiuzy@imr.tohoku.ac.jp; Hou, D. [WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Spin Quantum Rectification Project, ERATO, Japan Science and Technology Agency, Aoba-ku, Sendai 980-8577 (Japan); Uruichi, M. [Research Center of Integrative Molecular Systems (CIMoS), Institute for Molecular Science, Okazaki 444-8585 (Japan); Uchida, K. [Spin Quantum Rectification Project, ERATO, Japan Science and Technology Agency, Aoba-ku, Sendai 980-8577 (Japan); Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); PRESTO, Japan Science and Technology Agency, Saitama 332-0012 (Japan); Yamamoto, H. M. [Research Center of Integrative Molecular Systems (CIMoS), Institute for Molecular Science, Okazaki 444-8585 (Japan); RIKEN, 2-1 Hirosawa, Wako 351-0198 (Japan); Saitoh, E. [WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Spin Quantum Rectification Project, ERATO, Japan Science and Technology Agency, Aoba-ku, Sendai 980-8577 (Japan); Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, Tokai 319-1195 (Japan)

    2015-05-15

    Spin-current injection into an organic semiconductor κ-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br film induced by the spin pumping from an yttrium iron garnet (YIG) film. When magnetization dynamics in the YIG film is excited by ferromagnetic or spin-wave resonance, a voltage signal was found to appear in the κ-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br film. Magnetic-field-angle dependence measurements indicate that the voltage signal is governed by the inverse spin Hall effect in κ-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br. We found that the voltage signal in the κ-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br/YIG system is critically suppressed around 80 K, around which magnetic and/or glass transitions occur, implying that the efficiency of the spin-current injection is suppressed by fluctuations which critically enhanced near the transitions.

  20. Transport Properties of the Organic Conductor (TMTSF)2BrO4: Evidence of Variable Range Hopping

    DEFF Research Database (Denmark)

    Mortensen, Kell; Jacobsen, Claus Schelde; Bechgaard, Klaus

    1984-01-01

    A study of d.c. and microwave conductivity and thermoelectric power of the organic conductor (TMTSF)2BrO4 is presented. The transport properties are in qualitative agreement with charge transport via variable-range hopping among localized states. The localization is attributed to the anions, which...

  1. Coordination variation of hydrated Cu2+/Br1- ions traversing the interfacial water in mesopores

    Science.gov (United States)

    Wang, Q.; Huang, X. F.; Li, C. X.; Pan, L. Q.; Wu, Z. H.; Hu, T. D.; Jiang, Z.; Huang, Y. Y.; Cao, Z. X.; Sun, G.; Lu, K. Q.

    2012-06-01

    Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm) by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ˜35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  2. Coordination variation of hydrated Cu2+/Br1− ions traversing the interfacial water in mesopores

    Directory of Open Access Journals (Sweden)

    Q. Wang

    2012-06-01

    Full Text Available Resolution of the atomistic and electronic details about the coordination structure variation of hydrated ions in the interfacial water is still a tough challenge, which is, however, essentially important for the understanding of ion adsorption, permeation and other similar processes in aqueous solutions. Here we report the tracing of coordination structure variation for hydrated Cu2+/Br1- ions traversing the interfacial water in Vycor mesopores (ϕ = 7.6 nm by employing both X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopies. By controlled desorption/adsorption of water, the filling fraction of the mesopores, thus the water layer thickness, can be adjusted, which in turn effects the variation of coordination structure of the ions therein. It is found that both Cu2+ and Br1- ions prefer staying exclusively in the core water, and in this circumstance no ion pairs have been detected in the solution of concentrations up to 1.0 M. Following capillary decondensation occurring at a filling fraction of ∼35% which corresponds to a water layer of about three monolayers, Br1- ions begin immediately to reconstruct their first coordination shell, characterized by ionic dehydration, shrinkage of ion-water bond length, and formation of ion pairs. In contrast, Cu2+ ions can retain a bulk-like coordination structure till being driven to bond directly to the pore surface when the filling fraction is below 20%. At the final stage of dehydration via thermal vacuum treatment at 110°C, Cu2+ ions can be completely reduced to the Cu1+ state, and recover at room temperature only when the filling fraction is above 14%. These results may be inspirable for the investigation of similar problems concerning hydrated ions in water solution under different confining conditions.

  3. Finding the missing stratospheric Bry: a global modeling study of CHBr3 and CH2Br2

    Directory of Open Access Journals (Sweden)

    L. Ott

    2009-11-01

    Full Text Available Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3 and dibromomethane (CH2Br2, with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere (LS obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr−1 for CHBr3 and 57 Gg Br yr−1 for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from the source gas degradation (BryVSLS in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv of the bromine from the inclusion of CHBr3 and CH2Br2 near the tropical tropopause and its contribution rapidly increases to ~100% as altitude increases. More than 85% of the wet scavenging of BryVSLS occurs in large-scale precipitation below 500 hPa and BryVSLS in the stratosphere is not sensitive to convection.

  4. Finding the missing stratospheric Bry: a global modeling study of CHBr3 and CH2Br2

    Directory of Open Access Journals (Sweden)

    D. R. Blake

    2010-03-01

    Full Text Available Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3 and dibromomethane (CH2Br2, with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr−1 for CHBr3 and 57 Gg Br yr−1 for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BryVSLS in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv of the bromine from the inclusion of CHBr3 and CH2Br2 near the tropical tropopause and its contribution rapidly increases to ~100% as altitude increases. More than 85% of the wet scavenging of BryVSLS occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that BryVSLS in the stratosphere is not sensitive to convection. Convective scavenging only accounts for

  5. Solutions to the -dimensional radial Schrödinger equation for the potential $ar^2 + br − c/r$

    Indian Academy of Sciences (India)

    Ramesh Kumar; Fakir Chand

    2014-07-01

    Approximate solutions to the -dimensional radial Schrödinger equation for the potential $ar^2 + br − c/r$ are obtained by employing the formulation described in Ciftci et al, J. Phys. A 43, 415206 (2010). The problem, for some special cases, is solved numerically. Using this analysis, the energy spectra of a two-dimensional two-electron quantum dot (QD) in a magnetic field are also obtained. The results of this study are in good agreement with the other studies.

  6. Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2

    Science.gov (United States)

    Liang, Q.; Stolarski, R. S.; Kawa, S. R.; Nielsen, J. E.; Douglass, A. R.; Rodriguez, J. M.; Blake, D. R.; Atlas, E. L.; Ott, L. E.

    2010-01-01

    Recent in situ and satellite measurements suggest a contribution of 5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes 5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BrSLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only

  7. Photocatalytic transformations of CCl{sub 3}Br, CBr{sub 3}F, CHCl{sub 2}Br and CH{sub 2}BrCl in aerobic and anaerobic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Calza, P.; Minero, C.; Pelizzetti, E. [Dipartimento di Chimica Analitica, Universita di Torino, 10125 Torino (Italy); Hiskia, A.; Papaconstantinou, E. [Institute of Physical Chemistry, NCSR Demokritos, 15310 Athens (Greece)

    2001-01-01

    Phototransformations of halomethanes containing chlorine and bromine (CCl{sub 3}Br, CHCl{sub 2}Br, CH{sub 2}ClBr) or bromine and fluorine (CBr{sub 3}F) have been investigated under aerobic and anaerobic conditions both in homogeneous system and heterogeneous photocatalysis. For all of those compounds, the complete disappearance of the primary compound and the stoichiometric concentration of halides was achieved. Several halogenated intermediates and oxygenated compounds were identified, so that it was possible to predict the degradation pathways followed by such halomethanes. Whereas the reductive steps are predominant in the initial degradation of CCl{sub 3}Br and CBr{sub 3}F, the oxidative steps are predominant in the initial CH{sub 2}ClBr steps. The two pathways have comparable importance for CHCl{sub 2}Br degradation. Methanol, acting as a hole scavenger, strongly increases the rate of disappearance for CCl{sub 3}Br and CBr{sub 3}F.

  8. 81Br NQR for Uncoordinated Br ions in trans-[CoBr2(en)2][H5O2]Br2 and trans-[CoBr2(en)2] [D5O2]Br2

    Science.gov (United States)

    Honda, H.; Sasane, A.; Miyagi, K.; Ishikawa, A.; Mori, Y.

    1994-02-01

    The temperature dependence of the 81Br NQR frequencies (vD) for uncoordinated Br- ions in trans-[CoBr2(en)2] [D5O2]Br2(D) has been determined by a continuous-wave spectrometer. vD amounted to 16.200 MHz at 273 K. This is lower by 418 kHz than the 81Br NQR frequency (vH) for trans-[CoBr2 (en2] [H5O2 ]Br2 (H). The frequency difference (Δv = vH -vD) remained almost constant in the temperature range studied. A shortening of the O-H bond length caused by deuteration could explain the magnitude and the sign of Av on the basis of a point charge model calculation. The compounds D and H yielded 81Br NQR lines in the range 110-320 K and 90-343 K, respectively. As to the 59Co NQR frequencies (7/2 - 5/2), the observed isotope frequency shifts (Δv1 = v1H - v1D) between D and H were smaller than 5 kHz. Below 160 K, 59Co resonances were only available by pulsed experiments. 59Co NQR spin-lattice relaxation times T1Q of 0.54 ms at 194 K and 4.8 s at 77 K for H have been observed.

  9. Organic-inorganic halide perovskite solar cell with CH3NH3PbI2Br as hole conductor

    Science.gov (United States)

    Zhang, Shufang; Zhang, Chenming; Bi, Enbing; Miao, Xiaoliang; Zeng, Haibo; Han, Liyuan

    2017-01-01

    Perovskite solar cells (PSCs) have attracted enormous interest as the most remarkably growing photovoltaic devices. With the power conversion efficiencies of PSCs excessing 20%, great challenges have been focused on the issues of cost and long-term stability which are majorly related to the hole transport materials. In contrast, the PSCs without special hole conductors show great potential for commercial applications due to their cost-effective and fairly stable features. However, the inferior charge separation at the CH3NH3PbI3 (MAPbI3) and back electrode interface limits the cells for high efficiency. Our strategy is to arrange suitable energy band alignment at the interface to enhance the charge separation. We herein report a MAPbI3/MAPbI2Br cascade structured PSC with MAPbI2Br majorly acting as a hole conductor. The conversion efficiency of the PSCs is greatly improved and a high efficiency of 15.83% is achieved. This new design of using organic-inorganic halide perovskites as hole conductors provides an efficient approach for improving the performance of low-cost PSCs.

  10. {[Cu2Br3]n[Cu(H-Leof)2]·2H2O} where Leof is Levofloxacin%{[Cu2Br3]n[Cu(H-Leof)2]·2H2O}(Leof是左氟沙星)

    Institute of Scientific and Technical Information of China (English)

    王锡森; 唐云志; 熊仁根

    2005-01-01

    The crystal structure of {[Cu2Br3]n[Cu(H-Leof)2]· 2H2O} (1) comprises of [Cu(H-Leof)2] + cations, [Cu2Br3]nanions and lattice water molecules. And anion is a 1-D chain formed through alternative Cu-Br dimer and triangular geometry. CCDC: 274841.

  11. Influence of collision energy and vibrational excitation on the dynamics for the H+HBr → H2 + Br reaction

    Indian Academy of Sciences (India)

    Yanhua Wang; Min Peng; Jianying Tong; Yuliang Wang

    2015-08-01

    Quasi-classical trajectory (QCT) calculations of H+HBr → H2 + Br reaction have been performed on a recently proposed ab initio potential energy surface. The reaction probability and integral cross section are found to be in fairly good agreement with the available quantum mechanical (QM) results on this surface. The behavior of reactivity is well consistent with properties of exothermic reaction. Once the energy of vibrational excited HBr is larger than the barrier height, the integral cross sections for the reaction diverge at very low collision energies close to the threshold, similarly to capture reaction. In addition, differential cross sections show that scattering of the product H2 shift from backward to forward directions as the collision energy and vibrational quantum number increase. All the theoretical findings are reasonably explained by the properties of the surface, as well as reactive mechanisms.

  12. Br2, BrCl, BrO and surface ozone in coastal Antarctica: a meteorological and chemical analysis

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2012-04-01

    Full Text Available There is much debate over the source of bromine radicals in the atmosphere that drives polar boundary layer ozone depletion events (ODEs, but there is strong evidence to suggest a source associated with the sea ice zone. Here we report the first high temporal resolution measurements of Br2, BrCl and BrO in coastal Antarctica, made using a Chemical Ionisation Mass Spectrometer (CIMS. Mixing ratios ranged from instrumental detection limits to 13 pptv for BrO, 45 pptv for Br2, and 6 pptv for BrCl. We find evidence for blowing snow as a source of reactive bromine both directly during a storm and subsequently from recycling of bromide deposited on the continental snowpack. An unusual event of trans-continental air mass transport might have been responsible for severe surface ozone depletion observed at Halley. The halogen source region was the Bellingshausen Sea, to the west of the Antarctic Peninsula, the air mass having spent 3 1/2 days in complete darkness prior to arrival at Halley. We, further, identify an artefact in daytime BrCl measurements arising from conversion of HOBr, similar to that already identified for CIMS observations of Br2. Model calculations using the MISTRA 0-D model suggest a 50–60% conversion of HOBr to Br2, and 5–10% conversion to BrCl. Careful data filtering enabled us to use the halogen observations, in conjunction with the MISTRA model, to explore the temperature dependence of the Br2:BrCl ratio. We find evidence of a ratio shift towards Br2 at temperatures below ~−21 °C, suggesting a relationship with hydrohalite (NaCl.2H2O precipitation. This suite of Antarctic data provides the first analogue to similar measurements made in the Arctic.

  13. Quantum mechanical calculations of vibrational population inversion in chemical reactions - Numerically exact L-squared-amplitude-density study of the H2Br reactive system

    Science.gov (United States)

    Zhang, Y. C.; Zhang, J. Z. H.; Kouri, D. J.; Haug, K.; Schwenke, D. W.

    1988-01-01

    Numerically exact, fully three-dimensional quantum mechanicl reactive scattering calculations are reported for the H2Br system. Both the exchange (H + H-prime Br to H-prime + HBr) and abstraction (H + HBR to H2 + Br) reaction channels are included in the calculations. The present results are the first completely converged three-dimensional quantum calculations for a system involving a highly exoergic reaction channel (the abstraction process). It is found that the production of vibrationally hot H2 in the abstraction reaction, and hence the extent of population inversion in the products, is a sensitive function of initial HBr rotational state and collision energy.

  14. Electron spin resonance insight into broadband absorption of the Cu3Bi(SeO32O2Br metamagnet

    Directory of Open Access Journals (Sweden)

    A. Zorko

    2016-05-01

    Full Text Available Metamagnets, which exhibit a transition from a low-magnetization to a high-magnetization state induced by the applied magnetic field, have recently been highlighted as promising materials for controllable broadband absorption. Here we show results of a multifrequency electron spin resonance (ESR investigation of the Cu3Bi(SeO32O2Br planar metamagnet on the kagome lattice. Its mixed antiferromagnetic/ferromagnetic phase is stabilized in a finite range of applied fields around 0.8 T at low temperatures and is characterized by enhanced microwave absorption. The absorption signal is non-resonant and its boundaries correspond to two critical fields that determine the mixed phase. With decreasing temperature these increase like the sublattice magnetization of the antiferromagnetic phase and show no frequency dependence between 100 and 480 GHz. On the contrary, we find that the critical fields depend on the magnetic-field sweeping direction. In particular, the higher critical field, which corresponds to the transition from the mixed to the ferromagnetic phase, shows a pronounced hysteresis effect, while such a hysteresis is absent for the lower critical field. The observed hysteresis is enhanced at lower temperatures, which suggests that thermal fluctuations play an important role in destabilizing the highly absorbing mixed phase.

  15. Relativistic and correlation effects on molecular properties .1. The dihalogens F-2, Cl-2, Br-2, I-2, and At-2

    NARCIS (Netherlands)

    Visscher, L; Dyall, K.G.

    1996-01-01

    A benchmark study of a number of relativistic correlation methods is presented. Bond lengths, harmonic frequencies, and dissociation energies of the molecules F-2, Cl-2, Br-2, I-2, and At-2 are calculated at various levels of theory, using both the Schrodinger and the Dirac-Coulomb-(Gaunt) Hamiltoni

  16. New molecular species of potential interest to atmospheric chemistry: isomers on the [H, S2, Br] potential energy surface.

    Science.gov (United States)

    de Oliveira-Filho, Antonio Gustavo S; Aoto, Yuri Alexandre; Ornellas, Fernando R

    2009-02-19

    This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

  17. Slice imaging of the UV photodissociation of CH2BrCl from the maximum of the first absorption band.

    Science.gov (United States)

    Chicharro, D V; Marggi Poullain, S; González-Vázquez, J; Bañares, L

    2017-07-07

    The photodissociation dynamics of bromochloromethane (CH2BrCl) have been investigated at the maximum of the first absorption band, at the excitation wavelengths 203 and 210 nm, using the slice imaging technique in combination with a probe detection of bromine-atom fragments, Br((2)P3/2) and Br*((2)P1/2), via (2 + 1) resonance enhanced multiphoton ionization. Translational energy distributions and angular distributions reported for both Br((2)P3/2) and Br*((2)P1/2) fragments show two contributions for the Br((2)P3/2) channel and a single contribution for the Br*((2)P1/2) channel. High level ab initio calculations have been performed in order to elucidate the dissociation mechanisms taking place. The computed absorption spectrum and potential energy curves indicate the main contribution of the populated 4A″, 5A', and 6A' excited states leading to a C-Br cleavage. Consistently with the results, the single contribution for the Br*((2)P1/2) channel has been attributed to direct dissociation through the 6A' state as well as an indirect dissociation of the 5A' state requiring a 5A' → 4A' reverse non-adiabatic crossing. Similarly, a faster contribution for the Br((2)P3/2) channel characterized by a similar energy partitioning and anisotropy than those for the Br*((2)P1/2) channel is assigned to a direct dissociation through the 5A' state, while the slower component appears to be due to the direct dissociation on the 4A″ state.

  18. Specific features of the electronic structure and optical properties of KPb2Br5: DFT calculations and X-ray spectroscopy measurements

    Science.gov (United States)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Denysyuk, N. M.; Shkumat, P. N.; Tarasova, A. Y.; Isaenko, L. I.; Khyzhun, O. Y.

    2016-03-01

    Density functional theory (DFT) calculations are made in order to explore the total and partial densities of states of potassium dilead pentabromide, KPb2Br5, by using the augmented plane wave + local orbitals (APW + lo) method as incorporated in the WIEN2k package. The present calculations reveal that the principle contributors to the valence band of KPb2Br5 are the Pb 6s and Br 4p states contributing predominantly at the bottom and at the top of the band, respectively, while the bottom of the conduction band is formed mainly from contributions of the unoccupied Pb 6p states. The curves of total density of states derived by the present DFT calculations of KPb2Br5 are found to be in agreement with the experimental X-ray photoelectron valence-band spectrum of the compound studied. Comparison on a common energy scale of the X-ray emission bands representing the energy distribution of the valence Br p and K s states and the X-ray photoelectron valence-band spectrum of the KPb2Br5 single crystal indicate that the Br 4p and K 4s states contribute mainly at the top and in the upper portion of the valence band, respectively, being in agreement with data of the present DFT band-structure calculations of this compound. Principal optical characteristics of KPb2Br5, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity are also studied by the DFT calculations.

  19. Infrared absorption of gaseous CH{sub 2}BrOO detected with a step-scan Fourier-transform absorption spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yu-Hsuan [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Lee, Yuan-Pern, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

    2014-10-28

    CH{sub 2}BrOO radicals were produced upon irradiation, with an excimer laser at 248 nm, of a flowing mixture of CH{sub 2}Br{sub 2} and O{sub 2}. A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to record temporally resolved infrared (IR) absorption spectra of reaction intermediates. Transient absorption with origins at 1276.1, 1088.3, 961.0, and 884.9 cm{sup −1} are assigned to ν{sub 4} (CH{sub 2}-wagging), ν{sub 6} (O–O stretching), ν{sub 7} (CH{sub 2}-rocking mixed with C–O stretching), and ν{sub 8} (C–O stretching mixed with CH{sub 2}-rocking) modes of syn-CH{sub 2}BrOO, respectively. The assignments were made according to the expected photochemistry and a comparison of observed vibrational wavenumbers, relative IR intensities, and rotational contours with those predicted with the B3LYP/aug-cc-pVTZ method. The rotational contours of ν{sub 7} and ν{sub 8} indicate that hot bands involving the torsional (ν{sub 12}) mode are also present, with transitions 7{sub 0}{sup 1}12{sub v}{sup v} and 8{sub 0}{sup 1}12{sub v}{sup v}, v = 1–10. The most intense band (ν{sub 4}) of anti-CH{sub 2}BrOO near 1277 cm{sup −1} might have a small contribution to the observed spectra. Our work provides information for directly probing gaseous CH{sub 2}BrOO with IR spectroscopy, in either the atmosphere or laboratory experiments.

  20. Crystal structures of MBi{sub 2}Br{sub 7} (M = Rb, Cs) - filled variants of AX{sub 7} sphere packing

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Jen-Hui; Wolff, Alexander [Fachrichtung Chemie und Lebensmittelchemie, Technische Universitaet Dresden, 01062 Dresden (Germany); Ruck, Michael [Fachrichtung Chemie und Lebensmittelchemie, Technische Universitaet Dresden, 01062 Dresden (Germany); Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany)

    2016-03-15

    The reinvestigation of the pseudo-binary systems MBr-BiBr{sub 3} (M = Rb, Cs) revealed two new phases with composition MBi{sub 2}Br{sub 7}. Both compounds are hygroscopic and show brilliant yellow color. The crystal structures were solved from X-ray single crystal diffraction data. The isostructural compounds adopt a new structure type in the triclinic space group P anti 1. The lattice parameters are a = 755.68(3) pm, b = 952.56(3) pm, c = 1044.00(4) pm, α = 76.400(2) , β = 84.590(2) , γ = 76.652(2) for RbBi{sub 2}Br{sub 7} and a = 758.71(5) pm, b = 958.23(7) pm, c = 1060.24(7) pm, α = 76.194(3) , β = 83.844(4) , γ = 76.338(3) for CsBi{sub 2}Br{sub 7}. The crystal structures consist of M{sup +} cations in anticuboctahedral coordination by bromide ions and bromidobismuthate(III) layers {sup 2}{sub ∞}[Bi{sub 2}Br{sub 7}]{sup -}. The 2D layers comprise pairs of BiBr{sub 6} octahedra sharing a common edge. The Bi{sub 2}Br{sub 10} double octahedra are further connected by common vertices. The bismuth(III) atoms increase their mutual distance in the double octahedra by off-centering so that the BiBr{sub 6} octahedra are distorted. The CsBi{sub 2}Br{sub 7} type can be interpreted as a common hexagonal close sphere packing of M and Br atoms, in which 1/4 of the octahedral voids are filled by Bi atoms. The structure type was systematically analyzed and compared with alternative types of common packings. The existence of a compound with the suggested composition CsBiBr{sub 4} could not be verified experimentally. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Kinetics of the reactions of HBr with O3 and HO2: The yield of HBr from HO2 + BrO

    Science.gov (United States)

    Mellouki, Abdelwahid; Talukdar, Ranajit K.; Howard, Carleton J.

    1994-01-01

    An upper limit on the yield of HBr from reaction (R1) (HO2 + BrO yields products) has been determined by measuring an upper limit for the rate coefficient of the reverse reaction (R1') (HBr + O3 yields HO2 + BrO). The limits measured at 300 and 441 K were extrapolated to low temperatures to determine that the yield of HBr from reaction (R1) is negligible throughout the stratosphere (less than 0.01% of k(sub 1)). An upper limit for the rate coefficient of the reaction of HO2 with HBr was also determined to be very low less than or equal to 3 x 10(exp -17) cu cm/molecule/sec at 300 K and less than or equal to 3 x 10(exp -16) cu cm/molecule/sec at 400 K. The implications of these results to stratospheric chemistry are discussed.

  2. Synthesis, Structure and Photoluminescent Properties of the 2D Coordination Polymers Based on Cu2Br2 Unit with Flexible Thioether%基于柔性硫醚与Cu2Br2单元二维配位聚合物的合成、结构和荧光性质

    Institute of Scientific and Technical Information of China (English)

    李冬青; 时文娟

    2009-01-01

    A complex [Cu2Br2(L)2]2 (1) (L=bis (2-pyrimidinylthio)methane) has been synthesized and structurally characterized. Complex 1 contains dinuclear Cu2Br2 units, which are linked by ditopic L to form a 2D layer structure with a 36-membered macrometallocycle. The adjacent layers are further connected through interpyrimidyl rings C-H strong green solid-state photoluminescence, due to metal-to-ligand charge-transfer (MLCT) at room temperature. CCDC: 711434.

  3. Ultrafast dynamics of strong-field dissociative ionization ofCH2Br2 probed by femtosecond soft x-ray transient absorptionspectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Loh, Zhi-Heng; Leone, Stephen R.

    2008-01-15

    Femtosecond time-resolved soft x-ray transient absorption spectroscopy based on a high-order harmonic generation source is used to investigate the dissociative ionization of CH{sub 2}Br{sub 2} induced by 800 nm strong-field irradiation. At moderate peak intensities (2.0 x 10{sup 14} W/cm{sup 2}), strong-field ionization is accompanied by ultrafast C-Br bond dissociation, producing both neutral Br ({sup 2}P{sub 3/2}) and Br* ({sup 2}P{sub 1/2}) atoms together with the CH{sub 2}Br{sup +} fragment ion. The measured rise times for Br and Br* are 130 {+-} 22 fs and 74 {+-} 10 fs, respectively. The atomic bromine quantum state distribution shows that the Br/Br* population ratio is 8.1 {+-} 3.8 and that the Br {sup 2}P{sub 3/2} state is not aligned. The observed product distribution and the timescales of the photofragment appearances suggest that multiple field-dressed potential energy surfaces are involved in the dissociative ionization process. In addition, the transient absorption spectrum of CH{sub 2}Br{sub 2}{sup +} suggests that the alignment of the molecule relative to the polarization axis of the strong-field ionizing pulse determines the electronic symmetry of the resulting ion; alignment of the Br-Br, H-H, and C{sub 2} axis of the molecule along the polarization axis results in the production of the ion {tilde X}({sup 2}B{sub 2}), {tilde B}({sup 2}B{sub 1}) and {tilde C}({sup 2}A{sub 1}) states, respectively. At higher peak intensities (6.2 x 10{sup 14} W/cm{sup 2}), CH{sub 2}Br{sub 2}{sup +} undergoes sequential ionization to form the metastable CH{sub 2}Br{sub 2}{sup 2+} dication. These results demonstrate the potential of core-level probing with high-order harmonic transient absorption spectroscopy for studying ultrafast molecular dynamics.

  4. Disorder-induced gap in the normal density of states of the organic superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br.

    Science.gov (United States)

    Diehl, Sandra; Methfessel, Torsten; Tutsch, Ulrich; Müller, Jens; Lang, Michael; Huth, Michael; Jourdan, Martin; Elmers, Hans-Joachim

    2015-07-01

    The local density of states (DOS) of the organic superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br, measured by scanning tunneling spectroscopy on in situ cleaved surfaces, reveals a logarithmic suppression near the Fermi edge persisting above the critical temperature T(c). The experimentally observed suppression of the DOS is in excellent agreement with a soft Hubbard gap as predicted by the Anderson-Hubbard model for systems with disorder. The electronic disorder also explains the diminished coherence peaks of the quasi-particle DOS below T(c).

  5. Electronic structure and properties of Cd4As2Br3 and Cd4Sb2I3, analogues of CdSe and CdTe

    Science.gov (United States)

    Roy, Anand; Suchitra; Manjunath, K.; Ahmad, Tokeer; Waghmare, Umesh V.; Rao, C. N. R.

    2017-04-01

    Substitution of aliovalent anions in metal oxides and chalcogenides significantly affects the electronic structure and properties of the materials. Thus, substitution of P3- and Cl- in CdS decreases the band gap and favorably influences the photocatalytic activity. Complete substitution of a trivalent (A3-) and a monovalent (B-) anions in a cadmium chalcogenides, CdX, should give rise to a material of the composition Cd A0.5B0.5 or Cd2AB, but a compound with the composition Cd4P2Cl3 (or Cd2PCl1.5) is obtained in the case of CdS. We have investigated the analogous compounds, Cd4As2Br3 and Cd4Sb2I3, wherein the anions in CdSe and CdTe are substituted by As, Br and Sb, I respectively. These compounds are direct band gap semiconductors with a band gap of 1.8-1.9 eV and a photoluminescence band in the visible region. First-principles calculations show both Cd4As2Br3 and Cd4Sb2I3 to be direct band gap semiconductors. The arsenic bromide is predicted to be photochemically more active for HER than the antimony iodide.

  6. Synthesis and Structural Studies of a New Complex of Di[hexabromobismuthate (III] 2,5-Propylaminepyrazinium [C10H28N4]Bi2Br10

    Directory of Open Access Journals (Sweden)

    Mohamed El Mehdi Touati

    2015-01-01

    Full Text Available A new organic-inorganic hybrid material, [C10H28N4]Bi2Br10, has been synthesized and characterized. The compound crystallizes in monoclinic P21/c space group with a = 11.410(4 Å, b = 11.284(4 Å, c = 12.599(3 Å, β = 115.93(2°, and V = 1458.8(8 Å3. The structure consists of discrete dinuclear [Bi2Br10]4− anions and [C10H28N4]4+ cations. It consists of a 0-D anion built up of edge-sharing bioctahedron. The crystal net contains N–H⋯Br hydrogen bonds. The differential scanning calorimetry (DSC reveals an irreversible phase transition at −17°C. The frontier molecular orbital and the energy gap between the highest occupied molecular orbital (HOMO and the lowest unoccupied molecular orbital (LUMO calculation allow the classification of the material as an insulator.

  7. Thermodynamic investigations of the quasi-2d triangular Heisenberg antiferromagnet Cs{sub 2}CuCl{sub 2}Br{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Tutsch, Ulrich; Postulka, Lars; Wolf, Bernd; Lang, Michael; Well, Natalija van; Ritter, Franz; Krellner, Cornelius; Assmus, Wolf [Physikalisches Institut, Goethe-University Frankfurt (Germany)

    2015-07-01

    The system Cs{sub 2}CuCl{sub 4-x}Br{sub x} (0 ≤ x ≤ 4) is a quasi-two-dimensional Heisenberg antiferromagnet with a triangular in-plane arrangement of the spin-spin couplings. The ratio J{sup '}/J of the corresponding coupling constants determines the degree of frustration in the system and has been found to be 0.34 (x = 0) and 0.74 (x = 4) for the border compounds. One may ask whether for some intermediate Br concentration an even higher degree of frustration can be reached. Indeed, some indications have been reported by Ono et al. Here, we present specific heat C and susceptibility χ measurements below 1 K in magnetic fields B up to 13.5 T for the intermediate compound Cs{sub 2}CuCl{sub 2}Br{sub 2}, which, due to site-selective substitution, shows a well-ordered halide sublattice. Indications for an antiferromagnetic transition are observed around 90 mK for B = 0. A small field of B = 0.14 T is sufficient to fully suppress this anomaly. Taking into account the high saturation field of about 20 T, extrapolated from χ(T = const, B) scans at low temperatures, this small ordered region in the B-T plane clearly indicates a high degree of frustration in Cs{sub 2}CuCl{sub 2}Br{sub 2}.

  8. Synthesis and Structure of a New Copper(II)Complex Cu(C13H9N3O2Br)2·H2O

    Institute of Scientific and Technical Information of China (English)

    张修堂; 詹晓平; 吴鼎铭; 杨文斌; 卢灿忠

    2002-01-01

    The new copper(II) complex Cu(C13H9N3O2Br)2@H2O (N-(2-hydroxy-5-bromo- benzoyl)-N?-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-dimethylformamide mix solvent. Crystal data: triclinic, space group P ī, a = 10.8620(3), b = 11.7453 (3), c = 12.4417(2) ?, α = 62.255(0), β = 79.097(2), γ = 86.764(2)°, V = 1378.52(6) ?3, Z = 2, Mr = 719.835, Dc = 1.734 g/cm3, F(000) = 714, μ(MoKα) = 3.739 mm-1, T = 293(2) K, final R = 0.0594 and wR = 0.1416 for 2943 observed reflections with I > 2.0σ(I). The structure of Cu(C13H9N3O2Br)2@H2O has been determined by X-ray analysis and revealed that two L-1 ligands coordinate to the copper(Ⅱ) ion through two oxygen and two nitrogen atoms from the hydrazine groups and two pyridine nitrogen atoms to form an elongated and distorted square-bipyramidal environment for Cu(Ⅱ). The complex is also characterized by 1H NMR spectroscopies

  9. Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

    Science.gov (United States)

    Watson, R. T.; Sander, S. P.; Yung, Y. L.

    1979-01-01

    The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

  10. The NQR observation of spin-Peierls transition in an antiferromagnetic MX-chain complex [NiBr(chxn)2]Br2.

    Science.gov (United States)

    Takaishi, Shinya; Tobu, Yasuhiro; Kitagawa, Hiroshi; Goto, Atsushi; Shimizu, Tadashi; Okubo, Takashi; Mitani, Tadaoki; Ikeda, Ryuichi

    2004-02-18

    81Br Nuclear quadrupole resonance (NQR) measurement was performed in an S = 1/2 one-dimensional Heisenberg antiferromagnetic metal complex [NiBr(chxn)2]Br2 (chxn: 1R,2R-diaminocyclohexane), having a halogen-bridged MX chain structure -Br-Ni3+-Br-Ni3+-Br-. Two 81Br NQR signals were observed below 40 K, while a single signal was observed above 130 K, showing the presence of two nonequivalent bridging Br sites below 40 K. This NQR result together with previously reported magnetic susceptibility and X-ray results indicate the occurrence of a transition into a spin-Peierls state between 40 and 130 K. This communication reports the first spin-Peierls transition in metal complexes in which pure d electrons contribute to the magnetism. In addition, we demonstrated a new experimental method for studying a spin-Peierls system.

  11. Anomalous vortex dynamics in κ-[bis(ethylenedithio)tetrathiafulvalene]2Cu[N(CN)2]Br: Evidence for field-induced magnetic order and unconventional superconductivity

    Science.gov (United States)

    Lahaise, U. G.; Chen, Qun; de Long, L. E.; Brock, C. P.; Wang, H. H.; Carlson, K. D.; Schlueter, J. A.; Williams, J. M.

    1995-02-01

    Anisotropic superconducting flux-line behavior of single-crystal κ-[bis(ethylenedithio)tetrathiaful- valene]2Cu[N(CN)2]Br has been studied with dc magnetization and vibrating-reed (VR) techniques. A peak at T*(H) in the temperature dependence of the VR inverse quality factor 1/Q exhibits a shoulder for magnetic fields 0<μ0H<=0.5 T parallel to the conducting ac plane. The shoulder becomes unresolved near a kink in T*(H) at μ0H~=0.7 T. Discontinuities in 1/Q and the VR frequency shift occur for 0.1<=μ0H<=1.3 T applied perpendicular to the ac plane and temperatures T<=20 K, well into the normal state. These anomalies are preliminary evidence for a field-induced magnetic phase transition and unconventional superconductivity.

  12. Bromine-79 NQR for uncoordinated Br- ions in trans-[CoBr2(en)2][H5O2]Br2

    Science.gov (United States)

    Sasane, A.; Matsuda, T.; Honda, H.; Mori, Y.

    1992-02-01

    A single 79Br NQR line showing a frequency of 19.594 MHz at room temperature has been observed in the crystals of trans-[CoBr2(en)2] [ H5O2 ] Br2 and assigned to the Br - ions which are not coordinated to the central Co(III) atom. The electric field gradient (EFG) at the Br - nuclei arises from O-H • • • Br - hydrogen bond formation between the Br - ions and the terminal O - H hydrogen atoms in [ H5O2 ] + ions. The induced EFG is greater for the present bromine complex than that for the isostructural chlorine complex. A point charge model calculation explains well the relative magnitude of the EFG in the two crystals by introducing Sternheimer's antishielding factors for the halogen ions.

  13. Recent Progress in the Design of Advanced Cathode Materials and Battery Models for High-Performance Lithium-X (X = O2 , S, Se, Te, I2 , Br2 ) Batteries.

    Science.gov (United States)

    Xu, Jiantie; Ma, Jianmin; Fan, Qinghua; Guo, Shaojun; Dou, Shixue

    2017-07-01

    Recent advances and achievements in emerging Li-X (X = O2 , S, Se, Te, I2 , Br2 ) batteries with promising cathode materials open up new opportunities for the development of high-performance lithium-ion battery alternatives. In this review, we focus on an overview of recent important progress in the design of advanced cathode materials and battery models for developing high-performance Li-X (X = O2 , S, Se, Te, I2 , Br2 ) batteries. We start with a brief introduction to explain why Li-X batteries are important for future renewable energy devices. Then, we summarize the existing drawbacks, major progress and emerging challenges in the development of cathode materials for Li-O2 (S) batteries. In terms of the emerging Li-X (Se, Te, I2 , Br2 ) batteries, we systematically summarize their advantages/disadvantages and recent progress. Specifically, we review the electrochemical performance of Li-Se (Te) batteries using carbonate-/ether-based electrolytes, made with different electrode fabrication techniques, and of Li-I2 (Br2 ) batteries with various cell designs (e.g., dual electrolyte, all-organic electrolyte, with/without cathode-flow mode, and fuel cell/solar cell integration). Finally, the perspective on and challenges for the development of cathode materials for the promising Li-X (X = O2 , S, Se, Te, I2 , Br2 ) batteries is presented. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Stable and low-cost mesoscopic CH3NH3PbI2 Br perovskite solar cells by using a thin poly(3-hexylthiophene) layer as a hole transporter.

    Science.gov (United States)

    Zhang, Meng; Lyu, Miaoqiang; Yu, Hua; Yun, Jung-Ho; Wang, Qiong; Wang, Lianzhou

    2015-01-02

    Mesoscopic perovskite solar cells using stable CH3 NH3 PbI2 Br as a light absorber and low-cost poly(3-hexylthiophene) (P3HT) as hole-transporting layer were fabricated, and a power conversion efficiency of 6.64 % was achieved. The partial substitution of iodine with bromine in the perovskite led to remarkably prolonged charge carrier lifetime. Meanwhile, the replacement of conventional thick spiro-MeOTAD layer with a thin P3HT layer has significantly reduced the fabrication cost. The solar cells retained their photovoltaic performance well when they were exposed to air without any encapsulation, presenting a favorable stability. The combination of CH3 NH3 PbI2 Br and P3HT may render a practical and cost-effective solid-state photovoltaic system. The superior stability of CH3 NH3 PbI2 Br is also promising for other photoconversion applications.

  15. Vortex dynamics in organic superconductor {kappa}-(ET){sub 2}X(X=Cu(NCS){sub 2}, Cu[N(CN){sub 2}]Br)

    Energy Technology Data Exchange (ETDEWEB)

    Simizu, T. [Graduate School of Engineering, Iwate University, Morioka 020-8551 (Japan); Yoshimoto, N. [Graduate School of Engineering, Iwate University, Morioka 020-8551 (Japan); Nakanishi, Y. [Graduate School of Engineering, Iwate University, Morioka 020-8551 (Japan); Yoshizawa, M. [Graduate School of Engineering, Iwate University, Morioka 020-8551 (Japan)]. E-mail: yoshizawa@iwate-u.ac.jp

    2006-05-01

    Organic superconductors {kappa}-(ET){sub 2}X (X=Cu(NCS){sub 2}, Cu[N(CN){sub 2}]Br) show anomalous elastic properties in both normal and superconducting states. We have measured the sound velocity of these salts near the superconducting transition temperature T{sub c} in the selected magnetic fields with different directions. Under the magnetic field, the sound velocity as a function of temperature shows remarkable elastic anomalies. It was mainly caused by interplay between the vortices and the elastic strain. The {delta}C{sub S-N}, which is the difference of elastic constant C(T) in the superconducting state from the normal state, shows the softening toward lower temperature after following the jump at T{sub c}. This discontinuous jump at T{sub c} has been found on the longitudinal mode and on the transverse mode. It suggests that two-dimensional order parameter plays an important role in the superconductivity of {kappa}-(ET){sub 2}X system.

  16. CROSSED MOLECULAR BEAM STUDIES OF CHEMILUMINESCENT REACTIONS: F{sub 2} + I{sub 2}, Br{sub 2} and ICl

    Energy Technology Data Exchange (ETDEWEB)

    Kahler, C.C.; Lee, Y.T.

    1980-05-01

    The chemiluminescent bimolecular halogen-halogen reactions, F{sub 2} + I{sub 2}, Br{sub 2} and ICl, have been studied by the crossed molecular beam technique. Undispersed chemiluminescence was measured as a function of collision energy and, for I{sub 2} + F{sub 2}, as a function of the two beam pressures. Although no spectra were obtained to positively identify the emitters as IF*, ClF* and BrF*, arguments are given to support this identification. The observed reaction thresholds of 4.2 and 5.9 kcal/mole for I{sub 2} + F{sub 2} and ICl + F{sub 2} , respectively, are the same as the threshold energies for production of the stable trihalogens I{sub 2}F and ClF. This coincidence of threshold energies, as well as similar high collision energy behavior, implies that the chemiluminescent reaction proceeds via a stable trihalogen intermediate. This mechanism can explain our results and the results of other workers without resorting to a symmetry forbidden four center reaction mechanism. A threshold of 11.3 kcal/mole was found for Br{sub 2} + F{sub 2} , no threshold for Br{sub 2}F has been previously reported. Laser enhancement of the I{sub 2} + F{sub 2} reaction was attempted, but no enhancement was seen.

  17. Material purification, crystal growth, and spectroscopy of Tm-doped KPb2Cl5 and KPb2Br5 for 2 μm photonic applications

    Science.gov (United States)

    Brown, E.; Kumi-Barimah, E.; Hömmerich, U.; Bluiett, A. G.; Trivedi, S. B.

    2014-05-01

    Results of the material purification, crystal growth, and optical characterization of Tm-doped KPb2Cl5 (KPC) and KPb2Br5 (KPB) for 2 μm photonic applications are presented. Undoped KPC and KPB were synthesized from ultra dry starting materials and purified through multi-pass translation in a zone-refinement system. 1 wt% of ultra-dry Tm-halides (TmCl3 or TmBr3) were added to the purified host materials and molten under bubbling of HCl or HBr gas, respectively. Tm: KPC and Tm: KPB crystals were subsequently grown using the Bridgman technique. The good optical quality of the resulting crystals was indicated by infrared transmissions as high as 70-75%. Under optical pumping, both crystals exhibited broad infrared emission bands centered at 1.82 μm with nearly exponential decay times ranging from 2-3 ms. Judd-Ofelt intensity parameters were calculated to determine the radiative lifetimes of the 3F4→3H6 Tm3+ transition. The optical absorption and emission cross-sections of Tm: KPC and Tm: KPB were determined using the McCumber theory. The investigated crystals were also evaluated as potential solid-state materials for optical cooling applications.

  18. Reorganisation of alkyl chains in vesicles formed in aqueous solution by dialkyldimethylammonium bromide, R2N+Me2Br- where R = C12H25, C14H29, C16H33 or C18H37

    NARCIS (Netherlands)

    Blandamer, Michael J.; Briggs, Barbara; Cullis, Paul M.; Kirby, Stuart D.; Engberts, Jan B.F.N.

    1997-01-01

    Differential scanning calorimetry (DSC) scans are reported for aqueous solutions containing vesicles formed by four dialkyldimethylammonium bromides; R2N+Me2Br- where R = dodecyl (DDAB), tetradecyl (DTAB), hexadecyl (DHAB) or octadecyl (DOAB). Electron micrographs of DTAB (aq; 2x10-3 mol dm-3) confi

  19. Anisotropic magnetic interactions and spin dynamics in the spin-chain compound Cu (py) 2Br2 : An experimental and theoretical study

    Science.gov (United States)

    Zeisner, J.; Brockmann, M.; Zimmermann, S.; Weiße, A.; Thede, M.; Ressouche, E.; Povarov, K. Yu.; Zheludev, A.; Klümper, A.; Büchner, B.; Kataev, V.; Göhmann, F.

    2017-07-01

    We compare theoretical results for electron spin resonance (ESR) properties of the Heisenberg-Ising Hamiltonian with ESR experiments on the quasi-one-dimensional magnet Cu (py) 2Br2 (CPB). Our measurements were performed over a wide frequency and temperature range giving insight into the spin dynamics, spin structure, and magnetic anisotropy of this compound. By analyzing the angular dependence of ESR parameters (resonance shift and linewidth) at room temperature, we show that the two weakly coupled inequivalent spin-chain types inside the compound are well described by Heisenberg-Ising chains with their magnetic anisotropy axes perpendicular to the chain direction and almost perpendicular to each other. We further determine the full g tensor from these data. In addition, the angular dependence of the linewidth at high temperatures gives us access to the exponent of the algebraic decay of a dynamical correlation function of the isotropic Heisenberg chain. From the temperature dependence of static susceptibilities, we extract the strength of the exchange coupling (J /kB=52.0 K ) and the anisotropy parameter (δ ≈-0.02 ) of the model Hamiltonian. An independent compatible value of δ is obtained by comparing the exact prediction for the resonance shift at low temperatures with high-frequency ESR data recorded at 4 K . The spin structure in the ordered state implied by the two (almost) perpendicular anisotropy axes is in accordance with the propagation vector determined from neutron scattering experiments. In addition to undoped samples, we study the impact of partial substitution of Br by Cl ions on spin dynamics. From the dependence of the ESR linewidth on the doping level, we infer an effective decoupling of the anisotropic component J δ from the isotropic exchange J in these systems.

  20. Near-infrared to visible upconversion in Er3+ doped Cs3Lu2Cl9, Cs3Lu2Br9, and Cs3Y2I9 excited at 1.54 µm

    NARCIS (Netherlands)

    Lüthi, Stefan R.; Pollnau, Markus; Güdel, Hans U.; Hehlen, Markus P.

    1999-01-01

    A detailed study of upconversion processes in Cs3Er2X9 (X = Cl, Br, I) crystals and in the diluted systems Cs3Lu2Cl9:1% Er3+, Cs3Lu2Br9:1% Er3+, and Cs3Y2I9:1% Er3+ is presented. Efficient two-, three-, and four-step upconversion excitation along the sequence 4I15/2 4I13/2 4I9/2 4S3/2 2H9/2

  1. Investigation of the superconducting gap structure in κ-(BEDT-TTF)2Cu(NCS)2 and κ-(BEDT-TTF)2Cu[N(CN)2]Br by means of thermal-conductivity measurements

    Science.gov (United States)

    Kühlmorgen, S.; Schönemann, R.; Green, E. L.; Müller, J.; Wosnitza, J.

    2017-10-01

    We report temperature-dependent thermal-conductivity, κ, measurements on the layered quasi-two-dimensional organic superconductors κ-(BEDT-TTF)2Cu(NCS)2 and κ-(BEDT-TTF)2Cu[N(CN)2]Br down to 160 mK. The results for κ-(BEDT-TTF)2Cu(NCS)2 may be consistent with a nodal superconducting (SC) gap structure as indicated by a non-negligible remnant linear contribution when κ/T \\propto T2 is extrapolated to T = 0 . For κ-(BEDT-TTF)2Cu[N(CN)2]Br, contrary to expectations, higher κ values are observed in the superconducting regime as compared to the normal, high-field state evidencing a dominant phonon contribution to κ in the superconducting state. The strong increase of κ in the normal state below T c for both samples indicates strong electron–phonon scattering. Our results highlight the need for thermal-conductivity measurements performed down to significantly lower temperatures to determine the symmetry of the SC gap.

  2. 咪唑盐四环溴化银聚合物[[(CH3CH2{(CHNCHCHN)}CH2]2]n2+[(Ag2Br4)]n2﹣的合成与结构%Synthesis and Structure of 4 th ﹣ ring Silver Bromide Polymer [[(CH 3 CH 2{(CHNCHCHN)}CH2 ]2 ]n2 +[(Ag2 Br4)]n2 ﹣

    Institute of Scientific and Technical Information of China (English)

    王志国

    2015-01-01

    The reaction of the NHC Precursor[CH3 CH2(CHNCHCHN)CH2 ]2 2 +[Br]2 2 ﹣ with Ag2 O in a 1:2 molar ratio at 45 ℃ in CH3 CN yields the title comPlex [[( CH3 CH2{( CHNCHCHN )}CH2 ]2 ]n2 +[(Ag2 Br4 )]n2 ﹣ . The title comPound has been characterized by 1 HNMR and single ﹣ crystal X ﹣ ray diffraction and TGA analysis. Ⅰt crystallizes in monoclinic,sPace grouP P21 / c with a = 13. 862(4)/ nm,b = 12. 822(3)/nm,c = 11. 447(3)/ nm,α = 90. 00°,β = 113. 277(5)°,γ = 90. 00°,V = 1869. 0(9)nm3 ,Z = 2 ,D = 2. 621 0Mg / m3 ,μ = 7. 492 / mm ﹣ 1 and F(000)= 1108. 00. The structure was refined to R1 = 0. 0296 and wR2 =0. 0765 for 1696 observed reflections with F2 ﹥ 2σ(F2). The title salt consists of a carbon ﹣ bridged imidazoli-umcation[(CH3 CH2{(CHNCHCHN)}CH2 ]2 2 + and a 4th ﹣ ring silver bromide Polymer anionic[Ag2 Br4 ]2 ﹣ .%氮杂环卡宾前体[CH3 CH2(CHNCHCHN)CH2]22+[Br]22﹣与 Ag2 O 在45℃下在乙腈溶液中以1:2的摩尔比反应成功合成四环溴化银聚合物1,2﹣亚乙基,3,3'﹣乙基咪唑[[(CH3 CH2{(CHNCHCHN)}CH2]2]n2+[(Ag2 Br4)]n2﹣,产物通过元素分析,1 HNMR 和 X ﹣ ray 衍射及差热分析表征.晶体结构表明配合物属于单斜晶体,空间群均为 P2(1)/ c,化合物晶胞参数 a =13.862(4)nm,b =12.822(3)nm,c =11.447(3)nm,α=90.00°,β=113.277(5)°,γ=90.00°,V =1869.0(9)nm3,Z =2,F(000)=1108.00,D =2.6210 Mg/ m3,μ=7.492 mm ﹣1, R1=0.0296,wR2=0.0765.化合物由双咪唑阳离子[(CH3 CH2{(CHNCHCHN)}CH2]22+和四环溴化银阴离子[Ag2 Br4]2﹣构成.

  3. Layered ruthenium hexagonal perovskites: The new series [Ba 2Br 2-2x(CO 3) x][Ba n+1Ru nO 3n+3] with n=2, 3, 4, 5

    Science.gov (United States)

    Kauffmann, Matthieu; Roussel, Pascal; Abraham, Francis

    2007-07-01

    Single crystals of the title compounds were prepared by solid state reactions from barium carbonate and ruthenium metal using a BaBr 2 flux and investigated by X-ray diffraction method using Mo(Kα) radiation and a Charge Coupled Device (CCD) detector. A structural model for the term n=2, Ba 5Ru 2Br 2O 9 ( 1) was established in the hexagonal symmetry, space group P6 3/ mmc, a=5.8344(2) Å, c=25.637(2) Å, Z=2. Combined refinement and maximum-entropy method (MEM) unambiguously show the presence of CO 32- ions in the three other compounds ( 2, 3, 4). Their crystal structures were solved and refined in the trigonal symmetry, space group P3¯ml, a=5.8381(1) Å, c=15.3083(6) Å for the term n=3, Ba 6Ru 3Br 1.54(CO 3) 0.23O 12 ( 2), and space group R3¯m, a=5.7992(1) Å, c=52.866(2) Å and a=5.7900(1) Å, c=59.819(2) Å for the terms n=4, Ba 7Ru 4Br 1.46(CO 3) 0.27O 15 ( 3), and n=5, Ba 8Ru 5Br 1.64(CO 3) 0.18O 18 ( 4), respectively. The structures are formed by the periodic stacking along [0 0 1] of ( n+1) hexagonal close-packed [BaO 3] layers separated by a double layer of composition [Ba 2Br 2-2x(CO 3) x]. The ruthenium atoms occupy the n octahedral interstices created in the hexagonal perovskite slabs and constitute isolated dimers Ru 2O 9 of face-shared octahedra (FSO) in 1 and isolated trimers Ru 3O 12 of FSO in 2. In 3 and 4, the Ru 2O 9 units are connected by corners either directly ( 3) or through a slab of isolated RuO 6 octahedra ( 4) to form a bidimensional arrangement of RuO 6 octahedra. These four oxybromocarbonates belong to the family of compounds formulated [Ba 2Br 2-2x(CO 3) x][Ba n+1Ru nO 3n+3] where n represents the thickness of the octahedral string in hexagonal perovskite slabs. These compounds are compared to the oxychloride series.

  4. Synthesis of Ru2Br(μ-O2CC6H4–R4 (R = o-Me, m-Me, p-Me Using Microwave Activation: Structural and Magnetic Properties

    Directory of Open Access Journals (Sweden)

    Patricia Delgado-Martínez

    2014-09-01

    Full Text Available New bromidotetracarboxylatodiruthenium(II,III compounds of the type [Ru2Br(μ-O2CC6H4–R4]n [R = o-Me (1, m-Me (2, p-Me (3] have been prepared using microwave-assisted methods. Syntheses by means of solvothermal and conventional activations have also been carried out to compare different preparation methods. The crystal structure determination of complexes 1–3 is also described. All compounds display a typical carboxylate-bridged paddlewheel-type structure with the metal atoms connected by four bridging carboxylate ligands. The axial bromide ligands connect the dimetallic units giving one-dimensional zigzag chains. The magnetic properties of all compounds have also been analyzed. Weak antiferromagnetic intermolecular interactions mediated by the bromide ligands and an appreciable zero field splitting are calculated in the fits of the magnetic data of these complexes.

  5. Spectroscopic ellipsometry thin film and first-principles calculations of electronic and linear optical properties of [(C9H19NH3)2PbI2Br2] 2D perovskite

    Science.gov (United States)

    Abid, H.; Hlil, E. K.; Abid, Y.

    2017-03-01

    In this study we report results of first-principles density functional calculations using the full-potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. We employed the generalized gradient approximation (GGA) for the exchange-correlation energy to calculate electronic and linear optical properties of the (C9H19NH3)2PbI2Br2 compound. The linear optical properties, namely, the real ε1 (ω) and imaginary ε2 (ω) parts of dielectric function, the refractive index n (ω) and the extinction coefficient k (ω) are calculated and compared with experimental spectroscopic ellipsometry spectra. The reflectivity R (ω) and electron energy loss function L (ω) are calculated too. Our calculations performed for band structure and density of states show that the valence band maximum and conduction band minimum are located at Γ point resulting in a direct band gap of about (Γv -Γc) of 2.42 eV in good agreement with the experimental data. The investigated compound has a large uniaxial anisotropy of the dielectric function of about 0.0739 and a negative birefringence at zero energy Δn (0) =-0.11.

  6. Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co{sub 2}L{sub 2}Cl{sub 4}, Cu{sub 2}L{sub 2}Cl{sub 4} and Cu{sub 2}L{sub 2}Br{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Nemcsok, Denes [Institute of General and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellert ter 4, H-1111 Budapest (Hungary); Kovacs, Attila [Hungarian Academy of Sciences, Budapest University of Technology and Economics, Research Group of Technical Analytical Chemistry, Szt. Gellert ter 4, H-1111 Budapest (Hungary)], E-mail: akovacs@mail.bme.hu; Szecsenyi, Katalin Meszaros [Department of Chemistry, Faculty of Sciences, University of Novi Sad, 21000 Novi Sad, Trg D. Obradovica 3 (Serbia and Montenegro); Leovac, Vukadin M. [Department of Chemistry, Faculty of Sciences, University of Novi Sad, 21000 Novi Sad, Trg D. Obradovica 3 (Serbia and Montenegro)

    2006-09-29

    In the present paper we report a joint experimental and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and its complexes Co{sub 2}L{sub 2}Cl{sub 4}, Cu{sub 2}L{sub 2}Cl{sub 4} and Cu{sub 2}L{sub 2}Br{sub 2}. DFT computations were used to model the structural and bonding properties of the title compounds as well as to derive a reliable force field for the normal coordinate analysis of L. The computations indicated the importance of hydrogen bonding interactions in stabilising the global minimum structures on the potential energy surfaces. In contrast to the S-bridged binuclear Cu{sub 2}L{sub 2}Br{sub 2} complex found in the crystal, our computations predicted the formation of (CuLBr){sub 2} dimers in the isolated state stabilized by very strong (53 kJ/mol) N-H...Br hydrogen bonding interactions. On the basis of FT-IR and FT-Raman experiments and the DFT-derived scaled quantum mechanical force field we carried out a complete normal coordinate analysis of L. The FT-IR spectra of the three complexes were interpreted using the present assignment of L, literature data and computed results.

  7. Redetermination of the Crystal Structure of Al2Br6

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Poulsen, Finn W.; Nielsen, Kurt

    1997-01-01

    The structure of aluminium bromide has been reinvestigated by X-ray diffraction in three different ways: (a) on a single crystal grown in a glass capillary, (b) on powder in a Debye-Scherrer glass capillary and (c) on an area of powder placed in a protective container for Bragg-Brentano geometry....

  8. Magnetic field, frequency and temperature dependence of complex conductance of ultrathin La1.65Sr0.45CuO4/La2CuO4 films and the organic superconductors κ-(BEDT-TTF)2Cu[N(CN)2]Br

    Science.gov (United States)

    Gasparov, V. A.; He, Xi; Dubuis, G.; Pavuna, D.; Kushch, N. D.; Yagubskii, E. B.; Schlueter, J. A.; Bozovic, I.

    2015-09-01

    We used atomic-layer molecular beam epitaxy (ALL-MBE) to synthesize bilayer films of a cuprate metal (La1.65Sr0.45CuO4, LSCO) and a cuprate insulator (La2CuO4, LCO), in which interface superconductivity occurs in a layer that is just one-half unit cell thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω), of these films, and compared them to κ-(BEDT-TTF)2Cu[N(CN)2]Br single crystals. The magnetic field H was applied both parallel and perpendicular to the 2D conducting layers. Experiments have been carried out at frequencies between 23 kHz and 50 MHz using either two-coil mutual inductance technique, or the LC resonators with spiral or rectangular coils. The real and the imaginary parts of the mutual-inductance M(T,ω) between the coil and the sample were measured and converted to complex conductivity. For H perpendicular to the conducting layers, we observed almost identical behavior in both films and κ-Br single crystals: (i) the transition onset in the inductive response, Lk-1(T) occurs at a temperature lower by 2 K than in Reσ(T), (ii) this shift is almost constant with magnetic field up to 8 T; (iii) the vortex diffusion constant D(T) is exponential due to pinning of vortex cores. These results can be described by the extended dynamic theory of the Berezinski-Kosterlitz-Thouless (BKT) transition and dynamics of bound vortex-antivortex pairs with short separation lengths.

  9. Immobilization of [Cu(bpy){sub 2}]Br{sub 2} complex onto a glassy carbon electrode modified with {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes: Application to nanomolar detection of hydrogen peroxide and bromate

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)], E-mail: absalimi@uok.ac.ir; Korani, Aazam; Hallaj, Rahman; Khoshnavazi, Roshan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hadadzadeh, Hasan [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)

    2009-03-02

    A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy){sub 2}]Br{sub 2} was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, {alpha}-SiMo{sub 12}O{sub 40}{sup 4-} and single walled carbon nanotubes (SWCNTs){sub .} Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/{alpha}-SiMo{sub 12}O{sub 40}{sup 4-} modified electrodes shows excellent electrocatalytic activity toward reduction H{sub 2}O{sub 2} and BrO{sub 3}{sup -} at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1} and 3.0({+-}0.10) x 10{sup 3} M{sup -1} s{sup -1}, respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM{sup -1}, 10 nM-20 {mu}M, 1 nM, 5.5 nA nM{sup -1} and 10 nM-18 {mu}M, respectively.

  10. The atmospheric degradation of 1-bromopropane (CH3CH2CH2Br): The photochemistry of bromoacetone

    Science.gov (United States)

    Burkholder, James B.; Gilles, Mary K.; Gierczak, Tomasz; Ravishankara, A. R.

    2002-09-01

    The atmospheric degradation of 1-bromopropane and its degradation products are examined with respect to their ability to deplete stratospheric ozone. It is shown that the OH initiated oxidation of 1-bromopropane does not lead to long lived bromine containing species. Laboratory measurements of the UV absorption cross sections and photodissociation quantum yields of chloroacetone and bromoacetone are presented. The atmospheric photolysis lifetime of bromoacetone at mid-latitudes is determined to be on the order of hours.

  11. Kinetics of the HO2 + BrO Reaction Over the Temperature Range 233-348 K

    Science.gov (United States)

    Li, Z.; Friedl, R. R.; Sander, S. P.

    1997-01-01

    The reaction BrO + HO2 products is the rate-limiting step in a key catalytic ozone destruction cycle in the lower stratosphere. In this study a discharge flow reactor coupled with molecular beam mass spectrometry has been used to study the BrO + HO2 reaction over the temperature range 233-348 K.

  12. The Interaction of Complexes Mn(PPhMe2)Br2 and Mn(PEt3)Br2 with Sulfur Dioxide.

    Science.gov (United States)

    2014-09-26

    Montana College, tillings, Montana 59101 K ~Interactleus of the complexes 1k(Pitife*)1 sad NU(PZ?)Bh fiUu with 80𔃼omd .jto ’ have been investigated using...OFFICE SYMBOL 7&. NAME OF MONITORING ORGANIZATIONr applicebwe Auburn University JOffice of Naval Research - Code 413 6c. ADDRESS ( City . State end ZIP...Code) - - 7b. ADDRESS ( City . State nd ZIP Code) Department of Chemistry (Dr. S.D. Worley) 800 N. Qunicy Street Auburn University Arlington, VA 22217

  13. Volcanic SO2, BrO and plume height estimations using GOME‐2 satellite measurements during the eruption of Eyjafjallajökull in May 2010

    National Research Council Canada - National Science Library

    Rix, M; Valks, P; Hao, N; Loyola, D; Schlager, H; Huntrieser, H; Flemming, J; Koehler, U; Schumann, U; Inness, A

    2012-01-01

    ... plume heights are important for aviation safety. This paper describes the observations of SO 2 and BrO columns in the eruption plume and the determination of the SO 2 plume height using the GOME...

  14. Ground-based DOAS observations of stratospheric O3, NO2, BrO and OClO at two different Antarctic sites

    Science.gov (United States)

    Yela, Margarita; Prados-Roman, Cristina; González, David; Puentedura, Olga; Navarro-Comas, Mónica; Ochoa, Héctor

    2017-04-01

    BrO and OClO are two of the most important halogen radicals involved in the ozone destruction. Although chlorine dioxide (OClO) does not participate directly in the destruction of ozone, observations of OClO are a good indicator for chlorine activation in the polar vortex based on the assumption of OClO concentration is linearly dependent on the ClO concentration. Accurate measurements of both components (BrO, OClO) are important to understand the halogen chemistry in the highly perturbed spring atmosphere in the polar regions, especially in Antarctica, where BrO and OClO ground-based measurements are very sparse and satellite observations have some limitations. Ground-based MAXDOAS observations were performed at Belgrano (78°S) and Marambio (64°S) by IAA/INTA during 2015. Stations are located close in longitude but separated 14° in latitude. Belgrano is representative of an in-polar vortex station during the winter-spring season until the vortex breakdown, while Marambio is frequently located in the edge region of the vortex. Simultaneous measurements of halogen species in both stations, using the same kind of instrumentation developed at INTA, are key factor to characterize the distribution of halogens, ozone and NO2 in two different although close scenarios and, also, to get a better understanding of the mechanisms that release halogens into the atmosphere. We report on the UV/Vis spectroscopic measurements performed during 2015 showing stratospheric BrO, OClO, NO2 and O3 above both stations. We present the seasonal evolution of these gases, as well as their role in the ozone depletion observed during the austral spring. The south polar vortex of 2015 was unusually stable and long-lived, so ozone depletion lasted longer than seen in recent years. A detailed analysis of the heat flux and of the position of the stations with respect to the polar vortex will be presented using equivalent latitude al 550 and 475 K isentropic levels.

  15. Mn-Promoted Co3O4/TiO2 as an efficient catalyst for catalytic oxidation of dibromomethane (CH2Br2).

    Science.gov (United States)

    Mei, Jian; Zhao, Songjian; Huang, Wenjun; Qu, Zan; Yan, Naiqiang

    2016-11-15

    Brominated hydrocarbon is the typical pollutant in the exhaust gas from the synthesis process of Purified Terephthalic Acid (PTA), which may cause various environmental problems once emitted into atmosphere. Dibromomethane (DBM) was employed as the model compound in this study, and a series of TiO2-supported manganese and cobalt oxide catalysts with different Mn/Co molar ratio were prepared by the impregnation method and used for catalytic oxidation of DBM. It was found that the addition of Mn significantly enhanced the catalytic performance of Co/TiO2 catalyst. Among all the prepared catalysts, Mn(1)-Co/TiO2 (Mn/Co molar ratio was 1) catalyst exhibited the highest activity with T90 at about 325°C and good stability maintained for at least 30h at 500ppm DBM and 10% O2 at GHSV=60,000h(-1), and the final products in the reaction were COx, HBr and Br2, without the formation of Br-containing organics. The high activity and high stability might be attributed to the redox cycle (Co(2+)+Mn(4+)↔Co(3+)+Mn(3+)) over Mn-promoted Co3O4/TiO2 catalyst. Based on the results of in situ DRIFT studies and analysis of products, a plausible reaction mechanism for catalytic oxidation of DBM over Mn-Co/TiO2 catalysts was also proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Effect of non-graphitized carbon electrodes on the electrochemical characteristics of a thermocell with a Br 2/Br - redox couple

    Science.gov (United States)

    Shindo, Kazuhiko; Arakawa, Masayasu; Hirai, Toshiro

    Electrodes made from a non-graphitized carbon (Maxsorb) sheet with a large specific surface area greatly improved the electrochemical characteristics of thermocells with a bromine/bromide-ion redox couple and a KBr aqueous electrolyte saturated with Br 2. The Maxsorb electrodes provide a higher open-circuit voltage than graphite (Perma Foil) electrodes and the maximum discharge current density is 2.4 mA/cm 2 until the voltage reaches 0 V. The Maxsorb electrodes generate 5.68 mV/°C of thermoelectric power at a temperature difference greater than 40°C, which is 2.5 times the power reported previously. The Maxsorb electrodes also improve the cathodic polarization in the presence of a gas-liquid-solid interface in Br 2-free electrolyte, while the graphite electrodes do not. Nevertheless, this improvement is insufficient to observe when the KBr electrolyte is saturated with Br 2. An experimental cell with Maxsorb electrodes maintains a stable voltage up to 2.0 mA/cm 2 for over 450 h, even though the cell configuration has still to be optimized.

  17. Enriching Glucoraphanin in Brassica rapa Through Replacement of BrAOP2.2/BrAOP2.3 with Non-functional Genes

    Directory of Open Access Journals (Sweden)

    Zhiyuan Liu

    2017-08-01

    Full Text Available Sulforaphane, the hydrolytic product of glucoraphanin glucosinolate, is a potent anticarcinogen that reduces the risk of several human cancers. However, in most B. rapa vegetables, glucoraphanin is undetectable or only present in trace amounts, since the glucoraphanin that is present is converted to gluconapin by three functional BrAOP2 genes. In this study, to enrich beneficial glucoraphanin content in B. rapa, the functional BrAOP2 alleles were replaced by non-functional counterparts through marker-assisted backcrossing (MAB. We identified non-functional mutations of two BrAOP2 genes from B. rapa. The backcross progenies with introgression of both non-functional braop2.2 and braop2.3 alleles significantly increased the glucoraphanin content by 18 times relative to the recurrent parent. In contrast, replacement or introgression of single non-functional braop2.2 or braop2.3 locus did not change glucoraphanin content. Our results suggest that replacement of these two functional BrAOP2 genes with non-functional alleles has the potential for producing improved Brassica crops with enriched beneficial glucoraphanin content.

  18. Pressure studies on a low-resistance variant of the quasi-2D organic superconductor κ-(BEDT-TTF) 2Cu[N(CN) 2]Br

    Science.gov (United States)

    Lang, M.; Strack, Ch.; Akinci, C.; Wolf, B.; Schlueter, J. A.; Wosnitza, J.; Schweitzer, D.

    2005-04-01

    Measurements of the interlayer resistivity, ρ⊥( T), under hydrostatic pressure have been performed on a low (LR)- and high (HR)-resistance variant of the title organic superconductor. While the HR sample, synthesized according to the standard procedure, shows a semimetallic-like ρ( T) behavior at high temperatures followed by the pronounced maximum around 90 K, the LR crystal, which is the result of a somewhat modified synthesis route, remains metallic for T⩽300 K. Common to both variants is, however, an almost abrupt change in ρ(T) around T*=40 K, consistent with a density-wave-type instability, which below T≈12 K coexists with superconductivity, and a ρ∝ AT2 dependence for T⩽T⩽T0. While T* and Tc are sample independent, the values for A and T0 were found to differ markedly between both variants, inconsistent with the T2 dependence originating from coherent Fermi-liquid excitations.

  19. A combined theoretical and Cambridge Structural Database study of π-hole pnicogen bonding complexes between electron rich molecules and both nitro compounds and inorganic bromides (YO2Br, Y = N, P, and As).

    Science.gov (United States)

    Bauzá, Antonio; Ramis, Rafael; Frontera, Antonio

    2014-04-17

    Quantum calculations at the DFT-D3/def2-TZVPD level of theory have been used to examine complexes between O2YBr (Y═N, P, and As) molecules and several Lewis bases, that is, NH3, H2O, and HF. The interactions of the lone pair of the ammonia, water, and hydrogen fluoride with the σ-hole and π-hole of O2YBr molecules have been considered. In general, the complexes where the Lewis base lone pair interacts with the π-hole are more favorable than those with σ-hole. The nature of the interactions has been characterized with the Bader theory of atoms in molecules (AIM). We have also studied the ability of trifluoronitromethane and nitromethane to interact with anions using their π-hole along with an analysis the Cambridge Structural Database. We have found a large number of hits that provide strong experimental support for ability of the nitryl (-NO2) group to interact with anions and Lewis bases. In some X-ray structures, the π-hole interaction is crucial in the crystal packing and has a strong influence in the solid state architecture of the complexes. Finally, due to the relevance in atmospheric chemistry, we have studied noncovalent σ/π-hole complexes of nitryl bromide with ozone.

  20. In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

    Science.gov (United States)

    Anderson, James G.

    2001-01-01

    We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

  1. Chemistry, Dynamics, and Radiation of Ozone Loss: Airborne Measurements of OH, HO2, NO2, ClO, BrO, IO, ClONO2, BrONO2, ClOOCl, and H2O

    Science.gov (United States)

    Anderson, James G.

    2005-01-01

    This grant continued the research initially funded under NAG1-01095. This research addresses, through a combination of in situ and remote aircraft-borne instruments, the following scientific questions: Which mechanisms are responsible for the continuing erosion of ozone over midlatitudes of the Northern Hemisphere? Will the rapid loss of ozone over the Arctic in late winter continue to worsen over the next two decades? Are these large losses dynamically coupled to midlatitudes? Which mechanisms dictate the rate of exchange of material between the troposphere and stratosphere? How will these processes change in response to changes in climate? Will regional scale pollution episodes, that are emerging as predictable seasonal events, significantly affect the middle-to-upper troposphere chemical composition. If so, how will these changes alter the chemical composition of the middle world? What changes are predicted for the overworld? Why has the arctic stratosphere become colder in the late winter phase in recent years? Have increases in tropical upper troposphere temperatures increased the temperature gradient such as to change the trajectories of vertically propagating waves, thus reducing the effectiveness of the meridional circulation for transport of heat, momentum and ozone from the tropics to high latitudes?

  2. Nephrotoxicity of 2-bromo-(cystein-S-yl) hydroquinone and 2-bromo-(N-acetyl-L-cystein-S-yl) hydroquinone thioethers.

    Science.gov (United States)

    Monks, T J; Jones, T W; Hill, B A; Lau, S S

    1991-11-01

    The in vivo toxicity of isomeric cystein-S-yl and N-acetylcystein-S-yl conjugates of 2-bromohydroquinone was determined in male Sprague-Dawley rats. 2-Bromo-(dicystein-S-yl)hydroquinone [2-Br-(diCYS)HQ] and 2-bromo-(di-N-acetyl-L-cystein-S-yl)hydroquinone [2-Br-(diNAC)HQ] were considerably more nephrotoxic than their corresponding monosubstituted thioethers and 2-Br-(diCYS)HQ was more nephrotoxic than 2-Br-(diNAC)HQ. 2-Br-(diCYS)HQ caused elevations in blood urea nitrogen (BUN) concentrations and increases in the urinary excretion of glucose, lactate dehydrogenase (LDH), and gamma-glutamyl transpeptidase (gamma-GT) at a dose of 25 mumol/kg (iv). In contrast, 2-Br-(diNAC)HQ caused significant elevations in BUN at 100 mumol/kg and glucosuria and enzymuria at 50 mumol/kg. 2-Br-3-(CYS)HQ and 2-Br-5&6-(CYS)HQ caused increases in the biochemical indices of nephrotoxicity at doses between 50 and 150 mumol/kg whereas 2-Br-5-(NAC)HQ and 2-Br-6-(NAC)HQ required doses of 150-200 mumol/kg to cause smaller, though significant increases in urinary glucose, gamma-GT, and LDH excretion. The histological alterations caused by each thioether were qualitatively similar; only differences in the extent of the renal proximal tubular damage were observed. The initial lesion appears to involve the cells of the medullary ray and the S3M within the outer stripe of the outer medulla. The in vivo nephrotoxicity of 2-Br-(DiCYS)HQ, 2-Br-(diNAC)HQ, and the most potent monosubstituted thioethers, 2-Br-5&6-(CYS)HQ and 2-Br-6-(NAC)HQ, was investigated further. Pretreatment of animals with aminooxyacetic acid, an inhibitor of cysteine conjugate beta-lyase (beta-lyase), had no effect on the toxicity of 2-Br-(diCYS)HQ, partially inhibited the toxicity of 2-Br-5&6-(CYS)HQ, and almost completely protected against the toxicity of both 2-Br-6-(NAC)HQ and 2-Br-(diNAC)HQ. Thus, the nephrotoxicity of 2-Br-5&6-(CYS)HQ, 2-Br-6-(NAC)HQ, and 2-Br-(diNAC)HQ may be mediated, in part, via their processing by beta

  3. A theoretical investigation of the feasibility of Tannor-Rice type control: Application to selective bond breakage in gas-phase dihalomethanes

    DEFF Research Database (Denmark)

    Shu, Chuan-Cun; Rozgonyi, Tamas; Gonzalez, Leticia;

    2012-01-01

    Within the math absorption band of CH2BrCl, we theoretically analyze the laser-induced control of the Br/Cl branching ratio, Br + CH2Cl ← CH2BrCl → CH2Br + Cl, with CH2BrCl initially in its vibrational ground state. For weak-field excitation, the Br/Cl branching ratio increases as a function of w...

  4. Thermodynamic study of (alkyl esters + {alpha},{omega}-alkyl dihalides) VI. H{sub m}{sup E} and V{sub m}{sup E} for 20 binary mixtures {l_brace}xC{sub u-1}H{sub 2u-1}CO{sub 2}(CH{sub 2}){sub 3}CH{sub 3} + (1 - x){alpha},{omega}-BrCH{sub 2}(CH{sub 2}){sub v-2}CH{sub 2}Br{r_brace}, where u = 1 to 5, {alpha} = 1, and v = {omega} = 2 to 6

    Energy Technology Data Exchange (ETDEWEB)

    Navas, A. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071, Las Palmas de Gran Canaria, Canary Islands (Spain); Ortega, J. [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071, Las Palmas de Gran Canaria, Canary Islands (Spain)], E-mail: jortega@dip.ulpgc.es; Nuez, I. de la [Laboratorio de Termodinamica y Fisicoquimica de Fluidos, Parque Cientifico-Tecnologico, Campus Universitario de Tafira, Universidad de Las Palmas de Gran Canaria, 35071, Las Palmas de Gran Canaria, Canary Islands (Spain)

    2009-11-15

    This work shows the experimental values obtained for H{sub m}{sup E} and V{sub m}{sup E} at the temperature of 298.15 K and atmospheric pressure, for a set of 20 binary mixtures comprised of the first four butyl esters (methanoate to butanoate) with five {alpha},{omega}-dibromoalkanes (1,2-dibromoethane to 1,6-dibromohexane). The H{sub m}{sup E} are endothermic for mixtures with butyl methanoate, while for the other esters the H{sub m}{sup E} adopt a sigmoidal shape. The V{sub m}{sup E} are positive for mixtures with low molecular weight dibromoalkanes, becoming negative with contractive effects in the final mixture, as the dihalide chain increases. The results indicate that the mixtures present specific interactions, with simultaneous expansion/contraction and exothermic/endothermic effects, and an explanation is given for the different types of interaction taking place. Experimental data are correlated with a polynomial equation used in previous works with satisfactory results. Modelling of the experimental results of the mixtures is carried out on the H{sub m}{sup E} values, giving rise to an adequate definition of the different interactions taking place. Two versions of the UNIFAC method were used, and for Dang and Tassios' version different possibilities were considered for the interaction parameters of the ester (G)/dibromide (G'). The best estimations were obtained when the pair of interaction parameters, type a{sub G/G{sup '}}, depended on the number of carbon atoms in the compounds constituting the mixture.

  5. Long term halocarbon observations from a~coastal and an inland site in Sabah, Malaysian Borneo

    Directory of Open Access Journals (Sweden)

    A. D. Robinson

    2014-01-01

    Full Text Available Short lived halocarbons are believed to have important sources in the tropics where rapid vertical transport could provide a significant source to the stratosphere. In this study, quasi-continuous measurements of short-lived halocarbons are reported for two tropical sites in Sabah (Malaysian Borneo, one coastal and one inland (rainforest. We present the observations for C2Cl4, CHBr3, CH2Br2* (actually ~80% CH2Br2 and ~20% CHBrCl2 and CH3I from November 2008 to January 2010 made using our μDirac gas chromatographs with electron capture detection (GC-ECD. We focus on the first 15 months of observations, showing over one annual cycle for each compound and therefore adding significantly to the few limited-duration observational studies that have been conducted thus far in southeast Asia. The main feature in the C2Cl4 behaviour at both sites is its annual cycle with the winter months being influenced by northerly flow with higher concentrations, typical of the Northern Hemisphere, with the summer months influenced by southerly flow and lower concentrations representative of the Southern Hemisphere. No such clear annual cycle is seen for CHBr3, CH2Br2Br2* or CH3I. The baseline values for CHBr3 and CH2Br2Br2* are similar at the coastal (overall median: CHBr3 1.7 ppt; CH2Br2Br2* 1.4 ppt and inland sites (CHBr3 1.6 ppt, CH2Br2Br2* 1.1 ppt, but periods with elevated values are seen at the coast (overall 95th percentile: CHBr3 4.4 ppt; CH2Br2Br2* 1.9 ppt presumably resulting from the stronger influence of coastal emissions. Overall median bromine values from [CHBr3] + [CH2Br2Br2*] are 8.0 ppt at the coast and 6.8 ppt inland. The median values reported here are largely consistent with other limited tropical data and imply that southeast Asia generally is not, as has been suggested, a hot-spot for emissions of these compounds. These baseline values are consistent with the most recent emissions found for southeast Asia using the p-TOMCAT model. CH3I, which

  6. Structure-Stability Relationships of Phthalocyanine Copper Complexes

    Directory of Open Access Journals (Sweden)

    G. P. Shaposhnikov

    2000-06-01

    Full Text Available The influence of NO2, Br, and COOH function substituents in various positions of Cu(IIPc on the reactivity of the latter concerning the dissociation of the metal - nitrogen bonds in proton donor solvents is discussed.

  7. Functionalization of the corrole ring: the role of isocorrole intermediates.

    Science.gov (United States)

    Tortora, Luca; Nardis, Sara; Fronczek, Frank R; Smith, Kevin M; Paolesse, Roberto

    2011-04-14

    Bromination of 3-nitro-5,10,15-triarylcorrole selectively provides two regioisomers, depending on the reaction pathway. An isocorrole species is the key intermediate to drive the reaction towards the 2-Br-17-nitro regioisomer.

  8. Functionalization of the corrole ring: the role of isocorrole intermediates†

    Science.gov (United States)

    Tortora, Luca; Nardis, Sara; Fronczek, Frank R.; Smith, Kevin M.; Paolesse, Roberto

    2011-01-01

    Bromination of 3-nitro-5,10,15-triarylcorrole selectively provides two regioisomers, depending on the reaction pathway. An isocorrole species is the key intermediate to drive the reaction towards the 2-Br-17-nitro regioisomer. PMID:21350743

  9. Employment of Adaptive Learning Techniques for the Discrimination of Acoustic Emissions.

    Science.gov (United States)

    1983-11-01

    7F ..... .-...- -*. .. 92 % d Fiue366 TaeofBt ore civtd-mlaeul Wit Eco. P1~ ? %. Figure 3.6.7 Image of Both Sources Activated Simultaneously Without...C SUBROUTINE RBTR(INT, NN, BRO, BRI, BR2, BR3, BR4, BRS, BR6. BR7, ŕ,BI0 BI, B12, B13, B14, B15, B16, B17 ) DIMENSION...L(15), BRO(2), BRI(2), B82(2), B83(2), BR4(2), BR5(2), * 1BR6(2), BR7(2), B10(2), B11(2), B12(2), B13(2), B14(2), * 15(2), B16(2), B17 (2) COINION

  10. Platinum oxoboryl complexes as substrates for the formation of 1:1, 1:2, and 2:1 Lewis acid-base adducts and 1,2-dipolar additions.

    Science.gov (United States)

    Bertsch, Stefanie; Brand, Johannes; Braunschweig, Holger; Hupp, Florian; Radacki, Krzysztof

    2015-04-13

    The oxoboryl complex trans-[(Cy3 P)2 BrPt(B≡O)] (2) reacts with the Group 13 Lewis acids EBr3 (E=Al, Ga, In) to form the 1:1 Lewis acid-base adducts trans-[(Cy3 P)2 BrPt(B≡OEBr3 )] (6-8). This reactivity can be extended by using two equivalents of the respective Lewis acid EBr3 (E=Al, Ga) to form the 2:1 Lewis acid-base adducts trans-[(Cy3 P)2 (Br3 Al-Br)Pt(B≡OAlBr3 )] (18) and trans-[(Cy3 P)2 (Br3 Ga-Br)Pt(B≡OGaBr3 )] (15). Another reactivity pattern was demonstrated by coordinating two oxoboryl complexes 2 to InBr3 , forming the 1:2 Lewis acid-base adduct trans-[{(Cy3 P)2 BrPt(B≡O)}2 InBr3 ] (20). It was also possible to functionalize the B≡O triple bond itself. Trimethylsilylisothiocyanate reacts with 2 in a 1,2-dipolar addition to form the boryl complex trans-[(Cy3 P)2 BrPt{B(NCS)(OSiMe3 )}] (27). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Photodissociation/photoionization processes of chlorobromomethane induced by femtosecond laser pulses with pump-probe scheme

    Institute of Scientific and Technical Information of China (English)

    ZHANG Feng; WEI ZhengRong; CAO ZhenZhou; ZHANG ChangHua; ZHANG Bing

    2008-01-01

    The photodissociation/photoionization processes of chlorobromomethane (CH2BrCl) induced by femtosecond laser pulses have been investigated using pump-probe scheme combined with the time-of-flight mass spectra. The dominate photoproducts are observed at different delay time of the pump (400 nm) and probe (800 nm) pulses and the corresponding time-dependence of them is obtained. The results show that the decaying time of the molecule CH2BrCl in the A-band is in the 100 fs. The decaying tendencies of the fragment ions (CH2Cl+ and CH2Br+) and the parent ion (CH2BrCl+) are almost the same and the relative ratios of the yields of them keep constant during the delay time of 0 to 150 fs. These facts suggest that the fragment ions come from the fragmentation of the parent ions in excited electronic states. The probabilities to form CH2Cl+ and CH2Br+ are obtained from the relative ratio of the ion intensity and are about 71.6% and 14.2%, respectively.

  12. Microstructure and Phase Behavior of Cationic Gemini/Anionic Polyelectrolyte/Water Ternary System

    Institute of Scientific and Technical Information of China (English)

    皮瑛瑛; 尚亚卓; 彭昌军; 刘洪来

    2006-01-01

    The microstructure of cationic gemini surfactant 1,6-bis(dodecyldimethylammonium) hexane dibromide [C12H25(CH3)2N-(CH2)6-N(CH3)2C12H25·2Br] (12-6-12·2Br-) and oppositely charged polyelectrolyte poly(acrylic acid,sodium salt) (NaPA) in aqueous solution has been studied by using fluorescence, conductivity measurement, freeze-etching and TEM. The data obtained from fluorescence and conductivity measurement show that micelle-like or complex can form between the gemini surfactant (12-6-12.2Br-) and polyelectrolyte NaPA due to the static electric interaction and hydrophobic forces. Through freeze-etching and TEM, the microstructure of the mixture solution has been studied, which is consistent with the result from micropolarity. Comparing the fluorescence spectrum of system of dodecyltrimethylammonium bromide (DTAB) and NaPA with that of system of gemini surfactant (12-6-12.2Br-) and NaPA, it can be found that the interaction of (12-6-12.2Br-) and NaPA in aqueous solution has also been detected. It can be shown that the precipitate will transform into gel in higher NaPA concentration.

  13. 配位化学中的镜面对称性破缺(续)——纪念配位化学创始人维尔纳首次拆分八面体Co(Ⅲ)络合物100周年

    Institute of Scientific and Technical Information of China (English)

    章慧; 林丽榕

    2012-01-01

    2配位化学中的MSB实例及其机理和应用研究2.1经典络合物cis-[CoBr(NH3)(en)2]Br2的绝对不对称合成尽管Asakura等早在1990年就偶然发现在cis-[CoBr(NH3)(en)2]Br2的制备过程中存在着MSB现象(图3)[7,63],但直到1995年以ASS获得手性cis-[CoBr(NH3)(en)2]Br2的结果才被正式报道。1995年起,Asakura等基于该络合物绝对不对称合成的一系列研究认为[7,30,63-67],

  14. catena-Poly[di-μ3-bromido-bis-[(1-ethyl-1H-imidazole-κN (3))disilver(I)

    Science.gov (United States)

    Wang, Zhiguo; Bian, Qingquan; Guo, Ying

    2013-01-01

    The asymmetric unit of the title coordination complex, [Ag2Br2(C5H8N2)2] n , comprises a monodentate 1-ethyl-imida-zole ligand, an Ag(+) cation and a μ3-bridging Br(-) anion, giving a distorted tetra-hedral AgNBr3 stereochemistry about the Ag(+) cation [Ag-N = 2.247 (2) Å and Ag-Br = 2.7372 (4)-2.7523 (4) Å]. Two bridging bromide anions generate the dimeric [Ag2Br2(C5H8N)2] repeat unit [Ag⋯Ag = 3.0028 (5) Å], while a third Br(-) anion links the units through corner sharing in an inversion-related Ag2Br2 association [Ag⋯Ag = 3.0407 (4) Å], generating a one-dimensional ribbon step-polymer structure, extending along the c axis.

  15. An A2B Adenosine Receptor Agonist Promotes Th17 Autoimmune Responses in Experimental Autoimmune Uveitis (EAU) via Dendritic Cell Activation.

    Science.gov (United States)

    Chen, Mingjiazi; Liang, Dongchun; Zuo, Aijun; Shao, Hui; Kaplan, Henry J; Sun, Deming

    2015-01-01

    We have recently reported that, although adenosine receptor (AR) agonists have a suppressive effect on Th1 autoreactive T cells, their effect on Th17 autoreactive T cells and γδ T cells is stimulatory and this effect is mainly mediated via A2A adenosine receptors (A2ARs). In this study, we further demonstrate that treatment of C57BL/6 (B6) mice with a selective A2B adenosine receptor (A2BR) agonist greatly enhanced the development of experimental autoimmune uveitis (EAU), whereas treatment with an A2BR antagonist significantly ameliorated severity of EAU. The A2BR agonist-treated mice showed augmented Th17, but not Th1, responses. Mechanistic studies showed that the A2BR agonist-induced enhancement of the Th17 response was significantly lower when TCR-δ-/- mice received the same treatment and that transfer of γδ T cells into TCR-δ-/- mice partially restored this effect. We also showed that dendritic cells (DCs) from A2BR agonist-treated mice showed a significantly increased ability to activate γδ T cells and Th17 autoreactive T cells. Thus, our previous studies have shown that, in EAU, activated γδ T cells possess greatly increased ability to enhance Th17 autoimmune responses. In the present study, we showed that exposure of DCs to A2BR agonist facilitated γδ T cell activation, leading to augmented Th17 responses and progressive EAU development. Our results further support our previous finding that AR agonists have distinct effects on Th1 and Th17 autoimmune responses.

  16. Amine Catalyzed Solvent C-H Bond Activation as Deactivation Route for Cationic Decamethylzirconocene Olefin Polymerization Catalysts

    NARCIS (Netherlands)

    Rios, Itzel Guerrero; Novarino, Elena; van der Veer, Siebe; Hessen, Bart; Bouwkamp, Marco W.

    2009-01-01

    [Cp(2)ZrMe)(+) + Me(3)N + C(6)H(6) down arrow TS2 Cp(2)ZrMePh + (Me(3)NH](+) down arrow TS3 [Cp(2)ZrPh](+) + Me(3)N + CH(4) The C-D activation of bromobenzene-d(5), by [CP(2)*ZrMe(BrC(6)D(5)-kappa Br)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp(2)*Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)

  17. Bi(iii) polybromides: a new chapter in coordination chemistry of bismuth.

    Science.gov (United States)

    Adonin, Sergey A; Gorokh, Igor D; Samsonenko, Denis G; Sokolov, Maxim N; Fedin, Vladimir P

    2016-04-11

    A new family of bismuth coordination compounds - Bi(iii) polybromides - is introduced. Four representatives of this class - (N-EtPy)3[Bi2Br9](Br2)2 (1), (4-MePyH)3[Bi2Br9](Br2) (2), (H2bpe){[BiBr5]}(Br2) (3) and (BPB)2[BiBr5(Br3)](Br3)(Br2) (4) - were obtained in a simple way from HBr solutions of BiBr3 with added Br2, highlighting the diversity of the structural types in the new family of complexes.

  18. Amine Catalyzed Solvent C-H Bond Activation as Deactivation Route for Cationic Decamethylzirconocene Olefin Polymerization Catalysts

    NARCIS (Netherlands)

    Rios, Itzel Guerrero; Novarino, Elena; van der Veer, Siebe; Hessen, Bart; Bouwkamp, Marco W.

    2009-01-01

    [Cp(2)ZrMe)(+) + Me(3)N + C(6)H(6) down arrow TS2 Cp(2)ZrMePh + (Me(3)NH](+) down arrow TS3 [Cp(2)ZrPh](+) + Me(3)N + CH(4) The C-D activation of bromobenzene-d(5), by [CP(2)*ZrMe(BrC(6)D(5)-kappa Br)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp(2)*Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)] i

  19. Preliminary Screening Procedures and Criteria for Replacements for Halons 1211 and 1301

    Science.gov (United States)

    1991-07-01

    trace quantities of bromine (Br 2), carbonyl fluoride (COF2), and carbonyl bromide ( COBr 2). The most noticeable effect of exposure to the decomposition...products are mainly HF, HCI, HBr, Cl2, Br 2, and traces of the carbonyl halides - COF2, COC 2, and COBr 2. 3. Halon 2402 [17-191 Although halon 2402 is

  20. AlNbBr{sub 8} - preparation, crystal structure, and vapor pressure studies

    Energy Technology Data Exchange (ETDEWEB)

    Rogachev, Alexander V.; Zelenina, Ludmila N.; Chusova, Tamara P.; Virovets, Alexander V. [Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, pr. Lavrentyeva 3, 630090, Novosibirsk (Russian Federation); Sokolov, Maxim N. [Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, pr. Lavrentyeva 3, 630090, Novosibirsk (Russian Federation); Novosibirsk State University, ul. Pirogova 2, 630090, Novosibirsk (Russian Federation)

    2016-07-15

    The ternary niobium compound AlNbBr{sub 8} (1) was synthesized by degradation of NbS{sub 2}Br{sub 2} in AlBr{sub 3} and from elements. Crystal structure and thermodynamic properties of sublimation process were studied. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Drug: D02204 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D02204 Drug Hexamethonium bromide (JAN/INN); Hexamethonium bromide (TN) C12H30N2. 2Br 360.0776 362.188 D0220...1139 55584 57053 1141 1142 1143] Hexamethonium D02204 Hexamethonium bromide (JAN/INN) CAS: 55-97-0 PubChem: 7849264 LigandBox: D0220

  2. Investigation of gene–diet interactions in the incretin system and risk of type 2 diabetes: the EPIC-InterAct study

    NARCIS (Netherlands)

    Feskens, E.J.M.; Kuijsten, A.

    2016-01-01

    Aims/hypothesis. The gut incretin hormones glucagon-like
    peptide-1 (GLP-1) and glucose-dependent insulinotropic peptide
    (GIP) have a major role in the pathophysiology of type 2<br/>diabetes. Specific genetic and dietary factors have been found
    to influence the release and action of

  3. Drug: D05199 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available f Antisecretory; Anti-ulcerative CAS: 40759-33-9 PubChem: 47206918 LigandBox: D05199 ATOM 20 1 C8x C 5.8100 ...D05199 Drug Nolinium bromide (USAN/INN) C15H11Cl2N2. Br 367.9483 370.0712 D05199.gi

  4. Bending of the Flexible Spacer Chain of Gemini Surfactant Induced by Hydrophobic Interaction

    Institute of Scientific and Technical Information of China (English)

    YOU,Yi; JIANG,Rong; LING,Tingting; ZHAO,Jianxi

    2009-01-01

    In order to understand the special role of the flexible alkylene spacer of gemini surfactant in the self-assembly,three gemini surfactants,alkylene-α,ω-bis(didodecylmethylammonium bromide)that is designated as 2C12-s-2C12·2Br (s=3,6,8),were synthesized.When the spread films of 2C12-s-2C12·2Br on the surface of water were con-structed,they form the dense layer of the alkyl tails owing to four dodecyl chains per molecule.This induced the bending of the spacer chain toward the air-side at the s smaller than that of C12-s-C12·2Br adsorbed on the air/water interface owing to the enhanced hydrophobic interaction between the alkyl tails and the spacer chain, where C12-s-C12·2Br has only two alkyl tails per molecule. Conclusively.,the enhanced hydrophobic interaction between the alkyl tails and the spacer chain can effectively induce the bending of the latter toward the air-side.

  5. Resumen en español

    Directory of Open Access Journals (Sweden)

    Bogdan Patrut

    2010-04-01

    Full Text Available BRAIN. Broad Research in Artificial Intelligence and Neuroscience
    CEREBRO. Investigación Amplia en Inteligencia Artificial y Neurociencia
    Volumen 1, Número 2<br />Julio 2010: ¡Feliz Verano 2010!
    www.brain.edusoft.ro
    Editor Jefe: Bogdan Patrut

  6. Drug: D09402 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D09402 Drug Darotropium bromide (USAN/INN) C24H29N2. Br 424.1514 425.4045 D09402.gi...KO:K04129 K04130 K04131 K04132 K04133] Darotropium D09402 Darotropium bromide (USAN/INN) CAS: 850607-58-8 Pu

  7. Drug: D07273 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D07273 Drug Fazadinium bromide (INN) C28H24N6. 2Br 602.0429 604.3384 D07273.gif ATC...03 MUSCLE RELAXANTS M03A MUSCLE RELAXANTS, PERIPHERALLY ACTING AGENTS M03AC Other quaternary ammonium compounds M03AC08 Fazad...inium bromide D07273 Fazadinium bromide (INN) CAS: 49564-56-9 Pu

  8. Drug: D01463 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D01463 Drug Diponium bromide (JAN/INN); Dipenine bromide C20H38NO2. Br 403.2086 404...4131 K04132 K04133] Diponium D01463 Diponium bromide (JAN/INN) CAS: 2001-81-2 PubChem: 7848526 LigandBox: D0

  9. Bymixer provides on-line calibration of measurement of CO2 volume exhaled per breath.

    Science.gov (United States)

    Breen, P H; Serina, E R

    1997-01-01

    The measurement of CO2 volume exhaled per breath (VCO2.br) can be determined during anesthesia by the multiplication and integration of tidal flow (V) and PCO2. During side-stream capnometry, PCO2 must be advanced in time by transport delay (TD), the time to suction gas through the sampling tube. During ventilation, TD can vary due to sample line connection internal volume or flow rate changes. To determine correct TD and measure accurate VCO2.br during actual ventilation. TD can be iteratively adjusted (TDADJ) until VCO2-br/tidal volume equals PCO2 measured in a mixed expired gas collection (PECO2) (J Appl. Physiol. 72:2029-2035, 1992). However. PECO2 is difficult to measure during anesthesia because CO2 is absorbed in the circle circuit. Accordingly, we implemented a bypass flow-mixing chamber device (bymixer) that was interposed in the expiration limb of the circle circuit and accurately measured PECO2 over a wide range of conditions of ventilation of a test lung-metabolic chamber (regression slope = 1.01: R2 = 0.99). The bymixer response (time constant) varied from 18.1 +/- 0.03 sec (12.5 l/min ventilation) to 66.7 +/- 0.9 sec (2.5 l/min). Bymixer PECO2 was used to correctly determine TDADJ (without interrupting respiration) to enable accurate measurement of VCO2.br over widely changing expiratory flow patterns.

  10. Ordering of vacancies on Si(001)

    NARCIS (Netherlands)

    Zandvliet, H.J.W.

    1997-01-01

    Missing dimer vacancies are always present on the clean Si(001) surface. The vacancy density can be increased by ion bombardment (Xe+, Ar+), etching (O2, Br2, I2, etc.) or Ni contamination. The equilibrium shape at low vacancy concentrations (<0.2¿0.3 monolayers) of these vacancy islands is elongate

  11. The Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) Uses its C-Terminus to Regulate the A2B Adenosine Receptor.

    Science.gov (United States)

    Watson, Michael J; Lee, Shernita L; Marklew, Abigail J; Gilmore, Rodney C; Gentzsch, Martina; Sassano, Maria F; Gray, Michael A; Tarran, Robert

    2016-06-09

    CFTR is an apical membrane anion channel that regulates fluid homeostasis in many organs including the airways, colon, pancreas and sweat glands. In cystic fibrosis, CFTR dysfunction causes significant morbidity/mortality. Whilst CFTR's function as an ion channel has been well described, its ability to regulate other proteins is less understood. We have previously shown that plasma membrane CFTR increases the surface density of the adenosine 2B receptor (A2BR), but not of the β2 adrenergic receptor (β2AR), leading to an enhanced, adenosine-induced cAMP response in the presence of CFTR. In this study, we have found that the C-terminal PDZ-domain of both A2BR and CFTR were crucial for this interaction, and that replacing the C-terminus of A2BR with that of β2AR removed this CFTR-dependency. This observation extended to intact epithelia and disruption of the actin cytoskeleton prevented A2BR-induced but not β2AR-induced airway surface liquid (ASL) secretion. We also found that CFTR expression altered the organization of the actin cytoskeleton and PDZ-binding proteins in both HEK293T cells and in well-differentiated human bronchial epithelia. Furthermore, removal of CFTR's PDZ binding motif (ΔTRL) prevented actin rearrangement, suggesting that CFTR insertion in the plasma membrane results in local reorganization of actin, PDZ binding proteins and certain GPCRs.

  12. Unique formation of two high-nuclearity metallamacrocycles from a mononuclear complex [Zn(dmpzdtc)2] (dmpzdtc=3,5-dimethylpyrazole-1-dithiocarboxylate) via CS2 elimination.

    Science.gov (United States)

    Li, Hong-Xi; Wu, Hua-Zhou; Zhang, Wen-Hua; Ren, Zhi-Gang; Zhang, Yong; Lang, Jian-Ping

    2007-12-21

    Dissolution of a mononuclear complex [Zn(dmpzdtc)2] in BrCH2CH2Br or DMF saturated with water followed by CS2 elimination led to the formation of two unique high-nuclearity metallamacrocyclic complexes, [Zn4(micro-dmpz)6(micro-OH)2]2 and [Zn4(micro-dmpz)6(micro-OH)2]4.

  13. Electronic structure of some β-(C10H8S8)2X compounds as studied by infrared spectroscopy

    DEFF Research Database (Denmark)

    Jacobsen, Claus Schelde; Tanner, D. B.; Williams, Jack M.;

    1987-01-01

    Polarized reflectance measurements have been made on two isostructural conducting compounds of bis(ethylenedithio)tetrathiafulvalene [BEDT-TTF or ET, (C10H8S8)]: β-(ET)2AuI2 and β-(ET)2I2Br. The former is superconducting at ambient pressure with Tc=5 K, whereas the latter retains normal-metal con...

  14. Halocarbon emissions and sources in the equatorial Atlantic Cold Tongue

    Directory of Open Access Journals (Sweden)

    H. Hepach

    2015-04-01

    Full Text Available Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3, dibromomethane (CH2Br2, methyl iodide (CH3I and diiodomethane (CH2I2. Enhanced biological production during the Atlantic Cold Tongue (ACT season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 pmol L−1 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water,CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a~biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1, and the observed anticorrelation with global radiation was likely due to its strong photolysis. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and has an influence on emissions into the atmosphere. The calculated

  15. Bromocarbons in the tropical coastal and open ocean atmosphere during the Prime Expedition Scientific Cruise 2009 (PESC 09

    Directory of Open Access Journals (Sweden)

    M. S. Mohd Nadzir

    2014-01-01

    Full Text Available Atmospheric concentrations of very short-lived species (VSLS bromocarbons, including CHBr3, CH2Br2, CHCl2Br, CHClBr2, CH2BrCl, were measured in the Strait of Malacca and the South China and Sulu-Sulawesi Seas during a two month research cruise in June/July 2009. The highest bromocarbon concentrations were found in the Strait of Malacca, with smaller enhancements in coastal regions of Northern Borneo. CHBr3 was the most abundant bromocarbon, ranging from 5.2 pmol mol−1 in the Strait of Malacca to 0.94 pmol mol−1 over the open ocean. Other bromocarbons showed lower concentrations, in the range of 0.8–1.3 pmol mol−1 for CH2Br2, 0.1–0.5 pmol mol−1 (CHCl2Br and 0.1–0.4 pmol mol−1 (CHClBr2. There was no significant correlation between bromocarbons and in situ chlorophyll a. Together the short-lived bromocarbons contribute an average of 8.9 pmol mol−1 (range 5.2–21.4 pmol mol−1 to tropospheric bromine load, which is similar to that found in previous studies (Montzka et al., 2011. Statistical tests showed strong Spearman correlations amongst brominated compounds suggesting a common source. Log-log plots of CHBr3/CH2Br2 vs. CHBr2Cl/CH2Br2 show that both chemical reactions and dilution into the background atmosphere contribute to the composition of these halocarbons at each sampling point. We have used the correlation to make a crude estimate of the regional emissions of CHBr3 and derive a value of 63 Gg yr−1 for the South East (S.E. Asian region (10° N–20° S, 90–150° E. Finally, we note that satellite-derived chlorophyll a (chl a products do not always agree well with in situ measurements, particularly in coastal regions of high turbidity, meaning that satellite chl a may not always be a good proxy for marine productivity.

  16. Central serotonin(2B) receptor blockade inhibits cocaine-induced hyperlocomotion independently of changes of subcortical dopamine outflow.

    Science.gov (United States)

    Devroye, Céline; Cathala, Adeline; Di Marco, Barbara; Caraci, Filippo; Drago, Filippo; Piazza, Pier Vincenzo; Spampinato, Umberto

    2015-10-01

    The central serotonin2B receptor (5-HT2BR) is currently considered as an interesting pharmacological target for improved treatment of drug addiction. In the present study, we assessed the effect of two selective 5-HT2BR antagonists, RS 127445 and LY 266097, on cocaine-induced hyperlocomotion and dopamine (DA) outflow in the nucleus accumbens (NAc) and the dorsal striatum of freely moving rats. The peripheral administration of RS 127445 (0.16 mg/kg, i.p.) or LY 266097 (0.63 mg/kg, i.p.) significantly reduced basal DA outflow in the NAc shell, but had no effect on cocaine (10 mg/kg, i.p.)-induced DA outflow in this brain region. Also, RS 127445 failed to modify both basal and cocaine-induced DA outflow in the NAc core and the dorsal striatum. Conversely, both 5-HT2BR antagonists reduced cocaine-induced hyperlocomotion. Furthermore, RS 127445 as well as the DA-R antagonist haloperidol (0.1 mg/kg, i.p.) reduced significantly the late-onset hyperlocomotion induced by the DA-R agonist quinpirole (0.5 mg/kg, s.c.). Altogether, these results demonstrate that 5-HT2BR blockade inhibits cocaine-induced hyperlocomotion independently of changes of subcortical DA outflow. This interaction takes place downstream to DA neurons and could involve an action at the level of dorsostriatal and/or NAc DA transmission, in keeping with the importance of these brain regions in the behavioural responses of cocaine. Overall, this study affords additional knowledge into the regulatory control exerted by the 5-HT2BR on ascending DA pathways, and provides additional support to the proposed role of 5-HT2BRs as a new pharmacological target in drug addiction.

  17. Enhancement of NMDA receptor-mediated excitatory postsynaptic currents by gp120-treated macrophages: implications for HIV-1-associated neuropathology.

    Science.gov (United States)

    Yang, Jianming; Hu, Dehui; Xia, Jianxun; Liu, Jianuo; Zhang, Gang; Gendelman, Howard E; Boukli, Nawal M; Xiong, Huangui

    2013-09-01

    A plethora of prior studies has linked HIV-1-infected and immune activated brain mononuclear phagocytes (MP; blood borne macrophages and microglia) to neuronal dysfunction. These are modulated by N-methyl-D-aspartate receptor (NMDAR) antagonists and supporting their relevance for HIV-1-associated nervous system disease. The role of NMDAR subsets in HIV-1-induced neuronal injury, nonetheless, is poorly understood. To this end, we investigated conditioned media from HIV-1gp120-treated human monocyte-derived-macrophages (MDM) for its abilities to affect NMDAR-mediated excitatory postsynaptic currents (EPSC(NMDAR)) in rat hippocampal slices. Bath application of gp120-treated MDM-conditioned media (MCM) produced an increase of EPSC(NMDAR). In contrast, control (untreated) MCM had limited effects on EPSC(NMDAR). Testing NR2A NMDAR (NR2AR)-mediated EPSC (EPSC(NR2AR)) and NR2B NMDAR (NR2BR)-mediated EPSC (EPSC(NR2BR)) for MCM showed significant increased EPSC(NR2BR) when compared to EPSC(NR2AR) enhancement. When synaptic NR2AR-mediated EPSC was blocked by bath application of MK801 combined with low frequency stimulations, MCM retained its ability to enhance EPSC(NMDAR) evoked by stronger stimulations. This suggested that increase in EPSC(NMDAR) was mediated, in part, through extra-synaptic NR2BR. Further analyses revealed that the soluble factors with low (NR2BR but not NR2AR blockers. Taken together, these results indicate that macrophage secretory products induce neuronal injury through extra-synaptic NR2BRs.

  18. NR2B phosphorylation at tyrosine 1472 in spinal dorsal horn contributed to N-methyl-D-aspartate-induced pain hypersensitivity in mice.

    Science.gov (United States)

    Li, Shuai; Cao, Jing; Yang, Xian; Suo, Zhan-Wei; Shi, Lei; Liu, Yan-Ni; Yang, Hong-Bin; Hu, Xiao-Dong

    2011-11-01

    Calcium influx via N-methyl-D-aspartate (NMDA)-subtype glutamate receptors (NMDARs) regulates the intracellular trafficking of NMDARs, leading to long-lasting modification of NMDAR-mediated synaptic transmission that is involved in development, learning, and synaptic plasticity. The present study investigated the contribution of such NMDAR-dependent synaptic trafficking in spinal dorsal horn to the induction of pain hypersensitivity. Our data showed that direct activation of NMDARs by intrathecal NMDA application elicited pronounced mechanical allodynia in intact mice, which was concurrent with a specific increase in the abundance of NMDAR subunits NR1 and NR2B at the postsynaptic density (PSD)-enriched fraction. Selective inhibition of NR2B-containing NMDARs (NR2BR) by ifenprodil dose dependently attenuated the mechanical allodynia in NMDA-injected mice, suggesting the importance of NR2BR synaptic accumulation in NMDA-induced pain sensitization. The NR2BR redistribution at synapses after NMDA challenge was associated with a significant increase in NR2B phosphorylation at Tyr1472, a catalytic site by Src family protein tyrosine kinases (SFKs) that has been shown to prevent NR2B endocytosis. Intrathecal injection of a specific SFKs inhibitor, PP2, to block NR2B tyrosine phosphorylation eliminated NMDA-induced NR2BR synaptic expression and also attenuated the mechanical allodynia. These data suggested that activation of spinal NMDARs was able to accumulate NR2BR at synapses via SFK signaling, which might exaggerate NMDAR-dependent nociceptive transmission and contribute to NMDA-induced nociceptive behavioral hyperresponsiveness.

  19. Reaction of N({sup 2}D) atoms with bromomethyl radicals: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Cimas, A. [Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain); Rayon, V.M. [Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain); Barrientos, C. [Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain); Aschi, M. [Dipartimento di Chimica, Ingegneria Chimica e Materiali, Universita di L' Aquila, Via Vetoio (Coppito 2), I-67010 L' Aquila (Italy); Sordo, J.A. [Laboratorio de Quimica Computacional, Departamento de Quimica Fisica y Analitica, Facultad de Quimica, Universidad de Oviedo, 33006 Oviedo (Spain); Largo, A. [Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain)], E-mail: alargo@qf.uva.es

    2006-09-29

    The singlet potential energy surface for the N({sup 2}D) + CH{sub 2}Br reaction has been studied employing both MP2 and DFT(B3LYP) methods. The energies of the involved species have been refined using the G2, CBS and CCSD(T) methods, respectively. The reaction proceeds through the formation of an initial intermediate which does not involve any activation barrier. Based on the singlet PES, the most exothermic products result from elimination of either HBr or H{sub 2}, instead of elimination of either Br or H. The preferred channel is predicted to be HCN + HBr. The analysis of the possible spin crossing between the triplet and singlet [CH{sub 2}NBr] potential surfaces suggests that the N({sup 4}S) + CH{sub 2}Br reaction should take place with no change in the spin angular momentum.

  20. Microwave, High-Resolution Infrared, and Quantum Chemical Investigations of CHBrF2

    DEFF Research Database (Denmark)

    Cazzoli, Gabriele; Cludi, Lino; Puzzarini, Cristina

    2011-01-01

    analysis by high-level quantum chemical calculations at the coupled-cluster level. In this context, the importance of relativistic effects, which are of the order of 6.5% and included in the present work using second-order direct perturbation theory, needs to be emphasized for accurate predictions......A combined microwave, infrared, and computational investigation of CHBrF2 is reported. For the vibrational ground state, measurements in the millimeter- and sub-millimeter-wave regions for (CHBrF2)-Br-79 and (CHBrF2)-Br-81 provided rotational and centrifugal-distortion constants up to the sextic...... terms as well as the hyperfine parameters (quadrupole-coupling and spin-rotation interaction constants) of the bromine nucleus. The determination of the latter was made possible by recording of spectra at sub-Doppler resolution, achieved by means of the Lamb-dip technique, and supporting the spectra...

  1. Crossbreeding dual-purpose cattle for beef production in tropical regions.

    Science.gov (United States)

    Rodriguez-Voigt, A; Noguera, E; Rodriguez, H L; Huerta-Leidenz, N O; Morón-Fuenmayor, O; Rincón-Urdaneta, E

    1997-11-01

    Six breed types groups of six steer calves each were used to observe differences in growth and carcass traits: F1 Brown Swiss (F1BS), F1 Holstein (F1HO), F2 Brahman (F2BR), F2 Criollo Rio Limon (F2CRL), purebred Criollo Rio Limon (CRL), and Perija Mosaic (PMO). After 404 days of grazing, the heaviest F1BS and F2BR steers were different from F1HO and CRL counterparts (p carcass maturity, quality or yield grade, boneless cut percentages, bone percentage or percent trimmable fat did not vary among breed types. All steers were within the A maturity level and graded Standard. Results indicate the importance of feeding dual-purpose steers to heavier weights to please industry preferences.

  2. Syntheses and characterization of two novel 1D Pb(II) Halide supramolecular polymers possessing incomplete Cubane subunit directed by -conjugated Dication templates

    Indian Academy of Sciences (India)

    Chengjie Ma; Mei Liu; Wenli Zhang; Haijuan Du; Yao Li; Chaohai Wang; Yunyin Niu

    2015-07-01

    Two novel cation-templated complexes, {(1, 4-PMBP)[Pb4I10]·DMF} n(1) {(DBBP)2[Pb5I8Br6]} n(2), (1,4-PMBP·2Br =1,1”-[1,4-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide; DBBP·2Br = N, N’-dibenzyl- 4, 4’-bipyridinium dibromide) have been synthesized via the self-assembly reaction in solution. X-ray crystallography showed that compounds 1 and 2 can be regarded as 1D iodoplumbate examples which contain incomplete cubane subunit directed by -conjugated dication templates. It is the H-bonds and electrostatic interactions between the organic counter cations and inorganic moieties that contribute the crystal packing. These compounds have been further characterized by IR spectroscopy, UV-Vis spectra, elemental analysis and thermostability properties.

  3. PMO[KIT-5]-n: synthesis of highly ordered three-dimensional periodic mesoporous organosilicas with Fm3m symmetry.

    Science.gov (United States)

    Liang, Yucang; Hanzlik, Marianne; Anwander, Reiner

    2005-01-28

    Divalent surfactant [CH3(CH2)15N(CH3)2(CH2)3N(CH3)3]2+ - 2Br- (C16-3-1) was used as a structure directing agent (SDA) for the synthesis of highly ordered periodic mesoporous organosilicas (PMOs) with cubic Fm3m symmetry from 1,2-bis(triethoxylsilyl)ethane (BTEE) under basic conditions.

  4. Drug: D00667 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D00667 Drug Demecarium bromide (USP/INN); Humorsol (TN) C32H52N4O4. 2Br 714.2355 71...CALS S01E ANTIGLAUCOMA PREPARATIONS AND MIOTICS S01EB Parasympathomimetics S01EB04 Demecarium D00667 Demecarium bromide...ase (AChE) [HSA:43] [KO:K01049] Demecarium [ATC:S01EB04] D00667 Demecarium bromide

  5. Drug: D00764 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D00764 Drug Pipecuronium bromide (USAN/INN); Arduan (TN) C35H62N4O4. 2Br 760.3138 7...compounds M03AC06 Pipecuronium bromide D00764 Pipecuronium bromide (USAN/INN) Tar...uscle-type nicotinic cholinergic receptor [HSA:1134 1140 1144 1145 1146] [KO:K04803 K04812 K04816 K04817 K04818] Pipecuronium bromide... [ATC:M03AC06] D00764 Pipecuronium bromide (USAN/INN) CA

  6. Nickel(II) Complexes with [2 sup4.3sup1]Adamanzane, 1,4,7,10-Tetraazabicyclo[5.5.3]pentadecane

    DEFF Research Database (Denmark)

    Sanzenbacher, Ralf; Søtofte, Inger; Springborg, Johan

    1999-01-01

    Nickel(II)complexes with the bicyclic tetraamine L=[2 sup4.3 sup1]adamanzane, ,4,7,10- tetraaza- bicyclo[5.5.3]pentadecane) have been synthesized. The reaction of NiBr sub 2 with [2 sup4.3 sup1]adz in dimethylformamide gives a dibromo-bridged dinuclear complex [{Ni(L)}sub2(mu-Br)sub2]Br sub2. From...

  7. Reaction of 1Н,2Н,3Н,4Н-pyrido[4,3-d]pyrimidinium bromide derivatives with molecular iodine: Comparative structure and spectroscopic analysis

    Science.gov (United States)

    Chernov'yants, Margarita S.; Burykin, Igor V.; Kostrub, Vladimir V.; Tsupak, Evgeny B.; Starikova, Zoya A.; Kirsanova, Julia A.

    2012-02-01

    New salts C27H22N3O2BrI2 (1) and C27H19N3O2Br4I2·2CHCl3·2H2O (2) were synthesized by the iodination of derivatives of 1,3-dimethyl-2,4-dioxo-5,6,7-R-1Н,2Н,3Н,4Н-pyrido[4,3-d]pyrimidinium bromide (R = phenyl (1a), p-bromphenyl (2a)) with an equimolar amount of iodine. The positive values of enthalpy (ΔH) and entropy (ΔS) indicate that the complexation of organic bromide and iodine molecule in chloroform solution is mainly entropically driven. The molecular and crystal structures (1) and (2) are studied by X-ray diffraction analysis. The structure of diiodinebromide 1 is composed of separate almost liner BrI2- and 1,3-dimethyl-2,4-dioxo-5,6,7-thriphenyl-1Н,2Н,3Н,4Н-pyrido[4,3-d]pyrimidinium cation. The crystal structure 2 is built up of alternate layers of (CHNOBr3+)(I3-) (A) and (Br2I-)(СHСl3) (B), connected to each other by hydrogen bonds Br(BrI)⋯H(CHNOBr3+). The formation of the ions I3- and Br2I- occurs via the disproportionation of I2Br- under the action of solvent on C27H19N3O2Br4I2·2CHCl3·2H2O (2) crystallization.

  8. Serotonin markers show altered transcription levels in an experimental pig model of mitral regurgitation

    DEFF Research Database (Denmark)

    Cremer, Signe Emilie; Zois, Nora Elisabeth; Moesgaard, S. G.

    2015-01-01

    surgically induced MR or sham-operation, resulting in three MR groups: control (CON, n = 12), mild MR (mMR, n = 10) and severe MR (sMR, n = 6). The gene expression levels of 5-HT1BR, 5-HT2AR, 5-HT2BR, SERT and TPH-1 were analysed using quantitative PCR (qPCR) in the mitral valve (MV), anterior papillary...

  9. Multifunctional silicon surfaces: reaction of dichlorocarbene generated from Seyferth reagent with hydrogen-terminated silicon (111) surfaces.

    Science.gov (United States)

    Liu, Wenjun; Sharp, Ian D; Tilley, T Don

    2014-01-14

    Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.

  10. Synthesis, spectral analysis, antibacterial and antifungal activities of some 4,6-diaryl-4,5-dihydro-3-hydroxy-2[H]-indazole-a novel fused indazole derivative.

    Science.gov (United States)

    Gopalakrishnan, M; Sureshkumar, P; Thanusu, J; Kanagarajan, V

    2008-12-01

    A novel class of 4,6-diaryl-4,5-dihydro-3-hydroxy-2[H]-indazoles 25-32 were synthesized and evaluated for their in vitro antibacterial and antifungal activities. Four Compounds, which all possessed electron withdrawing functional groups (-Cl, -NO(2), -Br) 27, 28, 30 and 32 were more potent against the tested bacterial/fungal strains than the standard bacterial and fungal drugs ciprofloxacin and fluconazole respectively.

  11. Transient resonance Raman spectroscopy and density functional theory investigation of iso-CHBr 2Cl and iso-CCl 3Br photoproducts produced following ultraviolet excitation of CHBr 2Cl and CCl 3Br

    OpenAIRE

    Zheng, X; Lee, CW; Li, YL; Fang, WH; Phillips, DL

    2001-01-01

    Two polyhalomethanes that contain bromine and chlorine atoms (CHBr 2Cl and CCl 2Br) were studied. Transient resonance Raman spectra were obtained for the photoproducts produced after ultraviolet excitation of CHBr 2Cl and CCl 3Br in room temperature solutions and density functional theory calculations for species proposed to be products of the photodissociation reactions in the solution phase. It was found that the iso-CHBrCl-Br and iso-CHClBr-Br species are formed following ultraviolet excit...

  12. Di-μ-bromido-bis[(diethyl ether-κO(2,4,6-trimethylphenylmagnesium]: the mesityl Grignard reagent

    Directory of Open Access Journals (Sweden)

    Ömer Seven

    2013-07-01

    Full Text Available The crystal structure of the title compound, [Mg2Br2(C9H112(C4H10O2], features a centrosymmetric two-centre magnesium complex with half a molecule in the asymmetric unit. The Mg atom is in a considerably distorted Br2CO coordination. Bond lengths and angles are comparable with already published values. The crystal packing is stabilized by C—H...π interactions linking the complexes into sheets parallel to (0-11.

  13. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS): linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    OpenAIRE

    R. Hossaini; Patra, P. K.; Leeson, A.A.; Krysztofiak, G.; Abraham, N.L.; Andrews, S. J.; Archibald, A.T.; Aschmann, J.; E. L. Atlas; Belikov, D. A.; Bonisch, H.; Carpenter, L. J.; Dhomse, S.; Dorf, M.; Engel, A

    2016-01-01

    The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry– climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except for three model si...

  14. Alpha-smooth muscle actin and serotonin receptors 2A and 2B in dogs with myxomatous mitral valve disease

    DEFF Research Database (Denmark)

    Cremer, Signe Emilie; Moesgaard, S. G.; Rasmussen, C. E.

    2015-01-01

    Canine Myxomatous mitral valve disease (MMVD) is an age-related disease. Serotonin (5-HT) is implicated in the pathogenesis as locally-produced or platelet-derived. Involvement of the 5-HT2A receptor (R) and 5-HT2BR in the induction of myxomatous-mediating valvular myofibroblasts (MF) has been su...... a functional relationship, perhaps perpetuation of clinical MMVD. 5-HT2AR-expression and serum 5-HT showed no differences between groups....

  15. Biological Effects of Short, High-Level Exposure to Gases: Sulfur Dioxide.

    Science.gov (United States)

    1980-05-01

    penetration of lower airways and stimulation of vagosympathetic receptors, thus inducing mechanical pulmon - ary changes and allowing the direct action...situation. However, the results of the study by O’Donoghue ana Graesser45 suggest that irreversible changes in pulmon - i ary tissue may occur with a...Respir Dis 13:163-169, 1976 71. Peacock PR, Spence JB: Incidence of lung tumors in LX mice exposed to (1) free radicals, (2) SO2. Br J Cancer 21(3):606

  16. High-resolution infrared spectroscopy of the interacting v9, v5 + v6 and 3v6 levels of CH279BrF

    DEFF Research Database (Denmark)

    Visinoni, R.; Baldacci, A.; Larsen, R. Wugt

    2011-01-01

    The high-resolution (0.0030 cm(-1)) Fourier transform infrared spectrum of (CH2BrF)-Br-79 has been studied in part of the atmospheric window between 910 and 980 cm(-1), the region of the v(9) (935.847 cm(-1)) and V-5 + v(6) (961.239 cm(-1)) bands. The v9 fundamental consists of a pseudo a-type band...

  17. Thermal Decomposition of 3-Bromopropene. A Theoretical Kinetic Investigation.

    Science.gov (United States)

    Tucceri, María E; Badenes, María P; Bracco, Larisa L B; Cobos, Carlos J

    2016-04-21

    A detailed kinetic study of the gas-phase thermal decomposition of 3-bromopropene over wide temperature and pressure ranges was performed. Quantum chemical calculations employing the density functional theory methods B3LYP, BMK, and M06-2X and the CBS-QB3 and G4 ab initio composite models provide the relevant part of the potential energy surfaces and the molecular properties of the species involved in the CH2═CH-CH2Br → CH2═C═CH2 + HBr (1) and CH2═CH-CH2Br → CH2═CH-CH2 + Br (2) reaction channels. Transition-state theory and unimolecular reaction rate theory calculations show that the simple bond fission reaction ( 2 ) is the predominant decomposition channel and that all reported experimental studies are very close to the high-pressure limit of this process. Over the 500-1400 K range a rate constant for the primary dissociation of k2,∞ = 4.8 × 10(14) exp(-55.0 kcal mol(-1)/RT) s(-1) is predicted at the G4 level. The calculated k1,∞ values lie between 50 to 260 times smaller. A value of 10.6 ± 1.5 kcal mol(-1) for the standard enthalpy of formation of 3-bromopropene at 298 K was estimated from G4 thermochemical calculations.

  18. 溴化顺式-溴·氨·二(乙二胺)合钴(Ⅲ)绝对不对称合成与拆分机理%Absolute Asymmetric Synthesis and Resolution Mechanism of Chiral cis-bromoamminebis(ethylenediamine)cobalt(Ⅲ) Bromide

    Institute of Scientific and Technical Information of China (English)

    章慧; 王宪营; 陈雷奇; 方雪明; 高景星; 徐志固

    2006-01-01

    分别用绝对不对称合成和改进的拆分方法制备标题配合物A-(+)D-cis-[CoBr(NH3)(en)2]Br(1)和△-(-)D-cis-[CoBr(NH3)(en)2]Br2(2),以及制备了cis-[CoBr(NH3)(en)2]Br2·2H2O(3)(en=1,2-乙二胺).用元素分析、差热-热重、旋光度、UV-Vis、CD光谱等对产物进行了表征.通过CD光谱法获得了绝对不对称合成Co(Ⅲ)配合物的产物ee值分布图.当利用绝对不对称合成得到的手性Co(Ⅲ)配合物去"逆向拆分"外消旋溴代樟脑磺酸铵[NH4(dl-BCS)]时只获得部分拆分,初步认为这与交互拆分过程中阴阳离子之间的有效手性识别有关,对于手性Co(Ⅲ)配合物的绝对不对称合成还提出了一个新的反应机理,即"催化-结晶诱导"机理.

  19. Synthesis of Well-Defined Polyethylene-Based 3-Miktoarm Star Copolymers and Terpolymers

    KAUST Repository

    Zhang, Zhen

    2016-03-25

    Novel polyethylene (PE)-based 3-miktoarm star copolymers A2B, (AB)2B and terpolymers (AC)2(BC) [A: PE; B, C: polystyrene (PS) or poly(methyl methacrylate) (PMMA)] were synthesized by combining boron chemistry, polyhomologation, and atom transfer radical polymerization (ATRP). 1,4-Pentadiene-3-yl 2-bromo-2-methylpropanoate was first synthesized followed by hydroboration with thexylborane to afford B-thexylboracyclanes, a multi-heterofunctional initiator with two initiating sites for polyhomologation and one for ATRP. After polyhomologation of dimethylsulfoxonium methylide the α,ω-dihydroxyl polyethylene (PE-OH)2-Br produced served as macroinitiator for the ATRP of styrene to afford (PE-OH)2-(PS-Br). Both (PE-OH)2-Br and (PE-OH)2-(PS-Br) were transformed to two new trifunctional macroinitiators (PE-Br)2-Br and (PE-Br)2-(PS-Br) through esterification reactions and used for the synthesis of (AB)2B and (AC)2(BC) 3-miktoarm star co/terpolymers. All intermediates and final products were characterized by 1H NMR, high temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The synthetic method is a general one and can be used for the synthesis of complex PE-based architectures by combination with other living/living-controlled polymerization techniques. © 2016 American Chemical Society.

  20. Comparative studies between mice molars and incisors are required to draw an overview of enamel structural complexity

    Directory of Open Access Journals (Sweden)

    MICHEL eGOLDBERG

    2014-09-01

    Full Text Available In the field of dentistry, the murine incisor has long been considered as an outstanding model to study amelogenesis. However, it clearly appears that enamel from wild type mouse incisors and molars presents several structural differences. In incisor, exclusively radial enamel is observed. In molars, enamel displays a high level of complexity since the inner part is lamellar whereas the outer enamel shows radial and tangential structures. Recently, the serotonin 2B receptor (5-HT2BR was shown to be involved in ameloblast function and enamel mineralization. The incisors from 5HT2BR knockout (KO mice exhibit mineralization defects mostly in the outer maturation zone and porous matrix network in the inner zone. In the molars, the mutation affects both secretory and maturation stages of amelogenesis since pronounced alterations concern overall enamel structures. Molars from 5HT2BR KO mice display reduction in enamel thickness, alterations of inner enamel architecture including defects in Hunter-Schreger Bands arrangements, and altered maturation of the outer radial enamel. Differences of enamel structure were also observed between incisor and molar from other KO mice depleted for genes encoding enamel extracellular matrix proteins.

  1. Interaction of ozone and carbon dioxide with polycrystalline potassium bromide and its atmospheric implication

    Science.gov (United States)

    Levanov, Alexander V.; Isaikina, Oksana Ya.; Maksimov, Ivan B.; Lunin, Valerii V.

    2017-03-01

    It has been discovered for the first time that gaseous ozone in the presence of carbon dioxide and water vapor interacts with crystalline potassium bromide giving gaseous Br2 and solid salts KHCO3 and KBrO3. Molecular bromine and hydrocarbonate ion are the products of one and the same reaction described by the stoichiometric equation 2KBr(cr.) + O3(gas) + 2CO2(gas) + H2O(gas) → 2KHCO3(cr.) + Br2(gas) + O2(gas). The dependencies of Br2, KHCO3 and KBrO3 formation rates on the concentrations of O3 and CO2, humidity of initial gas mixture, and temperature have been investigated. A kinetic scheme has been proposed that explains the experimental regularities found in this work on the quantitative level. According to the scheme, the formation of molecular bromine and hydrocarbonate is due to the reaction between hypobromite BrO-, the primary product of bromide oxidation by ozone, with carbon dioxide and water; bromate results from consecutive oxidation of bromide ion by ozone Br- → +O3 , -O2 BrO- → +O3 , -O2 BrO2- → +O3, -O2 BrO3- .

  2. Depalmitoylation preferentially downregulates AMPA induced Ca2+ signaling and neurotoxicity in motor neurons.

    Science.gov (United States)

    Krishnamurthy, Karthik; Mehta, Bhupesh; Singh, Mahendra; Tewari, Bhanu P; Joshi, Preeti G; Joshi, Nanda B

    2013-09-05

    Excessive activation of AMPA receptor has been implicated in motor neuron degeneration in amyotrophic lateral sclerosis (ALS). However, it is not clear why motor neurons are preferentially sensitive to AMPA receptor mediated excessive [Ca(2+)]i rise and excitotoxicity. In the present study we examined whether palmitoylation regulates Ca(2+) permeability of AMPA receptor and excitotoxicity in cultured spinal cord neurons. We adapted chronic 2-bromopalmitate (2-BrP) treatment to achieve depalmitoylation and examined its effect on the cytotoxicity in spinal cord neurons exposed to AMPA. The change in AMPA induced signaling and cytotoxicity in motor neurons and other spinal neurons under identical conditions of exposure to AMPA was studied. 2-BrP treatment inhibited AMPA induced rise in [Ca(2+)]i and cytotoxicity in both types of neurons but the degree of inhibition was significantly higher in motor neurons as compared to other spinal neurons. The AMPA induced [Na(+)]i rise was moderately affected in both type of neurons on depalmitoylation. Depalmitoylation reduced the expression levels of AMPA receptor subunits (GluR1 and GluR2) and also PSD-95 but stargazin levels remained unaffected. Our results demonstrate that 2-BrP attenuates AMPA receptor activated Ca(2+) signaling and cytotoxicity preferentially in motor neurons and suggest that AMPA receptor modulation by depalmitoylation could play a significant role in preventing motor neuron degeneration. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Control of Bromate and THM Precursors Using Ozonation Combined System

    Institute of Scientific and Technical Information of China (English)

    SHU-GUANG XIE; DONG-WEN SHI; DONG-HUI WEN; RUI WANG; DAN-LI XI

    2007-01-01

    Objective To investigate the feasibility of reducing THM precursors and controlling bromate taste and odor in drinking water taken from the Yellow River by an ozonation combined system. Methods The appropriate ozone dosage was determined,and then the changes of TOC,UV254 and THM formation potential(THMFP)in the combined system were evaluated. Results One mg/L ozone could effectively remove taste and odor and meet the maximum allowable bromate level in drinking water.The pre-ozonation increased THMFP,but the conventional treatment system could effectively reduce the odor.The bio-ceramic filter could partly reduce CHCI3FP,but sometimes might increase CHCI2BrFP and CHCIBr2FP.The biological activated carbon(BAC)filter could effectively reduce CHCI3FP and CHCI2BrFP,but increase CHCIBr2FP.Compared with other filters.the fresh activated carbon(FAC)filter performed better in reducing THMFP and even reduced CHCIBrzFP.Conclusion The combined system can effectively reduce taste,odor,CHCI3FP,and CHCI2BrFP and also bring bromate under control.

  4. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jun Woo Park

    2016-02-01

    Full Text Available The regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU, for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems.

  5. Synthesis, characterization and theoretical study of a new asymmetrical tripodal amine containing morpholine moiety

    Directory of Open Access Journals (Sweden)

    Majid Rezaeivala

    2016-11-01

    Full Text Available A new asymmetrical tripodal amine, [H3L2]Br3 containing morpholine moiety was prepared from reacting of one equivalent of N-(3-aminopropylmorpholine and two equivalents of tosylaziridine, followed by detosylation with HBr/CH3COOH. The products were characterized by various spectroscopic methods such as FAB-MS, elemental analysis, 1H and 13C NMR spectroscopy. The crystal structure of the hydrobromide salt of the latter amine, [H3L2]Br3, was also determined. For triprotonated form of the ligand L2 we can consider several microspecies and/or conformers. A theoretical study at B3LYP/6-31G∗∗ level of theory showed that the characterized microspecies is the most stable microspecies for the triprotonated form of the ligand. It was shown that the experimental NMR data for [H3L2]Br3 in solution have good correlation with the corresponding calculated data for the most stable microspecies of [H3L2]3+ in the gas phase.

  6. catena-Poly[di-μ3-bromido-bis­[(1-ethyl-1H-imidazole-κN 3)disilver(I)

    Science.gov (United States)

    Wang, Zhiguo; Bian, Qingquan; Guo, Ying

    2013-01-01

    The asymmetric unit of the title coordination complex, [Ag2Br2(C5H8N2)2]n, comprises a monodentate 1-ethyl­imida­zole ligand, an Ag+ cation and a μ3-bridging Br− anion, giving a distorted tetra­hedral AgNBr3 stereochemistry about the Ag+ cation [Ag—N = 2.247 (2) Å and Ag—Br = 2.7372 (4)–2.7523 (4) Å]. Two bridging bromide anions generate the dimeric [Ag2Br2(C5H8N)2] repeat unit [Ag⋯Ag = 3.0028 (5) Å], while a third Br− anion links the units through corner sharing in an inversion-related Ag2Br2 association [Ag⋯Ag = 3.0407 (4) Å], generating a one-dimensional ribbon step-polymer structure, extending along the c axis. PMID:24046580

  7. Far infrared laser magnetic resonance spectroscopy of free radicals

    CERN Document Server

    Liu, Y

    1996-01-01

    determine the vibrational dependence of all the major molecular parameters. Several v=1 parameters have been determined for the first time. The results constitute the definitive parameters for the v=1 state of CF. Finally, the FIR LMR spectra of CH sub 2 Br, the first high resolution spectra of this radical in the gas phase, are described in Chapter 6. Due to the complexity of the spectra and the lack of spectroscopic information from other high resolution techniques, the CH sub 2 Br spectra have not yet been completely assigned and analysed. However, this study did allow the determination of the (B+C) value of the radical. In this dissertation both theoretical and experimental aspects of FIR LMR spectroscopy are discussed with particular emphasis on the radicals CF and CH sub 2 Br. Chapter 1 reviews the development and salient features of LMR. After a discussion of the basic concepts and principles of LMR in Chapter 2, Chapter 3 gives a detailed description of the Cambridge FIR LMR spectrometer used to searc...

  8. Relative reactivities of halogen-substituted substrates (R-Br, R-Cl) toward the halophilic attack by a carbanion

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Relative reactivities of bromine-substituted substrates (R-Br) or chlorine-substituted substrates (R-Cl) toward bromophilic or chlorophilic attack by a carbanion have been evaluated by the intermolecular competition kinetics. Relative reactivity orders are CF3CFBr2 >CF3CBr3≥CBr4>CHBr3>CF3CFBrCF2Br>CF2Br2>BrCF2CF2Br>BrCH2CO2Et≥BrCF2CFHBr>CH2Br2 > BrCH2CH2Br, and Cl3CNO2>Cl3CCN>Cl3CCOPh >cyclo-C5Cl6>Cl3CCOCl>CCl3CF2Cl>CCl3CF3≥CCl4>CCl3CCl3≥CCl3(CF2)2Cl>Cl3CCOCCl3>CCl3(CF2)6Cl>Cl3CCO2Et>Cl3CF >Cl3CPh>Cl3CCH2O2CCH3.

  9. Pyrazolato metal complexes: synthesis, characterization and X-ray crystal structures of rhenium(I) derivaties

    Energy Technology Data Exchange (ETDEWEB)

    Ardizzoia, G.A; LaMonica, G.; Maspero, A. [Milan Univ. (Italy). Dipt. di Chimica Inorganica, Metallorganica e Analitica; Moret, M.; Masciocchi, N. [Milan Univ. (Italy). Dipt. di Chimica Strutturale e Stereochimica Inorganica

    1998-10-01

    The mononuclear complexes [Re(CO){sub 3}(Hpz){sub 2}Br] (1) and [Re(CO){sub 3}(Hdmpz){sub 2}Br] (2) were obtained by treating [Re(CO){sub 5}Br] with pyrazole (Hpz) or 3,5-dimethylpyrazole (Hdmpz). Complex 1 reacted with triethylamine affording a mixture of the ionic dinuclear derivative (Et{sub 3}NH)[Re{sub 2}(CO){sub 6}(pz){sub 2}Br] (3) and of the mononuclear species [Re(CO){sub 3}(Hpz){sub 2}(pz)] (4). Complex 4 was obtained in a pure form by carrying out the reaction in the presence of excess free pyrazole. Treatment of 4 with pyridine afforded the [Re(CO){sub 3}(py)(Hpz)(pz)] species (6). The analogues of 4 and 6 with Hdmpz, i.e. [Re(CO){sub 3}(Hdmpz){sub 2}(dmpz)] (7) and [Re(CO){sub 3}(py)(Hdmpz)(dmpz)] (8) were also synthesized. All species were characterized in solution by {sup 1}H-NMR spectroscopy, while the crystal structures of complexes 1, 3, 4 and 6 were determined by single-crystal X-ray diffraction analysis. The [(CO){sub 3}Re({mu}-pz){sub 2}({mu}-Br)Re(CO){sub 3}]{sup -} anion represents the first structurally characterized species containing rhenium(I) atoms bridged by mu-pyrazolate ligands. (orig.)

  10. Bromidobis[3-(1H-pyrazol-1-yl-κN2propionamide-κO]copper(II bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Thomas Wagner

    2012-10-01

    Full Text Available The title copper(II N-pyrazolylpropanamide (PPA complex, [CuBr(PPA2]Br, was obtained in 78% yield by treatment of CuBr2 with an excess of the ligand in methanol. Crystallization from the mother liquid afforded the title compound, i.e. the methanol solvate [CuBr(C6H9N3O2]Br·CH3OH or [CuBr(PPA2]Br·MeOH, as bright green crystals. In the solid state, the title salt comprises isolated [CuBr(PPA2]+ cations, separated bromide ions and methanol of crystallization. In the cation, the central CuII ion is coordinated by two N,O-chelating PPA ligands and one Br− ion. The coordination geometry around the CuII ion is distorted trigonal–bipyramidal with the bromide ligand and the amide O atoms occupying the equatorial positions [Cu—Br = 2.4443 (4 Å; Cu—O = 2.035 (2 and 2.179 (2 Å], while the pyrazole N atoms coordinate in the axial positions [Cu—N = 1.975 (2 and 1.976 (2 Å]. In the crystal, the three constituents are linked by N—H...Br, O—H...Br, and N—H...O hydrogen bonds, forming a three-dimensional network.

  11. A role for aberrant protein palmitoylation in FFA-induced ER stress and β-cell death.

    Science.gov (United States)

    Baldwin, Aaron C; Green, Christopher D; Olson, L Karl; Moxley, Michael A; Corbett, John A

    2012-06-01

    Exposure of insulin-producing cells to elevated levels of the free fatty acid (FFA) palmitate results in the loss of β-cell function and induction of apoptosis. The induction of endoplasmic reticulum (ER) stress is one mechanism proposed to be responsible for the loss of β-cell viability in response to palmitate treatment; however, the pathways responsible for the induction of ER stress by palmitate have yet to be determined. Protein palmitoylation is a major posttranslational modification that regulates protein localization, stability, and activity. Defects in, or dysregulation of, protein palmitoylation could be one mechanism by which palmitate may induce ER stress in β-cells. The purpose of this study was to evaluate the hypothesis that palmitate-induced ER stress and β-cell toxicity are mediated by excess or aberrant protein palmitoylation. In a concentration-dependent fashion, palmitate treatment of RINm5F cells results in a loss of viability. Similar to palmitate, stearate also induces a concentration-related loss of RINm5F cell viability, while the monounsaturated fatty acids, such as palmoleate and oleate, are not toxic to RINm5F cells. 2-Bromopalmitate (2BrP), a classical inhibitor of protein palmitoylation that has been extensively used as an inhibitor of G protein-coupled receptor signaling, attenuates palmitate-induced RINm5F cell death in a concentration-dependent manner. The protective effects of 2BrP are associated with the inhibition of [(3)H]palmitate incorporation into RINm5F cell protein. Furthermore, 2BrP does not inhibit, but appears to enhance, the oxidation of palmitate. The induction of ER stress in response to palmitate treatment and the activation of caspase activity are attenuated by 2BrP. Consistent with protective effects on insulinoma cells, 2BrP also attenuates the inhibitory actions of prolonged palmitate treatment on insulin secretion by isolated rat islets. These studies support a role for aberrant protein palmitoylation as a

  12. Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers.

    Science.gov (United States)

    Vinogradova, Katerina A; Krivopalov, Viktor P; Nikolaenkova, Elena B; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Boguslavsky, Evgenii G; Bushuev, Mark B

    2016-01-14

    Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine () and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (), and a series of mixed-valence copper(i,ii) halide complexes, [Cu(L(2))2Br]2[Cu2Br4] (), [Cu(L(2))2Cl][CuCl2] (), and [Cu2L(3)Br3]n (), have been synthesized. The complex [Cu(L(2))2Br]2[Cu2Br4] was prepared by the reaction of with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L(2))2Cl][CuCl2], was synthesized by the reaction between , CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand acts as a chelating one. In the structures of the complexes [Cu(L(2))2Br]2[Cu2Br4] and [Cu(L(2))2Cl][CuCl2] the Cu(2+) ion is in the cationic part of the complex whereas the Cu(+) ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [Cu2L(3)Br3]n is to react CuBr2 with in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [Cu2L(3)Br3]n the ligand shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of and (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N(1) pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [Cu2L(3)Br3]n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(i,ii) compounds. The ligands and show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [Cu2L(3)Br3]n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R

  13. Delivery of halogenated very short-lived substances from the west Indian Ocean to the stratosphere during the Asian summer monsoon

    Science.gov (United States)

    Fiehn, Alina; Quack, Birgit; Hepach, Helmke; Fuhlbrügge, Steffen; Tegtmeier, Susann; Toohey, Matthew; Atlas, Elliot; Krüger, Kirstin

    2017-06-01

    Halogenated very short-lived substances (VSLSs) are naturally produced in the ocean and emitted to the atmosphere. When transported to the stratosphere, these compounds can have a significant influence on the ozone layer and climate. During a research cruise on RV Sonne in the subtropical and tropical west Indian Ocean in July and August 2014, we measured the VSLSs, methyl iodide (CH3I) and for the first time bromoform (CHBr3) and dibromomethane (CH2Br2), in surface seawater and the marine atmosphere to derive their emission strengths. Using the Lagrangian particle dispersion model FLEXPART with ERA-Interim meteorological fields, we calculated the direct contribution of observed VSLS emissions to the stratospheric halogen burden during the Asian summer monsoon. Furthermore, we compare the in situ calculations with the interannual variability of transport from a larger area of the west Indian Ocean surface to the stratosphere for July 2000-2015. We found that the west Indian Ocean is a strong source for CHBr3 (910 pmol m-2 h-1), very strong source for CH2Br2 (930 pmol m-2 h-1), and an average source for CH3I (460 pmol m-2 h-1). The atmospheric transport from the tropical west Indian Ocean surface to the stratosphere experiences two main pathways. On very short timescales, especially relevant for the shortest-lived compound CH3I (3.5 days lifetime), convection above the Indian Ocean lifts oceanic air masses and VSLSs towards the tropopause. On a longer timescale, the Asian summer monsoon circulation transports oceanic VSLSs towards India and the Bay of Bengal, where they are lifted with the monsoon convection and reach stratospheric levels in the southeastern part of the Asian monsoon anticyclone. This transport pathway is more important for the longer-lived brominated compounds (17 and 150 days lifetime for CHBr3 and CH2Br2). The entrainment of CHBr3 and CH3I from the west Indian Ocean to the stratosphere during the Asian summer monsoon is lower than from previous

  14. Delivery of halogenated very short-lived substances from the west Indian Ocean to the stratosphere during the Asian summer monsoon

    Directory of Open Access Journals (Sweden)

    A. Fiehn

    2017-06-01

    Full Text Available Halogenated very short-lived substances (VSLSs are naturally produced in the ocean and emitted to the atmosphere. When transported to the stratosphere, these compounds can have a significant influence on the ozone layer and climate. During a research cruise on RV Sonne in the subtropical and tropical west Indian Ocean in July and August 2014, we measured the VSLSs, methyl iodide (CH3I and for the first time bromoform (CHBr3 and dibromomethane (CH2Br2, in surface seawater and the marine atmosphere to derive their emission strengths. Using the Lagrangian particle dispersion model FLEXPART with ERA-Interim meteorological fields, we calculated the direct contribution of observed VSLS emissions to the stratospheric halogen burden during the Asian summer monsoon. Furthermore, we compare the in situ calculations with the interannual variability of transport from a larger area of the west Indian Ocean surface to the stratosphere for July 2000–2015. We found that the west Indian Ocean is a strong source for CHBr3 (910 pmol m−2 h−1, very strong source for CH2Br2 (930 pmol m−2 h−1, and an average source for CH3I (460 pmol m−2 h−1. The atmospheric transport from the tropical west Indian Ocean surface to the stratosphere experiences two main pathways. On very short timescales, especially relevant for the shortest-lived compound CH3I (3.5 days lifetime, convection above the Indian Ocean lifts oceanic air masses and VSLSs towards the tropopause. On a longer timescale, the Asian summer monsoon circulation transports oceanic VSLSs towards India and the Bay of Bengal, where they are lifted with the monsoon convection and reach stratospheric levels in the southeastern part of the Asian monsoon anticyclone. This transport pathway is more important for the longer-lived brominated compounds (17 and 150 days lifetime for CHBr3 and CH2Br2. The entrainment of CHBr3 and CH3I from the west Indian Ocean to the stratosphere during the

  15. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS): linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    Science.gov (United States)

    Hossaini, R.; Patra, P. K.; Leeson, A. A.; Krysztofiak, G.; Abraham, N. L.; Andrews, S. J.; Archibald, A. T.; Aschmann, J.; Atlas, E. L.; Belikov, D. A.; Bönisch, H.; Carpenter, L. J.; Dhomse, S.; Dorf, M.; Engel, A.; Feng, W.; Fuhlbrügge, S.; Griffiths, P. T.; Harris, N. R. P.; Hommel, R.; Keber, T.; Krüger, K.; Lennartz, S. T.; Maksyutov, S.; Mantle, H.; Mills, G. P.; Miller, B.; Montzka, S. A.; Moore, F.; Navarro, M. A.; Oram, D. E.; Pfeilsticker, K.; Pyle, J. A.; Quack, B.; Robinson, A. D.; Saikawa, E.; Saiz-Lopez, A.; Sala, S.; Sinnhuber, B.-M.; Taguchi, S.; Tegtmeier, S.; Lidster, R. T.; Wilson, C.; Ziska, F.

    2016-07-01

    The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry-climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993-2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements - including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model-measurement correlation (r ≥ 0.7) at most sites. In a given model, the absolute model-measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations

  16. Dielectric barrier discharge molecular emission spectrometer as multichannel GC detector for halohydrocarbons.

    Science.gov (United States)

    Li, Wei; Zheng, Chengbin; Fan, Guangyu; Tang, Li; Xu, Kailai; Lv, Yi; Hou, Xiandeng

    2011-07-01

    A novel microplasma molecular emission spectrometer based on an atmospheric pressure dielectric barrier discharge (DBD) is described and further used as a promising multichannel GC detector for halohydrocarbons. The plasma is generated in a DBD device consisting of an outer electrode (1.2 mm in diameter) and an inner electrode (1.7 mm in diameter) within a small quartz tube (3.0 mm i.d. × 5.0 mm o.d. × 50 mm), wherein analyte molecules are excited by the microplasma to generate molecular emission. Therefore, the analytes are selectively and simultaneously detected with a portable charge-coupled device (CCD) via multichannel detection of their specific emission lines. The performance of this method was evaluated by separation and detection of a model mixture of chlorinated hydrocarbons (CHCl(3) and CCl(4)), brominated hydrocarbons (CH(2)Br(2) and CH(2)BrCH(2)Br), and iodinated hydrocarbons (CH(3)I and (CH(3))(2)CHI) undergoing GC with the new detector. The completely resolved identification of the tested compounds was achieved by taking advantages of both chromatographic and spectral resolution. Under the optimized conditions with the CCD spectrometer set at 258, 292, and 342 nm channels for determination of chlorinated hydrocarbons, brominated hydrocarbons, and iodinated hydrocarbons, respectively, this detector with direct injection provided detection limits of 0.07, 0.06, 0.3, 0.04, 0.05, and 0.02 μg mL(-1) for CCl(4), CHCl(3), CH(2)Cl(2), CH(3)I, CH(3)CH(2)I, and (CH(3))(2)CHI, respectively.

  17. 20th century trends and budget implications of chloroform and related tri-and dihalomethanes inferred from firn air

    Directory of Open Access Journals (Sweden)

    D. R. Worton

    2006-01-01

    Full Text Available Four trihalomethane (THM; CHCl3, CHBrCl2, CHBr2Cl and CHBr3 and two dihalomethane (DHM; CH2BrCl and CH2Br2 trace gases have been measured in air extracted from polar firn collected at the North Greenland Icecore Project (NGRIP site. CHCl3 was also measured in firn air from Devon Island (DI, Canada, Dronning Maud Land (DML, Antarctica and Dome Concordia (Dome C, Antarctica. All of these species are believed to be almost entirely of natural origin except for CHCl3 where anthropogenic sources have been reported to contribute ~10% to the global burden. A 2-D atmospheric model was run for CHCl3 using reported emission estimates to produce historical atmospheric trends at the firn sites, which were then input into a firn diffusion model to produce concentration depth profiles that were compared against the measurements. The anthropogenic emissions were modified in order to give the best model fit to the firn data at NGRIP, Dome C and DML. As a result, the contribution of CHCl3 from anthropogenic sources, mainly from pulp and paper manufacture, to the total chloroform budget appears to have been considerably underestimated and was likely to have been close to ~50% at the maximum in atmospheric CHCl3 concentrations around 1990, declining to ~29% at the beginning of the 21st century. We also show that the atmospheric burden of the brominated THM's in the Northern Hemisphere have increased over the 20th century while CH2Br2 has remained constant over time implying that it is entirely of natural origin.

  18. Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

    KAUST Repository

    Huang, Jian

    2013-10-07

    Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2LBBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H 2LCBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5- lutidinium bromide), the linear [MnIIIMnII 2L2X4]+ building block has been assembled into one-dimensional coordination networks: [MnIIIMn II 2(LA)2(Br)4(CH 3OH)4(N3)]·((C2H 5)2O)1.25 (2∞), [MnIIIMn II 2(LB)2(Br)4(C 2H5OH)(CH3OH)(H2O) 2(N3)]·(H2O)0.25 (3∞), and [MnIIIMnII 2(LC) 2(Cl)3.8(Br)0.2(C2H 5OH)3(CH3OH)(N3)] (4∞). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn3]-based materials are reported. © 2013 American Chemical Society.

  19. Convective Transport of Very-short-lived Bromocarbons to the Stratosphere

    Science.gov (United States)

    Liang, Qing; Atlas, Elliot Leonard; Blake, Donald Ray; Dorf, Marcel; Pfeilsticker, Klaus August; Schauffler, Sue Myhre

    2014-01-01

    We use the NASA GEOS Chemistry Climate Model (GEOSCCM) to quantify the contribution of two most important brominated very short-lived substances (VSLS), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLS from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the Western Pacific warm pool, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies 8 ppt total bromine to the base of the Tropical Tropopause Layer (TTL, 150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (7.8-8.4 ppt) in the above active convective lofting regions. Of the total 8 ppt VSLS-originated bromine that enters the base of TTL at 150 hPa, half is in the form of source gas injection (SGI) and half as product gas injection (PGI). Only a small portion (< 10%) the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On global and annual average, CHBr3 and CH2Br2, together, contribute 7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep convection strength between maximum and minimum convection conditions can introduce a 2.6 pptv uncertainty in the contribution of VSLS to inorganic bromine in the stratosphere (BryVSLS). Contrary to the conventional wisdom, minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, thus a significant increase in PGI (2-3 ppt), greatly exceeds the relative minor decrease in SGI (a few 10ths ppt.

  20. Superconductivity and magnetic field induced spin density waves in the (TMTTF)2X family

    Science.gov (United States)

    Balicas, L.; Behnia, K.; Kang, W.; Canadell, E.; Auban-Senzier, P.; Jérome, D.; Ribault, M.; Fabre, J. M.

    1994-10-01

    We report magnetotransport measurements in the quasi one dimensional (Q-1-D) organic conductor (TMTTF)2Br at pressures up to 26 kbar, clown to 0.45 K in magnetic fields up to 19 T along the c^{ast} direction. It is found that a superconducting ground state is stabilized under 26 kbar at T_C = 0.8 K. No magnetic field induced spin density wave (FISDW) transitions are observed below 19T unlike other Q-1-D superconductors pertaining to the selenium series. The computed amplitude of the interchain coupling along transverse directions is unable to explain the missing; FISDW instability.

  1. Crystal electric field and dimer splitting in Cs{sub 3}Er{sub 2}X{sub 9} (X=Cl, Br)

    Energy Technology Data Exchange (ETDEWEB)

    Allenspach, P.; Furrer, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Guedel, H.U.; Furer, N. [Bern Univ. (Switzerland); Buettner, H. [Institut Max von Laue - Paul Langevin, 75 - Paris (France)

    1997-09-01

    Inelastic neutron scattering technique was used to measure the crystal electric field (CEF) splitting of Cs{sub 3}Er{sub 2}Cl{sub 9}. Besides a low lying magnetic excitation at around 2 meV all the other transitions are in agreement with CEF transitions found in optical measurements. Similar additional low-lying magnetic transitions were found in Cs{sub 3}Er{sub 2}Br{sub 9}. While excitations of the rare-earth dimers most likely play a role, the size of the splitting and its absence in optical spectra still remain a mystery. (author) 2 figs., 5 refs.

  2. Properties and ATRP activity of copper complexes with substituted tris(2-pyridylmethyl)amine-based ligands.

    Science.gov (United States)

    Kaur, Aman; Ribelli, Thomas G; Schröder, Kristin; Matyjaszewski, Krzysztof; Pintauer, Tomislav

    2015-02-16

    Synthesis, characterization, electrochemical studies, and ATRP activity of a series of novel copper(I and II) complexes with TPMA-based ligands containing 4-methoxy-3,5-dimethyl-substituted pyridine arms were reported. In the solid state, Cu(I)(TPMA*(1))Br, Cu(I)(TPMA*(2))Br, and Cu(I)(TPMA*(3))Br complexes were found to be distorted tetrahedral in geometry and contained coordinated bromide anions. Pseudo-coordination of the aliphatic nitrogen atom to the copper(I) center was observed in Cu(I)(TPMA*(2))Br and Cu(I)(TPMA*(3))Br complexes, whereas pyridine arm dissociation occurred in Cu(I)(TPMA*(1))Br. All copper(I) complexes with substituted TPMA ligands exhibited a high degree of fluxionality in solution. At low temperature, Cu(I)(TPMA*(1))Br was found to be symmetrical and monomeric, while dissociation of either unsubstituted pyridine and/or 4-methoxy-3,5-dimethyl-substituted pyridine arms was observed in Cu(I)(TPMA*(2))Br and Cu(I)(TPMA*(3))Br. On the other hand, the geometry of the copper(II) complexes in the solid state deviated from ideal trigonal bipyramidal, as confirmed by a decrease in τ values ([Cu(II)(TPMA*(1))Br][Br] (τ = 0.92) > [Cu(II)(TPMA*(3))Br][Br] (τ = 0.77) > [Cu(II)(TPMA*(2))Br][Br] (τ = 0.72)). Furthermore, cyclic voltammetry studies indicated a nearly stepwise decrease (ΔE ≈ 60 mV) of E1/2 values relative to SCE (TPMA (-240 mV) > TPMA*(1) (-310 mV) > TPMA*(2) (-360 mV) > TPMA*(3) (-420 mV)) on going from [Cu(II)(TPMA)Br][Br] to [Cu(II)(TPMA*(3))Br][Br], confirming that the presence of electron-donating groups in the 4 (-OMe) and 3,5 (-Me) positions of the pyridine rings in TPMA increases the reducing ability of the corresponding copper(I) complexes. This increase was mostly the result of a stronger influence of substituted TPMA ligands toward stabilization of the copper(II) oxidation state (log β(I) = 13.4 ± 0.2, log β(II) = 19.3 (TPMA*(1)), 20.5 (TPMA*(2)), and 21.5 (TPMA*(3))). Lastly, ARGET ATRP kinetic studies show that with

  3. Drug: D01453 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D01453 Drug Caffeine hydrate (JP16); Caffeine monohydrate; Caffeine (TN) C8H10N4O2....:br08301] 2 Agents affecting individual organs 21 Cardiovascular agents 211 Cardiotonics 2115 Caffeines D01453 Caffeine...M N06 PSYCHOANALEPTICS N06B PSYCHOSTIMULANTS, AGENTS USED FOR ADHD AND NOOTROPICS N06BC Xanthine derivatives N06BC01 Caffeine... D01453 Caffeine hydrate (JP16) Target-based classification of d...rugs [BR:br08310] G Protein-coupled receptors Rhodopsin family Adenosine adenosine A1 receptor [HSA:134] [KO:K04265] Caffeine

  4. Dinuclear Silver(Ⅰ) Complex Based on 1-Picolyl-3-propylbenzimidazolium Salt: Crystal Structure and Weak Interactions

    Institute of Scientific and Technical Information of China (English)

    XIAO Shan; GE Shu-Sheng; WANG Xiu-Guang; LIU Qing-Xiang

    2012-01-01

    1-Picolyl-3-propylbenzimidazolium bromide (LBr) was prepared from benzimida- zole by alkylation with 2-chloromethyl-pyridine in the presence of NaH, followed by quaternization with 1-bromopropane. Ligand LBr was treated with AgBr in CH2Cl2 to afford a dinuclear silver(I) complex L2Ag2Br4 (1). In complex 1, a 2-D supramolecular layer is formed through two types of π-π stacking interactions. Fluorescent emission spectra of ligand LBr and complex 1 are described.

  5. Di-μ-bromido-bis[bromido(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′mercury(II

    Directory of Open Access Journals (Sweden)

    Amin Ebadi

    2008-11-01

    Full Text Available The asymmetric unit of the title compound, [Hg2Br4(C12H12N22], contains one half-molecule. The HgII atom is five-coordinated in a trigonal–bipyramidal configuration by two N atoms from the chelating 4,4′-dimethyl-2,2′-bipyridine ligand, two bridging Br and one terminal Br atom, leading to a centrosymmetric dimeric molecule. There is a π–π contact between the pyridine rings [centroid-to-centroid distance = 3.756 (5 Å].

  6. Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

    A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (LH2Br2) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4′-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer.

  7. Electroactive materials for rechargeable batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Huiming; Amine, Khalil; Abouimrane, Ali

    2016-10-25

    A secondary battery including a cathode having a primary cathode active material and an alkaline source material selected from the group consisting of Li.sub.2O, Li.sub.2O.sub.2, Li.sub.2S, LiF, LiCl, Li.sub.2Br, Na.sub.2O, Na.sub.2O.sub.2, Na.sub.2S, NaF, NaCl, and a mixture of any two or more thereof; an anode having an anode active material; an electrolyte; and a separator.

  8. Phase diagram of the CsBr-CaBr2 system

    Institute of Scientific and Technical Information of China (English)

    BAO Xinhua; CHEN Nianyi; LU Wencong; CHENG Zhixuan; LUO Yunyun; LU Weiying; XIA Yiben

    2006-01-01

    The phase diagram of the CsBr-CaBr2 system was re-determined by using differential thermal analysis and high temperature and room temperature X-ray diffraction analysis. It is concluded that there are three intermediate compounds in this system: a congruently melting compound, CsCaBr3, with a melting point of 823℃ and two incongruently melting compounds, Cs2CaBr4 and Cs3Ca2Br7, whose peritectic points being 597℃ and 635℃, respectively. X-ray diffraction analysis indicated that compound CsCaBr3 is of slightly distorted perovskite structure.

  9. Dihydronium hexakis[bromido/chlorido(0.75/0.25]dicadmate(II–triphenylphosphine oxide (1/6

    Directory of Open Access Journals (Sweden)

    Kong Mun Lo

    2009-07-01

    Full Text Available In the salt, (H3O2[Cd2Br4.5Cl1.5]·6C18H15OP, the hydronium cation forms short O—H...O hydrogen bonds to the O atoms of the triphenylphosphine oxide units. The centrosymmetric dinuclear anion has two halide atoms functioning in a bridging mode, which confers tetrahedral coordination to the Cd atom. The three independent halide atoms are each a mixture of bromide and chloride; the occupancies of the Br atoms are 0.6434 (11, 0.7468 (11 and 0.8598 (11.

  10. Synthesis, electronic structure, and magnetism of [Ni(6-Mes)2]+: a two-coordinate nickel(I) complex stabilized by bulky N-heterocyclic carbenes.

    Science.gov (United States)

    Poulten, Rebecca C; Page, Michael J; Algarra, Andrés G; Le Roy, Jennifer J; López, Isidoro; Carter, Emma; Llobet, Antoni; Macgregor, Stuart A; Mahon, Mary F; Murphy, Damien M; Murugesu, Muralee; Whittlesey, Michael K

    2013-09-18

    The two-coordinate cationic Ni(I) bis-N-heterocyclic carbene complex [Ni(6-Mes)2]Br (1) [6-Mes =1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene] has been structurally characterized and displays a highly linear geometry with a C-Ni-C angle of 179.27(13)°. Density functional theory calculations revealed that the five occupied metal-based orbitals are split in an approximate 2:1:2 pattern. Significant magnetic anisotropy results from this orbital degeneracy, leading to single-ion magnet (SIM) behavior.

  11. Electroweak precision data and gravitino dark matter

    Indian Academy of Sciences (India)

    S Heinemeyer

    2007-11-01

    Electroweak precision measurements can provide indirect information about the possible scale of supersymmetry already at the present level of accuracy. We review present day sensitivities of precision data in mSUGRA-type models with the gravitino as the lightest supersymmetric particle (LSP). The 2 fit is based on , sin2 eff, ( - 2) BR( → ) and the lightest MSSM Higgs boson mass, ℎ. We find indications for relatively light soft supersymmetry-breaking masses, offering good prospects for the LHC and the ILC, and in some cases also for the Tevatron.

  12. catena-Poly[[[diaquacopper(II]-μ-2,2′-{[p-phenylenebis(oxymethylene]bis(pyridinium-3,1-diyl}diacetate] dibromide

    Directory of Open Access Journals (Sweden)

    Wei-Cheng Pan

    2010-06-01

    Full Text Available The title centrosymmetric coordination polymer, {[Cu(C22H20N2O6(H2O2]Br2}n, formed by the reaction of the flexible double betaine ligand 2,2′-{[p-phenylenebis(oxymethylene]bis(pyridine-3,1-diyl}diacetic acid with CuBr2, contains a Cu(II atom (overline1 symmetry which is surrounded by two water molecules and bridged by two anions in a square-planar coordination. In the crystal, polymeric zigzag chains are linked via O—H...Br interactions, forming a two-dimensional network extending parallel to (011.

  13. Coadsorption of organic cations and different anions at the solution/mercury and solution/air interface

    Energy Technology Data Exchange (ETDEWEB)

    Damaskin, B.B.; Gerovich, V.M.; Podgornaya, M.I.

    1986-07-01

    The adsorption of tetraethylammonium ions was studied in the presence of anions SO/sub 4//sup 2 -/, Br/sup -/, and I/sup -/ at the solution/mercury interface by measuring capillary curves, and at the solution/air interface by measuring the maximum pressure in air bubbles. It was concluded from the potential dependence of adsorption energy that two potentials of maximum adsorption exist in the case of TEA bromide and TEA iodide; they are associated with two different orientations of the ion pairs TEA cation-halide anion in the compact double-layer part.

  14. Convective transport of very-short-lived bromocarbons to the stratosphere

    Directory of Open Access Journals (Sweden)

    Q. Liang

    2014-01-01

    CH2Br2, together, contribute ∼7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep convection strength between maximum and minimum convection conditions can introduce a ∼2.6 pptv uncertainty in the contribution of VSLS to inorganic bromine in the stratosphere (BryVSLS. Contrary to the conventional wisdom, minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, thus a significant increase in PGI (2–3 ppt, greatly exceeds the relative minor decrease in SGI (a few 10ths ppt.

  15. Drug: D00487 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D00487 Drug Pyridostigmine bromide (JP16/USP/INN); Mestinon (TN) C9H13N2O2. Br 260....12 Agents affecting peripheral nervous system 123 Autonomic nervous system agents 1239 Others D00487 Pyridostigmine bromide...terases N07AA02 Pyridostigmine D00487 Pyridostigmine bromide (JP16/USP/INN) USP drug classification [BR:br08...302] Antimyasthenic Agents Parasympathomimetics Pyridostigmine D00487 Pyridostigmine bromide...esterase (AChE) [HSA:43] [KO:K01049] Pyridostigmine [ATC:N07AA02] D00487 Pyridostigmine bromide (JP16/USP/IN

  16. Drug: D02535 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D02535 Drug Timepidium bromide hydrate (JP16); Sesden (TN) C17H22NOS2. Br. H2O 417....9 Others D02535 Timepidium bromide hydrate (JP16) Anatomical Therapeutic Chemical (ATC) classification [BR:b...ry ammonium compounds A03AB19 Timepidium bromide D02535 Timepidium bromide hydrate (JP16) Target-based class...31 K04132 K04133] Timepidium bromide [ATC:A03AB19] D02535 Timepidium bromide hydrate (JP16) PubChem: 1739670

  17. Drug: D01228 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D01228 Drug Distigmine bromide (JP16/INN); Ubretid (TN) C22H32N4O4. 2Br 574.079 576...s system 123 Autonomic nervous system agents 1231 Quaternary ammoniums D01228 Distigmine bromide (JP16/INN) ...13 Agents affecting sensory organs 131 Ophthalmic agents 1312 Miotic agents D01228 Distigmine bromide...SYSTEM N07 OTHER NERVOUS SYSTEM DRUGS N07A PARASYMPATHOMIMETICS N07AA Anticholinesterases N07AA03 Distigmine D01228 Distigmine bromid

  18. Drug: D00995 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D00995 Drug Neostigmine bromide (JAN/USP/INN); Vagostigmin (TN) C12H19N2O2. Br 302....igmines D00995 Neostigmine bromide (JAN/USP/INN) Anatomical Therapeutic Chemical ...N07AA Anticholinesterases N07AA01 Neostigmine D00995 Neostigmine bromide (JAN/USP/INN) Target-based classifi...43] [KO:K01049] Neostigmine [ATC:N07AA01 S01EB06] D00995 Neostigmine bromide (JAN/USP/INN) CAS: 114-80-7 Pub

  19. 段階溶出法を用いた単一カラムイオンクロマトグラフィーにおける差クロマトグラム法の効果

    OpenAIRE

    綿谷, 敏彦; 早川, 和一; 能村, 京子; 宮崎, 元一

    1994-01-01

    The differential chromatogram method was useful to reduce large changes in background response in single column ion chromatography using stepwise elution. Cations (Na^+, K^+, Mg^ and Ca^) were separated on cation exchange column by stepwise elution using both 0.01 mM and 3.0 mM copper sulfate eluents and detected at 230 nm by indirect photometry. Anions (lactate, acetate, propionate, formate, citrate, Cl^-, NO_2^-, Br^-, NO_3^-, SO_4^, S_2O_3^ and I^-) were separated on an anion exchange colu...

  20. Effects of maturation, artery size, and chronic hypoxia on 5-HT receptor type in ovine cranial arteries.

    Science.gov (United States)

    Teng, G Q; Williams, J; Zhang, L; Purdy, R; Pearce, W J

    1998-09-01

    To test the hypothesis that variations in cerebrovascular reactivity to 5-HT among arteries of different size or type, during maturation, or during acclimatization to high altitude involve differences in serotonergic receptor subtype, we determined relative agonist potency orders and antagonist affinities in common carotid (Com), main branch middle cerebral (Main), and second branch middle cerebral (2BR) arteries from term fetal lambs and nonpregnant adult sheep acclimatized at sea level or at an altitude of 3,820 m for approximately 110 days. In normoxic adult Com segments, agonist potency order was 5-hydroxytryptamine (5-HT) > 5-carboxamidotryptamine (5-CT) >/= 8-hydroxy-2(di-n-propylamino)tetraline (8-OH-DPAT); sumatriptan (Suma) produced no contractile response; and antagonist dissociation constant (pKb) values were 9.4 and 9.5 for ketanserin against 5-HT and 5-CT, 7.5 for GR-127935 against 5-HT, and 7.2 for SB-206553 against 5-HT. In normoxic adult Main segments, agonist potency order was 5-HT > 5-CT >/= Suma >/= DPAT, and pKb values were 9.1 and 9.2 for ketanserin against 5-HT and 5-CT and 7.4 and 8.5 for GR-127935 against 5-HT and Suma, respectively. In the 2BR segments from normoxic adults, agonist potency order was 5-CT > 5-HT > Suma > DPAT and pKb values were 7.4 and 7.2 for ketanserin against 5-HT and 5-CT and 10.0 and 8.7 for GR-127935 against 5-HT and Suma, respectively. Compared with normoxic adults, none of these values were significantly different in hypoxic adults and in fetuses only the pKb values for ketanserin against 5-HT in the 2BR segments (8.8) were greater. From these results we propose that the ratio of 5-HT2 to 5-HT1 receptors is greatest in the Com and decreases progressively to its smallest values in 2BR or smaller segments. Because this gradient appears stable and relatively resistant to the effects of maturation and chronic hypoxia, changes in reactivity associated with these perturbations may involve alterations in receptor density

  1. Drug: D01862 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D01862 Drug Pitavastatin calcium (JAN); NK 104; Livalo (TN) (C25H23FNO4)2. Ca 880.2...:br08301] 2 Agents affecting individual organs 21 Cardiovascular agents 218 Hyperlipidemia agents 2189 Others D01862 Pita...10AA HMG CoA reductase inhibitors C10AA08 Pitavastatin D01862 Pitavastatin calcium (JAN) USP drug classifica...tion [BR:br08302] Cardiovascular Agents Dyslipidemics, HMG CoA Reductase Inhibitors Pita...Oxidoreductases hydroxymethylglutaryl coenzyme A (HMG-CoA) reductase [HSA:3156] [KO:K00021] Pitavastatin [ATC:C10AA08] D01862 Pita

  2. Structural, spectroscopic, and multiconfigurational quantum chemical investigations of the electron-rich metal-metal triple-bonded Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) complexes.

    Science.gov (United States)

    Poineau, Frederic; Forster, Paul M; Todorova, Tanya K; Gagliardi, Laura; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2010-07-19

    The compounds Tc(2)Cl(4)(PMe(3))(4) and Tc(2)Br(4)(PMe(3))(4) were formed from the reaction between (n-Bu(4)N)(2)Tc(2)X(8) (X = Cl, Br) and trimethylphosphine. The Tc(II) dinuclear species were characterized by single-crystal XRD, UV-visible spectroscopy, and cyclic voltammetry techniques, and the results are compared to those obtained from density functional theory and multiconfigurational (CASSCF/CASPT2) quantum chemical studies. The compound Tc(2)Cl(4)(PMe(3))(4) crystallizes in the monoclinic space group C2/c [a = 17.9995(9) A, b = 9.1821(5) A, c = 17.0090(9) A, beta = 115.4530(10) degrees ] and is isostructural to M(2)Cl(4)(PMe(3))(4) (M = Re, Mo, W) and to Tc(2)Br(4)(PMe(3))(4). The metal-metal distance (2.1318(2) A) is similar to the one found in Tc(2)Br(4)(PMe(3))(4) (2.1316(5) A). The calculated molecular structures of the ground states are in excellent agreement with the structures determined experimentally. Calculations of effective bond orders for Tc(2)X(8)(2-) and Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) indicate stronger pi bonds in the Tc(2)(4+) core than in Tc(2)(6+) core. The electronic spectra were recorded in benzene and show a series of low intensity bands in the range 10 000-26 000 cm(-1). Assignment of the bands as well as computing their excitation energies and intensities were performed at both TD-DFT and CASSCF/CASPT2 levels of theory. Calculations predict that the lowest energy band corresponds to the delta* --> sigma* transition, the difference between calculated and experimental values being 228 cm(-1) for X = Cl and 866 cm(-1) for X = Br. The next bands are attributed to delta* --> pi*, delta --> sigma*, and delta --> pi* transitions. The cyclic voltammograms exhibit two reversible waves and indicate that Tc(2)Br(4)(PMe(3))(4) exhibits more positive oxidation potentials than Tc(2)Cl(4)(PMe(3))(4.) This phenomenon is discussed and ascribed to stronger metal (d) to halide (d) back bonding in the bromo complex. Further analysis indicates that Tc

  3. Atmospheric volatile organic compound measurements: Distributions and effects on air quality in coastal marine, rural and remote continental environments

    Science.gov (United States)

    Zhou, Yong

    A detailed description of the analytical methods employed for whole air sampling and analysis of atmospheric volatile organic compounds is presented. The system described in this thesis produced high precision measurements for a large suite of nonmethane hydrocarbons, halocarbons, and alkyl nitrates, from part per billion by volume (ppbv) to part per trillion by volume (pptv) levels. The measurement precision for most gases ranged from 1-10%. Results from two subsequent field campaigns (2002 and 2003) conducted in Yellowstone National Park (YNP) are presented. The findings indicate that 2-stroke snowmobile engine emissions furnish large quantities of air toxics to the YNP air shed. Air toxics, which are major components of 2stroke engine exhaust, show large enhancements between the high traffic and low traffic sampling periods. Evaluation of the photochemical history of air masses sampled in the Park reveals that the air toxic emissions were recent and persistent throughout the region and consistent with the 2-stroke exhaust sample fingerprints. Using a box model, the emission fluxes from snowmobile usage in the Park are estimated to be 0.35, 1.12, 0.24, 1.45, and 0.36 Gg/yr for benzene, toluene, ethyl benzene, xylenes, and hexane, respectively. The U.S. annual emissions from snowmobile usage are significant (˜14-21%) with respect to EPA estimates. Results of the atmospheric measurements of short-lived halocarbons are presented from the New England Air Quality Study 2002 campaign, summer 2003 at Thompson Farm (TF) and Great Bay, and the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 campaign. Elevated levels of bromoform (CHBr3) were frequently observed, with maxima of 37.9 pptv and 47.4 pptv for TF and Appledore Island (AI), respectively. During the ICARTT 2004 campaign, the average levels of CHBr3 and dibromomethane (CH2Br2) were higher at AI (CHBr3 = 14.3 pptv, CH2Br2 = 3.2 pptv) compared to Thompson Farm (CHBr3

  4. Water-Quality Monitoring and Studies of the Formation and Fate of Trihalomethanes During the Third Injection, Storage, and Recovery Test at Lancaster, Antelope Valley, California, March 1998 Through April 1999

    Science.gov (United States)

    2002-01-01

    CHCl2Br, bromodichloromethane CHCl3, chloroform CHClBr2, dibromochloromethane Cl2, chlorine CO2, carbon dioxide KH2PO4, potassium dihydrogen phosphate ... dihydrogen phosphate (KH2PO4) (0.02 gram per liter), ammonium chloride (NH4Cl) (0.5 gram per liter), and vitamins including B12 (1 milliliter per liter...serum vials. A boric acid/sodium hydroxide buffer solution of pH 8.3 (1 molar boric acid and 0.11 molar sodium hydroxide) containing 6,000 mg/L of

  5. Drug: D01875 [KEGG MEDICUS

    Lifescience Database Archive (English)

    Full Text Available D01875 Drug Tiquizium bromide (JAN/INN); Thiaton (TN) C19H24NS2. Br 409.0534 410.43...vous system 123 Autonomic nervous system agents 1231 Quaternary ammoniums D01875 Tiquiz...odopsin family Acetylcholine (muscarinic) muscarinic cholinergic receptor M3 [HSA:1131] [KO:K04131] Tiquizium D01875 Tiquiz...29 1131 1132 1133] [KO:K04129 K04130 K04131 K04132 K04133] Tiquizium D01875 Tiquizium bromide (JAN/INN) CAS:

  6. Tetrabromidobis(dicyclohexylphosphane-κPdigallium(Ga—Ga

    Directory of Open Access Journals (Sweden)

    Dennis H. Mayo

    2012-10-01

    Full Text Available The title compound, a GaII dimer, [Ga2Br4(C12H23P2], was synthesized by reaction of GaBr(THFn (THF is tetrahydrofuran with dicyclohexylphosphine in toluene. At 150 K the crystallographically centrosymmetric molecule exhibits disorder in which one of the two independent cyclohexyl groups is modelled over two sites in a 62 (1:38 (1 ratio. In d6-benzene solution, the compound exhibits virtual C2h symmetry as determined by 1H NMR. The coordination environment of the GaII atom is distorted tetrahedral.

  7. A sandwich-shaped M3L2 zinc(ii) complex containing 1,3,5-tris(dimethyl(pyridin-3-yl)silyl)benzene: selective photoluminescence recognition of diiodomethane.

    Science.gov (United States)

    Lee, Sangseok; Lee, Haeri; Jung, Ok-Sang

    2017-05-09

    Self-assembly of Zn(ClO4)2 with 1,3,5-tris(dimethyl(pyridin-3-yl)silyl)benzene (L) as a new C3-symmetric tridentate N-donor gives rise to a discrete sandwich-shaped M3L2 architecture, [Zn3(μ-OH)3L2](ClO4)3·4CH3CN·2H2O. Its blue photoluminescence is significantly quenched only by CH2I2 among the various small molecules, CH2Cl2, CH2Br2, CHCl3, 1,2-dichloroethane, EtOH, CH3CN, benzene, toluene, and phenol.

  8. Studies on dissociation energies of diatomic molecules using vibrational spectroscopic constants

    Institute of Scientific and Technical Information of China (English)

    HOU; Shilin(侯世林); SUN; Weiguo(孙卫国)

    2003-01-01

    New analytical expression and numerical approach are suggested to calculate dissociation energies De of diatomic molecular states using an extreme value method (EVM). Studies on some electronic states of OH, BH, N2, Br2, ClF and CO molecules show that the accuracy of the EVM dissociation energies depends on the number of correct vibrational constants used in the calculations. The convergence qualities of De are suggested to be an alternative physical criterion to measure the qualities of the various sets of vibrational constants from different literature for the same diatomic state.

  9. Acid-Catalyzed Degradation of Poly(2-butyl-1,3,6-trioxocane.

    Science.gov (United States)

    1985-10-21

    case, n = 8, was not studied. The detailed investigation of ring formation by Illuminati and his coworkers 1 1 󈧐 show that formation of 8-membered... Illuminati et al. have evaluated the oxygen effect in eq. 8 by studying the effect of replacing X = CH2 with X= 0. a o- (CCHn 2Br B 8 0 X-(CH )-Br .(H) +B...Macrosol. 16, 21 1000. 10. S. Winsten, E. Allred, R. Heck and R. Olick, Tetrahedron, 10. 3, 1. 29 11. G. Illuminati and L. Mandolini, Acct Ce 14, 95. 12

  10. DDTC-Na-based colorimetric chemosensor for the sensing of cyanide in water

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Sodium diethyldithiocarbamate (DDTC-Na) was demonstrated to be a new colorimetric cyanide chemosensor by utilizing an indirect trick. First, some copper ions were added to the colorless aque- ous solution of DDTC-Na. Then, the resultant brown solution was studied upon the addition of different anions, including Cl-, I-, IO3-, SO42-, NO-2, Br-, H2PO4-, F-, SCN-, HSO-4, ClO-4 and CN-. It was observed by naked eyes that the brown solution changed to colorless immediately after the addition of the trace cyanide, but there were no changes towards other anions, making DDTC-Na a good selective cyanide chemosensor in pure water.

  11. An approach to the statistical model for the spectroscopy of heavy quarkonia with the Song-Lin potential

    Energy Technology Data Exchange (ETDEWEB)

    Bekmezci, A.; Ikdair, S.M.; Magdy, A.; Sever, R. [Middle East Technical Univ., Ankara (Turkey)

    1993-10-01

    The mass spectra of the lowest S, P, and D levels of the self-conjugate (QQ) and the non-self-conjugate (Qq) mesons are studied with the static quark-antiquark potential of the form V(r)={minus}ar{sup {minus}1/2}+br{sup 1/2}+c. The nonrelativistic form of statistical model is used without making any perturbation. The authors results are in reasonably excellent agreement with the experimental and theoretical findings. 11 refs., 1 tab.

  12. Mutual Neutralization of Atomic Rare-Gas Cations (Ne+, Ar+, Kr+, Xe+) with Atomic Halide Anions (Cl-, Br-, I-)

    Science.gov (United States)

    2015-01-07

    occur at intersections of the initial ionic potential curve and those describing the interaction between the atoms in their fi- nal states, as in...reactions, the halogen product is formed in excited states with sufficient energy to autoionize to form X+ + e−, Rg+ +X− → Rg +X∗, (3a) → Rg +X+ + e−. (3b...me- ters. The liquid reagents, CCl4 and CF2Br2, are purified via freeze-pump-thaw cycles prior to mixture preparation. The absolute electron density

  13. Coprecipitation of radon oxide with cesium fluoroxenate

    Energy Technology Data Exchange (ETDEWEB)

    Avrorin, V.V.; Krasikova, R.N.; Nefedov, V.D.; Toropova, M.A.

    1986-03-01

    This paper presents a study of the processes of coprecipitation of radon oxide with cesium fluoroxenate in aqueous solutions. It has been shown that the reason for the coprecipitation in the case at hand is the occurrence of a process of isomorphous cocrystallization. The results obtained are examined as a confirmation of the suggestion that the hydrolysis product of the radon fluoride which is formed on thermal initiation of reaction in the rn-F2-BrF5-NaF system is radon trioxide, Rno3.

  14. Understanding the two-dimensional ionization structure in luminous infrared galaxies. A near-IR integral field spectroscopy perspective

    CERN Document Server

    Colina, Luis; Arribas, Santiago; Riffel, Rogerio; Riffel, Rogemar A; Rodriguez-Ardila, Alberto; Pastoriza, Miriani; Storchi-Bergmann, Thaisa; Alonso-Herrero, Almudena; Sales, Dinalva

    2015-01-01

    We investigate the 2D excitation structure of the ISM in a sample of LIRGs and Seyferts using near-IR IFS. This study extends to the near-IR the well-known optical and mid-IR emission line diagnostics used to classify activity in galaxies. Based on the spatially resolved spectroscopy of prototypes, we identify in the [FeII]1.64/Br$\\gamma$ - H_2 1-0S(1)/Br$\\gamma$ plane regions dominated by the different heating sources, i.e. AGNs, young MS massive stars, and evolved stars i.e. supernovae. The ISM in LIRGs occupy a wide region in the near-IR diagnostic plane from -0.6 to +1.5 and from -1.2 to +0.8 (in log units) for the [FeII]/Br$\\gamma$ and H_2/Br$\\gamma$ line ratios, respectively. The corresponding median(mode) ratios are +0.18(0.16) and +0.02(-0.04). Seyferts show on average larger values by factors ~2.5 and ~1.4 for the [FeII]/Br$\\gamma$ and H_2/Br$\\gamma$ ratios, respectively. New areas and relations in the near-IR diagnostic plane are defined for the compact, high surface brightness regions dominated by ...

  15. The relationship between volatile halocarbons and phytoplankton pigments during a Trichodesmium bloom in the coastal eastern Arabian Sea

    Science.gov (United States)

    Roy, Rajdeep; Pratihary, Anil; Narvenkar, Gayatree; Mochemadkar, Sunita; Gauns, Mangesh; Naqvi, S. W. A.

    2011-11-01

    Eukaryotic phytoplankton such as diatoms and prymnesiophytes produce biogenic halocarbons in the ocean that serve as important sources of chlorine and bromine to the atmosphere, but the role of cyanobacteria in halocarbon production is not well established. We studied distributions of chloroform (CHCl 3), carbon tetrachloride (CCl 4), methylene bromide (CH 2Br 2) and bromoform (CHBr 3) in relation to phytoplankton composition, determined from pigment analysis complemented by microscopic examination, for one month in coastal waters of the eastern Arabian that experienced a Trichodesmium bloom that typically occurs during the Spring Intermonsoon season. High concentrations of zeaxanthin (23 μg l -1), alpha beta betacarotene (6 μg l -1) and chlorophyll a (67 μg l -1) were found within the bloom whereas the marker pigment concentrations were low outside the bloom. CHCl 3 and CCl 4 occurred in relatively high concentrations in surface waters whereas CH 2Br 2 and CHBr 3 were restricted to the subsurface layer. Chlorinated halocarbons were positively inter-correlated and with CHBr 3. The observed spatial and temporal trends in brominated compounds appear to be related to the abundance of Trichodesmium although correlations between concentrations of brominated compounds with various marker pigments were poor and statistically non-significant. The results support the existence of multiple sources and sinks of halogenated compounds, which might obscure the relationship between halocarbons and phytoplankton composition.

  16. A novel hydrogen-bonded cyclic dibromide in an organic diammonium salt

    Indian Academy of Sciences (India)

    Bikshandarkoil R srinivasan; Sunder N Dhuri; Jyoti V Sawant; Christian Näther; Wolfgang Bensch

    2006-03-01

    The organic diammonium salt N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium dibromide dihydrate, (dbtmen)Br2.2H2O (1), was prepared by the reaction of N,N,N',N'-tetramethylethylenediamine (tmen) with benzyl bromide. 1 crystallizes in the triclinic space group 1 with the following unit cell dimensions for C20H34Br2N2O2 (M = 494.31): = 8.6672(6) Å, = 11.7046(8) Å, = 11.7731(8) Å, = 76.988(8)°, = 88.978(8)°, = 76.198(8)° R, = 1129.26(13) Å3, = 2. Three components, namely the (dbtmen)2+ dication, two bromide anions and two crystal water molecules constitute the structural arrangement of 1. H2O molecules are linked to bromide anions via O-H$\\cdots$Br hydrogen bonding interactions resulting in the formation of a four-membered {O2Br2} cyclic dibromide. The {O2Br2} units and the dications are arranged as alternating layers extending in the crystallographic plane. The arrangement of anions and cations may be viewed as a typical lamellar structure. The crystal water molecules can be removed by heating 1 at 140°C and the anhydrous dibromide thus formed can be fully rehydrated as evidenced by IR spectra and X-ray powder patterns.

  17. Exploration of new second-order nonlinear optical materials of the Cs-Hg-Br-I system.

    Science.gov (United States)

    Wu, Qi; Huang, Yin; Meng, Xianggao; Zhong, Cheng; Chen, Xingguo; Qin, Jingui

    2014-06-21

    A first example of a Cs-Hg-Br-I system, namely Cs2Hg2Br2I4·H2O (1), has been synthesized by reaction in solution. It belongs to the polar monoclinic space group pc with a = 7.460(5) Å, b = 13.458(9) Å, c = 8.891(6) Å, and β = 92.448(9)°. The basic anionic group in the crystal is non-centrosymmetric [Hg2Br2I4](2-), and the groups are aligned in the same direction in the crystal. As a result, 1 exhibits a phase-matchable second harmonic generation (SHG) response as strong as 6 times that of KH2PO4 (KDP). For the purpose of comparison, the known compound Cs2Hg3I8·H2O (2) was also synthesized and its SHG properties were studied for the first time. Band structure and optical property calculations for the two compounds based on DFT methods were also performed. The comprehensive properties of 1 and 2 as well as their analog, Cs2HgCl2I2, have been compared and discussed.

  18. Thermal expansion and magnetostriction measurements of the mixed systems Cs{sub 2}CuCl{sub 4-x}Br{sub x} (0 ≤ x ≤ 4)

    Energy Technology Data Exchange (ETDEWEB)

    Thallapaka, Satya Krishna; Tutsch, Ulrich; Postulka, Lars; Wolf, Bernd; Lang, Michael; Well, Natalia van; Ritter, Franz; Krellner, Cornelius [Frankfurt Univ., Frankfurt am Main (Germany). Physics Inst., SFB/TR 49

    2015-07-01

    The mixed systems Cs{sub 2}CuCl{sub 4-x}Br{sub x} (0 ≤ x ≤ 4), including the two well-known end members Cs{sub 2}CuCl{sub 4} and Cs{sub 2}CuBr{sub 4}, are classified as quasi-two-dimensional quantum antiferromagnets with different degrees of magnetic frustration. Due to a site-selective substitution of the halide atoms two distinct critical concentrations (x = 1 and x = 2) had been identified. Especially the Cs{sub 2}CuCl{sub 2}Br{sub 2} compound exhibits the potential to be the system with the highest degree of frustration within this series. We present low-temperature thermal expansion measurements down to 40 mK and magnetostriction experiments up to 14 T on the Cs{sub 2}CuCl{sub 2}Br{sub 2} compound. While specific heat measurements reveal indications for magnetic order around 90 mK, no clear signatures were found in thermal expansion studies along the b axis. Here an in-T linear contribution was observed indicating a 1D character of the magnetic excitations. For fields above 5 T one finds a clear deviation from this linearity. These results are discussed with specific heat data and also compared with the thermodynamic properties of the pure Cs{sub 2}CuCl{sub 4} compound.

  19. Shocked Gas in IRAS F17207-0014: ISM Collisions and Outflows

    CERN Document Server

    Medling, Anne M; Rich, Jeffrey A; Kewley, Lisa J; Armus, Lee; Dopita, Michael A; Max, Claire E; Sanders, David; Sutherland, Ralph

    2015-01-01

    We combine optical and near-infrared AO-assisted integral field observations of the merging ULIRG IRAS F17207-0014 from the Wide-Field Spectrograph (WiFeS) and Keck/OSIRIS. The optical emission line ratios [N II]/H$\\alpha$, [S II]/H$\\alpha$, and [O I]/H$\\alpha$ reveal a mixing sequence of shocks present throughout the galaxy, with the strongest contributions coming from large radii (up to 100% at $\\sim$5 kpc in some directions), suggesting galactic-scale winds. The near-infrared observations, which have approximately 30 times higher spatial resolution, show that two sorts of shocks are present in the vicinity of the merging nuclei: low-level shocks distributed throughout our field-of-view evidenced by an H$_{2}$/Br$\\gamma$ line ratio of $\\sim$0.6-4, and strong collimated shocks with a high H$_{2}$/Br$\\gamma$ line ratio of $\\sim$4-8, extending south from the two nuclear disks approximately 400 pc ($\\sim$0.5 arcsec). Our data suggest that the diffuse shocks are caused by the collision of the interstellar media ...

  20. Cage-Like Porous Carbon with Superhigh Activity and Br2 -Complex-Entrapping Capability for Bromine-Based Flow Batteries.

    Science.gov (United States)

    Wang, Chenhui; Lai, Qinzhi; Xu, Pengcheng; Zheng, Daoyuan; Li, Xianfeng; Zhang, Huamin

    2017-06-01

    Bromine-based flow batteries receive wide attention in large-scale energy storage because of their attractive features, such as high energy density and low cost. However, the Br2 diffusion and relatively low activity of Br2 /Br(-) hinder their further application. Herein, a cage-like porous carbon (CPC) with specific pore structure combining superhigh activity and Br2 -complex-entrapping capability is designed and fabricated. According to the results of density functional theory (DFT) calculation, the pore size of the CPC (1.1 nm) is well designed between the size of Br(-) (4.83 Å), MEP(+) (9.25 Å), and Br2 complex (MEPBr3 12.40 Å), wherein Br(-) is oxidized to Br2 , which forms a Br2 complex with the complexing agent immediately and is then entrapped in the cage via pore size exclusion. In addition, the active sites produced during the carbon dioxide activation process dramatically accelerate the reaction rate of Br2 /Br(-) . In this way, combining a high Br2 -entrapping-capability and high specific surface areas, the CPC shows very impressive performance. The zinc bromine flow battery assembled with the prepared CPC shows a Coulombic efficiency of 98% and an energy efficiency of 81% at the current density of 80 mA cm(-2) , which are among the highest values ever reported. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. A thermodynamic description of the KBr–EuBr{sub 2} system

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Weiping, E-mail: gwp@hzu.edu.cn [Laboratory of Electronic Functional Materials, Huizhou University, Huizhou 516001, Guangdong (China); Gaune-Escard, Marcelle [Ecole Polytechnique, Mecanique Energetique, Technopole De Chateau-Gombert, 5 Rue Enrico Fermi, 13453 Marseille Cedex 13 (France)

    2014-01-25

    Highlights: • CALPHAD method was used to derive thermodynamic parameters of the system. • Heat capacities of K{sub 2}EuBr{sub 4} and KEu{sub 2}Br{sub 5} were fitted to literature data. • Phase diagram of KBr–EuBr{sub 2} was calculated. • More investigations were necessary to check the stability of the compounds. -- Abstract: Critical thermodynamic description on KBr–EuBr{sub 2} system was carried out by CALPHAD method. The thermodynamic parameters of the pure KBr and EuBr{sub 2} compounds were taken from the SGTE recommended database and the authors’ previous assessment, respectively. A two-sublattice ionic solution model for the liquid, denoted as (K{sup +}){sub P}:(Br{sup −}, EuBr{sub 4}{sup -2}, EuBr{sub 2}){sub Q}, was employed to represent phase diagram and enthalpy of mixing data. To reach a self-consistent thermodynamic description for the constituent phases in the system, the experimental heat capacity data of the intermediate compounds K{sub 2}EuBr{sub 4} and KEu{sub 2}Br{sub 5} were evaluated.

  2. Unconventional Density Waves in Organic Conductors and in Superconductors

    Science.gov (United States)

    Maki, K.; Dóra, B.; Virosztek, A.

    Unconventional density waves (UDW) are one of the ground states in metallic crystalline solids and have been speculated already in 1968. However, more focused studies on UDWstarted only recently, perhaps after the identification of the low temperature phase in α-(BEDT-TTF)2KHg(SCN)4 as unconventional charge density wave (UCDW) in 2002. More recently, the metallic phase of Bechgaard salts (TMTSF)2X with X=PF6 and ReO4 under both pressure and magnetic field appears to be unconventional spin density wave (USDW). The pseudogap regime of high T c superconductors LSCO, YBCO, Bi2212 and the one in CeCoIn5 belong to d-wave density waves (d-DW). In these identifications, the angular dependent magnetoresistance and the giant Nernst effect have played the crucial role. These are the simplest manifestations of the Landau quantization of quasiparticle energy in UDW in the presence of magnetic field (the Nersesyan effect). Also we speculate that UDW will be most likely found in α-(BEDT-TTF)2I3, α-(BEDT-TTF)2I2Br, κ-(BEDT-TTF)2Cu(NCS)2, κ-(BEDT-TTF)2Cu(CN)2Br, γ-(BEDT)2GaCl4 and in many other organic compounds.

  3. Molecular cloning and characterization of the Dicer-like 2 gene from Brassica rapa.

    Science.gov (United States)

    Yan, Fei; Peng, Jiejun; Lu, Yuwen; Lin, Lin; Zheng, Hongying; Chen, Hairu; Chen, Jianping; Adams, Michael J

    2009-07-01

    Dicer-like proteins (DCLs) are involved in small RNA-mediated development and viral defense in plants. In model plants, at least four DCLs have been found and a number of studies have helped to understand their function. However, the function of the Dicer or DCLs in other plants is still unclear. Here, we report the full-length cDNA sequence of Brassica rapa ssp. chinensis DCL2 (BrDCL2) gene, which contains a 4,179 bp open reading frame (ORF) encoding a protein of 1,392 amino acids. At the 3' end of BrDCL2, clones with three different lengths of 3' untranslated region were found. An alternative splice variant of BrDCL2, BrDCL2sv, in which one intron was retained between exon9 and exon10, was also cloned. Because of a change in the coding sequence resulting in a premature terminal codon, BrDCL2sv was expected to translate a short peptide containing the whole DEXHc domain.

  4. Detonation Properties of Bromonitromethane

    Science.gov (United States)

    Davis, Lloyd L.; Sheffield, Stephen A.; Engelke, Ray

    1999-06-01

    Bromonitromethane (CH_2BrNO_2)(BrNM) is chemically similar to nitromethane (NM), with one hydrogen atom replaced by bromine. It is a liquid explosive with an initial density of 2.009 g/cm^3. We have shown its sensitivity to shock to be similar to neat NM. However, its performance (CJ pressure) appears to be about twice that of NM. The sound speed of BrNM was measured to be 1.16 km/s and was used in the Universal Liquid Hugoniot (R. W. Woolfolk, M. Cowperthwaite and R. Shaw, Thermochimica Acta, 5), 409 (1983). to predict the unreacted Hugoniot. Shock Hugoniot measurements were shown to be consistent with this prediction. In addition, we report the BrNM detonation velocity, failure diameter in brass, and diameter effect curve. Detonation wave profiles obtained using VISAR to record the interface particle velocity between the detonating BrNM and a polymethyl methacrylate (PMMA) window have also been measured. There are interesting features in these measurements that may provide information about the reactions occurring in the BrNM and/or the effect of the confinement.

  5. Spectral characterisation of Z-isomers of lycopene formed during heat treatment and solvent effects on the E/Z isomerisation process.

    Science.gov (United States)

    Honda, Masaki; Takahashi, Naoto; Kuwa, Takahiro; Takehara, Munenori; Inoue, Yoshinori; Kumagai, Tsutomu

    2015-03-15

    The geometric isomerisation of (all-E)-lycopene, purified from tomato paste, was investigated in various organic solvents. Isomerisation ratios to the Z-isomers of lycopene in CH2Cl2 and CHCl3 over 24h were calculated to be 19.7% and 11.4% at 4°C and 77.8% and 48.4% at 50°C, respectively. In CH2Br2, more than 60% was attained in the first several hours, independent of temperature. The predominant Z-isomers obtained thermally, (9Z)-lycopene and (13Z)-lycopene, were purified and their absorption maxima and molar extinction coefficients in hexane were determined for the first time. Absorption values at 460 nm were also measured for both Z-isomers along with (all-E)-lycopene to accurately evaluate their concentrations by HPLC analysis. This approach successfully revealed that (13Z)-lycopene formed predominantly in benzene or CHCl3 at 50°C; in contrast, the 5Z-isomer was preferentially obtained in CH2Cl2 or CH2Br2.

  6. Vibrational, conformational and electronic structure investigations of α,α'-dibromo-o-xylene, α,α'-dibromo-m-xylene and α,α'-dibromo-p-xylene.

    Science.gov (United States)

    Arjunan, V; Saravanan, I; Mythili, C V; Balakrishnan, K; Mohan, S

    2012-06-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of α,α'-dibromo-o-xylene (DBOX), α,α'-dibromo-m-xylene (DBMX) and α,α'-dibromo-p-xylene (DBPX) of the configuration BrCH(2)C(6)H(4)CH(2)Br have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The conformational analysis of these compounds was performed. The complete vibrational assignment and analysis of the fundamental modes of the most stable conformer of the compounds were carried out using the experimental FTIR and FT-Raman data, and quantum mechanical studies. The observed vibrational frequencies were compared with the wavenumbers derived theoretically for the optimized geometry of the compounds from the DFT-B3LYP gradient calculations employing the standard 6-31G**, high level 6-311++G** and cc-pVTZ basis sets. The structural parameters and vibrational wavenumbers obtained from the DFT method are in good agreement with the experimental data. The potential energy distributions of the fundamental modes were also calculated with DFT force fields utilizing Wilson's FG matrix method. The effect of -CH(2)Br group on the skeletal vibrations has been discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Vacancy cascades in small molecules following x-ray inner shell photoionization

    Science.gov (United States)

    Ray, D.; Dunford, R. W.; Southworth, S. H.; Kanter, E. P.; Doumy, G.; Gao, Y.; Ho, P. J.; Picon, A.

    2014-05-01

    We are investigating molecular effects in vacancy cascades of small molecules containing heavy atoms - IBr, Br2 and CH2BrI - following K-shell ionization. In addition to fundamental interest in the physics of such decay processes, there are practical applications such as medical treatments that use energetic fragmentation of iodinated compounds with high energy x-rays to selectively treat tumorous cells. Other biological applications are also promising. We utilize the tunable monochromatic x-ray beam at the Advanced Photon Source to trigger K-shell photoionization of Br and I, and measure charge distributions and the kinetic energies released to the fragment ions. A newly designed detection device allows us to do multi-fold coincidence measurements involving momentum imaging of all the ion fragments with very high detection efficiency in coincidence with x-ray fluorescence detection. By comparing the molecular fragmentation probabilities and the kinetic energies released in Br2, IBr and CH2BrI we aim to gain understanding of the fragmentation mechanism as a function of the bond distance between I and Br. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

  8. Products and mechanisms of the oxidation of organic compounds in atmospheric air plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Marotta, Ester; Schiorlin, Milko; Paradisi, Cristina [Department of Chemical Sciences, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy); Rea, Massimo, E-mail: cristina.paradisi@unipd.i [Department of Electrical Engineering, Universita di Padova, 35131 Padova (Italy)

    2010-03-31

    Atmospheric plasma-based technologies are developing as a powerful means for air purification, specifically for the oxidation of organic pollutants. To achieve a better control on the emissions produced by such treatments mechanistic insight is needed in the complex reactions of volatile organic compounds (VOCs) within the plasma. An account is given here of our comparative studies of the behaviour of model VOCs in response to different corona regimes (+dc, -dc and +pulsed) implemented within the same flow reactor. Model VOCs considered include two alkanes (n-hexane and i-octane), one aromatic hydrocarbon (toluene) and two halogenated methanes, dibromomethane (CH{sub 2}Br{sub 2}) and dibromodifluoromethane (CF{sub 2}Br{sub 2}, halon 1202). Efficiency and product data are reported and discussed as well as various possible initiation reactions. A powerful diagnostic tool is ion analysis, performed by atmospheric pressure chemical ionization-mass spectrometry: it provides a map of major ions and ion-molecule reactions and a rationale for interpreting current/voltage characteristics of dc coronas. It is shown that, depending on the specific VOC and corona regime adopted, different initiation steps prevail in the VOC-oxidation process and that the presence of a VOC, albeit in small amounts (500 ppm), can greatly affect some important plasma properties (ion population, current/voltage profile, post-discharge products).

  9. Simple and rapid determination of trace iodide by cathodic stripping voltammetry.

    Science.gov (United States)

    Yang, Lingxi; Zou, Lina; Li, Gaiping; Ye, Baoxian

    2016-01-15

    This work establishes a highly sensitive and simple stripping voltammetric method for the direct determination of trace iodide. In the presence of abounding bromide and appropriate amount of cetylpyridine bromide (CPB), the iodine was accumulated on the glassy carbon electrode surface as ion association complex (CPBI2Br). After accumulation for a period of time, a linear sweep potential with negative scanning was applied and the I2 in CPBI2Br was reduced again into the solution. Under the optimization conditions, the stripping signals (peak current) were linear relationship with iodide concentration in range of 3.81×10(-3)µg/mL to 0.114 μg/mL and 0.127μg/mL to 2.54μg/mL, with a detection limit of 1.02ng/mL (S/N=3) for a accumulation time of 180s. Determination of trace iodine in pharmaceutical sample, kelp and table salt were performed with high accuracy and satisfactory recovery results. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Synthesis and structure of new mononuclear octahedral cobalt(III) dioximates derived from isonicotinic hydrazide

    Science.gov (United States)

    Cocu, Maria; Bulhac, Ion; Coropceanu, Eduard; Melnic, Elena; Shova, Sergiu; Ciobanica, Olga; Gutium, Victoria; Bourosh, Paulina

    2014-04-01

    New organic ligand L (1) resulting from isonicotinic hydrazide and 2,4-pentanedione has been prepared and investigated by physicochemical methods, including elemental analysis, 1H and 13C NMR, IR spectroscopy and X-ray studies. The X-ray investigation revealed that the condensation of 2,4-pentanedione with isonicotinic hydrazide is accompanied by the formation of a five-membered ring including three carbon atoms of 2,4-pentanedione and two nitrogen atoms of the isonicotinic hydrazide fragment. The reaction between [Co(DfgH)2Br(H2O)] (DfgH2 = diphenylglyoxime) and L resulted in the formation of the mononuclear octahedral complex [Co(DfgH)2BrL] (2) with the substitution of the water molecule in the apical position by the ligand L. The reaction starting from [Co(DmgH)2Cl(H2O)] (DmgH = dimethylglyoxime) and L resulted in the mononuclear octahedral Co(III) complex with the composition [Co(DmgH)2ClL‧] (3), where L‧ unexpectedly represents a dehydrated derivative of L. The two coordination compounds are characterized by X-ray diffraction method. The IR, 1H NMR spectral studies of new compounds are also reported.

  11. Regulation of PINK1 by NR2B-containing NMDA receptors in ischemic neuronal injury.

    Science.gov (United States)

    Shan, Yuexin; Liu, Baosong; Li, Lijun; Chang, Ning; Li, Lei; Wang, Hanbin; Wang, Dianshi; Feng, Hua; Cheung, Carol; Liao, Mingxia; Cui, Tianyuan; Sugita, Shuzo; Wan, Qi

    2009-12-01

    Dysfunction of PTEN-induced kinase-1 (PINK1) is implicated in neurodegeneration. We report here that oxygen-glucose deprivation (OGD), an in vitro insult mimicking ischemic neuron injury, resulted in a significant reduction of PINK1 protein expression in cultured cortical neurons. The decrease of PINK1 expression was blocked by the antagonists of NMDA receptors. We revealed that the overactivation of NR2B-containing NMDA receptors (NR2BRs) was responsible for the OGD-induced PINK1 reduction. The overactivated NR2BRs also inhibited the phosphorylation, but not the protein expression, of the cell survival-promoting kinase Akt after OGD insult, indicating that OGD-induced reduction of PINK1 protein is specific in the injury paradigm. We further showed that enhancing the protein expression of PINK1 antagonized OGD-induced reduction of Akt phosphorylation, suggesting that Akt may be a downstream target of PINK1 in ischemic neuron injury. Importantly, we provided evidence that both NR2BR antagonist and PINK1 over-expression protected against OGD-induced neuronal death. These results suggest that the overactivation of NR2BRs may contribute to ischemic neuron death through suppressing PINK1-dependent survival signaling. Thus, selectively antagonizing NR2BR signal pathway-induced neurotoxicity may be a potential neuroprotection strategy.

  12. CD73-derived adenosine and tenascin-C control cytokine production by epicardium-derived cells formed after myocardial infarction.

    Science.gov (United States)

    Hesse, Julia; Leberling, Stella; Boden, Elisabeth; Friebe, Daniela; Schmidt, Timo; Ding, Zhaoping; Dieterich, Peter; Deussen, Andreas; Roderigo, Claudia; Rose, Christine R; Floss, Doreen M; Scheller, Jürgen; Schrader, Jürgen

    2017-03-31

    Epicardium-derived cells (EPDCs) play a fundamental role in embryonic cardiac development and are reactivated in the adult heart in response to myocardial infarction (MI). In this study, EPDCs from post-MI rat hearts highly expressed the ectoenzyme CD73 and secreted the profibrotic matricellular protein tenascin-C (TNC). CD73 on EPDCs extensively generated adenosine from both extracellular ATP and NAD. This in turn stimulated the release of additional nucleotides from a Brefeldin A-sensitive intracellular pool via adenosine-A2BR signaling, forming a positive-feedback loop. A2BR activation in addition strongly promoted the release of major regulatory cytokines, such as IL-6, IL-11, and VEGF. TNC was found to stimulate EPDC migration and, together with ATP-P2X7R signaling, to activate inflammasomes in EPDCs via TLR4. Our results demonstrate that EPDCs are an important source of various proinflammatory factors in the post-MI heart controlled by purinergic and TNC signaling.-Hesse, J., Leberling, S., Boden, E., Friebe, D., Schmidt, T., Ding, Z., Dieterich, P., Deussen, A., Roderigo, C., Rose, C. R., Floss, D. M., Scheller, J., Schrader, J. CD73-derived adenosine and tenascin-C control cytokine production by epicardium-derived cells formed after myocardial infarction.

  13. Modeling and experimental studies to optimize the performance of a hydrogen - bromine fuel cell

    Science.gov (United States)

    Yarlagadda, Venkata Raviteja

    The regenerative Hydrogen-Bromine (H2-Br 2) fuel cells are considered to be one of the viable systems for large scale energy storage because of their high energy conversion efficiency, flexible operation, highly reversible reactions and low capital cost. The preliminary performance of a H2-Br2 fuel cell using both conventional as well as novel materials (Nafion and electrospun composite membranes along with platinum and rhodium sulfide electrocatalysts) was discussed. A maximum power density of 0.65 W/cm2 was obtained with a thicker Br 2 electrode (780 mum) and cell temperature of 45°C. The active area and wetting characteristics of Br2 electrodes were improved upon by either pre-treating with HBr or boiling them in de-ionized water. On the other hand, similar or better performances were obtained using dual fiber electrospun composite membranes (maximum power densities of 0.61 W/cm2 and 0.45 W/cm2 obtained with 25 mum and 65 mum electrospun membranes at 45°C) versus using Nafion membranes (maximum power densities of 0.52 W/cm 2 and 0.41 W/cm2 obtained with Nafion 212 and Nafion 115 membranes at 45°C). The rhodium sulfide (RhxSy) electrocatalyst proved to be more stable in the presence of HBr/Br2 than pure Pt. However, the H2 oxidation activity on RhxS y was quite low compared to that of Pt. In conclusion, a stable H 2 electrocatalyst that can match the hydrogen oxidation activity obtained with Pt and a membrane with low Br2/Br- permeability are essential to prolong the lifetime of a H2-Br2 fuel cell. A 1D mathematical model was developed to serve as a theoretical guiding tool for the experimental studies. The impact of convective and diffusive transport and kinetic rate on the performance of a H2-Br2 fuel cell is shown in this study. Of the two flow designs (flow-by and flow-through) incorporated in this study, the flow-through design demonstrated better performance, which can be attributed to the dominant convective transport inside the porous electrode. Both

  14. Multi-photon disso ciation dynamics of Freon 114B2 under UV radiation by femtosecond laser pulse%氟利昂F114B2分子在飞秒紫外辐射下的解离动力学∗

    Institute of Scientific and Technical Information of China (English)

    刘玉柱; 邓绪兰; 李帅; 管跃; 李静; 龙金友; 张冰

    2016-01-01

    含氟利昂在内的卤代烷烃在太阳光辐射下解离生成破坏臭氧的游离态卤素原子,是破坏大气臭氧层的主要元凶.利用飞秒激光技术结合飞行时间质谱以及离子速度成像探测技术研究了氟利昂F114B2(四氟二溴乙烷)分子在267 nm飞秒激光辐射作用下的多光子电离解离动力学.利用飞行时间质谱技术,得到了四氟二溴乙烷在267 nm飞秒激光脉冲作用下发生多光子解离产生的质谱,发现三个主要碎片离子C2 F4 Br+, C2F+4,和CF2Br+,分别对应了三种主要的解离机理:1)单个C—Br键断裂C2F4Br+2→C2F4Br++Br;2)两个C—Br键断裂C2F4Br+2→C2F+4+2Br;3) C—C键断裂C2F4Br+2→CF2Br++CF2Br.实验采用离子速度成像技术对最主要的碎片离子C2F4Br+进行成像,发现该碎片离子的动能分布可由三个高斯分布曲线拟合,说明单个C—Br键断裂机理对应于三种解离通道.通过影像进一步分析还得到了三个通道的平动能和角分布各向异性参数等详尽的动力学信息.通过密度泛函理论计算对解离动力学进行了进一步的分析和讨论.%The ozone layer which absorbs harmful solar UV radiation is a necessary umbrella for human beings and biosphere. A large amount of alkyl halide including freon exhausted by human into the atmosphere poses a great threat to the ozone layer. Freon dissociates into the product of halogen radical, like Br and Cl, induced by UV sunlight radiation, which is found to be the main culprit for the destruction of atmospheric ozone. In this paper, time-of-flight (TOF) mass spectrometry and velocity map imaging technique are employed for investigating the multiphoton dissociation dynamics of Freon F114B2 (C2F4Br2) induced by femtosecond UV radiation at 267 nm. Fragment mass spectra of C2F4Br2 under UV radiation at 266 nm are obtained by TOF mass spectrometry. Three daughter ions C2F4Br+, C2F+4 and CF2Br+are discovered together with the parent ions C2F4Br+2 . And

  15. Cytotoxic copper(II), cobalt(II), zinc(II), and nickel(II) coordination compounds of clotrimazole.

    Science.gov (United States)

    Betanzos-Lara, Soledad; Gómez-Ruiz, Celedonio; Barrón-Sosa, Lidia R; Gracia-Mora, Isabel; Flores-Álamo, Marcos; Barba-Behrens, Noráh

    2012-09-01

    Sixteen novel mononuclear Cu(II), Co(II), Zn(II), and Ni(II) complexes of the biologically active ligand clotrimazole (clotri) of the forms [M(clotri)(2)Cl(2)]·nH(2)O (1-4), [M(clotri)(2)Br(2)]·nH(2)O (5-7), [M(clotri)(3)Br(2)] (8), [M(clotri)(3)NO(3)]NO(3)·nH(2)O (9, 11), [M(clotri)(3)(NO(3))(2)]·nH(2)O (10), and [M(clotri)(3)(OH(2))(2)NO(3)]NO(3)·nH(2)O (12) were synthesized and fully characterized. Dinuclear [Cu(2)(clotri)(4)μ(2)-Cl(4)]·2H(2)O (1a) and [Cu(2)(clotri)(4)μ(2)-Br(2)]·2H(2)O (5b) as well as tetranuclear [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) complexes were also isolated. Complexes 1-7, 9, and 11 present a tetrahedral geometry; complex 8 exhibits a pentacoordinated structure; complexes 1a, 10 and 12 an octahedral geometry. X-ray crystal structures of [Cu(clotri)(2)Cl(2)](1), [Cu(clotri)(2)(EtOH)Cl(2)](1·EtOH), [Zn(clotri)(2)Cl(2)] (3), [Zn(clotri)(2)Br(2)] (7), and [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) were obtained. Complexes 1-12 were tested for cytotoxic activity against the human carcinoma cell lines HeLa (cervix-uterine), PC3 (prostate), and HCT-15 (colon) displaying IC(50) values <30 μM. Confocal microscopy and nuclear dying (DAPI) for complex 1 showed condensation of cromatin and nuclear membrane fragmentation. Immunocytochemical detection/expression of biomarkers suggests that complexes 1 and 9 induce cell death via apoptosis. TUNEL assay detected DNA fragmentation in HeLa cells, resulting from apoptotic signaling cascades induced by Cu(II) complexes 1 and 9. (1)H NMR studies of the Zn(II) complexes showed that they can bind to nucleotides.

  16. Very short-lived bromomethanes measured by the CARIBIC observatory over the North Atlantic, Africa and South-East Asia during 2009-2013

    Science.gov (United States)

    Wisher, A.; Oram, D. E.; Laube, J. C.; Mills, G. P.; van Velthoven, P.; Zahn, A.; Brenninkmeijer, C. A. M.

    2013-11-01

    Short-lived organic brominated compounds make up a significant part (~20%) of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009-2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10-12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLS-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr3 and CH2Br2 accounted for 34% (4.7-71) and 48% (14-73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54-89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340-350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ~100 ppb O3 corresponding to the extra-tropical tropopause layer.

  17. Very short-lived bromomethanes measured by the CARIBIC observatory over the North Atlantic, Africa and Southeast Asia during 2009-2013

    Science.gov (United States)

    Wisher, A.; Oram, D. E.; Laube, J. C.; Mills, G. P.; van Velthoven, P.; Zahn, A.; Brenninkmeijer, C. A. M.

    2014-04-01

    Short-lived organic brominated compounds make up a significant part of the organic bromine budget in the atmosphere. Emissions of these compounds are highly variable and there are limited measurements, particularly in the extra-tropical upper troposphere/lower stratosphere and tropical troposphere. Measurements of five very short-lived bromomethanes (VSLB) were made in air samples collected on the CARIBIC project aircraft over three flight routes; Germany to Venezuela/Columbia during 2009-2011, Germany to South Africa during 2010 and 2011 and Germany to Thailand/Kuala Lumpur, Malaysia during 2012 and 2013. In the tropical troposphere, as the most important entrance region to the stratosphere, we observe a total mean organic bromine derived from these compounds across all flights at 10-12 km altitude of 3.4 ± 1.5 ppt. Individual mean tropical tropospheric mixing ratios across all flights were 0.43, 0.74, 0.14, 0.23 and 0.11 ppt for CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CH2BrCl respectively. The highest levels of VSLB-derived bromine (4.20 ± 0.56 ppt) were observed in flights between Bangkok and Kuala Lumpur indicating that the South China Sea is an important source region for these compounds. Across all routes, CHBr3 and CH2Br2 accounted for 34% (4.7-71) and 48% (14-73) respectively of total bromine derived from the analysed VSLB in the tropical mid-upper troposphere totalling 82% (54-89). In samples collected between Germany and Venezuela/Columbia, we find decreasing mean mixing ratios with increasing potential temperature in the extra-tropics. Tropical mean mixing ratios are higher than extra-tropical values between 340-350 K indicating that rapid uplift is important in determining mixing ratios in the lower tropical tropopause layer in the West Atlantic tropics. O3 was used as a tracer for stratospherically influenced air and we detect rapidly decreasing mixing ratios for all VSLB above ∼100 ppb O3 corresponding to the extra-tropical tropopause layer.

  18. Evaluating Global Emission Inventories of Biogenic Bromocarbons

    Science.gov (United States)

    Hossaini, Ryan; Mantle, H.; Chipperfield, M. P.; Montzka, S. A.; Hamer, P.; Ziska, F.; Quack, B.; Kruger, K.; Tegtmeier, S.; Atlas, E.; Sala, S.; Engel, A.; Bonisch, H.; Keber, T.; Oram, D.; Mills, G.; Ordonez, C.; Saiz-Lopez, A.; Warwick, N.; Liang, Q.; Feng, W.; Moore, F.; Miller, F.; Marecal, V.; Richards, N. A. D.; Dorf, M.; Pfeilsticker, K.

    2013-01-01

    Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidizing capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38 %) to 0.78 (115 %) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24 %) to 1.25 (167 %) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (Br(VSLS/y)). Our simulations show Br(VSLS/y) ranges from approximately 4.0 to 8.0 ppt depending on the inventory. We report an optimized estimate at the lower end of this range (approximately 4 ppt

  19. Fundamental chemistry of iodine. The reaction of di-iodine towards thiourea and its methyl-derivative: formation of aminothiazoles and aminothiadiazoles through dicationic disulfides.

    Science.gov (United States)

    Biesiada, M; Kourkoumelis, N; Kubicki, M; Owczarzak, A M; Balas, V; Hadjikakou, S K

    2014-03-28

    The reactivity of di-iodine towards thiourea (TU) and its derivative methylthiourea (MeTU) was studied. A diversity of products was obtained from these reactions. TU reacted with di-iodine in the absence or presence of hydroiodic or hydrochloric acids in a 1 : 1, 1 : 1 : 1 or 1 : 1 : 2 (TU : I2 : HX (X = I, Cl)) molar ratio to form the ionic compounds [(TU2)(2+)2(I(-))·H2O] (1), [2(TU2) (2+)·(Cl(-))·2(I(-))·(I3(-))] (2) and [(TUH)(+) (I3(-))] (3). The compounds [(TU2)(2+)(Br(-))(I3(-))] (4) and [(TU2)(2+)2(Br(-))·H2O] (5) were derived from the reactions of TU with di-iodine in the presence of hydrobromic acid in a 1 : 1 : 1 or 1 : 2 : 1 (TU : I2 : HBr) molar ratio. However, when the product of the reaction between TU and di-iodine in a 2 : 1 (TU : I2) molar ratio was crystallized in acetone-ethylether media the ionic salt of formula [(DAThdH(+))(I(-))] (6) (DAThd = 3,5-diamino-1,2,4-thiadiazole) was obtained. Methylthiourea (MeTU) reacted with di-iodine in the presence of hydrobromic acid (1 : 1 : 1, MeTU : I2 : HBr) in dichloromethane to form a solid product which gives [2(MeTU2) (2+)·(2Br(-))(I4(2-))] (7). Moreover, MeTU reacted with I2 in 2 : 1 (MeTU : I2) to form an intermediate powder product which was crystallized in acetone to give the 2-amino-3,4-dimethylthiazolium cation in [(DMeAThH(+))(I(-))(H2O)] (8). Upon changing the crystallization medium to ethanol, instead of acetone, the cationic 5-amino-3-methylamino-4-methyl-1,2,4-thiadiazolium (AMeAThdH)(+) in [(AMeAThdH(+))(I3(-))] (9) was formed. The compounds were characterized by m.p., FT-IR, UV-Vis, (1)H-NMR spectroscopy and mass spectrometry. The crystal structures of compounds 1-9 were determined by X-ray crystallography.

  20. Palladium-Catalyzed Alkylation with Alkyl Halides by C(sp(3) )-H Activation.

    Science.gov (United States)

    Wu, Zhuo; Ma, Ding; Zhou, Bo; Ji, Xiaoming; Ma, Xiaotian; Wang, Xiaoling; Zhang, Yanghui

    2017-09-25

    Utilizing halogens as traceless directing goups represents an attractive strategy for C-H functionalization. A two C-H alkylation system, initiated by the oxidative addition of organohalides to Pd(0) , has been developed. The first reaction involves an intermolecular alkylation of palladacycles to form C(sp(3) )-C(sp(2) ) bonds followed by C(sp(2) )-H activation/cyclization to deliver alkylated benzocyclobutenes as the final products. In the second reaction, two C-C bonds are formed by the reaction of palladacycles with CH2 Br2 , and provides a facile and efficient method for the synthesis of indanes. The alkylated benzocyclobutene products can be transformed into tricyclic hyrocarbons, and the indane derivatives are essential structural motifs in bioactive and odorant molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. catena-Poly[[(tetrahydrofuran-κOlithium(I]-bis(μ-trimethylsilanolato-κ2O:O-gallium(III-bis(μ-trimethylsilanolato-κ2O:O-[(tetrahydrofuran-κOlithium(I]-μ-bromido

    Directory of Open Access Journals (Sweden)

    Jerzy Pikies

    2010-10-01

    Full Text Available The title chain polymer compound, [GaLi2Br(C3H9OSi4(C4H8O2]n, was obtained in the reaction of GaBr3 with Me3SiOLi in toluene/tetrahydrofuran. The GaIII atom, located on a twofold rotation axis, is coordinated by four trimethylsilanolate ligands and has a distorted tetrahedral geometry. The LiI atom is four coordinated by one bridging Br atom located on an inversion centre, two trimethylsilanolate ligands and one tetrahydrofurane molecule in a distorted tetrahedral geometry. The polymeric chains extend along [001]. The tetrahydrofurane molecule is disordered over two positions with site-occupancy factors of 0.57 (2 and 0.43 (2.

  2. Mass-analyzed threshold ionization spectroscopy of 1-bromopropane through dissociative intermediate states

    Science.gov (United States)

    Zhang, Song; Wang, Yanmei; Tang, Bifeng; Zheng, Qiusha; Zhang, Bing

    2006-02-01

    One-color two-photon ionization of 1-bromopropane, resulting in the 1-C 3H 7Br + ions in the X2E and X2E electronic states, is investigated using mass-analyzed threshold ionization (MATI) spectroscopy. The adiabatic ionization energies of two spin states are found to be 82 257 ± 5 and 84 823 ± 5 cm -1, respectively. The two-photon MATI spectrum exhibits an extensive vibrational structure. The active modes, including the C-Br stretching, the CH 2-Br wagging, the CH 2 and the CH 3 rocking modes, are observed and reliable values for these vibrational frequencies are obtained. We have also performed ab initio and density functional calculations, which provide interpretation for our experimental finding.

  3. Dibromidobis{1-[4-(pyridin-4-ylphenyl]ethanone-κN}mercury(II

    Directory of Open Access Journals (Sweden)

    Wen-Shen Zhang

    2011-12-01

    Full Text Available In the title compound, [HgBr2(C13H11NO2], the HgII atom adopts a four-coordinated HgN2Br2 geometry, formed by two pyridine N atoms from two ligands and two bromide anions. The complex is located on a twofold axis. The coordination geometry is close to forming a see-saw (SS-4 polyhedron, the symmetry-related organic ligands being almost perpendicular; the dihedral angles between the two pyridine rings and between the two benzene rings are 85.5 (4 and 87.7 (4°, respectively. Within the organic ligand, the pyridine ring is nearly coplanar with the benzene ring [dihedral angle = 13.1 (8°]. In the crystal, the molecular complexes are connected through weak intermolecular C—H...Br contacts.

  4. Kinetics and product studies of the BrO + ClO reaction - Implications for Antarctic chemistry

    Science.gov (United States)

    Sander, Stanley P.; Friedl, Randall R.

    1988-01-01

    Discharge flow-mass spectrometry and flash photolysis-UV spectrometry were used to investigate the reaction of ClO with BrO over the temperature range of 220-400 K and the pressure range of 1-760 Torr. Rate constants were determined for: (1) Br + ClOO, (2) Br + OClO, and (3) BrCl + O2. It is found that the rate constants for the overall reaction and each reaction branch are inversely dependent on temperature and independent of pressure. For temperatures found in the Antarctic stratosphere, the rate coefficients for the channels yielding ClOO and OClO are a factor of 2-3 larger than previously estimated.

  5. Neurolinguistics Aspects of Second Language Acquisition

    Directory of Open Access Journals (Sweden)

    Laleh Fakhraee Faruji

    2011-12-01

    Full Text Available   Fundamental breakthroughs in the neurosciences, combined with technical innovations for measuring brain activity, are shedding new light on the neural basis of second language (L2<br />processing, and on its relationship to native language processing (L1 (Perani & Abutalebi, 2005.  Over the past two decades, a large body of neuroimaging studies has been devoted to the study of the neural organization of language (De´monet, Thierry, & Cardebat, 2005; Indefrey & Levelt, 2004; Price, 2000 as cited in Abutalebi, 2008. The value that functional neuroimaging adds to language research is to improve the perspective on the distributed anatomy of language. Thus, it can be used with considerable precision to identify the neural networks underlying the different domains of language processing. In this paper some main issues related to neurolinguistics and second language acquisition with a focus on bilingualism will be discussed.

  6. Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

    KAUST Repository

    Altaher, Maryam

    2015-05-01

    Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

  7. The Adenosinergic System in Diabetic Retinopathy

    Directory of Open Access Journals (Sweden)

    J. Vindeirinho

    2016-01-01

    Full Text Available The neurodegenerative and inflammatory environment that is prevalent in the diabetic eye is a key player in the development and progression of diabetic retinopathy. The adenosinergic system is widely regarded as a significant modulator of neurotransmission and the inflammatory response, through the actions of the four types of adenosine receptors (A1R, A2AR, A2BR, and A3R, and thus could be revealed as a potential player in the events unfolding in the early stages of diabetic retinopathy. Herein, we review the studies that explore the impact of diabetic conditions on the retinal adenosinergic system, as well as the role of the said system in ameliorating or exacerbating those conditions. The experimental results described suggest that this system is heavily affected by diabetic conditions and that the modulation of its components could reveal potential therapeutic targets for the treatment of diabetic retinopathy, particularly in the early stages of the disease.

  8. A one-pot-three-step route to triazolotriazepinoindazolones from oxazolino-2H-indazoles.

    Science.gov (United States)

    Conrad, Wayne E; Rodriguez, Kevin X; Nguyen, Huy H; Fettinger, James C; Haddadin, Makhluf J; Kurth, Mark J

    2012-08-03

    A one-pot-three-step method has been developed for the conversion of oxazolino-2H-indazoles into triazolotriazepinoindazolones with three points of diversity. Step one of this process involves a propargyl bromide-initiated ring opening of the oxazolino-2H-indazole (available by the Davis-Beirut reaction) to give an N(1)-(propargyl)-N(2)-(2-bromoethyl)-disubstituted indazolone, which then undergoes -CH(2)Br → -CH(2)N(3) displacement (step two) followed by an uncatalyzed intramolecular azide-alkyne 1,3-dipolar cycloaddition (step three) to form the target heterocycle. Employing 7-bromooxazolino-2H-indazole allows for further diversification through, for example, palladium-catalyzed coupling chemistry, as reported here.

  9. Producción electroquímica de gluconato de calcio

    Directory of Open Access Journals (Sweden)

    Mario Grajales T.

    2010-07-01

    Full Text Available Se estudió experimentalmente el efecto del potencial anódico, densidad de corriente y concentración del ion bromuro en la producción electroquímica de gluconato de calcio a partir de glucosa, usando el sistema Br2 / Br' como mediador. Las condiciones de operación de la celda electroquímica con ánodo de grafito y cátodo de acero inoxidable fueron: Potencial anódico 1.3 V (vs ESC, 46 °C, densidad de corriente 26 mA / cmS y un medio acuoso compuesto por una solución de Glucosa 0.60 M -I- NaBr 0.20 M conteniendo CaCO, en suspensión (0. 30 mol / L. La eficiencia de corriente fue del 98% y la.pureza del gluconato obtenido del 99.7 %.

  10. Synthesis, Characterization, and Photochemical Properties of a New Square Mn(I-Ru(II Complex Using Pyrazine as Bridge Ligand

    Directory of Open Access Journals (Sweden)

    Inara de Aguiar

    2013-01-01

    Full Text Available The photochemical properties of the complexes cis,fac- (I, cis-[Ru(phen2(pz2]2+ (II, and fac-Mn(CO3(pz2Br (III where phen is phenanthroline and pz is pyrazine in acetonitrile solution are reported. The three complexes were characterized using 1H NMR, UV-vis and FTIR spectroscopy and electrochemical (cyclic voltammetry and spectroelectrochemical techniques. The complexes show intense absorption in the visible region assigned to the population of MLCT excited states. The absorption spectrum of I is the sum of the spectra of the mononuclear species II and III, and the two oxidation potentials at +1.10 and +1.56 V versus Ag/AGCl observed in I are ascribed to the different coordination environments of metal centers. The photolysis in the acetonitrile solution resulted in the pz dissociation to give the monoacetonitrile complexes for I, II, and III, respectively.

  11. Resonance raman spectra of metal II/IV dimer chain complexes of platinum and palladium. Analysis of the component structure to the band assigned to the symmetric XMX chain stretching mode (X = Cl or Br)

    Science.gov (United States)

    Clark, Robin J. H.; Michael, David J.

    1988-10-01

    Resonance Raman spectra of the linear-chain, mixed-valence, halogen-bridged complexes [Pt(pn) 2] [Pt(pn) 2X 2] (ClO 4) 4, where X = Cl or Br, and [Pd(pn) 2] [Pd(pn) 2Br 2] (ClO 4) 4 have been obtained over the range of excitation wavelengths 457.9 to 647.1 nm. Of particular interest is the symmetric metal—halogen stretch, ν 1, which has several components. The relative intensities of these components change with variation of the wavenumber of excitation within the intervalence electronic absorption. This effect and the origin of the different components are discussed.

  12. A theoretical study of the carbenoids LiCH2X (X = Cl, Br, I) cyclopropanation reaction with ketene

    Indian Academy of Sciences (India)

    Xing Hui Zhang; Fu Long Zhang; Zhi Yuan Geng

    2010-05-01

    A computational study for the [2 + 1] addition of the lithium carbenoids LiCH2X (X = Cl, Br, I) with ketene have been investigated by means of the B3LYP hybrid density functional method. All the reactions examined displayed similar concerted mechanisms for the cyclopropanation of these reagents. The lithium carbenoids react with ketene via an asynchronous attack on one CH2 or C group of ketene with relatively low barrier to reaction in the range of 25.34-33.74 kJ/mol in THF solvent. The trend of the lithium carbenoids reaction barrier with ketene is LiCH2Cl < LiCH2Br < LiCH2I. The results show that the reactions could be highly chemical reactivity with low barriers and could be favoured in experiment. The reactions could proceed easily at lower temperature. The computational results are briefly compared to other carbenoid reactions and related species.

  13. Kinetics and product studies of the BrO + ClO reaction - Implications for Antarctic chemistry

    Science.gov (United States)

    Sander, Stanley P.; Friedl, Randall R.

    1988-01-01

    Discharge flow-mass spectrometry and flash photolysis-UV spectrometry were used to investigate the reaction of ClO with BrO over the temperature range of 220-400 K and the pressure range of 1-760 Torr. Rate constants were determined for: (1) Br + ClOO, (2) Br + OClO, and (3) BrCl + O2. It is found that the rate constants for the overall reaction and each reaction branch are inversely dependent on temperature and independent of pressure. For temperatures found in the Antarctic stratosphere, the rate coefficients for the channels yielding ClOO and OClO are a factor of 2-3 larger than previously estimated.

  14. Residence time, mineralization processes and groundwater origin within a carbonate coastal aquifer with a thick unsaturated zone

    Science.gov (United States)

    Santoni, S.; Huneau, F.; Garel, E.; Vergnaud-Ayraud, V.; Labasque, T.; Aquilina, L.; Jaunat, J.; Celle-Jeanton, H.

    2016-09-01

    This study aims at establishing groundwater residence times, identifying mineralization processes and determining groundwater origins within a carbonate coastal aquifer with thick unsaturated zone and lying on a granitic depression. A multi-tracer approach (major ions, SiO2, Br-, Ba+, Sr2+, 18O, 2H, 13C, 3H, Ne, Ar) combined with a groundwater residence time determination using CFCs and SF6 allows defining the global setting of the study site. A typical mineralization conditioned by the sea sprays and the carbonate matrix helped to validate the groundwater weighted residence times from using a binary mixing model. Terrigenic SF6 excesses have been detected and quantified, which permits to identify a groundwater flow from the surrounding fractured granites towards the lower aquifer principally. The use of CFCs and SF6 as a first hydrogeological investigation tool is possible and very relevant despite the thick unsaturated zone and the hydraulic connexion with a granitic environment.

  15. The Synthesis and Characterization of Ionic Liquids for Alkali-Metal Batteries and a Novel Electrolyte for Non-Humidified Fuel Cells

    Science.gov (United States)

    Tucker, Telpriore G.

    This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy. Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl 4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC. Battery testing based on [EMI+][FeCl4 -] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br 7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4 +][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements. Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases

  16. Spectrophotometric Method for the Determination of Oxidative IonsWith Decoloring Reaction Using HCPCF

    Institute of Scientific and Technical Information of China (English)

    KOU Zongyan; NIU Jiwei; WANG Shuwen; GONG Xiaoming; KOU Mingze

    2001-01-01

    @@ HCPCF is a color reagent for the determination of vanadium, zinc and magnesium, etc. To the best of our knowledge, no work on the decoloring reaction for analytical use of HCPCF for the determination of oxidative anions has been report. In this work, we found that some oxidative anions can oxidize HCPCF in acid medium, forming a colorless product. In addition, surfactant was used in this work, because of the low solubility of HCPCF in aqueous solutions. The purpose of this work is to establish a new, rapid and simple spectrophotometric method for the determination of NO2-, BrO3-,IO3-, IO4-and Cr2O7-based on the reaction between HCPCF and analytes in the presence of emulsion OP.

  17. Spectrophotometric Method for the Determination of Oxidative IonsWith Decoloring Reaction Using HCPCF

    Institute of Scientific and Technical Information of China (English)

    KOU; Zongyan

    2001-01-01

    HCPCF is a color reagent for the determination of vanadium, zinc and magnesium, etc. To the best of our knowledge, no work on the decoloring reaction for analytical use of HCPCF for the determination of oxidative anions has been report. In this work, we found that some oxidative anions can oxidize HCPCF in acid medium, forming a colorless product. In addition, surfactant was used in this work, because of the low solubility of HCPCF in aqueous solutions. The purpose of this work is to establish a new, rapid and simple spectrophotometric method for the determination of NO2-, BrO3-,IO3-, IO4-and Cr2O7-based on the reaction between HCPCF and analytes in the presence of emulsion OP.……

  18. Two photon absorption energy transfer in the light-harvesting complex of photosystem II (LHC-II) modified with organic boron dye.

    Science.gov (United States)

    Chen, Li; Liu, Cheng; Hu, Rui; Feng, Jiao; Wang, Shuangqing; Li, Shayu; Yang, Chunhong; Yang, Guoqiang

    2014-07-15

    The plant light-harvesting complexes of photosystem II (LHC-II) play important roles in collecting solar energy and transferring the energy to the reaction centers of photosystems I and II. A two photon absorption compound, 4-(bromomethyl)-N-(4-(dimesitylboryl)phenyl)-N-phenylaniline (DMDP-CH2Br), was synthesized and covalently linked to the LHC-II in formation of a LHC-II-dye complex, which still maintained the biological activity of LHC-II system. Under irradiation with femtosecond laser pulses at 754 nm, the LHC-II-dye complex can absorb two photons of the laser light effectively compared with the wild type LHC-II. The absorbed excitation energy is then transferred to chlorophyll a with an obvious fluorescence enhancement. The results may be interesting and give potentials for developing hybrid photosystems.

  19. Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH

    Science.gov (United States)

    Leedham Elvidge, Emma C.; Sturges, William T.; Malin, Gill; Abd Rahman, Noorsaadah

    2017-01-01

    Five tropical seaweeds, Kappaphycus alvarezii (Doty) Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner) C. Agardh), Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh) Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient), 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3), dibro­momethane (CH2Br2), iodomethane (CH3I), diiodomethane (CH2I2), bromoiodomethane (CH2BrI), bromochlorometh­ane (CH2BrCl), bromodichloromethane (CHBrCl2), and dibro­mochloromethane (CHBr2Cl). These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm) prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of photosynthesis

  20. Vertical ionization energies of halogen anions in solution

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

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

  1. 含苯四甲酸的邻菲啰啉铜配合物的合成、晶体结构及电化学性质研究%Synthesis, Crystal Structure and Electrochemical Property of Copper Complex Based on 1,10-Phenanthroline and 1,2,4,5-Benzenetetracarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    朱禹; 黄文浩; 朱敏; 吴云龙; 谢吉民

    2013-01-01

    A Cu(Ⅱ) complex [Cu (phen)2Br] (H3BTEC) (1,phen =1,10-phenanthroline,H4BTEC =1,2,4,5-benzenetetracarboxylic acid) was synthesized,and charactered by elemental analysis,IR spectra,UV-Vis spectra,single crystal X-ray diffraction,TG analysis and electrochemical property.The complex crystallizes in triclinic,space group P1 with a=0.971 00(19) nm,b=1.212 0(2) nm,c=1.4290(3) nm; α=102.21(3)°,β=99.57(3)°,γ=107.64(3)°,V=1.51774(7) nm3,Z=2,C34H21BrCuN4O8,Mr=757,Dc=1.656 g·cm-3,μ=2.098 mm-1,F(000)=762,S=1.059,the final R=0.044 9 and wR=0.086 4 for 4 657 observed reflections with I>2o(I).Two types of one-dimensional chains are demonstrated in the structure.On one hand,the C-H… Br hydrogen bonds and Br…π stacking interactions connect the [Cu(phen)2Br]+ cations into one-dimensional chains; on the other hand,the O-H… O hydrogen bonds aggregate the mono-deprotonated anions into one-dimensional double-layer chains.The two different kinds of chains are further packed into a three-dimensional framework with C-H…O contacts.CCDC:858948.%本文合成了铜配合物[Cu(phen)2Br](H3BTEC)(1,phen=1,10-phenanthroline,H4BTEC=1,2,4,5-benzenetetracarboxylic acid),并对其进行了元素分析、红外、紫外、单晶衍射、热重和电化学性质等表征.测定结果表明,该配合物晶体属三斜晶系,空间群P(1-),晶胞参数a=0.971 00(19) nm,b=1.212 0(2) nm,c=1.429 0(3) nm;α=102.21 (3)°,β=99.57(3)°,γ=107.64(3)°,V=1.517 74(7) nm3,Z=2,C34H21BrCuN4O8,M=757,Dc=1.656 g·cm-3,μ=2.098 mm-1,F(000)=762,S=1.059,最终偏离因子R=0.044 9,wR=0.086 4.该配合物中发现了两种不同类型的一维链.一方面,氢键(C-H…Br)和Br…π堆积作用将[Cu(phen)2Br]+连接成一个一维阳离子链;另外,分子间的O-H…O氢键将均苯四甲酸连成一个双层的一维阴离子链.通过结构中的C-H…O氢键作用及其他弱作用将这两条不同的一维链堆积成一个三维结构.

  2. Role of anion size, magnetic moment, and disorder on the properties of the organic conductor {kappa}-(BETS){sub 2}Ga{sub 1-x}Fe{sub x}Cl{sub 4-y}Br{sub y}

    Energy Technology Data Exchange (ETDEWEB)

    Steven, E.; Cui, H.B.; Kismarahardja, A. [Physics Department and National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Brooks, J.S., E-mail: brooks@magnet.fsu.ed [Physics Department and National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Graf, D. [Physics Department and National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Kobayashi, H. [Department of Chemistry, College of Humanities and Sciences, Nihon University, Sakurajosui 3-25-40, Setagaya-Ku, Tokyo 156-8550 (Japan)

    2010-06-01

    Shubnikov-de Haas and angular dependent magnetoresistance oscillations have been used to explore the role of anion size, magnetic moment, and disorder in the organic conductors {kappa}-(BETS){sub 2}GaBr{sub 4} and {kappa}-(BETS){sub 2}FeCl{sub 2}Br{sub 2} in the isomorphic class {kappa}-(BETS){sub 2}Ga{sub 1-x}Fe{sub x}Cl{sub 4-y}Br{sub y}. The results, combined with previous work, show correlations between the anion composition (Ga{sub 1-x}Fe{sub x}Cl{sub 4-y}Br{sub y}) and the superconducting transition temperature, effective mass, Fermi surface topology, and the mean free path.

  3. Hydrolytic cleavage of bis(-nitrophenyl) phosphate by Schiff base MnIII complexes containing morpholine pendants in Gemini 16-6-16 micelles

    Indian Academy of Sciences (India)

    Weidong Jiang; Bin Xu; Junbo Zhong; Jianzhang Li; Fuan Liu

    2008-07-01

    Catalytic efficiency of two Schiff base manganese(III) complexes toward the hydrolysis of bis(-nitrophenyl) phosphate (BNPP) was evaluated in a micellar media formed by bis(hexadecyldimethylammonium) hexane bromide (abbr.16-6-16, 2Br-) at 25°C. Effects of various reaction conditions on the hydrolysis of BNPP were systematically investigated. The observations obtained indicate that the two Mn(III) catalysts can efficiently promote hydrolysis of BNPP with a six order of magnitude rate enhancement relative to the background rate constant (k0). Different structures of the two complexes lend to their distinguishing activities each other. Furthermore, rates of BNPP hydrolysis in Gemini 16-6-16 micellar medium are much higher than that in hexadecyltrimethylammonium bromide (CTAB) and -lauroylsarcosine sodium (LSS) micelles.

  4. Study of particle size distribution and formation mechanism of radioactive aerosols generated in high-energy neutron fields

    CERN Document Server

    Endo, A; Noguchi, H; Tanaka, S; Iida, T; Furuichi, S; Kanda, Y; Oki, Y

    2003-01-01

    The size distributions of sup 3 sup 8 Cl, sup 3 sup 9 Cl, sup 8 sup 2 Br and sup 8 sup 4 Br aerosols generated by irradiations of argon and krypton gases containing di-octyl phthalate (DOP) aerosols with 45 MeV and 65 MeV quasi-monoenergetic neutrons were measured in order to study the formation mechanism of radioactive particles in high energy radiation fields. The effects of the size distribution of the radioactive aerosols on the size of the added DOP aerosols, the energy of the neutrons and the kinds of nuclides were studied. The observed size distributions of the radioactive particles were explained by attachment of the radioactive atoms generated by the neutron-induced reactions to the DOP aerosols. (author)

  5. Aspects of unconventional density waves

    Science.gov (United States)

    Maki, Kazumi; Dóra, Balázs; Virosztek, Attila

    2003-12-01

    Recently many people discuss unconventional density waves (i.e. unconventional charge density waves (UCDW) and unconventional spin density waves (USDW)). Unlike in conventional density waves, the quasiparticle spectrum in these systems is gapless. Also these systems remain metallic. Indeed it appears that there are many candidates for UDW. The low temperature phase of α-(BEDT-TTF)2KHg(SCN)4, the antiferromagnetic phase in URu2Si2, the CDW in transition metal dichalcogenite NbSe2, the pseudogap phase in high Tc cuprate superconductors, the glassy phase in organic superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br. After a brief introduction on UCDW and USDW, we shall discuss some of the above systems, where we believe we have evidence for unconventional density waves.

  6. Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base,Thiophene Diamide Ligands Respectively and Their Catalytic Activities for α-Olefin Polymerization

    Institute of Scientific and Technical Information of China (English)

    HUANG, Ji-Ling(黄吉玲); LIAN, Bing(廉兵); YONG, Li(雍莉); QIAN, Yan-Long(钱延龙)

    2004-01-01

    Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4 (M=Ti, Zr) with the corresponding Schiff-base ligand in 1 :1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120 ℃. All complexes are well characterized by 1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex 1f (R1 =CH3, R2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.

  7. Antiferromagnetic fluctuations in a quasi-two-dimensional organic superconductor detected by Raman spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Drichko, Natalia; Hackl, Rudi; Schlueter, John A.

    2015-10-15

    Using Raman scattering, the quasi-two-dimensional organic superconductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Br (T-c = 11.8 K) and the related antiferromagnet kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Cl are studied. Raman scattering provides unique spectroscopic information about magnetic degrees of freedom that has been otherwise unavailable on such organic conductors. Below T = 200 K a broad band at about 500 cm(-1) develops in both compounds. We identify this band with two-magnon excitation. The position and the temperature dependence of the spectral weight are similar in the antiferromagnet and in the metallic Fermi liquid. We conclude that antiferromagnetic correlations are similarly present in the magnetic insulator and the Fermi-liquid state of the superconductor.

  8. Preparation and characterisation of high-density ionic liquids incorporating halobismuthate anions.

    Science.gov (United States)

    Cousens, Nico E A; Taylor Kearney, Leah J; Clough, Matthew T; Lovelock, Kevin R J; Palgrave, Robert G; Perkin, Susan

    2014-07-28

    A range of ionic liquids containing dialkylimidazolium cations and halobismuthate anions ([BiBr(x)Cl(y)I(z)](-) and [Bi2Br(x)Cl(y)I(z)](-)) were synthesised by combining dialkylimidazolium halide ionic liquids with bismuth(III) halide salts. The majority were room temperature liquids, all with very high densities. The neat ionic liquids and their mixtures with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide were characterised using Densitometry, Viscometry, NMR Spectroscopy, Electrospray Ionisation Mass Spectrometry (ESI), Liquid Secondary Ion Mass Spectrometry (LSIMS), Matrix-assisted Laser Desorption/Ionization Mass Spectrometry (MALDI), X-Ray Photoelectron Spectroscopy (XPS) and Thermogravimetric Analysis (TGA), to establish their speciation and suitability for high-temperature applications.

  9. Parametric and energy consumption optimization of Basic Red 2 removal by electrocoagulation/egg shell adsorption coupling using response surface methodology in a batch system.

    Science.gov (United States)

    de Carvalho, Helder Pereira; Huang, Jiguo; Zhao, Meixia; Liu, Gang; Yang, Xinyu; Dong, Lili; Liu, Xingjuan

    2016-01-01

    In this study, response surface methodology (RSM) model was applied for optimization of Basic Red 2 (BR2) removal using electrocoagulation/eggshell (ES) coupling process in a batch system. Central composite design was used to evaluate the effects and interactions of process parameters including current density, reaction time, initial pH and ES dosage on the BR2 removal efficiency and energy consumption. The analysis of variance revealed high R(2) values (≥85%) indicating that the predictions of RSM models are adequately applicable for both responses. The optimum conditions when the dye removal efficiency of 93.18% and energy consumption of 0.840 kWh/kg were observed were 11.40 mA/cm(2) current density, 5 min and 3 s reaction time, 6.5 initial pH and 10.91 g/L ES dosage.

  10. DDTC-Na-based colorimetric chemosensor for the sensing of cyanide in water

    Institute of Scientific and Technical Information of China (English)

    LOU XiaoDing; LI Zhen; QIN JinGui

    2009-01-01

    Sodium diethyldithiocarbamate (DDTC-Na) was demonstrated to be a new colorimetrlc cyanide chemosensor by utilizing an indirect trick. First, some copper ions were added to the colorless aque-ous solution of DDTC-Na. Then, the resultant brown solution was studied upon the addition of different anions, including CI-, I-, IO-3, SO2-4, NO-2, Br-, H2PO--4, F-, SCN-, HSO-4, CIO-4 and CN-. It was observed by naked eyes that the brown solution changed to colorless immediately after the addition of the trace cyanide, but there were no changes towards other anions, making DDTC-Na a good selective cyanide chemosensor in pure water.

  11. catena-Poly[[μ-bromido-(μ-hydroxydi-2-pyridylmethanolato-κ4N,O:O,N′dicopper(II(Cu—Cu]-di-μ-bromido

    Directory of Open Access Journals (Sweden)

    Allen D. Hunter

    2008-09-01

    Full Text Available The title complex, [Cu2Br3(C11H9N2O2]n, was one of three isolated by slow evaporation of an acetonitrile reaction mixture of CuBr2 with di-2-pyridyl ketone (1:1 molar ratio. The title complex contains a 2:1 metal-to-ligand ratio of copper(II with the hydrated form of the ligand, di-2-pyridylmethanediol. The two copper centers are bridged by a bromide ion and the alkoxy O atom, and the Cu—Cu distance is 2.9801 (5 Å. The dimeric units are further linked by bromide ions, leading to a two-dimensional extended bridged structure. O—H...O hydrogen bonds are present in the crystal structure.

  12. Di-μ-bromido-bis[bromido(di-2-pyridylmethanediol-κ2N,N′copper(II] dihydrate

    Directory of Open Access Journals (Sweden)

    Matthias Zeller

    2008-09-01

    Full Text Available The centrosymmetric title complex, [Cu2Br4(C11H10N2O22]·2H2O, was one of three complexes isolated by slow evaporation of an acetonitrile reaction mixture of CuBr2 with di-2-pyridyl ketone (1:1 molar ratio. The title complex contains a 1:1 metal-to-ligand ratio of copper(II with the hydrated form of the ligand di-2-pyridylmethanediol. The copper centers are bridged by bromide donors, leading to a Cu—Cu distance of 4.090 (6 Å. The crystals form as non-merohedral twins with two components related by a 180° rotation around the normal to [100]; the selected sample had a twin ratio of 0.63:0.37.

  13. Di-μ-bromido-bis-[bromido(di-2-pyridylmethane-diol-κN,N')copper(II)] dihydrate.

    Science.gov (United States)

    Westcott, Barry L; Kopp-Vaughn, Kristin M; Daniels, Lee M; Zeller, Matthias

    2008-08-06

    The centrosymmetric title complex, [Cu(2)Br(4)(C(11)H(10)N(2)O(2))(2)]·2H(2)O, was one of three complexes isolated by slow evaporation of an acetonitrile reaction mixture of CuBr(2) with di-2-pyridyl ketone (1:1 molar ratio). The title complex contains a 1:1 metal-to-ligand ratio of copper(II) with the hydrated form of the ligand di-2-pyridylmethane-diol. The copper centers are bridged by bromide donors, leading to a Cu-Cu distance of 4.090 (6) Å. The crystals form as non-merohedral twins with two components related by a 180° rotation around the normal to [100]; the selected sample had a twin ratio of 0.63:0.37.

  14. Kinetics and mechanism of the oxidative bromination of o-xylene in solution

    Energy Technology Data Exchange (ETDEWEB)

    Dorfman, Ya.A.; Emel' yanova, V.S.; Efremenko, I.G.; Doroshkevich, D.M.; Korolev, A.V.

    1988-07-01

    The kinetics of oxidative bromination of aromatic compounds have been studied in HNO/sub 3/-HBr-H/sub 2/SO/sub 4/-H/sub 2/O-O/sub 2/ solution. A kinetic equation which describes the results was derived for P/sub O/sub 2// > 5 /times/ 10/sup 4/ Pa. The equation parameters were determined at a temperature of 323 K. Quantum mechanical CNDO calculations were carried out in order to study the nature of the reactive intermediates involved: NO/sub 2/ NO(OH)/sup +/, N(OH)/sub 2//sup 2 +/, NO(OH)Br, and N(OH)/sub 2/Br/sup +/. A mechanism has been proposed to account for the oxidative bromination of aromatic compounds in HNO/sub 3/-H/sub 2/SO/sub 4/-HBr-O/sub 2/-H/sub 2/ solution.

  15. A new cloud algorithm for gome data

    Science.gov (United States)

    Grzegorski, M.; Beierle, S.; Friedeburg, C.; Hollwedel, J.; Khokhar, F.; Kühl, S.; Platt, U.; Wenig, M.; Wilms-Grabe, W.; Wagner, T.

    2003-04-01

    The Global Ozone Monitoring Experiment (GOME) on the ERS-2 satellite allows the measurement of many tropospheric trace gases (e.g. NO_2, SO_2, BrO, HCHO, H_2O) using the DOAS technique. Cloud algorithms are essential for the accurate retrieval of the tropospheric vertical column density of these trace gases. A new algorithm using PMD-data is presented. The results are validated through comparison with other algorithms (e.g. FRESCO, CRUSA). Problems found in existing algorithms such as overestimated cloud fractions over desert regions and negative values over oceans are significantly improved with the new algorithm. Also other possible errorsources like the systematic intensity decrease across the subpixels influences the calculation of the cloud fractions. The new algorithm tries to correct this effect.

  16. Relações quantitativas entre a estrutura química e a atividade antimicrobiana de análogos à nifuroxazida

    OpenAIRE

    1993-01-01

    Com o objetivo de estudar as relações quantitativas entre a estrutura química e a atividade antimicrobiana de análogos à nifuroxazida (5-nitro2-furfurilideno 4-hidroxi benzidrazida), prepararam-se quatorze 5-nitro-2-furfurilideno benzidrazidas X3,X4,X5-substituídas em que X3 e X5 = H e X4 = NO2, Br, Cl, H, CH3, OCH3, OH, NH2 COCH3, OC2H5, CF3, N(CH3)2, SO2NH2 e X3,X4,X5 = OCH3. Nove entre os quatorze compostos obtidos ainda não estão descritos na literatura. Os compostos obtidos foram identif...

  17. Ceramic silicon-boron-carbon fibers from organic silicon-boron-polymers

    Science.gov (United States)

    Riccitiello, Salvatore R. (Inventor); Hsu, Ming-Ta S. (Inventor); Chen, Timothy S. (Inventor)

    1993-01-01

    Novel high strength ceramic fibers derived from boron, silicon, and carbon organic precursor polymers are discussed. The ceramic fibers are thermally stable up to and beyond 1200 C in air. The method of preparation of the boron-silicon-carbon fibers from a low oxygen content organosilicon boron precursor polymer of the general formula Si(R2)BR(sup 1) includes melt-spinning, crosslinking, and pyrolysis. Specifically, the crosslinked (or cured) precursor organic polymer fibers do not melt or deform during pyrolysis to form the silicon-boron-carbon ceramic fiber. These novel silicon-boron-carbon ceramic fibers are useful in high temperature applications because they retain tensile and other properties up to 1200 C, from 1200 to 1300 C, and in some cases higher than 1300 C.

  18. ACCESSING ACADEMIC LANGUAGE: THE BENEFITS OF AN EXPLICIT STUDY OF LATIN AND GREEK ROOTS

    Directory of Open Access Journals (Sweden)

    Gail Solomons

    2012-03-01

    Full Text Available Many students in South Africa are entering university linguistically underprepared to cope with the meta-language of academe. Reasons for this are proposed by Language Development staff in the Academic Development Programme at UCT (Thesen et al., 1997:1-2:<br /> First, the language system, or code (in this case English, which is also the medium of instruction can pose problems for students for whom it is not a main language. Second, the new formal register which students meet in the transition from school to university presents difficulties for almost all first time entering students. A third factor is previous educational experience.Students who have not had practice in the more abstract cognitively demanding tasks (in English or any other language through which quality schooling prepares students for the transition to university, are at a disadvantage.

  19. Halocarbons associated with Arctic sea ice

    OpenAIRE

    Atkinson, Helen M.; Hughes, Claire; Shaw, Marvin J.; Roscoe, Howard K.; Carpenter, Lucy J.; Liss, Peter S.

    2014-01-01

    Short-lived halocarbons were measured in Arctic sea-ice brine, seawater and air above the Greenland and Norwegian seas (∼81°N, 2 to 5°E) in mid-summer, from a melting ice floe at the edge of the ice pack. In the ice floe, concentrations of C2H5I, 2-C3H7I and CH2Br2 showed significant enhancement in the sea ice brine, of average factors of 1.7, 1.4 and 2.5 times respectively, compared to the water underneath and after normalising to brine volume. Concentrations of mono-iodocarbons in air are t...

  20. Poly[tetraaqua-μ4-bromido-di-μ2-bromido-μ2-hydroxido-di-μ3-isonicotinato-tetra-μ2-isonicotinato-tetracopper(Idithulium(III

    Directory of Open Access Journals (Sweden)

    Hui-Luan Liu

    2008-10-01

    Full Text Available A new thulium(III–copper(I heterometallic coordination polymer, [Cu4Tm2Br3(C6H4NO26(OH(H2O4]n, has been prepared by a hydrothermal method. The Tm and both Cu atoms lie on mirror planes. The Tm atom is seven-coordinate with a capped distorted trigonal–prismatic coordination geometry, while the Cu atoms adopt trigonal CuBrN2 and tetrahedral CuBr3N coordination modes, respectively. The Cu atom in the trigonal coordination environment is disordered over two sites of equal occupancy. The crystal structure is constructed from two distinct units of dimeric [Tm2(μ2-OH(IN6(H2O4] cores (IN = isonicotinate and one-dimensional inorganic [Cu4Br3]n chains, which are linked together, forming heterometallic Cu–halide–lanthanide–organic layers.

  1. Equivalence of Electron-Vibration Interaction and Charge-Induced Force Variations: A New O(1 Approach to an Old Problem

    Directory of Open Access Journals (Sweden)

    Tunna Baruah

    2012-04-01

    Full Text Available Calculating electron-vibration (vibronic interaction constants is computationally expensive. For molecules containing N nuclei it involves solving the Schrödinger equation for Ο(3N nuclear configurations in addition to the cost of determining the vibrational modes. We show that quantum vibronic interactions are proportional to the classical atomic forces induced when the total charge of the system is varied. This enables the calculation of vibronic interaction constants from O(1 solutions of the Schrödinger equation. We demonstrate that the O(1 approach produces numerically accurate results by calculating the vibronic interaction constants for several molecules. We investigate the role of molecular vibrations in the Mott transition in κ-(BEDT-TTF2Cu[N(CN2]Br.

  2. Semiempirical and ab initio calculations versus dynamic NMR on conformational analysis of cyclohexyl-N,N-dimethylcarbamate

    Directory of Open Access Journals (Sweden)

    Basso Ernani A.

    2001-01-01

    Full Text Available Axial-equatorial conformational proportions for cyclohexyl-N,N-dimethyl carbamate have been measured, for the first time, by the Eliel method, ¹H and 13C dynamic nuclear magnetic resonance (DNMR. The results were compared against those determined by theoretical calculations. By the Eliel method at least five experimentally independent measureables were used in CCl4, CDCl3 and CD3CN. The ¹H and 13C low temperature experiments were performed in CF2Br2/CD2Cl2 . Semiempirical methods MNDO, AM1 and PM3 and ab initio molecular orbital calculations at the HF/STO-3G and HF/6-31G(d,p levels have been performed on the axial and equatorial conformers populations. All applied methods correctly predict the equatorial conformer preference over the axial one. The resulting equatorial preferences determined by NMR data and theoretical calculations are in good agreement.

  3. Photodissociation of HBr/LiF(001): A quantum mechanical model

    Science.gov (United States)

    Seideman, Tamar

    1993-01-01

    The photodissociation dynamics of HBr adsorbed on a LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation lineshape and the Br(P(sub 1/2)-2)/Br(P(sub 3/2)-2) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. The field polarization is found to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

  4. Photodissociation of HBr/LiF(001) - A quantum mechanical model

    Science.gov (United States)

    Seideman, Tamar

    1993-01-01

    The photodissociation dynamics of HBr adsorbed on an LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation line shape and the Br(2P(1/2))/Br(2P(3/2)) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. We find the field polarization to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

  5. Absolute rate constants for the reaction of NO with a series of peroxy radicals in the gas at 295 K

    DEFF Research Database (Denmark)

    Sehested, J.; Nielsen, O.J.; Wallington, T.J.

    1993-01-01

    The rate constants for the reaction of NO with a series of peroxy radicals: CH3O2, C2H5O2, (CH3)3CCH2O2, (CH3)3CC(CH3)2CH2O2, CH2FO2, CH2ClO2, CH2BrO2, CHF2O2, CF2ClO2, CHF2CF2O2, CF3CF2O2, CFCl2CH2O2 and CF2ClCH2O2 were measured at 298 K and a total pressure of 1 atm. The rate constants were obt...... obtained using the absolute technique of pulse radiolysis combined with time-resolved UV-VIS spectroscopy. The results are discussed in terms of reactivity trends and the atmospheric chemistry of peroxy radicals....

  6. μ-1,2-Bis(diphenylphosphinoethane-κ2P:P′-bis{[1,2-bis(diphenylphosphinoethane-κ2P,P′]bromidocopper(I} acetone disolvate

    Directory of Open Access Journals (Sweden)

    Wen-Juan Shi

    2008-10-01

    Full Text Available In the crystal structure of the title compound, [Cu2Br2(dppe3]·2CH3COCH3 [dppe is 1,2-bis(diphenylphosphinoethane, C26H24P2], the two Cu centers are bridged by a dppe ligand and each metal center carries one chelating dppe unit, with the fourth coordination site available for the Br− anion. The molecule is centrosymmetric, with the center of symmetry located between the methylene C atoms of the bridging dppe ligand. The crystal structure is stabilized by intramolecular C—H...Br hydrogen bonds and intermolecular π–π interactions, with a centroid-to-centroid distance of 3.2055 (1 Å.

  7. Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH

    Directory of Open Access Journals (Sweden)

    Paramjeet Kaur Mithoo-Singh

    2017-01-01

    Full Text Available Five tropical seaweeds, Kappaphycus alvarezii (Doty Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner C. Agardh, Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient, 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3, dibro­momethane (CH2Br2, iodomethane (CH3I, diiodomethane (CH2I2, bromoiodomethane (CH2BrI, bromochlorometh­ane (CH2BrCl, bromodichloromethane (CHBrCl2, and dibro­mochloromethane (CHBr2Cl. These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of

  8. Influence of Anion and Mole Ratio on the Coordination Behavior of an NO2S3-Macrocycle: The Formation of a Dumbbell-Shaped Macrocyclic Cadmium(II) Iodide Complex.

    Science.gov (United States)

    Lee, Hyeong-Hwan; Lee, Eunji; Ju, Huiyeong; Kim, Seulgi; Park, In-Hyeok; Lee, Shim Sung

    2016-03-01

    Anion and mole ratio dependent formations of cadmium(II) complexes with an NO2S3-macrocycle (L) incorporating a pyridine subunit are reported. When the cadmium(II) salts (1-10 equiv) with different halide ions (Br(-) or I(-)) were reacted with L, CdBr2 afforded a monomer complex, [Cd(L)Br]2[Cd2Br6]·CH2Cl2 (1), with three separated parts in the whole mole ratio range: two 1:1 stoichiometric complex cation parts and one Cd2Br6 cluster anion part. After separation of 1 by filtration, [Cd(L)Br]2[CdBr4]·CH2Cl2 (2) with similar composition was afforded, except the cluster was isolated from the filtrate. Unlike the CdBr2 complexation, CdI2 afforded the mole ratio dependent products (3-5). Below 2.5 equiv of CdI2, [Cd(L)I]2[CdI4]·CH2Cl2 (3) and [Cd(L)I]2[Cd2I6]·0.5CH2Cl2 (4) with different cadmium(II) iodide clusters were isolated as kinetic (3) and a thermodynamic (4) products. Notably, the use of 3 equiv or above amount of CdI2 gave a dumbbell-shaped complex, {[Cd(L)]2(μ-Cd4I12)} (5), in which two mononuclear macrocyclic complex units are linked by a (μ-Cd4I12)(4-) cluster. To monitor the mole ratio dependency as well as their reactivities, the systematic powder X-ray diffraction (PXRD) analysis has also been applied.

  9. The structure of the homogeneous oxidation catalyst, Mn(II)(Br(-1))x, in supercritical water: an X-ray absorption fine-structure study.

    Science.gov (United States)

    Chen, Yongsheng; Fulton, John L; Partenheimer, Walter

    2005-10-12

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br(-1) ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.14 and 2.46 A, respectively. Direct contact ion pairs form with about 2 Br(-1) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br(-1))2] in supercritical water (scH2O). When an excess of Br(-1) ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  10. The structure of the homogeneous oxidation catalyst, Mn(II)-Br(-I)x, in supercritical water: An x-ray absorption fine structure study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walt

    2005-10-12

    Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) and Br(-I) ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.11 and 2.46 ?, respectively. Direct contact ion pairs form with about 2 Br(-I) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br)2] in supercritical water (scH2O). When an excess of a Br(-I) ion is added, the bromide coordination increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  11. The Structure of the Homogeneous Oxidation Catalyst, Mn(II)(Br[superscript -1])[subscript x], in Supercritical Water: An X-ray Absorption Fine-Structure Study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter (PNNL)

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br{sup -1} ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr{sub 2} in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH{sub 2} and Mn-Br are 2.14 and 2.46 {angstrom}, respectively. Direct contact ion pairs form with about 2 Br{sup -1} ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr{sub 2}, below 1.0 m, changes from essentially [Mn(II)(H{sub 2}O){sub 6}]{sup +2} to [Mn(II)(H{sub 2}O){sub 2}(Br{sup -1}){sub 2}] in supercritical water (scH{sub 2}O). When an excess of Br{sup -1} ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr{sub 2} catalyst in scH{sub 2}O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  12. Easy oxidative addition of the carbon-halogen bond by dimethylplatinum(II) complexes containing a related series of diimine ligands: Synthesis, spectral characterization and crystal structure

    Science.gov (United States)

    Momeni, Badri Z.; Fathi, Nastaran; Mohagheghi, Arezoo

    2015-01-01

    Dimethylplatinum(II) complexes [PtMe2(NN)] {NN = 4,4‧-Me2bpy (4,4‧-dimethyl-2,2‧-bipyridine); 5,5‧-Me2bpy (5,5‧-dimethyl-2,2‧-bipyridine)} were reacted with alkyl halides (RX = EtI, EtBr) to yield the organoplatinum(IV) complexes [PtMe2RX(NN)]. On the basis of NMR data, the platinum(IV) product of each reaction contains almost exclusively the trans isomer but small traces of the cis isomers are also observed. On the other hand, the reaction of [PtMe2(NN)] {NN = bu2bpy (4,4‧-di-tert-butyl-2,2‧-bipyridine); 4,4‧-Me2bpy; 5,5‧-Me2bpy} with CH2Br2 gave a mixture of cis and trans-[PtMe2(CH2Br)Br(NN)] formed by the oxidative addition of one of the C-Br bonds. The formation of the cis isomer increases in the order of 5,5‧-Me2bpy > bu2bpy > 4,4‧-Me2bpy. The reaction of [PtMe2(NN)] {NN = bpy (2,2‧-bipyridine), phen (1,10-phenanthroline)} with 1,8-dibromooctane or 1,9-dibromononane afforded the mononuclear complexes [PtMe2{(CH2)nBr}Br(NN)] (n = 8-9). The products were fully characterized by elemental analysis, 1H, 13C, HH COSY, HMQC, DEPT and DEPTQ-135 NMR spectroscopy. The crystal structure of [PtMe2EtI(4,4‧-Me2bpy)] reveals that Pt(IV) atom is six-coordinated in a slightly distorted octahedral geometry with the ethyl group trans to iodide.

  13. Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore.

    Science.gov (United States)

    Biswas, Sujoy; Pathak, P N; Roy, S B

    2012-06-01

    An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λ(max)) for UO(2)(2+)-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol(-1)cm(-1)). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to > 24h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO(2)(2+)-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ± 2%. This method can be used to determine 2.5-250 μg mL(-1) uranium in ore leach solutions with high accuracy and precision.

  14. Comparison of UV/hydrogen peroxide and UV/peroxydisulfate processes for the degradation of humic acid in the presence of halide ions.

    Science.gov (United States)

    Lou, Xiaoyi; Xiao, Dongxue; Fang, Changling; Wang, Zhaohui; Liu, Jianshe; Guo, Yaoguang; Lu, Shuyu

    2016-03-01

    This study compared the behaviors of two classic advanced oxidation processes (AOPs), hydroxyl radical-based AOPs ((•)OH-based AOPs) and sulfate radical-based AOPs (SO4 (•-)-based AOPs), represented by UV/ hydrogen peroxide (H2O2) and UV/peroxydisulfate (PDS) systems, respectively, to degrade humic acid (HA) in the presence of halide ions (Cl(-) and Br(-)). The effects of different operational parameters, such as oxidant dosages, halide ions concentration, and pH on HA degradation were investigated in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes. It was found that the oxidation capacity of H2O2 and PDS to HA degradation in the presence of halides was nearly in the same order. High dosage of peroxides would lead to an increase in HA removal while excess dosage would slightly inhibit the efficiency. Both Cl(-) and Br(-) would have depressing impact on the two AOPs, but the inhibiting effect of Br(-) was more obvious than that of Cl(-), even the concentration of Cl(-) was far above that of Br(-). The increasing pH would have an adverse effect on HA decomposition in UV/H2O2 system, whereas there was no significant impact of pH in UV/PDS process. Furthermore, infrared spectrometer was used to provide the information of degraded HA in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes, and halogenated byproducts were identified in using GC-MS analysis in the four processes. The present research might have significant technical implications on water treatment using advanced oxidation technologies.

  15. Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

    2016-10-15

    PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

  16. Modeling daily variation of trihalomethane compounds in drinking water system, Houston, Texas.

    Science.gov (United States)

    Chaib, Embarka; Moschandreas, Demetrios

    2008-03-01

    Total trihalomethanes (TTHM) concentrations vary widely and periodically between 70 and 130 ppb. Data from the National Environmental Services Laboratory, Houston, Texas indicate that pH and free residual chlorine contribute minimally to the wide variability of TTHM levels. Temperature variation in drinking fluctuates from 11 to 27 degrees C. The objective of this research is to formulate a model that delineates more clearly the daily variations of the most prevalent volatile trihalomethane by-products: chloroform (CHCl3), bromodichloromethane (CHBr2Cl), and bromoform (CHBr3) levels from drinking water. This model simulates the daily fluctuation of THM at a single location and at any time during the day as a function of the water temperature and the average concentration of TTHM, which can be estimated. The hypothesis of this study is that observed daily fluctuations of TTHM, CHCl3, CHCl2Br, CHClBr2, and CHBr3 are periodic. This hypothesis is tested using autocorrelation functions and it is shown that for the series of pH the correlation coefficient is maximal at zero lags, rapidly decreases to zero, and increases again between 4- and 6-h period. Such pattern suggests random fluctuation unrelated to time. However, the series of free residual chlorine, temperature, TTHM, CHCl3, CHCl2Br, CHClBr2, and CHBr3 suggest a different pattern. The correlation coefficient increases when the time-shift approaches 24 h. These repetitions in fluctuation of content over a 24-h period are statistically significant. The model formulated in this study provides insights in TTHM variation and is a necessary tool to reduce the error when estimating potential risk from exposure to trihalomethane compounds in drinking water system. In general, calculation of potential risk by using a value measured early morning or late afternoon concentrations were found minimal lead to an underestimation of the population risk.

  17. Half-Lantern Pt(II and Pt(III Complexes. New Cyclometalated Platinum Derivatives

    Directory of Open Access Journals (Sweden)

    Violeta Sicilia

    2014-08-01

    Full Text Available The divalent complex [{Pt(bzq(μ-L}2] (1 [Hbzq = benzo[h]quinolone, HL = CF3C4H2N2SH: 4-(trifluoromethylpyrimidine-2-thiol] was obtained from equimolar amounts of [Pt(bzq(NCMe2]ClO4 and 4-(trifluoromethylpyrimidine-2-thiol with an excess of NEt3. The presence of a low intensity absorption band at 486 nm (CH2Cl2, assignable to a metal-metal-to-ligand charge transfer transition (1MMLCT [dσ*(Pt2→π*(bzq], is indicative of the existence of two platinum centers located in close proximity because the rigidity of the half-lantern structure allows the preservation of these interactions in solution. Compound 1 undergoes two-electron oxidation upon treatment with halogens X2 (X2: Cl2, Br2 or I2 to give the corresponding dihalodiplatinum (III complexes [{Pt(bzq(μ-LX}2] (L = CF3C4H2N2S-κN,S; X: Cl 2, Br 3, I 4. Complexes 2–4 were also obtained by reaction of 1 with HX (molar ratio 1:2, 10% excess of HX in THF with yields of about 80% and compound 2 was also obtained by reaction of [{Pt(bzq(μ-Cl}2] with HL (4-(trifluoromethylpyrimidine-2-thiol in molar ratio 1:2 in THF, although in small yield. The X-ray structures of 2 and 3 confirmed the half-lantern structure and the anti configuration of the molecules. Both of them show Pt–Pt distances (2.61188(15 Å 2, 2.61767(16 Å 3 in the low range of those observed in Pt2(III,IIIX2 half-lantern complexes.

  18. Effect of organic chain length on structure, electronic composition, lattice potential energy, and optical properties of 2D hybrid perovskites [(NH3)(CH2) n (NH3)]CuCl4, n = 2-9

    Science.gov (United States)

    Abdel-Aal, Seham K.; Kocher-Oberlehner, Gudrun; Ionov, Andrei; Mozhchil, R. N.

    2017-08-01

    Diammonium series of Cu hybrid perovskites of the formula [(NH3)(CH2) n (NH3)]CuCl4, n = 6-9 are prepared from an ethanolic solution in stoichiometric ratio 1:1 (organic/inorganic). Formation of the desired material was confirmed and characterizes by microchemical analysis, FTIR, XRD and XPS spectra. The structure consists of corner-shared octahedron [CuCl4]2- anion alternative by organic [(NH3)(CH2) n (NH3)]2+ cations. The organic and inorganic layers form infinite 2D sheet that are connected via NH···Cl hydrogen bond. The calculated lattice potential energy U pot (kJ/mol) and lattice enthalpy Δ H L (kJ/mol) are inversely proportional to the molecular volume V m (nm3) and organic chain length. Optical properties show strong absorption peak at UV-visible range. The band gap energy calculated using Kubelka-Munk equation shows the decrease of the energy gap as organic chain length increases. The introduction of bromide ion to [(NH3)(CH2) n (NH3)]CuCl2Br2 denoted 2C7CuCB hybrid has shifted the energy gap to lower values from 2.6 to 2.18 eV for 2C7CuCl (yellow) and 2C7CuCB (brown), respectively, at the same organic chain length. All elements of [(NH3)(CH2)9(NH3)]CuCl4 and [(NH3)(CH2)7(NH3)]CuCl2Br2 were found in XPS spectra, as well as valence band spectra.

  19. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fischbach, Andreas; Bazinet, Patrick R.; Waterman, Rory; Tilley, T. Don

    2007-10-28

    The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-31

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

  1. Dimethylselenide as a probe for reactions of halogenated alkoxyl radicals in aqueous solution. Degradation of dichloro- and dibromomethane.

    Science.gov (United States)

    Makogon, Oksana; Flyunt, Roman; Tobien, Thomas; Naumov, Sergej; Bonifacić, Marija

    2008-07-03

    Using pulse radiolysis and steady-state gamma-radiolysis techniques, it has been established that, in air-saturated aqueous solutions, peroxyl radicals CH 2HalOO (*) (Hal = halogen) derived from CH 2Cl 2 and CH 2Br 2 react with dimethyl selenide (Me 2Se), with k on the order of 7 x 10 (7) M (-1) s (-1), to form HCO 2H, CH 2O, CO 2, and CO as final products. An overall two-electron oxidation process leads directly to dimethyl selenoxide (Me 2SeO), along with oxyl radical CH 2HalO (*). The latter subsequently oxidizes another Me 2Se molecule by a much faster one-electron transfer mechanism, leading to the formation of equal yields of CH 2O and the dimer radical cation (Me 2Se) 2 (*+). In absolute terms, these yields amount to 18% and 28% of the CH 2ClO (*) and CH 2BrO (*) yields, respectively, at 1 mM Me 2Se. In competition, CH 2HalO (*) rearranges into (*)CH(OH)Hal. These C-centered radicals react further via two pathways: (a) Addition of an oxygen molecule leads to the corresponding peroxyl radicals, that is, species prone to decomposition into H (+)/O 2 (*-) and formylhalide, HC(O)Hal, which further degrades mostly to H (+)/Hal (-) and CO. (b) Elimination of HHal yields the formyl radical H-C(*)=O with a rate constant of about 6 x 10 (5) s (-1) for Hal = Cl. In an air-saturated solution, the predominant reaction pathway of the H-C(*)=O radical is addition of oxygen. The formylperoxyl radical HC(O)OO (*) thus formed reacts with Me 2Se via an overall two-electron transfer mechanism, giving additional Me 2SeO and formyloxyl radicals HC(O)O(*). The latter rearrange via a 1,2 H-atom shift into (*)C(O)OH, which reacts with O2 to give CO2 and O2(*)(-). The minor fraction of H-C(*)=O undergoes hydration, with an estimated rate constant of k approximately 2 x 10(5) s(-1). The resulting HC(*)(OH)2 radical, upon reaction with O2, yields HCO 2H and H (+)/O2(*-). Some of the conclusions about the reactions of halogenated alkoxyl radicals are supported by quantum chemical

  2. Behavior of the hypsometric relationship of Araucaria angustifolia in the forest copse of the faculty of forest – Federal University of Paraná, Brazil Comportamento da relação hipsométrica de Araucaria angustifolia no capão da Engenharia Florestal da UFPR

    Directory of Open Access Journals (Sweden)

    Sebastião do Amaral Machado

    2010-03-01

    éticos, logarítmicos e não-lineares adaptados, como os de Chapman & Richards e de Mitscherlich
    ou Monomolecular. Os modelos não-lineares foram ajustados pelo algoritmo de Levenberg-Marquardt. Utilizaramse,
    como critérios estatísticos de seleção dos melhores ajustes, a análise gráfica dos resíduos, o erro padrão da
    estimativa em porcentagem (Syx% e o coeficiente de determinação ajustado (R2<br />aj. Foi encontrado R2<br />aj muito
    baixo para todos os modelos ajustados, caracterizando um estágio avançado e assintótico da espécie em estudo.
    O melhor modelo para estimativa da variável ht foi o proposto por Stoffels & Van Soest, e para hf a equação de
    Curtis na sua forma logarítmica. A equação linear ajustada para estimar a altura total em função da altura do fuste
    apresentou R2<br />aj= 0,88 e Syx%= 5 %, caracterizando uma forte relação entre as duas variáveis.

  3. Kinetics of the R + HBr ⇄ RH + Br (CH 3CHBr, CHBr 2 or CDBr 2) equilibrium. Thermochemistry of the CH 3CHBr and CHBr 2 radicals

    Science.gov (United States)

    Seetula, Jorma A.; Eskola, Arkke J.

    2008-07-01

    The kinetics of the reaction of the CH 3CHBr, CHBr 2 or CDBr 2 radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH 3CHBr (or CHBr 2 or CDBr 2) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH 3CHBr 2 (or CHBr 3 or CDBr 3). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH 3CHBr + HBr) and from 288 to 477 K (CHBr 2 + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm 3 molecule -1 s -1, no error limits for the third reaction): k(CH 3CHBr + HBr) = (1.7 ± 1.2) × 10 -13 exp[+ (5.1 ± 1.9) kJ mol -1/ RT], k(CHBr 2 + HBr) = (2.5 ± 1.2) × 10 -13 exp[-(4.04 ± 1.14) kJ mol -1/ RT] and k(CDBr 2 + HBr) = 1.6 × 10 -13 exp(-2.1 kJ mol -1/ RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH 3CHBr and CHBr 2 radicals and an experimental entropy value at 298 K for the CH 3CHBr radical were obtained using a second-law method. The result for the entropy value for the CH 3CHBr radical is 305 ± 9 J K -1 mol -1. The results for the enthalpy of formation values at 298 K are (in kJ mol -1): 133.4 ± 3.4 (CH 3CHBr) and 199.1 ± 2.7 (CHBr 2), and for α-C-H bond dissociation energies of analogous compounds are (in kJ mol -1): 415.0 ± 2.7 (CH 3CH 2Br) and 412.6 ± 2.7 (CH 2Br 2), respectively.

  4. Analysis of Etched CdZnTe Substrates

    Science.gov (United States)

    Benson, J. D.; Bubulac, L. O.; Jaime-Vasquez, M.; Lennon, C. M.; Arias, J. M.; Smith, P. J.; Jacobs, R. N.; Markunas, J. K.; Almeida, L. A.; Stoltz, A.; Wijewarnasuriya, P. S.; Peterson, J.; Reddy, M.; Jones, K.; Johnson, S. M.; Lofgreen, D. D.

    2016-09-01

    State-of-the-art as-received (112)B CdZnTe substrates have been examined for surface impurity contamination and polishing residue. Two 4 cm × 4 cm and one 6 cm × 6 cm (112)B state-of-the-art as-received CdZnTe wafers were analyzed. A maximum surface impurity concentration of Al = 1.7 × 1015 atoms cm-2, Si = 3.7 × 1013 atoms cm-2, Cl = 3.12 × 1015 atoms cm-2, S = 1.7 × 1014 atoms cm-2, P = 1.1 × 1014 atoms cm-2, Fe = 1.0 × 1013 atoms cm-2, Br = 1.2 × 1014 atoms cm-2, and Cu = 4 × 1012 atoms cm-2 was observed on the as-received CdZnTe wafers. CdZnTe particulates and residual SiO2 polishing grit were observed on the surface of the as-received (112)B CdZnTe substrates. The polishing grit/CdZnTe particulate density on CdZnTe wafers was observed to vary across a 6 cm × 6 cm wafer from ˜4 × 107 cm-2 to 2.5 × 108 cm-2. The surface impurity and damage layer of the (112)B CdZnTe wafers dictate that a molecular beam epitaxy (MBE) preparation etch is required. The contamination for one 4 cm × 4 cm and one 6 cm × 6 cm CdZnTe wafer after a standard MBE Br:methanol preparation etch procedure was also analyzed. A maximum surface impurity concentration of Al = 2.4 × 1015 atoms cm-2, Si = 4.0 × 1013 atoms cm-2, Cl = 7.5 × 1013 atoms cm-2, S = 4.4 × 1013 atoms cm-2, P = 9.8 × 1013 atoms cm-2, Fe = 1.0 × 1013 atoms cm-2, Br = 2.9 × 1014 atoms cm-2, and Cu = 5.2 × 1012 atoms cm-2 was observed on the MBE preparation-etched CdZnTe wafers. The MBE preparation-etched surface contamination consists of Cd(Zn)Te particles/flakes. No residual SiO2 polishing grit was observed on the (112)B surface.

  5. Deriving an atmospheric budget of total organic bromine using airborne in situ measurements from the western Pacific area during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-07-01

    During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  6. Opposite control of mesocortical and mesoaccumbal dopamine pathways by serotonin2B receptor blockade: Involvement of medial prefrontal cortex serotonin1A receptors.

    Science.gov (United States)

    Devroye, Céline; Haddjeri, Nasser; Cathala, Adeline; Rovera, Renaud; Drago, Filippo; Piazza, Pier Vincenzo; Artigas, Francesc; Spampinato, Umberto

    2017-06-01

    Recent studies have shown that serotonin2B receptor (5-HT2BR) antagonists exert opposite facilitatory and inhibitory effects on dopamine (DA) release in the medial prefrontal cortex (mPFC) and the nucleus accumbens (NAc), respectively, thereby leading to the proposal that these compounds could provide an interesting pharmacological tool for treating schizophrenia. Although the mechanisms underlying these effects remain unknown, several data in the literature suggest that 5-HT1ARs located into the mPFC could participate in this interaction. The present study, using in vivo microdialysis and electrophysiological recordings in rats, assessed this hypothesis by means of two selective 5-HT1AR (WAY 100635) and 5-HT2BR (RS 127445) antagonists. WAY 100635, administered either subcutaneously (0.16 mg/kg, s.c) or locally into the mPFC (0.1 μM), blocked the changes of mPFC and NAc DA release induced by the intraperitoneal administration of RS 127445 (0.16 mg/kg, i.p.). The administration of RS 127445 (0.16 mg/kg, i.p.) increased both dorsal raphe nucleus (DRN) 5-HT neuron firing rate and 5-HT outflow in the mPFC. Likewise, mPFC 5-HT outflow was increased following the intra-DRN injection of RS 127445 (0.032 μg/0.2 μl). Finally, intra-DRN injection of RS 127445 increased and decreased DA outflow in the mPFC and the NAc, respectively, these effects being reversed by the intra-mPFC perfusion of WAY 100635. These results demonstrate the existence of a functional interplay between mPFC 5-HT1ARs and DRN 5-HT2BRs in the control of the DA mesocorticolimbic system, and highlight the clinical interest of this interaction, as both receptors represent an important pharmacological target for the treatment of schizophrenia. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Overview of SCIAMACHY validation: 2002–2004

    Directory of Open Access Journals (Sweden)

    A. J. M. Piters

    2006-01-01

    Full Text Available SCIAMACHY, on board Envisat, has been in operation now for almost three years. This UV/visible/NIR spectrometer measures the solar irradiance, the earthshine radiance scattered at nadir and from the limb, and the attenuation of solar radiation by the atmosphere during sunrise and sunset, from 240 to 2380 nm and at moderate spectral resolution. Vertical columns and profiles of a variety of atmospheric constituents are inferred from the SCIAMACHY radiometric measurements by dedicated retrieval algorithms. With the support of ESA and several international partners, a methodical SCIAMACHY validation programme has been developed jointly by Germany, the Netherlands and Belgium (the three instrument providing countries to face complex requirements in terms of measured species, altitude range, spatial and temporal scales, geophysical states and intended scientific applications. This summary paper describes the approach adopted to address those requirements. Since provisional releases of limited data sets in summer 2002, operational SCIAMACHY processors established at DLR on behalf of ESA were upgraded regularly and some data products – level-1b spectra, level-2 O3, NO2, BrO and clouds data – have improved significantly. Validation results summarised in this paper and also reported in this special issue conclude that for limited periods and geographical domains they can already be used for atmospheric research. Nevertheless, current processor versions still experience known limitations that hamper scientific usability in other periods and domains. Free from the constraints of operational processing, seven scientific institutes (BIRA-IASB, IFE/IUP-Bremen, IUP-Heidelberg, KNMI, MPI, SAO and SRON have developed their own retrieval algorithms and generated SCIAMACHY data products, together addressing nearly all targeted constituents. Most of the UV-visible data products – O3, NO2, SO2, H2O total columns; BrO, OClO slant columns; O3, NO2, BrO profiles

  8. Crystal structure solid-state cross polarization magic angle spinning 13C NMR correlation in luminescent d10 metal-organic frameworks constructed with the 1,2-Bis(1,2,4-triazol-4-yl)ethane ligand.

    Science.gov (United States)

    Habib, Hesham A; Hoffmann, Anke; Höppe, Henning A; Steinfeld, Gunther; Janiak, Christoph

    2009-03-02

    Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(II), zinc(II), and cadmium(II) salts have yielded the dinuclear complexes [Zn2Cl4(mu2-btre)2] (1) and [Zn2Br4(mu2-btre)2] (2), the one-dimensional coordination polymer infinity1[Zn(NCS)2(2-btre)] (3), the two-dimensional networks infinity2[Cu2(mu2-Cl)2(mu4-btre)] (4), infinity2[Cu2(mu2-Br)2(mu4-btre)] (5), and infinity2{[Cd6(mu3-OH)2(mu3-SO4)4(mu4-btre)3(H2O)6](SO4).6H2O} (6), and the three-dimensional frameworks infinity3{[Cu(mu4-btre)]ClO4.0.25H2O} (7), 3{[Zn(mu4-btre)(mu2-btre)](ClO4)2} (8), infinity3{[Cd(mu4-btre)(mu2-btre)](ClO4)2} (9), and infinity3[Cu2(mu2-CN)2(mu4-btre)] (10, 2-fold 3D interpenetrated framework). The copper-containing products 4, 5, 7, and 10 contain the metal in the +1 oxidation state, from a simultaneous redox and self-assembly reaction of the Cu(II) starting materials. The cyanide-containing framework 10 has captured the CN- ions from the oxidative btre decomposition. The perchlorate frameworks 7, 8, or 9 react in an aqueous NH4+PF6- solution with formation of the related PF6--containing frameworks. The differences in the metal-btre bridging mode (mu2-kappaN1:N1', mu2-kappaN1:N2 or mu4-kappaN1:N2:N1':N2') and the btre ligand symmetry can be correlated with different signal patterns in the 13C cross polarization magic angle spinning (CPMAS) NMR spectra. Compounds 2, 4, 5 and 7 to 10 exhibit fluorescence at 403-481 nm upon excitation at 270-373 nm which is not seen in the free btre ligand.

  9. Ecología y Salud Indígena

    Directory of Open Access Journals (Sweden)

    Alberto Pinzón Sánchez

    1989-09-01

    Full Text Available

    Uno de los pocos estudios hechos en el país desde el punto de vista de la Salud Pública y realizado en terreno sobre población indígena, es el estudio médico-antropológico de la Amazonia Colombiana realizado por el Doctor Ney Guzmán Gómez, de la Universidad del Valle en 1968. (1

    A pesar de algunas deficiencias en el análisis antropológico, es el primer buen estudio de ese tipo, en donde se combinan los datos cualitativos y cuantitativos del nivel de salud, de un Universo Poblacional de 2.478 personas de las cuales 2.158 (87% eran indígenas, moradores de las riberas de los grandes ríos del trapecio amazónico; Putumayo, Caraparaná, Igaraparaná, Pupuña, Icatué y perteneciente a los grupos étnicos: Witotos, Borás y Ticunas.

    Los indicadores más relevantes y que nos recuerdan la situación del país a comienzos de este siglo, son:

    1. Pirámide poblacional con predominio de menores de 15 años.(54%
    2. Elevadas tasas de natalidad 62 x 1000
    3. Elevada tasa de mortalidad general 20 x 1000 – Con una elevada tasa de mortalidad de menores de una añ0 87 x 1000
    4. Edad media al morir ................................25,5 años
    5. Las principales causas de mortalidad:
    – Gastroenteritis ...................16%
    – Tuberculosis ...............10%
    – Anemia.......... 6%
    – Colitis. ........................... 6%
    – Accidentes de selva............................. 6%
    – Bronconeumonía................................. 4%
    – Sarampión.................................... 2%<br />6. Las principales causas de morbilidad clínica fueron:
    – Poli parasitismo intestinal................................... 30%
    – Enfermedades respiratorias............................14%
    – Enfermedades de la piel ............................. 6%
    – Avitaminosis y anemia.............................. 6%
    – Gastroenteritis...................................4

  10. Anion and Cation Ionic Conductivity of Dragon Fruit

    Science.gov (United States)

    Hajar, Nadya; Asiah, M. N.; Abdullah, S.; Rusop, M.

    2010-07-01

    The separation of all ions in a synthetic solution was achieved with an anion eluent containing 0.3392 g Na2CO3 and 0.084 g NaHCO2 and the run around 20 min. Cation eluent containing 0.60 g Tartaric acid and 0.125 g Dipicolinic acid and the run around 16 min. This method was applied to dragon fruit juice with success and has shown sensitivity. Moreover, sample preparation was a simple 1:1, 1:10, 1:100 and 1:1000 ppm with 0.20 mm filtration and direct injection without prior sample clean-up. Due to the use of eluent generator, very low conductance background conductivity can be obtained and sensitivity of dragon fruit has been greatly improved. Under the experimental condition, several inorganic anions, such as F-, NO3-, NO2-, Br- and PO43- obtained from dragon fruit. For cation, inorganic ions that occurred during the experiment were NH3+, Ca+, and Mg+. Conductivity for anion of F-, NO3-, NO2-, Br- and PO43- were approximately 20, 17, 16, 16 and 20 μS/cm, respectively. Concentration for F- is 1.57 mg/l, NO3- is 1.92 mg/l, NO2- is 0.30 mg/l, Br- is 0.45 mg/l and PO43- is 4.45 mg/l. Conductivity for cation of NH3+, Ca+, and Mg+ were approximately 537, 538 and 531 μS/cm, respectively. Concentration for cation of NH3+ is 0.93 mg/l, Ca+ is 1.15 mg/l, and Mg+ 7.285 is mg/l. The method has successfully applied to the determination of inorganic ions in dragon fruit. An ion chromatography method is described for the simultaneous determination of ionic conductivity for dragon fruit juice using a selected anion and cation eluent. The detection of ionic conductivity in dragon fruit juice has been studied.

  11. Antiproton-proton annihilation at rest into two-body final states

    Energy Technology Data Exchange (ETDEWEB)

    Amsler, C.; Dombrowski, S. v.; Mayer, C.A.; Noble, A.; Ould-Saada, F.; Schmid, B.; Urner, D. (Zurich Univ. (Switzerland)); Armstrong, D.S.; Birien, P.; Bistirlich, J.; Bossingham, R.; Bossy, H.; Case, T.; Crowe, K.M. (California Univ., LBL, Berkeley, CA (United States)); Augustin, I.; Bluem, P.; Engelhardt, D.; Winter, N. (Karlsruhe Univ. (Germany)); Baker, C.A.; Batty, C.J. (Rutherford Appleton Lab., Chilton (United Kingdom)); Barnett, B.M.; Brose, J.; Chung, S.U.; Hackmann, R.; Kalinowsky, H.; Klempt, E.; Merkel, M.; Merlo, J.P.; Schaefer, E.; Spanier, S.; Strassburger, C.; Walter, F. (Mainz Univ. (Germany)); Beuchert, K.; Koch, H.; Kunze, M.; Luedemann, J.; Matthaey, H.; Peters, K.; Ravndal, S.; Walther, D. (Bochum Univ. (Germany)); Braune, K.; Dietz, H.P.; Duennweber, W.; Englert, M.; Faessler, M.A.; Felix, C.; Folger, G.; Illinger, P.; Jamnik, D.; Kisiel, J.; Kolo, C.; Koenigsmann, K.; Meyer-Berkhout, U.; Voelcker, C.; Zupancic, C. (Muenchen Univ. (Germany)); Bugg, D.V.; Co; Crystal Barrel Collaboration

    1993-05-01

    We report measurements of branching ratios for production of a series of two meson final states in anti pp annihilations at rest in liquid hydrogen. We find: BR(anti pp[yields][pi][sup +][pi][sup -])=(3.07[+-]0.13).10[sup -3], BR(anti pp[yields]K[sup +]K[sup -])=(0.99[+-]0.05).10[sup -3], BR(anti pp[yields][pi][sup 0][pi][sup 0])=(6.93[+-]0.43).10[sup -4], BR(anti pp[yields][yields][pi][sup 0][eta])=(2.12[+-]0.12).10[sup -4], BR(anti pp[yields][pi][sup 0][omega])=(5.73[+-]0.47).10[sup -3], BR(anti pp[yields][pi][sup 0][eta]')=(1.23[+-]0.13).10[sup -4], BR(anti pp[yields][eta][eta])=(1.64[+-]0.10).10[sup -4], BR(anti pp[yields][eta][omega])=(1.51[+-]0.12).10[sup -2], BR(anti pp[yields][eta][eta]')=(2.16[+-]0.25).10[sup -4], BR(anti pp[yields][omega][omega])=(3.32[+-]0.34).10[sup -2], BR(anti pp[yields][omega][eta]')=(0.78[+-]0.08).10[sup -2]. These are the first measurements of the channels [eta][eta]' and [omega][eta]' and in almost all of the other channels are more precise than previous results. We also obtain, in a more precise fashion, the following ratios of branching ratios: K[sup +]K[sup -]/[pi][sup +][pi][sup -]=0.323[+-]0.013, [pi][sup 0][eta]'/[pi][sup 0][eta]=0.548[+-]0.056, [eta][eta]'/[eta][eta]=1.31[+-]0.15, [omega][eta]'/[omega][eta]=0.515[+-]0.040, [pi][sup 0][eta]/[pi][sup 0][pi][sup 0]=0.303[+-]0.010, [eta][eta]/[pi][sup 0][pi][sup 0]=0.232[+-]0.011 and [pi][sup 0][omega]/[eta][omega]=0.377[+-]0.012. The measurements are made for different [eta] and [eta]' decays, and we thus obtain [Gamma]sub([eta][yields]3[pi][sup 0])/[Gamma][sub [eta][yields][gamma][gamma

  12. A comparison of very short lived halocarbon (VSLS) and DMS aircraft measurements in the tropical west Pacific from CAST, ATTREX and CONTRAST

    Science.gov (United States)

    Andrews, Stephen J.; Carpenter, Lucy J.; Apel, Eric C.; Atlas, Elliot; Donets, Valeria; Hopkins, James R.; Hornbrook, Rebecca S.; Lewis, Alastair C.; Lidster, Richard T.; Lueb, Richard; Minaeian, Jamie; Navarro, Maria; Punjabi, Shalini; Riemer, Daniel; Schauffler, Sue

    2016-10-01

    We present a comparison of aircraft measurements of halogenated very short lived substances (VSLSs) and dimethyl sulphide (DMS, C2H6S) from a co-ordinated campaign in January-February 2014 in the tropical west Pacific. Measurements were made on the NASA Global Hawk, NCAR Gulfstream-V High-performance Instrumented Airborne Platform for Environmental Research (GV HIAPER) and UK Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 (see Sect. 2.2) using four separate gas chromatography-mass spectrometry (GC-MS) instruments: one operated by the University of Miami (UoM), one from the National Center for Atmospheric Research (NCAR) and two from the University of York (UoY). DMS was measured on the BAe-146 and GV. The instruments were inter-calibrated for halocarbons during the campaign period using two gas standards on separate scales: a National Oceanic and Atmospheric Administration (NOAA) SX-3581 standard representative of clean low-hydrocarbon air, and an Essex canister prepared by UoM, representative of coastal air, which was higher in VSLS and hydrocarbon content. UoY and NCAR use the NOAA scale/standard for VSLS calibration, and UoM uses a scale based on dilutions of primary standards calibrated by GC with FID (flame ionisation detector) and AED (atomic emission detector). Analysis of the NOAA SX-3581 standard resulted in good agreement for CH2Cl2, CHCl3, CHBr3, CH2Br2, CH2BrCl, CHBrCl2, CHBr2Cl, CH3I, CH2ICl and CH2I2 (average relative standard deviation (RSD) geographic area of the tropical west Pacific. This study shows that the international VSLS calibration scales and instrumental techniques discussed here are in generally good agreement (within ˜ 10 % across a range of VSLSs), but that losses in aircraft sampling lines can add a major source of uncertainty. Overall, the measurement uncertainty of bromocarbons during these campaigns is much less than the uncertainty in the quantity of VSLS bromine estimated to reach the stratosphere of between 2 and

  13. Seasonal Variation of Cumulative CO2 Emission from a Vertisol Under Apricot Orchard in Semi-Arid Southeast Turkey

    Institute of Scientific and Technical Information of China (English)

    G.YILMAZ

    2012-01-01

    Understanding the factors affecting the CO2 emission from agricultural practices is crucial for global warming.A study was performed in an apricot orchard field in the experimental farm of the Harran University,Southeast Turkey,to i) quantify weekly and seasonal variations of the CO2 emissions from a Vertisol under apricot orchard; ii) evaluate the difference in CO2 emission between the area under trees and rows; and iii) assess the relationships between the amounts of CO2 emissions and environmental parameters for better use and management of the soils from the view point of carbon balance and flux in a semi-arid environment under drip irrigation.Soil CO2 emission measurements were performed during May 2008 and May 2010,from both under tree crowns (CO2-UC) and between tree rows (CO2-BR),on a weekly basis in southeast Turkey with a semi-arid climate.CO2 emissions were statistically correlated with weather and soil parameters such as air temperature,relative humidity,rainfall,soil water content,and soil temperature at various depths from 5 to 100 cm.The weekly emissions ranged from 82 to 1 110 kg CO2 ha-1 week-1 and from 96 to 782 kg CO2 ha-1 week-1 in CO2-UC and CO2-BR,respectively.Increase in CO2 emission in the second year was due to increases in mean air and soil temperatures.The weekly and monthly cumulative CO2 emissions were positively correlated with the air and soil temperatures.Multiple linear regression analysis explained 35% and 83% variations in average weekly and monthly CO2 emissions,by using meteorological data.Including the interaction effects of meteorological parameters in regression equations nearly doubled the variance explained by the regression models.According to stepwise regression analysis,soil and air temperatures were found to have the most significant impact on the temporal variability of the soil CO2 emission.

  14. Optical properties of Pr3+-, Ce3+-, and Eu3+-doped ternary lead halides

    Science.gov (United States)

    Brown, Ei E.; Bluiett, Althea; Hömmerich, Uwe; Trivedi, Sudhir B.

    2015-03-01

    The luminescent properties of rare-earth doped solids have been under intense exploration for a wide range of applications ranging from displays and lasers to scintillators. In this work, the material purification, crystal growth, and spectroscopic properties of Ce3+-, and Eu3+- doped KPb2Cl5 as well as Pr3+ doped KPb2Cl5 and KPb2Br5 were investigated for possible applications in infrared lasers and radiation detectors. The studied materials were synthesized through careful purification of starting materials including multi-pass zone-refinement and halogination. The growth of the purified materials was then carried out through vertical or horizontal Bridgman technique. The trivalent praseodymium ion (Pr3+) offers a large number of laser transitions in the visible and infrared (IR) spectral regions. Using ~1.45 μm and 1.9 μm pumping, IR emissions at ~1.6, ~2.4, and ~4.6 μm were observed from Pr: KPb2Cl5 and Pr: KPb2Br5 corresponding to the 4f-4f transitions of 3F4/3F3-->3H4, 3F2/3H6-->3H4, and 3H5-->3H4, respectively. Large emission cross-sections in the range of (4.8-6.1) x 10-20 cm2 (near-IR, ~1.6 μm) and (5.5-6.0) x 10-20 cm2 (mid-IR, ~4.6 μm) were observed for both crystals. Emission characteristics of the ~1.6 μm Pr3+ transition including IR to visible upconversion emission studies were also discussed. Under Xenon lamp excitation, preliminary spectroscopic results showed allowed 5d-4f Ce3+ emission centered at ~375 nm in Ce3+ doped KPb2Cl5. In addition, commercial Ce:YAG and Ce:YAP crystals are included in this study for comparison. Pr3+ and Eu2+ 5d-4f emissions were not observed from Pr3+/Eu2+ doped KPb2Cl5 crystals.

  15. Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage.

    Science.gov (United States)

    Hu, Bo; DeBruler, Camden; Rhodes, Zayn; Liu, T Leo

    2017-01-25

    Redox flow batteries (RFBs) are a viable technology to store renewable energy in the form of electricity that can be supplied to electricity grids. However, widespread implementation of traditional RFBs, such as vanadium and Zn-Br2 RFBs, is limited due to a number of challenges related to materials, including low abundance and high costs of redox-active metals, expensive separators, active material crossover, and corrosive and hazardous electrolytes. To address these challenges, we demonstrate a neutral aqueous organic redox flow battery (AORFB) technology utilizing a newly designed cathode electrolyte containing a highly water-soluble ferrocene molecule. Specifically, water-soluble (ferrocenylmethyl)trimethylammonium chloride (FcNCl, 4.0 M in H2O, 107.2 Ah/L, and 3.0 M in 2.0 NaCl, 80.4 Ah/L) and N(1)-ferrocenylmethyl-N(1),N(1),N(2),N(2),N(2)-pentamethylpropane-1,2-diaminium dibromide, (FcN2Br2, 3.1 M in H2O, 83.1 Ah/L, and 2.0 M in 2.0 M NaCl, 53.5 Ah/L) were synthesized through structural decoration of hydrophobic ferrocene with synergetic hydrophilic functionalities including an ammonium cation group and a halide anion. When paired with methyl viologen (MV) as an anolyte, resulting FcNCl/MV and FcN2Br2/MV AORFBs were operated in noncorrosive neutral NaCl supporting electrolytes using a low-cost anion-exchange membrane. These ferrocene/MV AORFBs are characterized as having high theoretical energy density (45.5 Wh/L) and excellent cycling performance from 40 to 100 mA/cm(2). Notably, the FcNCl/MV AORFBs (demonstrated at 7.0 and 9.9 Wh/L) exhibited unprecedented long cycling performance, 700 cycles at 60 mA/cm(2) with 99.99% capacity retention per cycle, and delivered power density up to 125 mW/cm(2). These AORFBs are built from earth-abundant elements and are environmentally benign, thus representing a promising choice for sustainable and safe energy storage.

  16. X-ray and NQR studies of bromoindate(III) complexes. [C{sub 2}H{sub 5}NH{sub 3}]{sub 4}InBr{sub 7}, [C(NH{sub 2}){sub 3}]{sub 3}InBr{sub 6}, and [H{sub 3}NCH{sub 2}C(CH{sub 3}){sub 2}CH{sub 2}NH{sub 3}]InBr{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Iwakiri, Takeharu; Ishihara, Hideta [Saga Univ. (Japan). Faculty of Culture and Education; Terao, Hiromitsu [Tokushima Univ. (Japan). Faculty of Integrated Arts and Sciences; Lork, Enno; Gesing, Thorsten M. [Bremen Univ. (Germany). Inst. of Inorganic Chemistry and Crystallography

    2017-03-01

    The crystal structures of [C{sub 2}H{sub 5}NH{sub 3}]{sub 4}InBr{sub 7}(1), [C(NH{sub 2}){sub 3}]{sub 3}InBr{sub 6}(2), and [H{sub 3}NCH{sub 2}C(CH{sub 3}){sub 2}CH{sub 2}NH{sub 3}]InBr{sub 5}(3) were determined at 100(2) K: monoclinic, P2{sub 1}/n, a=1061.94(3), b=1186.40(4), c=2007.88(7) pm, β= 104.575(1) , Z=4 for 1; monoclinic, C2/c, a=3128.81(12), b=878.42(3), c=2816.50(10) pm, β=92.1320(10) , Z=16 for 2; orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=1250.33(5), b=1391.46(6), c=2503.22(9) pm, Z=4 for 3. The structure of 1 contains an isolated octahedral [InBr{sub 6}]{sup 3-} ion and a Br{sup -} ion. The structure of 2 contains three different isolated octahedral [InBr{sub 6}]{sup 3-} ions. The structure of 3 has a corner-shared double-octahedral [In{sub 2}Br{sub 11}]{sup 5-} ion and an isolated tetrahedral [InBr{sub 4}]{sup -} ion. The {sup 81}Br nuclear quadrupole resonance (NQR) lines of the terminal Br atoms of the compounds are widely spread in frequency, and some of them show unusual positive temperature dependence. These observations manifest the N-H..Br-In hydrogen bond networks developed between the cations and anions to stabilize the crystal structures. The {sup 81}Br NQR and differential thermal analysis (DTA) measurements have revealed the occurrence of unique phase transitions in 1 and 3. When the bond angles were estimated from the electric field gradient (EFG) directions calculated by the molecular orbital (MO) methods, accurate values were obtained for [InBr{sub 6}]{sup 3-} of 1 and for [In{sub 2}Br{sub 11}]{sup 5-} and [InBr{sub 4}]{sup -} of 3, except for several exceptions in those for the latter two ions. On the other hand, the calculations of {sup 81}Br NQR frequencies have produced up to 1.4 times higher values than the observed ones.

  17. 气相中BrO-与CH3Cl反应机理的理论研究%Theoretical study on the reaction mechanism of BrO- with CH3C1 in gas phase

    Institute of Scientific and Technical Information of China (English)

    耿志远; 王秀红; 王永成; 周婧; 吴建花; 刘宏强

    2011-01-01

    采用二阶微扰(MP2)计算方法,在aug-cc-pVDZ基组下对反应中各驻点进行了全几何结构参数优化,并在相同基组下进一步用CCSD(T)方法进行了单点能计算.结果表明,BrO与CH3Cl的反应先通过一个传统的SN2反应,生成富能中间体IM2(BrOCH3…Cl),接着中间体IM2解离为SN2机理的产物P1(BrOCH3+Cl);而且还能继续发生氧、碳间的消除反应和氧上的取代反应,前者生成P2(CH2O+Br-+HCl),后者生成P3(CH3OCl+Br-).其中,传统的SN2为主反应通道,SN2诱导消除反应和取代反应为竞争的次反应通道,计算结果与实验相吻合.%The reaction mechanism of BrO- with CH3Cl has been investigated using the MP2 level of theory with aug-cc-pVDZ basis set. The single-point energies have also been refined at the CCSD(T)/augcc-pVDZ level to get more accurate energies. Computational results indicate that BrO- +CH3Cl initially proceed a traditional SN2 mechanism, generating an energy-enriched intermediate IM2 (BrOCH3 … Cl),then followed by decomposition of IM2 produce P1 (BrOCH3+Cl) in SN2 mechanism. IM2 can also occur an elimination reaction between carbon and oxygen atoms. Further substitution reaction takes place on oxygen atom. The former primary generates P2 (CH2O+ HCl+Br- ), the latter primary produces P3 (CH3OCl+Br-). The channel of traditional SN2 reaction is the main reaction channel, while the minor channels of SN2-induction elimination reactions and substitution reactions are the competitive reaction channels. It is very reasonable and considerably consistent with the experimental.

  18. Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

    Directory of Open Access Journals (Sweden)

    F. Ziska

    2013-09-01

    Full Text Available Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3, dibromomethane (CH2Br2 and methyl iodide (CH3I. The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere database (https://halocat.geomar.de/. Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol Br yr−1 for CH3I (robust fit/ordinary least squares regression techniques. Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the

  19. ALMA backed NIR high resolution integral field spectroscopy of the NUGA galaxy NGC 1433

    CERN Document Server

    Smajic, Semir; Eckart, Andreas; Valencia-S., Monica; Combes, Francoise; Horrobin, Matthew; Garcia-Burillo, Santiago; Garcia-Marin, Macarena; Fischer, Sebastian; Zuther, Jens

    2014-01-01

    We present the results of near-infrared (NIR) H- and K-band European Southern Observatory SINFONI integral field spectroscopy (IFS) of the Seyfert 2 galaxy NGC 1433. We present emission and absorption line measurements in the central kpc of NGC 1433. We detect a narrow Balmer line and several H2 lines. We find that the stellar continuum peaks in the optical and NIR in the same position, indicating that there is no covering of the center by a nuclear dust lane. A strong velocity gradient is detected in all emission lines at that position. The position angle of this gradient is at 155\\deg whereas the galactic rotation is at a position angle of 201\\deg. Our measures of the molecular hydrogen lines, hydrogen recombination lines, and [Feii] indicate that the excitation at the nucleus is caused by thermal excitation, i.e. shocks which can be associated with active galactic nuclei emission, supernovae or outflows. The line ratios [Feii]/Pa{\\beta} and H2/Br{\\gamma} show a Seyfert to LINER identification of the nucleu...

  20. Exploring a Lead-free Semiconducting Hybrid Ferroelectric with a Zero-Dimensional Perovskite-like Structure.

    Science.gov (United States)

    Sun, Zhihua; Zeb, Aurang; Liu, Sijie; Ji, Chengmin; Khan, Tariq; Li, Lina; Hong, Maochun; Luo, Junhua

    2016-09-19

    Perovskite lead halides (CH3 NH3 PbI3 ) have recently taken a promising position in photovoltaics and optoelectronics because of remarkable semiconducting properties and possible ferroelectricity. However, the potential toxicity of lead arouses great environmental concern for widespread application. A new chemically tailored lead-free semiconducting hybrid ferroelectric is reported, N-methylpyrrolidinium)3 Sb2 Br9 (1), which consists of a zero-dimensional (0-D) perovskite-like anionic framework connected by corner- sharing SbBr6 coordinated octahedra. It presents a large ferroelectric spontaneous polarization of approximately 7.6 μC cm(-2) , as well as notable semiconducting properties, including positive temperature-dependent conductivity and ultraviolet-sensitive photoconductivity. Theoretical analysis of electronic structure and energy gap discloses a dominant contribution of the 0-D perovskite-like structure to the semiconducting properties of the material. This finding throws light on the rational design of new perovskite-like hybrids, especially lead-free semiconducting ferroelectrics.

  1. Source regions of stratospheric VSLS in the Indian Ocean

    Science.gov (United States)

    Quack, Birgit; Hepach, Helmke; Atlas, Elliot; Bracher, Astrid; Endres, Sonja; Arevalo-Martinez, Damian; Bange, Hermann; Lennartz, Sinikka; Steinhoff, Tobias; Booge, Dennis; Zarvasky, Alexander; Marandino, Christa; Patey, Matt; Achterberg, Eric; Dengler, Markus; Fiehn, Alina; Tegtmeier, Susann; Krüger, Kirstin

    2016-04-01

    Halogenated very-short-lived substances (VSLS), which are naturally produced in the ocean, play a significant role in present day ozone depletion, in particular in combination with enhanced stratospheric sulfate aerosol, which is also partly derived from oceanic VSLS. The decline of anthropogenic chlorine in the stratosphere within the 21st century will increase the relative importance of the natural emissions on stratospheric ozone destruction. Especially, oceanic sources and source regions of the compounds need to be better constrained, in order to improve the future prediction. During boreal summer the Asian monsoon circulation transports air masses from the Indian Ocean to the stratosphere, while the contribution of VSLS from this ocean to stratospheric halogen and sulfur is unknown. During the research cruises SO 234/2 and SO 235 in July-August 2014 onboard RV SONNE oceanic and atmospheric halogenated VSLS such as bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) were measured in the subtropical and tropical West Indian Ocean for the first time. Here we present the oceanic sources of the halogenated compounds and their relation to other biogeochemical parameters (short- and longlived trace gases, phytoplankton and nutrients) along the cruise track, which covered coastal, upwelling and open ocean regimes and the Seychelles-Chagos thermocline ridge as important source region for stratospheric bromine.

  2. Death Associated Protein Kinases: Molecular Structure and Brain Injury

    Directory of Open Access Journals (Sweden)

    Claire Thornton

    2013-07-01

    Full Text Available Perinatal brain damage underlies an important share of motor and neurodevelopmental disabilities, such as cerebral palsy, cognitive impairment, visual dysfunction and epilepsy. Clinical, epidemiological, and experimental studies have revealed that factors such as inflammation, excitotoxicity and oxidative stress contribute considerably to both white and grey matter injury in the immature brain. A member of the death associated protein kinase (DAPk family, DAPk1, has been implicated in cerebral ischemic damage, whereby DAPk1 potentiates NMDA receptor-mediated excitotoxicity through interaction with the NR2BR subunit. DAPk1 also mediate a range of activities from autophagy, membrane blebbing and DNA fragmentation ultimately leading to cell death. DAPk mRNA levels are particularly highly expressed in the developing brain and thus, we hypothesize that DAPk1 may play a role in perinatal brain injury. In addition to reviewing current knowledge, we present new aspects of the molecular structure of DAPk domains, and relate these findings to interacting partners of DAPk1, DAPk-regulation in NMDA-induced cerebral injury and novel approaches to blocking the injurious effects of DAPk1.

  3. DDE-MURR Status Report of Conceptual Design Activities

    Energy Technology Data Exchange (ETDEWEB)

    N.E. Woolstenhulme; R.B. Nielson; M.H. Sprenger; G.K. Housley

    2013-09-01

    The Design Demonstration Experiment for the University of Missouri Research Reactor (DDE-MURR) is intended to facilitate Low Enriched Uranium (LEU) conversion of the MURR by demonstrating the performance and fabrication of the LEU fuel element design through an irradiation test in a 200mm channel at the Belgium Reactor 2 (BR2). Revision 0 of this report was prepared at the end of government fiscal year 2012 when most of the resources for furthering DDE design work were expected to be postponed. Hence, the conceptual design efforts were summarized to provide the status of key objectives, notable results, and provisions for future design work. Revision 1 of this report was prepared at the end of fiscal year 2013 in order to include results from a neutronic study performed by BR2, to incorporate further details that had been achieved in the engineering sketches of the irradiation devices, and to provide an update of the DDE-MURR campaign in relation to program objectives and opportunities for its eventual irradiation. These updates were purposed to bring the DDE-MURR conceptual design to level of maturity similar to that of the other two DDE efforts (DDE-MITR and DDE-NBSR). This report demonstrates that the DDE-MURR design effort is well on the path to producing a suitable irradiation experiment, but also puts forth several recommendations in order to facilitate success of the irradiation campaign.

  4. Collection Usage Pre- and Post-Summon Implementation at the University of Manitoba

    Directory of Open Access Journals (Sweden)

    Lisa O’Hara

    2012-12-01

    Full Text Available Objectives – This study examines the use of print and electronic collections bothbefore and after implementation of Summon at the University of Manitoba Libraries.Summon is a web-scale discovery service which allows discovery of all of thematerials the library owns or has access to from a simple search box on the library’sweb page.Methods – COUNTER statistics were used to determine database, e-journal, and ebookstatistics, including database search statistics (DR1 from the COUNTERDatabase Report 1, full-text article downloads from the COUNTER Journal Report 1(JR1, and successful section search requests from the COUNTER Book Report 2 (BR2for electronic resources. Sirsi, the University of Manitoba’s integrated library system,provided statistics on checkouts for the libraries’ circulating print monograph andserial collections. The percentage change from the pre-Summon implementationperiod to the post-Summon implementation period was calculated and these numberswere used to determine whether usage had increased or decreased for both print andelectronic collections.Results – As expected, searches in citation databases decreased because searches wereno longer being carried out in the native database as the metadata from the databaseis included in Summon. E-journal usage increased dramatically and e-book usage alsoincreased for four of six providers examined. Print usage decreased, but the resultswere inconclusive.Conclusions – Summon implementation had a favourable impact on collection usage.

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

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL

    2012-01-01

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

  6. Conversion of bromine during thermal decomposition of printed circuit boards at high temperature.

    Science.gov (United States)

    Jin, Yu-qi; Tao, Lin; Chi, Yong; Yan, Jian-hua

    2011-02-15

    The conversion of bromine during the thermal decomposition of printed circuit boards (PCBs) was investigated at isothermal temperatures ranging from 800°C to 1100°C by using a quartz tube furnace. The influence of temperature, oxygen concentrations (0%, 10% and 21% in the nitrogen-oxygen atmosphere) and content of steam on conversion of bromine was studied. With the increment of temperature, the conversion from organic bromine in the PCBs to inorganic bromine in the gaseous fraction increased from 69.0% to 96.4%. The bromine was mainly evolved as HBr and Br(2) in oxidizing condition and the Br(2)/HBr mass ratio increased at stronger oxidizing atmosphere. The experimental results also indicated that the existence of steam can reduce the formation of Br(2). Furthermore, co-combustion of PCBs with S and CaO, both as addition agents, was investigated, respectively. In the presence of SO(2), Br(2)/HBr mass ratio obviously decreased. Moreover, the utilization of calcium oxide can efficiently promote the conversion of organic bromine to inorganic bromine. According to the experimental results, incinerating PCBs at high temperature can efficiently destroy the organobrominated compounds that are considered to be possible precursors of polybrominated dibenzeo-p-dioxins and dibenzofurans (PBDD/Fs), but the Br(2) and HBr in flue gas should be efficiently controlled.

  7. Studies on crystal structures, optical and electrical properties of viologen cation salts of d10 metal halide anions

    Science.gov (United States)

    Du, Haijuan; Li, Yaru; Xu, Manman; Niu, Yunyin; Hou, Hongwei

    2017-04-01

    Construction of viologen cation salts of d10 metal halide anions (inorganic-organic hybrid materials) with semiconducting properties via supramolecular design and aggregate enable the hybrid materials multifunctionality. Our interest focused on the use of the viologen derivatives as the building units because they were redox-active units and more suited to yield new generation of multifunctional networks. In the present investigation, three new inorganic-organic hybrid semiconductors {[bbpyb]·[AgBr3]}n (1) [1, 3-PMBP][Zn2Cl5.1Br0.9] (2) and [1, 3-PMBP][Zn2Br6] (3) (bbpyb = 1,1″-(1,4-butanediyl)bis[4,4‧-bipyridinium]bis[bromide], 1,3-PMBP = 1,1″-[1,3-phenylene-bis(methylene)]bis-4,4‧-bipyridinium-bisbromide) were synthesized. More importantly, great efforts were devoted to investigate their properties, such as optical and electrical properties. 1-3 exhibited photochromism, which can be ascribed to the intermolecular charge transfer to yield radicals. Fabricating the appropriate inorganic and organic units controllably within photosensitive materials at a molecular level is critical for the development of new photochromic inorganic-organic hybrids.

  8. Synthesis, Chemosensory Properties, and Self-Assembly of Terpyridine-Containing Conjugated Polycarbazole through RAFT Polymerization and Heck Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Po-Chih Yang

    2017-09-01

    Full Text Available We report the responsive fluorescence chemosensory phenomena of a carbazole-functionalized crosslinked polymer (PCaT with pendent terpyridine (tpy groups as receptors of metal ions. The polymer was synthesized using Heck polymerization between 3,6-dibromide groups in a carbazole-based polymer (PC2Br and divinyl tpy monomer. The effects of the polymeric structure on the optical and chemosensory properties of the PCaT were compared with those of a carbazole-tpy alternating conjugated polymer (PCT. Photoluminescence titrations demonstrated that the PCaT and PCT had the high sensing ability toward Fe3+ ions, with Stern–Volmer constants of 8.10 × 104 and 6.68 × 104 M−1, respectively. The limit of detection (LOD toward Fe3+ of the PCaT and PCT was estimated to be 1.31 × 10−6 and 1.81 × 10−6 M, respectively, and the superior LOD of the PCaT was ascribed to its lowly crosslinked structure. The fluorescence of the solutions of these polymers that were quenched by Fe3+ ions recovered when trace CN− anions were added because of the high stability constant of the CN−–Fe3+ complex. Micellar aggregates with a mean diameter of approximately 239.5 nm were formed by dissolving the PCaT in tetrahydrofuran (THF solution. Our results suggest that the PCaT is a promising material for chemosensory applications.

  9. Comparative study between 1-Propyl-3-methylimidazolium bromide and trimethylene bis-methylimidazolium bromide ionic liquids by FTIR/ATR and FT-RAMAN spectroscopies

    Science.gov (United States)

    Kadari, Mohamed; Belarbi, El Habib; Moumene, Taqiyeddine; Bresson, Serge; Haddad, Boumediene; Abbas, Ouissam; Khelifa, Brahim

    2017-09-01

    In this study, we synthesized two ionic liquids based on imidazolium: one is a monocationic and the other is a dicationic. They are respectively 1-Propyl-3-methylimidazolium bromide ([PrMIM+][Br-]) and trimethylene bis-methylimidazolium bromide ([M(CH2)3IM2+][2Br-]). The structures of these two ionic liquids which are composed of ions with atoms of the same nature were first identified by 1H,13C NMR, and then compared in a study by FT-RAMAN and FTIR/ATR spectroscopies. FT-RAMAN spectras of the dicationic ionic liquid are richer in modes in the different spectral regions. Hence this richness seems to be a consequence of the passage from one to two rings in the imidazolium cation. In particular, the vibrational modes in the spectral ranges 700-600 cm-1, 1700-1500 cm-1 and 3200-2700 cm-1 by FTIR/ATR seem to be sensitive to the change from mono to dicationic than in FT-RAMAN. The spectral range in which the intermolecular interactions are present (200-50 cm-1) is a marker of differentiation between the mono and the dicationic. The spectral ranges on 1700-1200 cm-1 and 3200-2700 cm-1 also show signs of upheaval between our two samples. We can also notice that there are much more active modes in FT-RAMAN spectroscopy than in FTIR/ATR spectroscopy.

  10. Syntheses, crystal structures, reactivity, and photochemistry of gold(III) bromides bearing N-heterocyclic carbenes.

    Science.gov (United States)

    Hirtenlehner, Christa; Krims, Charlotte; Hölbling, Johanna; List, Manuela; Zabel, Manfred; Fleck, Michel; Berger, Raphael J F; Schoefberger, Wolfgang; Monkowius, Uwe

    2011-10-14

    Gold(I) complexes bearing N-heterocyclic carbenes (NHC) of the type (NHC)AuBr (3a/3b) [NHC = 1-methyl-3-benzylimidazol-2-ylidene (= MeBnIm), and 1,3-dibenzylimidazol-2-ylidene (= Bn(2)Im)] are prepared by transmetallation reactions of (tht)AuBr (tht = tetrahydrothiophene) and (NHC)AgBr (2a/2b). The homoleptic, ionic complexes [(NHC)(2)Au]Br (6a/6b) are synthesized by the reaction with free carbene. Successive oxidation of 3a/3b and 6a/6b with bromine gave the respective (NHC)AuBr(3) (4a/4b) and [(NHC)(2)AuBr(2)]Br (7a/7b) in good overall yields as yellow powders. All complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex. Irradiation of the Au(III) complexes with UV light yield the Au(I) congeners in a clean photo-reaction.

  11. Synthesis, characterization and spectrochemical studies on a few binuclear -oxo molybdenum(V) complexes of pyrimidine derived Schiff base ligands

    Indian Academy of Sciences (India)

    Samik Gupta; Somnath Roy; Tarak Nath Mandal; Kinsuk Das; Sangita Ray; Ray J Butcher; Susanta Kumar Kar

    2010-03-01

    Ten new binuclear singly oxo-bridged molybdenum complexes (complexes 1-10) were prepared using five pyrimidine derived Schiff base ligands and two Mo(V) precursors (NH4)2MoOCl5 and (NH4)2MoOBr5. The ligands are prepared by the condensation of 4,6-dimethyl 2-hydrazino pyrimidine with salicylaldehyde (for HL1), -hydroxy acetophenone (for HL2) and substituted salicylaldehydes (for HL3, HL4 and HL5) respectively. These ligands are already reported as good donors for Mo(VI) state. The -oxo Mo(V) complexes reported here bears a distorted octahedral geometry around each Mo atom with either N2O2Cl or N2O2Br chromophores. Fine variations in the spectroscopic behaviour of the complexes are observed in accordance with the varying electron donating properties of the ligands. All the complexes are unstable in solution and X-ray quality crystal of complex 1 could be isolated. All the complexes are characterized by IR and UV-Vis spectra.

  12. FATE OF REVERSE OSMOSIS (RO) MEMBRANES DURING OXIDATION BY DISINFECTANTS USED IN WATER TREATMENT: IMPACT ON MEMBRANE STRUCTURE AND PERFORMANCES

    KAUST Repository

    Maugin, Thomas

    2013-12-01

    Providing pretreatment prior RO filtration is essential to avoid biofouling and subsequent loss of membrane performances. Chlorine is known to degrade polymeric membrane, improving or reducing membrane efficiency depending on oxidation conditions. This study aimed to assess the impact of alternative disinfectant, NH2Cl, as well as secondary oxidants formed during chloramination of seawater, e.g. HOBr, HOI, or used in water treatment e.g. ClO2, O3, on membrane structure and performances. Permeability, total and specific rejection (Cl-, SO4 2-, Br-, Boron), FTIR profile, elemental composition were analyzed. Results showed that each oxidant seems to react differently with the membrane. HOCl, HOBr, ClO2 and O3 improved membrane permeability but decreased rejection in different extent. In comparison, chloramines resulted in identical trends but oxidized membrane very slowly. On the contrary, iodine improved membrane rejection e.g. boron, but decreased permeability. Reaction conducted with chlorine, bromine, iodine and chloramines resulted in the incorporation of halogen in the membrane structure. All oxidant except iodine were able to break amide bonds of the membrane structure in our condition. In addition, chloramine seemed to react with membrane differently, involving a potential addition of nitrogen. Chloramination of seawater amplified membrane performances evolutions due to generation of bromochloramine. Moreover, chloramines reacted both with NOM and membrane during oxidation in natural seawater, leading to additional rejection drop.

  13. Substitution of conventional high-temperature syntheses of inorganic compounds by near-room-temperature syntheses in ionic liquids

    KAUST Repository

    Groh, Matthias Friedrich

    2013-01-01

    The high-temperature syntheses of the low-valent halogenides P2I4, Te2Br, α-Te4I4, Te4(Al2Cl7)2, Te4(Bi6Cl20), Te8(Bi4Cl14),Bi8(AlCl4)2, Bi6Cl7,and Bi6Br7, as well as of WSCl4 andWOCl4 have been replaced by resource-efficient low-temperature syntheses in room temperature ionic liquids (RTILs). The simple one-pot syntheses generally do not require elaborate equipment such as twozone furnaces or evacuated silica ampoules. Compared to the published conventional approaches, reduction of reaction time (up to 80%) and temperature (up to 500 K) and, simultaneously, an increase in yield were achieved. In the majority of cases, the solid products were phase-pure. X-Ray diffraction on single crystals (redetermination of 11 crystal structures) has demonstrated that the quality of the crystals from RTILs is comparable to that of products obtained by chemical transport reactions. © 2013 Verlag der Zeitschrift für Naturforschung, Tübingen.

  14. Oxidative Carbonylation of Methanol to Dimethyl Carbonate Over Cu(II)-1,10-Phenanthroline Bromide Complexes☆

    Institute of Scientific and Technical Information of China (English)

    Zhiping Du⁎; Lihua Xiong; Zhikun Lin; Xuli Li; Yigang Ding; Yuanxin Wu

    2014-01-01

    In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate (DMC), CuBr2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2, [Cu(phen)2Br]Br and [Cu(phen)3]Br2 (phen=1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2 exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)−1 with selectivity of 92.8%under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1 (below the explosion limit of CO) and catalyst concentration of 0.011 mol·L−1. Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.

  15. Mid-infrared Emission and Energy Transfer Properties of Sensitized Nd^3+ Ions in Low Phonon-Energy Hosts

    Science.gov (United States)

    Bluiett, Althea; Jacobitz, Natasha; Stokes, Natasha; Brown, Eiei; Hommerich, Uwe; Trivedi, Sudhir; Zavada, John

    2008-10-01

    Mid-infrared emission (4-6 μm) stemming from the first excited state of Nd^3+ can be generated in KPb2Cl5 by pumping its ^4F5/2 absorption band at ˜800 nm. It has been proposed that 4-6 μm emission of Nd^3+ could be enhanced by directly pumping the ^4I15/2 absorption band centered at ˜1650 nm. This pumping scheme could initiate a 3-for-1 cross relaxation, which ultimately increases the population in the first excited state of Nd^3+. Unfortunately, the ^4I15/2 absorption band of Nd^3+ is weak and diode laser pumping of this level is not practical. To more efficiently populate the ^4I15/2 level in Nd: KPb2Cl5, Tm sensitization of Nd^3+ via ˜1700 nm excitation is under exploration. Experimental results show that the Tm♢Nd energy transfer was successful with energy transfer efficiencies ranging from 46% - 98%. The energy transfer was followed by strong 4-6 μm emission from co-doped Tm, Nd: KPb2Cl5 samples. Preliminary results on Tm, Nd: KPb2Br5 will also be discussed.

  16. Orientation towards asymmetric transfer hydrogenation of ketones catalyzed by (pyrazolyl)ethyl)pyridine Fe(II) and Ni(II) complexes

    Science.gov (United States)

    Magubane, Makhosazane N.; Alam, Mohd Gulfam; Ojwach, Stephen O.; Munro, Orde Q.

    2017-05-01

    Compounds 2-[1-(3,5-dimethylpyrazol-1-yl)ethyl]pyridine (L1) and 2-[1-(3,5-diphenylpyrazol-1-yl)ethyl]pyridine (L2) were obtained in a three-step procedure which involved the reduction of acetylpyridine using NaBH4, chlorination of the alcohol intermediate using SOCl2 and subsequent reaction with appropriate pyrazoles. Reactions of L1 and L2 with Ni(II) and Fe(II) halides produced the respective complexes Ni(L1)Br2 (1), Ni(L1)Cl2 (2), Fe(L1)Cl2 (3) and Ni(L2)Br2 (4) as racemic mixtures in moderate yields. The molecular structures of complexes 1 and 4 are dinuclear and mononuclear respectively. All the complexes (1-4) formed active catalysts for the transfer hydrogenation of ketones (THK) in 2-propanol at 82 °C affording conversions of 58%-84% within 48 h. The influence of catalyst structure, reaction conditions and identity of ketone substrates in the TH reactions have been successfully established.

  17. Phase Separation and Microstructure of Mixed Surfactants Solution Containing Cationic Geminis and Traditional Anionic Surfactant

    Institute of Scientific and Technical Information of China (English)

    尚亚卓; 刘洪来; 胡英

    2004-01-01

    The properties of aqueous two-phase system (ATPS) of mixed solution containing gemini cationic surfactant trimethylene-l,3-bis(dodecyldimethyl ammonium) bromide (12-3-12, 2Br-) and traditional anionic surfactant sodium dodecyl sulfate (SDS) with or without added salt have been studied. An ATPS is formed in a narrow region of the ternary phase diagram different from that of traditional aqueous cationic-anionic surfactant systems. In ATPS region, the lowest total concentration of surfactants varies with the mixing ratio of geminis to SDS. Photographs obtained from freeze-etching, negative-staining and transmission electron microscopy show that the microstructures of two phases are different from each other. Micelles and vesicles can coexist in a single phase. The addition of salts can change the phase diagram of ATPS. Furthermore, the added salts promote the aggregation of rod-like micelles to form coarse network structure that increase the viscosity of solutions. The negative ions of the added salts are the determining factor.

  18. Octafluorodirhenate(III) Revisited: Solid-State Preparation, Characterization, and Multiconfigurational Quantum Chemical Calculations.

    Science.gov (United States)

    Mariappan Balasekaran, Samundeeswari; Todorova, Tanya K; Pham, Chien Thang; Hartmann, Thomas; Abram, Ulrich; Sattelberger, Alfred P; Poineau, Frederic

    2016-06-01

    A simple method for the high-yield preparation of (NH4)2[Re2F8]·2H2O has been developed that involves the reaction of (n-Bu4N)2[Re2Cl8] with molten ammonium bifluoride (NH4HF2). Using this method, the new salt [NH4]2[Re2F8]·2H2O was prepared in ∼90% yield. The product was characterized in solution by ultraviolet-visible light (UV-vis) and (19)F nuclear magnetic resonance ((19)F NMR) spectroscopies and in the solid-state by elemental analysis, powder X-ray diffraction (XRD), and infrared (IR) spectroscopy. Multiconfigurational CASSCF/CASPT2 quantum chemical calculations were performed to investigate the molecular and electronic structure, as well as the electronic absorption spectrum of the [Re2F8](2-) anion. The metal-metal bonding in the Re2(6+) unit was quantified in terms of effective bond order (EBO) and compared to that of its [Re2Cl8](2-) and [Re2Br8](2-) analogues.

  19. Crystal Structure of an LSD-Bound Human Serotonin Receptor

    Energy Technology Data Exchange (ETDEWEB)

    Wacker, Daniel; Wang, Sheng; McCorvy, John D.; Betz, Robin M.; Venkatakrishnan, A.J.; Levit, Anat; Lansu, Katherine; Schools, Zachary L.; Che, Tao; Nichols, David E.; Shoichet, Brian K.; Dror, Ron O.; Roth, Bryan L. (UNCSM); (UNC); (Stanford); (Stanford-MED); (UCSF)

    2017-01-01

    The prototypical hallucinogen LSD acts via serotonin receptors, and here we describe the crystal structure of LSD in complex with the human serotonin receptor 5-HT2B. The complex reveals conformational rearrangements to accommodate LSD, providing a structural explanation for the conformational selectivity of LSD’s key diethylamide moiety. LSD dissociates exceptionally slow from both 5-HT2BR and 5-HT2AR—a major target for its psychoactivity. Molecular dynamics (MD) simulations suggest that LSD’s slow binding kinetics may be due to a “lid” formed by extracellular loop 2 (EL2) at the entrance to the binding pocket. A mutation predicted to increase the mobility of this lid greatly accelerates LSD’s binding kinetics and selectively dampens LSD-mediated β-arrestin2 recruitment. This study thus reveals an unexpected binding mode of LSD; illuminates key features of its kinetics, stereochemistry, and signaling; and provides a molecular explanation for LSD’s actions at human serotonin receptors.

  20. Palladium(Ⅱ)-dppe-arylazoimidazole Complexes: Synthesis and Spectroscopic Charecterization

    Institute of Scientific and Technical Information of China (English)

    PRITHWIRA Byabartta

    2008-01-01

    Reaction of [Pd(dppe)Cl2/Br2] with AgOTf in a dichloromethane medium followed by ligand addition led to [Pd(dppe)(OSO2CF3)2] and then [Pd(dppe)(RaaiR')](OSO2CF3)2 [RaaiR'-p-R-C6H4-NN-C3H2-NN-1-R',(1-3),abbreviated as a N,N'-chelator,where N(imidazole)and N(azo)are represented by N and N',respectively;R=H(a),Me(b),Cl(c)and R'=Me(1),CH2CH3(2),CH2Ph(3),OSO2CF3 is the triflate anion,dppe=1,2-bis-(diphenylphosphinoethane)].31p NMR confirmed that due to the two phosphorus atom interaction in the azoimine symmetrical environment one sharp peak was formed.The 1H NMR spectral measurements suggest that azo-imine links with lot of phenyl protons in the aromatic region.13C NMR spectrum,1H-1H COSY and 1H-13C HMQC spec-trum assign the solution structure and stereo-retentive conformation in each complex.

  1. Formation of reactive halide species by myeloperoxidase and eosinophil peroxidase.

    Science.gov (United States)

    Spalteholz, Holger; Panasenko, Oleg M; Arnhold, Juergen

    2006-01-15

    The formation of chloro- and bromohydrins from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine following incubation with myeloperoxidase or eosinophil peroxidase in the presence of hydrogen peroxide, chloride and/or bromide was analysed by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. These products were only formed below a certain pH threshold value, that increased with increasing halide concentration. Thermodynamic considerations on halide and pH dependencies of reduction potentials of all redox couples showed that the formation of a given reactive halide species in halide oxidation coupled with the reduction of compound I of heme peroxidases is only possible below a certain pH threshold that depends on halide concentration. The comparison of experimentally derived and calculated data revealed that Cl(2), Br(2), or BrCl will primarily be formed by the myeloperoxidase-H(2)O(2)-halide system. However, the eosinophil peroxidase-H(2)O(2)-halide system forms directly HOCl and HOBr.

  2. An experimental and theoretical investigation of the N + C2 reaction at low temperature

    CERN Document Server

    Loison, Jean-Christophe; Han, Shanyu; Hickson, Kevin M; Guo, Hua; Xie, Daiqian

    2014-01-01

    Rate constants for the N + C2 reaction have been measured in a continuous supersonic flow reactor over the range 57 K to 296 K by the relative rate technique employing the N + OH - H + NO reaction as a reference. Excess concentrations of atomic nitrogen were produced by the microwave discharge method and C2 and OH radicals were created by the in-situ pulsed laser photolysis of precursor molecules C2Br4 and H2O2 respectively. In parallel, quantum dynamics calculations were performed based on an accurate global potential energy surfaces for the three lowest lying quartet states of the C2N molecule. The 14A" potential energy surface is barrierless, having two deep potential wells corresponding to the NCC and CNC intermediates. Both the experimental and theoretical work show that the rate constant decreases to low temperature, although the experimentally measured values fall more rapidly than the theoretical ones except at the lowest temperatures. Astrochemical simulations indicate that this reaction could be the...

  3. Laser photolysis-resonance fluorescence technique (LP-RF) applied to the study of reactions of atmospheric interest

    Science.gov (United States)

    Albaladejo, J.; Cuevas, C. A.; Notario, A.; Martínez, E.

    Atomic chlorine is highly reactive with a variety of organic and inorganic compounds so that relatively small concentrations can compete with the tropospheric oxidants (OH, O3 and NO3) in determining the tropospheric fate of such compounds [1]. Besides, there is a lot of evidence that bromine compounds play significant role in the ozone chemistry both in the troposphere and in the stratosphere [2]. In this work we show the laser photolysis-resonance fluorescence technique (LP-RF) applied to the study of gas phase reactions of halogen atoms with volatile organic compounds (VOCs) of interest in atmospheric chemistry [3]. By means of this technique is possible to measure the rate constants of theses reactions, and subsequently obtain the Arrhenius parameters. Halogens atoms are produced in a excess of the VOC and He, by photolyzing Cl2 at 308 nm to obtain Cl atoms, or CF2Br2 at 248 nm for Br atoms, both cases using a pulsed excimer laser. The radiation (135 nm) from a microwave-driven lamp, through which He containing a low concentrations of Cl2 or Br2 was flowed, was used to excite the resonance fluorescence from the corresponding halogen atom in the jacketed Pyrex reaction cell. Signal were obtained using photon-counting techniques in conjunction with multichannel scaling. The fluorescence signal from the PMT was processed by a preamplifier and sent to an multichannel scaler to collect the time-resolved signal. The multichannel scaler was coupled to a microcomputer for further kinetics analysis.

  4. Iron Hydride Detection and Intramolecular Hydride Transfer in a Synthetic Model of Mono-Iron Hydrogenase with a CNS Chelate.

    Science.gov (United States)

    Durgaprasad, Gummadi; Xie, Zhu-Lin; Rose, Michael J

    2016-01-19

    We report the identification and reactivity of an iron hydride species in a synthetic model complex of monoiron hydrogenase. The hydride complex is derived from a phosphine-free CNS chelate that includes a Fe-C(NH)(═O) bond (carbamoyl) as a mimic of the active site iron acyl. The reaction of [((O═)C(HN)N(py)S(Me))Fe(CO)2(Br)] (1) with NaHBEt3 generates the iron hydride intermediate [((O═)C(HN)N(py)S(Me))Fe(H)(CO)2] (2; δFe-H = -5.08 ppm). Above -40 °C, the hydride species extrudes CH3S(-) via intramolecular hydride transfer, which is stoichiometrically trapped in the structurally characterized dimer μ2-(CH3S)2-[((O═)C(HN)N(Ph))Fe(CO)2]2 (3). Alternately, when activated by base ((t)BuOK), 1 undergoes desulfurization to form a cyclometalated species, [((O═)C(NH)NC(Ph))Fe(CO)2] (5); derivatization of 5 with PPh3 affords the structurally characterized species [((O═)C(NH)NC)Fe(CO)(PPh3)2] (6), indicating complex 6 as the common intermediate along each pathway of desulfurization.

  5. Time dependent profile retrieval of UV/vis absorbing radicals from balloon-borne limb measurements – a case study on NO2 and O3

    Directory of Open Access Journals (Sweden)

    R. Schofield

    2010-07-01

    Full Text Available A new "Bayesian" minimization algorithm for the retrieval of the diurnal variation of UV/vis absorbing radicals (O3, NO2, BrO, OClO and HONO from balloon-borne limb scattered skylight observations is discussed. The method evaluates spectroscopic measurements in combination with radiative transfer calculations to drive a mathematical inversion on a discrete time and height grid. Here, the proposed method is applied to data obtained during two deployments of the mini-DOAS instrument on different balloon payloads in northern Brazil in June 2005. The retrieval is tested by comparing the inferred profiles to in-situ ozone sounding data and to measurements of the ENVISAT/SCIAMACHY satellite instrument performed during a collocated overpass. The comparison demonstrates the strength and validity of our approach. In particular for time-varying radical concentrations, photochemical corrections due to temporal mismatch of the corresponding observations are rendered dispensable. Thus, limb scanning UV/vis spectrometry from balloon platforms offers a more direct and concise approach for satellite validation of radical measurements than solar occultation measurements. Furthermore, monitoring of the diurnal variation of stratospheric radicals allows us to constrain photochemical parameters which are critical for stratospheric ozone chemistry, such as the photolysis frequency of N2O5 by observations of the diurnal variation of NO2.

  6. A Class of Promising Acaricidal Tetrahydroisoquinoline Derivatives: Synthesis, Biological Evaluation and Structure-Activity Relationships

    Directory of Open Access Journals (Sweden)

    Rui Yang

    2014-06-01

    Full Text Available As part of our continuing research on isoquinoline acaricidal drugs, this paper reports the preparation of a series of the 2-aryl-1-cyano-1,2,3,4-tetrahydroisoquinolines with various substituents on the N-phenyl ring, their in vitro acaricidal activities against Psoroptes cuniculi, a mange mite, and discusses their SAR as well. The structures of all compounds, including 12 new ones, were elucidated by analysis of UV, IR, NMR, ESI-MS, HR-MS spectra and X-ray diffraction experiments. All target compounds showed varying degrees of activity at 0.4 mg/mL. Compound 1 showed the strongest activity, with a 50% lethal concentration value (LC50 of 0.2421 μg/mL and 50% lethal time value (LT50 of 7.79 h, comparable to the standard drug ivermectin (LC50 = 0.2474 μg/mL; LT50 = 20.9 h. The SAR showed that the substitution pattern on the N-aromatic ring exerted a significant effect on the activity. The substituents 2'-F, 3'-F, 2'-Cl, 2'-Br and 2'-CF3 remarkably enhanced the activity. Generally, for the isomers with the same substituents at different positions, the order of the activity was ortho > meta > para. It was concluded that the target compounds represent a class of novel promising candidates or lead compounds for the development of new tetrahydroisoquinoline acaricidal agents.

  7. A Survey of Irradiated Pillars, Globules, and Jets in the Carina Nebul

    CERN Document Server

    Hartigan, P; Smith, N; Bally, J

    2015-01-01

    We present wide-field, deep narrowband H$_2$, Br$\\gamma$, H$\\alpha$, [S II], [O III], and broadband I and K-band images of the Carina star formation region. The new images provide a large-scale overview of all the H$_2$ and Br$\\gamma$ emission present in over a square degree centered on this signature star forming complex. By comparing these images with archival HST and Spitzer images we observe how intense UV radiation from O and B stars affects star formation in molecular clouds. We use the images to locate new candidate outflows and identify the principal shock waves and irradiated interfaces within dozens of distinct areas of star-forming activity. Shocked molecular gas in jets traces the parts of the flow that are most shielded from the intense UV radiation. Combining the H$_2$ and optical images gives a more complete view of the jets, which are sometimes only visible in H$_2$. The Carina region hosts several compact young clusters, and the gas within these clusters is affected by radiation from both the...

  8. Two novel two-dimensional copper(II) coordination polymers with 1-(4-aminobenzyl)-1,2,4-triazole: Synthesis, crystal structure, magnetic characterization and absorption of anion pollutants

    Science.gov (United States)

    Zhang, Xin; Wu, Xiang Xia; Guo, Jian-Hua; Huo, Jian-Zhong; Ding, Bin

    2017-01-01

    In this work a flexible multi-dentate 1-(4-aminobenzyl)-1,2,4-triazole (abtz) ligand has been employed, two novel triazole-Cu(II) coordination polymers {[Cu(abtz)2(Br)2]·(H2O)2}n (1) and {[Cu(abtz)2]·(SiF6)·(H2O)2}n (2) have been isolated under solvo-thermal conditions. 1 is a 2D neutral CuII coordination polymer while 2 is 2D cation micro-porous CuII coordination polymer with the channel dimensionalities of 11.852(1) Å × 11.852(1) Å (metal-metal distances). Variable-temperature magnetic susceptibility data of 1 and 2 have been recorded in the 2-300 K temperature range indicating weak anti-ferromagnetic interactions. Further absorption properties of anion pollutants for 2 also have been investigated. 2 presents the novel example of cationic triazole-copper(II) coordination framework for effectively capturing anion pollutants Cr2O72- in the water solutions and selectively capturing Congo Red in the methanol solutions.

  9. Extraction and separation of U(VI and Th(IV from hydrobromic acid media using Cyanex-923 extractant

    Directory of Open Access Journals (Sweden)

    Ghag Snehal M.

    2010-01-01

    Full Text Available A systematic study of the solvent extraction of uranium(VI and thorium(IV from hydrobromic acid media was performed using the neutral phosphine oxide extractant Cyanex-923 in toluene. These metal ions were found to be quantitatively extracted with Cyanex-923 in toluene in the acidity range 5x10-5-1x10-4 M and 5x10-5-5x10-3 M, respectively, and they are stripped from the organic phase with 7.0 M HClO4 and 2.0- 4.0 M HCl, respectively. The effect of the equilibrium period, diluents, diverse ions and stripping agent on the extraction of U(VI and Th(IV was studied. The stoichiometry of the extracted species of these metal ions was determined based on the slope analysis method. The extraction reactions proceed by solvation and their probable extracted species found in the organic phase were UO2Br2•2Cyanex-923 and ThBr4•2Cyanex-923. Based on these results, a sequential procedure for their separation from each other was developed.

  10. Inhibition behavior of some new mixed additives upon copper electrowinning

    Institute of Scientific and Technical Information of China (English)

    YU Run-lan; LIU Qing-ming; QIU Guan-zhou; FANG Zheng; TAN Jian-xi; YANG Peng

    2008-01-01

    As thiourea and sulfur-containing mixed additives contaminate cathodic copper, inhibition behavior of some new mixed additives such as gelatin+hexadecylpyridinium bromide (HDPBr), gelatin+polyethylene glycol(PEG), gelatin+polyacryl amide (PAM), gelatin+PEG+cetyl-tri-methyl ammonium bromide (CTABr) and gelatin+PAM+CTABr was investigated by cyclic voltammetry as well as cathodic polarization in order to improve the quality of cathodic copper in bio-metallurgical process. The results indicate that the inhibition performances of these additives are dependent on complex and adsorption behaviors as well as the deposit potential. For a solution of acidic copper sulpate containing 40 g/L Cu2+ and 180 g/L H2SO4, the additive (gelatin+HDPBr) is the most efficient among the investigated additives because HDPBr with a large organic cation and π electron can adsorb on the cathodic surface to block the active sites and Br- ion can precipitate Cu,'2+. To form Cu2Br2. The additive (gelatin+PAM) also has a better inhibition performance, while the additives (gelatin+PEG), (gelatin+PEG+CTABr) and (gelatin+PAM+CTABr) are comparatively lower inhibition performance compared with the additive (gelatin+thiourea) which has been frequently used so far.

  11. Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2.

    Science.gov (United States)

    Chen, Jian Q; Hu, Zhi J; Wang, Nan X

    2012-01-01

    The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO(2). The effect of catalyst loading shows an optimal value (0.4 g L(-1)) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min(-1), which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K(2)S(2)O(8), H(2)O(2) and KBrO(3)) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S(2)O(8)(2-) > BrO(3)(-) > H(2)O(2). Finally, the Langmuir-Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO(2) surfaces and L-H model constants were also determined.

  12. Platinum(II) and platinum(IV) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes.

    Science.gov (United States)

    Khlebnikov, Vsevolod; Heckenroth, Marion; Müller-Bunz, Helge; Albrecht, Martin

    2013-03-28

    Platinum(II) complexes comprising abnormal diimidazolylidene ligands were synthesized from cis-PtMe(2)(DMSO)(2) using microwave-assisted double C-H bond activation. NMR analysis revealed an unusual solvolysis process, induced by coordinating solvents such as DMSO and MeCN, which has not been observed in related normal dicarbene complexes. NMR and IR spectroscopy and crystallographic analysis of the mono-substituted DMSO complex indicate a sulfur-bonding of the DMSO ligand to the platinum(II) center. Analysis of the DMSO exchange kinetics provided for the first time a quantitative measure of the trans effect of abnormal carbene ligands. The kinetic exchange rate in these bidentate abnormal dicarbene complexes is 0.050(±2) s(-1) and thus similar to analogous platinum(II) complexes containing phenylpyridine, yet significantly slower than that induced by pyridylidene pyridine. Reaction of the dicarbene platinum(II) complexes with PhICl(2), Br(2) and I(2) afforded the corresponding platinum(IV) complexes. Linkage isomerism of the Pt(IV)-bound DMSO was observed when the bromination reaction was performed in DMSO solution. Moreover, solvolysis was less pronounced in the platinum(IV) complexes than in the corresponding platinum(II) analogues.

  13. CD4 and MHC class I down-modulation activities of nef alleles from brain- and lymphoid tissue-derived primary HIV-1 isolates

    Science.gov (United States)

    Gray, Lachlan R.; Gabuzda, Dana; Cowley, Daniel; Ellett, Anne; Chiavaroli, Lisa; Wesselingh, Steven L.; Churchill, Melissa J.; Gorry, Paul R.

    2015-01-01

    HIV-1 nef undergoes adaptive evolution in the CNS, reflecting altered requirements for HIV-1 replication in macrophages/microglia and brain-specific immune selection pressures. The role of Nef in HIV-1 neurotropism and the pathogenesis of HIV-associated dementia (HAD) is unclear. In this study, we characterized 82 nef alleles cloned from brain, CSF, spinal cord and blood/lymphoid tissue-derived HIV-1 isolates from 7 subjects with HAD. CNS isolate-derived nef alleles were genetically compartmentalized and had reduced sequence diversity compared to those from lymphoid tissue isolates. Defective nef alleles predominated in a brain-derived isolate from one of the 7 subjects (MACS2-br). The ability of Nef to down-modulate CD4 and MHC class 1 (MHC-1) was generally conserved among nef alleles from both CNS and lymphoid tissues. However, the potency of CD4 and MHC-1 down-modulation was variable, which was associated with sequence alterations known to influence these Nef functions. These results suggest that CD4 and MHC-1 down-modulation are highly conserved functions among nef alleles from CNS- and lymphoid tissue-derived HIV-1 isolates that may contribute to viral replication and escape from immune surveillance in the CNS. PMID:21165790

  14. Anisotropic mobility and carrier dynamics in the β-type BEDT-TTF salts as studied by inter-layer transverse magnetoresistance

    Directory of Open Access Journals (Sweden)

    Shigeharu Sugawara and Masafumi Tamura

    2013-01-01

    Full Text Available A new method to estimate an in-plane conduction anisotropy in a quasi-two-dimensional (q2D layered conductor by measuring the inter-layer transverse magnetoresistance is proposed. We applied this method to layered organic conductors β-(BEDT-TTF2X (BEDT-TTF = bis(ethylenedithiotetrathiafulvalene, C10H8S8; X = IBr2, I2Br by applying magnetic field rotating within the basal plane at 4.2 K. We found the anisotropic behaviour of carrier mobility μ. From this, anomalous distribution of carrier lifetime τ on the Fermi surface is derived, by the use of Fermi surface data reported for the materials. Calculations of the non-uniform susceptibility χ0(q suggest that carrier scattering is enhanced at specific k-points related to partial nesting of the Fermi surface. The present method is thus demonstrated to be an efficient experimental tool to elucidate anisotropic carrier dynamics in q2D conductors.

  15. Kinetico-mechanistic information about alkene hydroamination with aniline in bromide-rich ionic media: importance of solvolysis.

    Science.gov (United States)

    Aullón, Gabriel; Gómez, Kerman; González, Gabriel; Jansat, Susanna; Martínez, Manuel; Poli, Rinaldo; Rodríguez-Zubiri, Mireia

    2011-06-20

    The study of the [PtBr(4)](2-) reactivity with hexene and aniline in highly ionic (Bu(4)P)Br/CH(2)Br(2) media has been studied from a Kinetico-Mechanistic perspective. The results indicate bromide ion association to the square-planar starting material to produce a stable diamagnetic compound that can be described as an ion pair of a [PtBr(5)](3-) square-pyramidal complex stabilized by several phosphonium countercations. While this species reacts rapidly with aniline, producing the known square-planar complex [PtBr(3)(PhNH(2))](-) with release of the apical bromide of the square-pyramidal intermediate, the reaction with hexene, producing the square-planar [PtBr(3)(hexene)](-) complex, is much slower. The thermal and pressure activation parameters determined for these processes fully agree with the proposed reactivity. The gross features of the platinum-catalyzed hydroamination mechanism, occurring via much higher energy transition states, are not necessarily altered by these new findings, given the fact that all ligand exchange reactions occur with relatively low activation barriers. Nevertheless, the nature of the catalyst resting state needs revision as demonstrated. The importance of explicitly considering the solvent for reactions conducted in noninnocent highly organized media is also highlighted. © 2011 American Chemical Society

  16. The effect of desiccation on the emission of volatile bromocarbons from two common temperate macroalgae

    Directory of Open Access Journals (Sweden)

    E. C. Leedham Elvidge

    2014-07-01

    Full Text Available Exposure of intertidal macroalgae during low tide has been linked to the emission of a variety of atmospherically-important trace gases into the coastal atmosphere. In recent years, several studies have investigated the role of inorganic iodine and organoiodides as antioxidants and their emission during exposure to combat oxidative stress, yet the role of organic bromine species during desiccation is less well understood. In this study the emission of dibromomethane (CH2Br2 and bromoform (CHBr3 during exposure and desiccation of two common temperate macroalgae, Fucus vesiculosus and Ulva intestinalis, is reported. Determination of the impact exposure may have on algal physiological processes is difficult as intertidal species are adapted to desiccation and may undergo varying degrees of desiccation before their physiology is affected. For this reason we include comparisons between photosynthetic capacity (Fv / Fm and halocarbon emissions during a desiccation time series. In addition, the role of rewetting with freshwater to simulate exposure to rain was also investigated. Our results show that an immediate flux of bromocarbons occurs upon exposure, followed by a decline in bromocarbon emissions. We suggest that this immediate bromocarbon pulse may be linked to volatilisation or emissions of existing bromocarbon stores from the algal surface rather than the production of bromocarbons as an antioxidant response.

  17. Molecular and Ionized Hydrogen in 30 Doradus. I. Imaging Observations

    CERN Document Server

    Yeh, Sherry C C; Matzner, Christopher D; Pellegrini, Eric W

    2015-01-01

    We present the first fully calibrated H$_2$, 1-0 S(1) image of the entire 30 Doradus nebula. The observations were conducted using the NOAO Extremely Wide-Field Infrared Imager on the CTIO 4-meter Blanco Telescope. Together with a NEWFIRM Br$\\gamma$ image of 30 Doradus, our data reveal the morphologies of the warm molecular gas and ionized gas in 30 Doradus. The brightest H$_2$-emitting area, which extends from the northeast to the southwest of R136, is a photodissociation region viewed face-on, while many clumps and pillar features located at the outer shells of 30 Doradus are photodissociation regions viewed edge-on. Based on the morphologies of H$_2$, Br$\\gamma$, $^{12}$CO, and 8$\\mu$m emission, the H$_2$ to Br$\\gamma$ line ratio and Cloudy models, we find that the H$_2$ emission is formed inside the photodissociation regions of 30 Doradus, 2 - 3 pc to the ionization front of the HII region, in a relatively low-density environment $<$ 10$^4$ cm$^{-3}$. Comparisons with Br$\\gamma$, 8$\\mu$m, and CO emissi...

  18. Crystal structure of bis-{(S)-1-[2-(di-phenyl-phosphan-yl)ferrocen-yl]-(R)-eth-yl}ammonium bromide di-chloro-methane monosolvate.

    Science.gov (United States)

    Zirakzadeh, Afrooz; Stöger, Berthold; Kirchner, Karl

    2017-02-01

    During the synthesis of an FeBr2 complex with the PNP ligand (R,R,SFc,SFc)-[Fe2(C5H5)2(C38H35NP2)] (1), single crystals of the di-chloro-methane monosolvate of the Br(-) salt of the protonated ligand 1H(+) were obtained serendipitously, i.e. [Fe2(C5H5)2(C38H36NP2)]Br·CH2Cl2. The crystal structure of 1H·Br·CH2Cl2 was determined by single-crystal X-ray diffraction. The mean bond lengths in the ferrocene units are Fe-C = 2.049 (3) Å and C-C = 1.422 (4) Å within the cyclo-penta-dienyl rings. The mean C-N bond length is 1.523 (4) Å. The inter-planar angle between the two connected cyclo-penta-dienyl rings is 49.2 (2)°. One ferrocene moiety adopts a staggered conformation, whereas the other is between staggered and eclipsed. The Br(-) ions and the CH2Cl2 mol-ecules are located in channels extending along . One ammonium H atom forms a hydrogen bond with the Br(-) ion [H⋯Br = 2.32 (4) Å and C-H⋯Br = 172 (3)°]. The second ammonium H atom is not involved in hydrogen bonding.

  19. Near-infrared line imaging of the circumnuclear starburst rings in the active galaxies NGC 1097 and NGC 6574

    CERN Document Server

    Kotilainen, J K; Laine, S; Ryder, S D

    1999-01-01

    We present high spatial resolution near-infrared broad-band JHK and Br_gamma 2.166 micron and H_2 1-0 S(1) 2.121 micron emission line images of the circumnuclear star formation rings in the LINER/Seyfert 1 galaxy NGC 1097 and the Seyfert 2 galaxy NGC 6574. We investigate the morphology, extinction, and the star formation properties and history of the rings, by comparing the observed properties with an evolutionary population synthesis model. The clumpy morphology in both galaxies varies strongly with wavelength, due to a combination of extinction, hot dust and red supergiants, and the age of the stellar populations. The near-infrared and radio morphologies are in general agreement, although there are differences in the detailed morphology. From the comparison of Br_gamma and H_alpha fluxes, we derive average extinctions toward the hot spots A_V = 1.3 for NGC 1097 and A_V = 2.1 for NGC 6574. The observed H_2/Br_gamma ratios indicate that in both rings the main excitation mechanism of the molecular gas is UV ra...

  20. Near-infrared line imaging of the starburst galaxies NGC 520, NGC 1614 and NGC 7714

    CERN Document Server

    Kotilainen, J K; Laine, S; Ryder, S D

    2001-01-01

    We present high spatial resolution (0.6 arcsec) near-infrared broad-band JHK images and Br_gamma 2.1661 micron and H_2 1-0 S(1) 2.122 micron emission line images of the nuclear regions in the interacting starburst galaxies NGC 520, NGC 1614 and NGC 7714. The near-infrared emission line and radio morphologies are in general agreement, although there are differences in details. In NGC 1614, we detect a nuclear double structure in Br_gamma, in agreement with the radio double structure. We derive average extinctions of A(K) = 0.41 and A(K) = 0.18 toward the nuclear regions of NGC 1614 and NGC 7714, respectively. For NGC 520, the extinction is much higher, A(K) = 1.2 - 1.6. The observed H_2/Br_gamma ratios indicate that the main excitation mechanism of the molecular gas is fluorescence by intense UV radiation from clusters of hot young stars, while shock excitation can be ruled out. The starburst regions in all galaxies exhibit small Br_gamma equivalent widths. Assuming a constant star formation model, even with a...

  1. Sensitivity study of SMILES-2 for chemical species

    Science.gov (United States)

    Suzuki, Makoto; Manago, Naohiro; Ozeki, Hiroyuki; Ochiai, Satoshi; Baron, Philippe

    2015-10-01

    Sensitivity studies of temperature and chemical species (Observed by ISS/JEM/SMILES: O3, HCl, ClO, HO2, BrO, HNO3, CH3CN, and Not observed by SMILES: Temperature, H2O, N2O, NO2, NO, CH3Cl, CO, H2CO, OH and O-atom) was carried out for the SMILES-2 proposal, a sub-mm and THz observation of limb emission from space over the spectral region from 400 GHz to 2.5 THz. Tentative but optimal candidate of frequency bands to cover these species was selected with 3 SIS (Superconductor-Insulator-Superconductor) mixers; SIS-1 (485-489 GHz + 523-527 GHz), SIS-2 (623-627 GHz + 648-652 GHz), SIS-3 (557 GHz + 576.3 GHz) and 2 HEB (Hot Electron Bolometer); HEB-1 (1.8 THz OH) and HEB-2 (2.06 THz O-atom). Temperature can be retrieved with 1 K precision and 1 km vertical resolution from 15 to 120 km. Other chemical species also showed very high single scan precision (random error) comparable to statistical standard error of previous satellite measurements.

  2. Cl2 Measurements in Polluted Coastal Air Using a Br- Addition CIMS Technique

    Science.gov (United States)

    Lawler, M. J.; Saltzman, E. S.

    2008-12-01

    Molecular chlorine (Cl2) was measured in ambient air using chemical ionization mass spectrometry (CIMS) with Br- as a reagent ion. Ionization was carried out by adding CHBr3 to ambient air and flowing the gas mixture through a 63Ni ion source maintained at 300 Torr. The resulting Cl2Br- adduct was collisionally dissociated in a triple quadrupole mass spectrometer and detected as Cl-. Ambient Cl2 measurements were made at Irvine, CA, from August 1-8, 2008. Air was drawn to the instrument from outside via a ~4m long laminar flow inlet. Inlet and instrument blanks were assessed by passing ambient air through carbonate-coated glass wool, and the instrument was calibrated with a Cl2 permeation tube. During this study, the mean detection limit for Cl2 was estimated at approximately 2 ppt. Cl2 showed a diel cycle on the days it was detectable, with nighttime mixing ratios up to about 15 ppt and daytime values of a few ppt or less. A rapid decrease in Cl2 in surface air was observed overnight in association with stagnation of the nocturnal surface layer.

  3. Two new CuI compounds with zwitterionic tetrazolate ligand: In situ synthesis, crystal structures, luminescence and photocatalytic properties

    Science.gov (United States)

    Zhang, Jian-Yong; Xing, Yuan-Yuan; Wang, Qing-Wei; Zhang, Na; Deng, Wei; Gao, En-Qing

    2015-12-01

    Two 2D new Cu(I) coordination polymers, namely [Cu2(mpTZ)2Br2]·H2O (1), and [Cu2(mpTZ)2N3]ClO4 (2) (mpTZ=N-methyl-4-pyridinium tetrazolate) have been synthesized under solvothermal conditions, in which the mpTZ ligands and CuI ions were obtained through in situ [2+3] cycloaddition reaction and reduction reaction of CuII salts, respectively. Both compounds have been structural characterized by single crystal X-ray diffraction, FT-IR, PXRD and EA. Compound 1 exhibits a 2D neutral coordination network, in which the CuI ions are bridged by η3-1, 2, 4-tetrazolate into 2D sheet. In compound 2, the CuI ions are linked by azide (in μ3-1, 1, 3 bridging mode) and tetrazolate (in η3-1, 2, 3 bridging mode) anions into 2D positively charged sheet, extended along the bc plane. Both compounds 1 and 2 exhibit intense bluish green luminescence in the solid state. Photocatalytic performances of the two compounds for the degradation of methylene blue (MB) under visible light were also investigated and the MB degradation in the presence of 1 was nearly complete (99%) after 150 min.

  4. Validation of respiratory inductive plethysmography (LifeShirt) in obesity hypoventilation syndrome.

    Science.gov (United States)

    Hollier, Carly A; Harmer, Alison R; Maxwell, Lyndal J; Menadue, Collette; Willson, Grant N; Black, Deborah A; Piper, Amanda J

    2014-04-01

    Validation of respiratory inductive plethysmography (LifeShirt system) (RIPLS) for tidal volume (VT), minute ventilation (V˙E), and respiratory frequency (fB) was performed among people with untreated obesity hypoventilation syndrome (OHS) and controls. Measures were obtained simultaneously from RIPLS and a spirometer during two tests, and compared using Bland Altman analysis. Among 13 OHS participants (162 paired measures), RIPLS-spirometer agreement was unacceptable for VT: mean difference (MD) 3 mL (1%); limits of agreement (LOA) -216 to 220 mL (±36%); V˙E MD 0.1 L min(-1) (2%); LOA -4.1 to 4.3 L min(-1) (±36%); and fB: MD 0.2 br min(-1) (2%); LOA -4.6 to 5.0 br min(-1) (±27%). Among 13 controls (197 paired measures), RIPLS-spirometer agreement was acceptable for fB: MD -0.1 br min(-1) (-1%); LOA -1.2 to 1.1 br min(-1) (±12%), but unacceptable for VT: MD 5 mL (1%); LOA -160 to 169 mL (±20%) and V˙E: MD 0.1 L min(-1) (1%); LOA -1.4 to 1.5 L min(-1) (±20%). RIPLS produces valid measures of fB among controls but not OHS patients, and is not valid for quantifying respiratory volumes among either group.

  5. Loss-of-Flow and Loss-of-Pressure Simulations of the BR2 Research Reactor with HEU and LEU Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Licht, J. [Argonne National Lab. (ANL), Argonne, IL (United States); Bergeron, A. [Argonne National Lab. (ANL), Argonne, IL (United States); Dionne, B. [Argonne National Lab. (ANL), Argonne, IL (United States); Sikik, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Van den Branden, G. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Koonen, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium)

    2016-01-01

    Belgian Reactor 2 (BR2) is a research and test reactor located in Mol, Belgium and is primarily used for radioisotope production and materials testing. The Materials Management and Minimization (M3) Reactor Conversion Program of the National Nuclear Security Administration (NNSA) is supporting the conversion of the BR2 reactor from Highly Enriched Uranium (HEU) fuel to Low Enriched Uranium (LEU) fuel. The reactor core of BR2 is located inside a pressure vessel that contains 79 channels in a hyperboloid configuration. The core configuration is highly variable as each channel can contain a fuel assembly, a control or regulating rod, an experimental device, or a beryllium or aluminum plug. Because of this variability, a representative core configuration, based on current reactor use, has been defined for the fuel conversion analyses. The code RELAP5/Mod 3.3 was used to perform the transient thermal-hydraulic safety analyses of the BR2 reactor to support reactor conversion. The input model has been modernized relative to that historically used at BR2 taking into account the best modeling practices developed by Argonne National Laboratory (ANL) and BR2 engineers.

  6. New method for the synthesis of N-methyl amino acids containing peptides by reductive methylation of amino groups on the solid phase.

    Science.gov (United States)

    Kaljuste, K; Undén, A

    1993-08-01

    Primary amino groups on the model peptide Xaa-Ala-Pro-Lys(ClZ)-Tyr(2BrZ), synthesized on a p-methylbenzhydryl amine resin with conventional Boc/benzyl protective group strategy, were reacted with 4,4'-dimethoxydityl chloride in dichloromethane, resulting in the introduction of the dimethoxydityl group, which is an acid-labile N-alkyl type of protective group. The secondary amino groups thereby formed can be methylated by treating the peptide-resin with formaldehyde and sodium cyanoborohydride in N,N-dimethylformamide. After the removal of the dimethoxydityl group with trifluoroacetic acid, the resulting N-methylated amino acid residues with a free secondary amino groups are accessible for acylation with the next activated Boc amino acid. With this method majority of the 20 common amino acids can be monomethylated directly on the resin and, in most cases, with very low levels of the side reactions. In the cases where the complete methylation is difficult to achieve, the remaining primary amino groups can be selectively acylated in the presence of secondary amino groups with trimethylacetic acid 1-hydroxybenzotriazole ester. The method provides a convenient general route to synthesize N-methylated derivatives of most of the occurring and synthetic amino acids.

  7. Photoluminescent mixed ligand complexes of CuX (X = Cl, Br, I) with PPh3 and a polydentate imino-pyridyl ligand - Syntheses, structural variations and catalytic property

    Science.gov (United States)

    Ghorai, Anupam; Mondal, Jahangir; Patra, Goutam K.

    2015-10-01

    Three ternary copper(I) complexes [CuI2Cl2(L1)(PPh3)4] (1), [CuI2Br2(L1) (PPh3)4] (2) and [CuI2(μ-I)2 (μ-L1) (PPh3)2]n (3) have been prepared by reactions of CuX (X = Cl, Br and I) with PPh3 and the polydentate imino-pyridyl ligand L1. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR and X-ray crystallography. From single crystal structural analysis it has been found that complexes 1 and 2 are homo-dinuclear having non-bridging halide ions whereas complex 3 is a 1-D zig-zag co-ordination polymer containing bridged iodide ions. Complexes 1, 2 and 3 are photoluminescent at room temperature in chloroform whereas ligand L1 is non-emissive. The E½ values of the CuIsbnd CuII couple of 1, 2 and 3 are 0.98 V, 0.92 V and 0.42 V respectively (vs Ag/AgCl in 1 M KCl, scan rate 100 mV s-1). All three complexes function as effective catalysts for the synthesis of 2-substituted benzoxazoles.

  8. A Selective Membrane Electrode for Thiocyanate Ion Based on a Bis-taurine-salicylic Binuclear Copper(Ⅱ) Complex as Ionophore

    Institute of Scientific and Technical Information of China (English)

    王福昌; 柴雅琴; 袁若; 陈春华; 戴建远; 徐岚

    2005-01-01

    The response characteristics of a new potentiometric membrane electrode with unique selectivity towards thiocyanate ion were reported. The electrode was prepared by incorporating bis-taurine-salicylic binuclear copper(Ⅱ) complex into a plasticized PVC-membrane. The resulting electrode exhibits anti-Hofmeister selectivity sequence: SCN->I-> ClO4- >Sal-> NO3- > NO2- >Br->Cl-> SO3- > SO42- and a near-Nernstian potential linear range for thiocyanate from 1.0×10-1 to 1.0× 10-6 mol·L-1 with a detection limit of 8.0× 10-7 mol·L-1 and a slope of - 56.5 mV/PCSCN- in phosphate buffer solution of pH 5.0 at 20 ℃. The UV/Vis spectra, IR spectroscopy and AC impedance studies showed that the excellent selectivity to thiocyanate was related to the unique interaction between the central metal and the analyte and a steric effect associated with the structure of the carrier. The electrode was successfully applied to the determination of thiocyanate in waste water and human urine samples.

  9. Synthesis, characterization, cytotoxicity and antiangiogenic activity of copper(II) complexes with 1-adamantoyl hydrazone bearing pyridine rings.

    Science.gov (United States)

    Rodić, Marko V; Leovac, Vukadin M; Jovanović, Ljiljana S; Spasojević, Vojislav; Joksović, Milan D; Stanojković, Tatjana; Matić, Ivana Z; Vojinović-Ješić, Ljiljana S; Marković, Violeta

    2016-06-10

    Three novel copper complexes with tridentate N2O ligand di(2-pyridil) ketone 1-adamantoyl hydrazone (Addpy) of the formula [Cu(II)2Cu(I)2(Addpy)2Br2(μ-Br4)] (1), catena-poly[CuCl(μ-Addpy)(μ-Cl)CuCl2]n (2) and [Cu(Addpy)(NCS)2] (3) were synthesized. Complexes are characterized by X-ray crystallography, spectral (UV-Vis, FTIR), electrochemical (CV) analyses, and magnetochemical measurements. Investigation of anticancer potential of Cu(II) complexes, mode of cell death, apoptosis, and inhibition of angiogenesis were performed. All tested malignant cell lines (HeLa, LS174, A549, K562, and MDA-MB-231) showed high sensitivity to the examined Cu(II) complexes. It has been shown that the complexes induce apoptosis in the caspase 3-dependent manner, whereas the anti-angiogenic effects of 1, 2, and 3 have been confirmed in EA.hy926 cells using a tube formation assay.

  10. Common Mathematical Model of Fatigue Characteristics

    Directory of Open Access Journals (Sweden)

    Z. Maléř

    2004-01-01

    Full Text Available This paper presents a new common mathematical model which is able to describe fatigue characteristics in the whole necessary range by one equation only:log N = A(R + B(R ∙ log Sawhere A(R = AR2 + BR + C and B(R = DR2 + AR + F.This model was verified by five sets of fatigue data taken from the literature and by our own three additional original fatigue sets. The fatigue data usually described the region of N 104 to 3 x 106 and stress ratio of R = -2 to 0.5. In all these cases the proposed model described fatigue results with small scatter. Studying this model, following knowledge was obtained:– the parameter ”stress ratio R” was a good physical characteristic– the proposed model provided a good description of the eight collections of fatigue test results by one equation only– the scatter of the results through the whole scope is only a little greater than that round the individual S/N curve– using this model while testing may reduce the number of test samples and shorten the test time– as the proposed model represents a common form of the S/N curve, it may be used for processing uniform objective fatigue life results, which may enable mutual comparison of fatigue characteristics.

  11. Function of Halides in Gold Dissolution Process of Au(Ⅰ)-sulfite Synthesizing%卤化物在合成亚硫酸金盐溶金过程中的作用

    Institute of Scientific and Technical Information of China (English)

    马彩莲; 袁守谦; 张良; 李东亮

    2011-01-01

    用离子交换膜电解法研究了金在Na2SO3溶液中加入Cl-、Br-后的阳极溶解机理.结果表明,在Na2 SO3溶液中加入Cl-和Br-后,由于竞争配位作用可以加快金的溶解速率.Br-在阳极表面被氧化生成初生态Br2,Br2可以快速氧化阳极金从而更有效地抑制SO32-氧化,有利于获得高纯度Na3 Au(SO3)2溶液.%Mechanism of gold anodic dissolution was studied by adding Cl , Br into sodium suliite solution through ion-exchange membrane electrolysis. Results indicated that gold dissolution rate in Na2SO3 solution was enhanced due to the competitive coordinate function of Cl ~ and Br " . On anode surface, Br ~ was easy to be oxidized to nascent Br2 which could oxidize the gold quickly, so oxidation of SO32- was inhibited and high purity Na3Au(SO3)2 solution was obtained effectively.

  12. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    Directory of Open Access Journals (Sweden)

    T. P. Bui

    2010-07-01

    Full Text Available Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4 campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE, in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  13. Vertical transport rates and concentrations of OH and Cl radicals in the Tropical Tropopause Layer from Observations of CO2 and halocarbons: implications for distributions of long- and short-lived chemical species

    Directory of Open Access Journals (Sweden)

    T. P. Bui

    2010-03-01

    Full Text Available Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4 campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE, in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

  14. Charge ordering in low dimensional organic conductors: Structural aspects

    Energy Technology Data Exchange (ETDEWEB)

    Pouget, Jean-Paul; Foury-Leylekian, Pascale [Laboratoire de Physique des Solides, Universite Paris-sud, CNRS UMR 8502, Batiment 510, 91405 Orsay Cedex (France); Alemany, Pere [Departament de Quimica Fisica and Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona, Diagonal 627, 08028 Barcelona (Spain); Canadell, Enric [Institut de Ciencia de Materials de Barcelona, CSIC, Campus UAB, 08193 Bellaterra (Spain)

    2012-05-15

    The paper points out the importance of the coupling between anions and donors in order to achieve the 4k{sub F} charge localization observed in (TMTTF){sub 2}PF{sub 6}, {delta}-(EDT-TTF-CONMe{sub 2}){sub 2}Br and (o-DMTTF){sub 2}Cl/Br salts, the 2k{sub F} charge density wave (CDW) ground state of {alpha}-(BEDT-TTF){sub 2}KHg(SCN){sub 4} and the metal to insulator transition of {alpha}-(BEDT-TTF){sub 2}I{sub 3}. This coupling leads to a cooperative displacement wave of the anions accompanied by a modulation of the density of {pi} holes on the donors. We distinguish two principal anion-donor coupling mechanisms: a direct mechanism via the Hartree anion potential on donor sites and an indirect mechanism via the polarization of {sigma} bonds activated by the modification of the H bonds network. Both kinds of interaction are tuned by the relative displacement of the anions with respect to the donors. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Quantitative Trait Locus Analysis of Seed Germination and Seedling Vigor in Brassica rapa Reveals QTL Hotspots and Epistatic Interactions.

    Science.gov (United States)

    Basnet, Ram K; Duwal, Anita; Tiwari, Dev N; Xiao, Dong; Monakhos, Sokrat; Bucher, Johan; Visser, Richard G F; Groot, Steven P C; Bonnema, Guusje; Maliepaard, Chris

    2015-01-01

    The genetic basis of seed germination and seedling vigor is largely unknown in Brassica species. We performed a study to evaluate the genetic basis of these important traits in a B. rapa doubled haploid population from a cross of a yellow-seeded oil-type yellow sarson and a black-seeded vegetable-type pak choi. We identified 26 QTL regions across all 10 linkage groups for traits related to seed weight, seed germination and seedling vigor under non-stress and salt stress conditions illustrating the polygenic nature of these traits. QTLs for multiple traits co-localized and we identified eight hotspots for quantitative trait loci (QTL) of seed weight, seed germination, and root and shoot lengths. A QTL hotspot for seed germination on A02 mapped at the B. rapa Flowering Locus C (BrFLC2). Another hotspot on A05 with salt stress specific QTLs co-located with the B. rapa Fatty acid desaturase 2 (BrFAD2) locus. Epistatic interactions were observed between QTL hotspots for seed germination on A02 and A10 and with a salt tolerance QTL on A05. These results contribute to the understanding of the genetics of seed quality and seeding vigor in B. rapa and can offer tools for Brassica breeding.

  16. Comparison of N-nitrosodimethylamine formation mechanisms from dimethylamine during chloramination and ozonation: A computational study.

    Science.gov (United States)

    Liu, Yong Dong; Zhong, Rugang

    2017-01-05

    N-nitrosodimethylamine (NDMA) as a disinfection by-product has recently become the focus of considerable research interest due to its unusually high carcinogenicity. In this study, the formation mechanisms of NDMA from dimethylamine (DMA) during chloramination and ozonation were investigated by using the quantum chemical G4 method. The reactivity of haloamines and hydroxylamine reacting with DMA was found in the order: NHCl2∼NHBrCl (Br-leaving)>NHBr2>NH2Cl∼NH2Br>NH2OH. This offers a theoretical support for the experimentally proposed mechanism that dimethylamine reacts with NHCl2 rather than NH2Cl to form chlorinated unsymmetrical dimethylhydrazine intermediate and the existence of bromochloramine in the presence of bromide during chloramination, and explains the observation that NDMA yield during ozonation is much lower than that during chloramination. Importantly, an N,N-dimethylaminonitrene was found to be a significant intermediate to form NDMA in oxidation reactions by molecular oxygen and ozone. Additionally, results suggest that the amines containing the second nitrogen source directly connecting or close to the N-(CH3)2 moiety are potential significant NDMA precursors upon ozonation. The findings of this study are helpful for expanding the knowledge of NDMA formation mechanism, and predicting potential NDMA precursors during disinfection. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Synthesis of /sup 14/C-labelled crotamiton

    Energy Technology Data Exchange (ETDEWEB)

    Chaudhuri, N.K.; Potdar, S.V.; Ball, T.J. (CIBA-GEIGY Corp., Ardsley, NY (USA). Pharmaceuticals Div.)

    1982-01-01

    The synthesis of /sup 14/C-labelled crotamiton, which is a fungicide, an insecticide as well as a scabicide is described. Starting from 2-bromonitrobenzene and Cu/sup 14/CN, o-toluidine, labelled with /sup 14/C at the methyl group was prepared by the following sequence of reactions: NO/sub 2/-C/sub 6/H/sub 4/-Br ..-->.. NO/sub 2/-C/sub 6/H/sub 4/-/sup 14/CN ..-->.. NO/sub 2/-C/sub 6/H/sub 4/-/sup 14/COOH ..-->.. NO/sub 2/-C/sub 6/H/sub 4/-/sup 14/CH/sub 2/OH ..-->.. NO/sub 2/-C/sub 6/H/sub 4/-/sup 14/CH/sub 2/Br ..-->.. NH/sub 2/-C/sub 6/H/sub 4/-/sup 14/CH/sub 3/. Labelled o-toluidine was then heated with crotonic anhydride to give crotonic acid o-toluidide which was then ethylated by treatment with sodium hydride and ethyl iodide to obtain labelled crotamiton.

  18. Synthesis, structural visualization, spectroscopic, and thermal studies of charge transfer Cu(II, Ni(II and Zn(II bromides-carbamide complexes at elevated temperature

    Directory of Open Access Journals (Sweden)

    Khlood Abou-Melha

    2015-09-01

    Full Text Available In the present study, the composition and structure of Cu(II, Ni(II and Zn(II compounds resulted from the chemical reactions of copper(II, nickel(II and zinc(II bromide salts with carbamide in aqueous media at 95 oC have been investigated, using IR, electron spin resonance ESR and x-ray powder diffraction spectroscopy as well as thermal analysis TG/DTG/DSC. The Cu2(OH3Br, [Ni2(NCO2(H2O2(Br2], and ZnCO3.xH2O compounds were achieved by a novel synthetic route through with a low cost precursor like carbamide. The infrared spectra of the results indicate absence of the individual bands of carbamide, but exhibited of the distinguished bands of hydroxyl, isocyanate, NCO, and ionic carbonate, CO32– for Cu(II, Ni(II and Zn(II compounds, respectively. Visualized investigations were performed to confirm crystal structure, validity and stability of the product compounds. A general reaction mechanisms describing the preparation of Cu(II, Ni(II, and Zn(II compounds were discussed.

  19. Synthesis and characterization of different zinc(II) oxide nano-structures from two new zinc(II)-Quinoxaline coordination polymers

    Science.gov (United States)

    Molaei, Fatemeh; Bigdeli, Fahime; Morsali, Ali; Joo, Sang Woo; Bruno, Giuseppe; Rudbari, Hadi Amiri

    2015-09-01

    Two new zinc(II) coordination polymers, [Zn(Quinoxaline)(NO3)2(H2O)2]nṡQuinoxaline·H2O (1) and [Zn(Quinoxaline)2(Br)2]n (2), Quinoxaline = Benzopyrazine, have been synthesized and characterized by IR spectroscopy. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are one-dimensional coordination polymers with coordination environment of octahedral and tetrahedral respectively. Nanostructures of zinc(II) oxide were obtained by thermolyses of compound 1 in oleic acid, calcination of compound 1 at 500 °C under air atmosphere and sol-gel processes. Also, nanopowders of zinc(II) oxide were obtained by calcination of compound 2 at 450 and 550 °C. The nanomaterials were characterized by scanning electron microscopy and X-ray powder diffraction (XRD). The thermal stability of compounds 1 and 2 both their bulk were studied by thermo-gravimetric (TGA) and differential thermal analyses (DTA). This study demonstrates the coordination polymers may be suitable precursors for the preparation of nanoscale materials.

  20. Hydrothermal syntheses and characterization of two novel luminescent Cadmium(II) frameworks: From 1D infinite triple Cd-(trz)-Cd bridges to a rare I2O0 network with 2D Cd-Br-Cd inorganic connectivity

    Science.gov (United States)

    Liu, Shi Xin; Li, Jian Hui; Wang, You You; Wu, Xiang Xia; Huo, Jian Zhong; Ding, Bin; Wang, Xiu Guang; Zhu, Zhao Zhou; Xia, Jun

    2015-05-01

    Using the 4-substituted-1,2,4-triazole derivate ligand 4-p-tolyl-1,2,4-triazole (L), two novel luminescent Cadmium(II) frameworks, namely {[Cd(μ2-L)3]·(NO3)2·L}n (1) and [Cd1.5(μ2-L)(μ2-Br)2(μ3-Br)]n (2) have been isolated under hydrothermal conditions. The structural analysis reveals that 1 presents a one-dimensional (1D) chain structural motif containing novel infinite triple Cd-(trz)-Cd bridges (triply trz-bridged M-M species). While 2 presents a rare I2O0 type framework, in which the infinite 2D Cd-Br-Cd inorganic connectivity with a 4-connected Kagome topology can be observed. The FT-IR, PXRD and thermal stabilities of 1-2 have investigated. The solid-state photo-luminescent spectra of organic ligand L and 1-2 also have been measured indicating strong emission bands.

  1. Polystyrene-divinylbenzene stationary phases agglomerated with quaternized multi-walled carbon nanotubes for anion exchange chromatography.

    Science.gov (United States)

    Huang, Zhongping; Wu, Hongwei; Wang, Fengli; Yan, Wenwu; Guo, Weiqiang; Zhu, Yan

    2013-06-14

    This work explores the potential of multi-walled carbon nanotubes as an agglomerated material for ion chromatography stationary phases for the separation of inorganic anions. Polyelectrolytes with quaternary ammonium groups were introduced onto the carbon nanotube surface, based on condensation polymerization of 1,4-butanediol diglycidyl ether (BDDE) and methylamine (MA). Quaternized multi-walled carbon nanotubes (Q-MWCNTs) were electrostatically adsorbed onto the surface of sulfonated polystyrene-divinylbenzene (PS-DVB) beads to generate the anion exchanger, which were confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). A 100mm×4.0mm i.d. column was packed with Q-MWCNTs agglomerated PS-DVB particles, with a capacity of 56μequiv./column. Separation of inorganic anions, such as F(-), Cl(-), NO2(-), Br(-), NO3(-), SO4(2-) and PO4(3-) were performed. The stationary phase was rigid, chemically stable and showed good ion-exchange characteristics.

  2. Crystal Structure of an LSD-Bound Human Serotonin Receptor.

    Science.gov (United States)

    Wacker, Daniel; Wang, Sheng; McCorvy, John D; Betz, Robin M; Venkatakrishnan, A J; Levit, Anat; Lansu, Katherine; Schools, Zachary L; Che, Tao; Nichols, David E; Shoichet, Brian K; Dror, Ron O; Roth, Bryan L

    2017-01-26

    The prototypical hallucinogen LSD acts via serotonin receptors, and here we describe the crystal structure of LSD in complex with the human serotonin receptor 5-HT2B. The complex reveals conformational rearrangements to accommodate LSD, providing a structural explanation for the conformational selectivity of LSD's key diethylamide moiety. LSD dissociates exceptionally slow from both 5-HT2BR and 5-HT2AR-a major target for its psychoactivity. Molecular dynamics (MD) simulations suggest that LSD's slow binding kinetics may be due to a "lid" formed by extracellular loop 2 (EL2) at the entrance to the binding pocket. A mutation predicted to increase the mobility of this lid greatly accelerates LSD's binding kinetics and selectively dampens LSD-mediated β-arrestin2 recruitment. This study thus reveals an unexpected binding mode of LSD; illuminates key features of its kinetics, stereochemistry, and signaling; and provides a molecular explanation for LSD's actions at human serotonin receptors. PAPERCLIP. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Disinfection byproduct formation in drinking water sources: A case study of Yuqiao reservoir.

    Science.gov (United States)

    Zhai, Hongyan; He, Xizhen; Zhang, Yan; Du, Tingting; Adeleye, Adeyemi S; Li, Yao

    2017-08-01

    This study investigated the potential formation of disinfection byproducts (DBPs) during chlorination and chloramination of 20 water samples collected from different points of Yuqiao reservoir in Tianjin, China. The concentrations of dissolved organic matter and ammonia decreased downstream the reservoir, while the specific UV absorbance (SUVA: the ratio of UV254 to dissolved organic carbon) increased [from 0.67 L/(mg*m) upstream to 3.58 L/(mg*m) downstream]. The raw water quality played an important role in the formation of DBPs. During chlorination, haloacetic acids (HAAs) were the major DBPs formed in most of the water samples, followed by trihalomethanes (THMs). CHCl3 and CHCl2Br were the major THM species, while trichloroacetic acid (TCAA) and dichloroacetic acid (DCAA) were the major HAA species. Chloramination, on the other hand, generally resulted in lower concentrations of THMs (CHCl3), HAAs (TCAA and DCAA), and haloacetonitriles (HANs). All the species of DBPs formed had positive correlations with the SUVA values, and HANs had the highest one (R(2) = 0.8). The correlation coefficients between the analogous DBP yields and the SUVA values in chlorinated samples were close to those in chloraminated samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Influencia de la soldadura sobre la rotura por tensiones en tubos de acero inoxidable austenitico del tipo 18-11NB(TP347

    Directory of Open Access Journals (Sweden)

    Gutiérrez de Saiz-Solabarria, S.

    2000-06-01

    Full Text Available This work has been undertaken to study the stress cracking failure in various 18Cr11Ni [TP347 (18-11Nb, TP 321 (18-11 Ti, TP304 (18-11 and TP316 (18-11-2] types austenitic stainless steel tubes. The material used was produced hot-rolling at 76,2 mm φ (3"φ x 2,54 mm (1/10" thickness. The study was carried out at 593ºC and applied stress of 50 Ton/in2.<br>
    Se estudia el efecto de la soldadura sobre la rotura por tensiones en tubos de acero inoxidable austenítico estabilizado con Nb o Ti de los tipos 18-11Nb (TP 347 y 18-11Ti (TP 321 así como sin estabilizar del tipo 18-11 (TP 304 y con Mo del tipo 18-11-2 (TP 316. Los tubos, en todos los casos, son de dimensiones 76,2 mm (3” φ x 2,54 mm (1/10” de espesor y la tensión aplicada (σ de 10 Ton/in2, para una temperatura de servicio de 593ºC.

  5. Loss-of-Flow and Loss-of-Pressure Simulations of the BR2 Research Reactor with HEU and LEU Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Licht, J. [Argonne National Lab. (ANL), Argonne, IL (United States); Bergeron, A. [Argonne National Lab. (ANL), Argonne, IL (United States); Dionne, B. [Argonne National Lab. (ANL), Argonne, IL (United States); Sikik, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Van den Branden, G. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Koonen, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium)

    2016-01-01

    Belgian Reactor 2 (BR2) is a research and test reactor located in Mol, Belgium and is primarily used for radioisotope production and materials testing. The Materials Management and Minimization (M3) Reactor Conversion Program of the National Nuclear Security Administration (NNSA) is supporting the conversion of the BR2 reactor from Highly Enriched Uranium (HEU) fuel to Low Enriched Uranium (LEU) fuel. The reactor core of BR2 is located inside a pressure vessel that contains 79 channels in a hyperboloid configuration (Figure 1). The core configuration is highly variable as each channel can contain a fuel assembly, a control or regulating rod, an experimental device, or a beryllium or aluminum plug. Because of this variability, a representative core configuration (Figure 2), based on current reactor use, has been defined for the fuel conversion analyses [1]. The code RELAP5/Mod 3.3 [2] was used to perform the transient thermal-hydraulic safety analyses of the BR2 reactor to support reactor conversion. The input model has been modernized relative to that historically used at BR2 taking into account the best modeling practices developed by Argonne National Laboratory (ANL) and BR2 engineers.

  6. Kinetics and mechanism of the oxidation of bromide by periodate in aqueous acidic solution.

    Science.gov (United States)

    Szél, Viktor; Csekő, György; Horváth, Attila K

    2014-11-13

    The periodate–bromide reaction has been studied spectrophotometrically mainly in excess of bromide ion, monitoring the formation of the total amount of bromine at 450 nm at acidic buffered conditions and at a constant ionic strength in the presence of a phosphoric acid/dihydrogen phosphate buffer. The stoichiometry of the reaction was established to be strictly IO4(–) + 2Br(–) + 2H(+) → Br2 + IO3(–) + H2O. The formal kinetic order of the reactants was found to be perfectly one and two in the cases of periodate and bromide, respectively, but that of the hydrogen ion lies between one and two. We have also provided experimental evidence that dihydrogen phosphate accelerates the formation of bromine, suggesting the appearance of strong buffer assistance. On the basis of the experiments, a simple two-step kinetic model is proposed involving BrIO3 as a key intermediate that perfectly explains all of the experimental findings. Furthermore, we have also shown that in huge excess of bromide, the apparent rate coefficient obtained from the individual curve fitting method of the absorbance–time series is necessarily independent of the initial periodate concentration that may falsely be interpreted as the rate of bromine formation is also independent of the concentration of periodate.

  7. A Near-infrared view of the Narrow Line Region of AGN

    Directory of Open Access Journals (Sweden)

    Alberto Rodríguez-Ardila

    2008-01-01

    Full Text Available Reportamos sobre el atlas espectral más completo de núcleos activos de galaxias en la región del infrarrojo cercano publicado a la fecha. El objetivo principal es construir una base homogénea de datos con una buena S/N y resolución espectral, que permita el estudio de las propiedades del continuo y de las líneas en fuentes individuales, y la comparación de éstas propiedades entre los diferentes tipos de AGN. Identificamos las líneas espectrales más importantes que fueron detectadas y confirmamos la utilidad del diagrama [Fe II]/Paβ vs H2/Brγ para separar los diferentes objetos emisores de líneas de acuerdo al nivel de actividad nuclear. Encontramos que el NIR oferece información valiosa sobre las regiones emisoras de líneas anchas y estrechas, añadiendo restricciones importantes al modelaje de las propiedades físicas del gas emisor.

  8. Ozone and Pollution Measuring Ultraviolet Spectrometer (OPUS): an overview

    Science.gov (United States)

    Kuze, A.; Suzuki, M.; Sano, T.; Watanabe, M.; Yoshida, S.; Yui, Y.; Okumura, S.; Shibasaki, K.; Ogawa, T.

    Atmospheric composition measurements from space are essential for monitoring earth's environment. Ozone and Pollution Measuring Ultraviolet Spectrometer (OPUS) is a nadir-looking, cross-track scanning ultraviolet spectrometer, which will be onboard Global Change Observation Mission-A1 (GCOM-A1). It will be placed in a 650 km non-sun-synchronous orbit in 2007, with an inclination angle of 69 deg. OPUS consists of a mechanical scanner, a Fastie-Ebert type polychromator with a one-dimensional UV Si-CMOS array detector, and a radiometer for cloud detection using O2 A band. It will provide information about cloud height and tropospheric O3 , SO2 , NO2 , BrO, OClO, HCHO, as well as the global distribution of total O3 , surface albedo, and aerosol in one day. This paper describes scientific objectives, instrument design, and retrieval algorithm. Pre-launch calibration, onboard calibration, and validation plan will be also presented. In addition, the ground test results using laboratory models will be discussed.

  9. Global Monitoring of Atmospheric Trace Gases, Clouds and Aerosols from UV/vis/NIR Satellite Instruments: Currents Status and Near Future Perspectives

    Science.gov (United States)

    Wagner, T.; Beirle, S.; Deutschmann, T.; Frankenberg, C.; Grzegorski, M.; Khokhar, M. F.; Kühl, S.; Marbach, T.; Mies, K.; de Vries, M. Penning; Platt, U.; Pukite, J.; Sanghavi, S.

    2008-04-01

    A new generation of UV/vis/near-IR satellite instruments like GOME (since 1995), SCIAMACHY (since 2002), OMI (since 2004), and GOME-2 (since 2006) allows to measure several important stratospheric and tropospheric trace gases like O3, NO2, OClO, HCHO, SO2, BrO, and H2O as well as clouds and aerosols from space. Because of its extended spectral range, the SCIAMACHY instrument also allows the retrieval of Greenhouse gases (CO2, CH4) and CO in the near IR. Almost all of the tropospheric trace gases are observed by these instruments for the first time. From satellite data it is possible to investigate the temporal and spatial variation. Also different sources can be characterised and quantified. The derived global distributions can serve as input and for the validation of atmospheric models. Here we give an overview on the current status of these new instruments and data products and their recent applications to various atmospheric and oceanic phenomena.

  10. Post Irradiation Examination of a Thermo-Mechanically Improved Version of EUROFER ODS

    Energy Technology Data Exchange (ETDEWEB)

    Lucon, E.; Leenaers, A.; Vandermeulen, W.

    2006-08-15

    EUROFER is a 9Cr-1W-0.2V-0.1Ta reduced activation ferritic/martensitic (RAFM) steel, presently considered within the European Union as the primary candidate structural material in a fusion power plant. Its mechanical strength properties currently prevent its use at temperatures higher than 500-550 degrees Celsius. In an effort to extend the range of operating temperatures to 600-650 degrees Celsius and therefore enhance the efficiency of the machine, a different production route, Oxide Dispersion Strengthening (ODS), is being investigated. The characteristics of different versions of EUROFER ODS have been assessed in recent years, leading to the improvement of the material by a combination of optimized production process and post-thermal treatment. Until recently, the mechanical properties of EUROFER ODS had only been investigated in the unirradiated condition, and no information was available for the irradiation response of the material. However, mechanical samples have been irradiated during 2004-2005 at 300 degrees Celsius in the Belgian Reactor 2 (BR2) in Mol to an accumulated dose of 1.73 dpa; tensile, Charpy impact and fracture toughness tests have been performed in the hot cell laboratories of the Belgian Nuclear Centre (SCK-CEN). Metallographic and microstructural investigations were also performed on the investigated material in both the unirradiated and irradiated condition.

  11. Magneto-optical studies of low-dimensional organic conductors

    Directory of Open Access Journals (Sweden)

    Hitoshi Ohta, Motoi Kimata and Yugo Oshima

    2009-01-01

    Full Text Available Our periodic orbit resonance (POR results on quasi-two-dimensional (q2D, highly anisotropic q2D and quasi-one-dimensional (q1D organic conductors are reviewed together with our rotational cavity magneto-optical measurement system. Higher order POR up to seventh order has been observed in the q2D system (BEDT-TTF2Br(DIA, and the experimental conditions to observe POR and the cyclotron resonance (CR are discussed. Highly anisotropic q2D Fermi surface (FS in β''-(BEDT-TTF(TCNQ, which was considered to have q1D FS previously, is proposed by our POR measurements, and the possible interpretations of other experimental results of β''-(BEDT-TTF(TCNQ are discussed assuming the highly anisotropic q2D FS. Finally, detailed q1D FS of (DMET2I3, obtained from our POR results, is discussed in connection with the typical q1D system (TMTSF2ClO4.

  12. The effect of desiccation on the emission of volatile bromocarbons from two common temperate macroalgae

    Science.gov (United States)

    Leedham Elvidge, E. C.; Phang, S.-M.; Sturges, W. T.; Malin, G.

    2015-01-01

    Exposure of intertidal macroalgae during low tide has been linked to the emission of a variety of atmospherically-important trace gases into the coastal atmosphere. In recent years, several studies have investigated the role of inorganic iodine and organoiodides as antioxidants and their emission during exposure to combat oxidative stress, yet the role of organic bromine species during desiccation is less well understood. In this study the emission of dibromomethane (CH2Br2) and bromoform (CHBr3) during exposure and desiccation of two common temperate macroalgae, Fucus vesiculosus and Ulva intestinalis, is reported. Determination of the impact exposure may have on algal physiological processes is difficult as intertidal species are adapted to desiccation and may undergo varying degrees of desiccation before their physiology is affected. For this reason we include comparisons between photosynthetic capacity (Fv/Fm) and halocarbon emissions during a desiccation time series. In addition, the role of rewetting with freshwater to simulate exposure to rain was also investigated. Our results show that an immediate flux of bromocarbons occurs upon exposure, followed by a decline in bromocarbon emissions. We suggest that this immediate bromocarbon pulse may be linked to volatilisation or emissions of existing bromocarbon stores from the algal surface rather than the production of bromocarbons as an antioxidant response.

  13. Visual MINTEQ Modeling Research on Trace Elements in Tea Infusion%茶叶浸泡液中微量元素形态的VisualMINTEQ软件模拟分析

    Institute of Scientific and Technical Information of China (English)

    杨新周; 周学进; 杨树科; 叶艳青; 李学森; 胡秋芬

    2011-01-01

    The Flame Atomic Absorption Spectrometry method was used in the determination of four trace amounts of tea infusion. The Ion Chromatography method was used in the determination of amounts of F-, Cl-, NO2-, Br-. NO3-, PO43- and SO42- in tea infusion. Moreover, Fe, Cu, Zn and Pb in the tea infusion were simulated by the software Visual MINTEQ. The results revealed that Fe(OH)2+, Cu2+, Zn2+ and Pb2+ were dominant species in the tea infusion.%利用火焰原子吸收光谱法测定茶叶浸泡液中常见的4种微量元素的含量,应用离子色谱法检测其中的F-、Cl-、NO2-、Br-、NO3-、PO43-、SO42-含量,结合Visual MINTEQ软件模拟茶叶浸泡液中Fe、Cu、Zn、Pb 4种微量元素的存在形态,表明Fe、Cu、Zn、Pb分别以Fe(OH)2+、Cu2+、Zn2+、pb2+为优势态存在于茶叶浸泡液中.

  14. Thermodynamic and kinetic characterization of host-guest association between bolaform surfactants and alpha- and beta-cyclodextrins.

    Science.gov (United States)

    Nilsson, Markus; Valente, Artur J M; Olofsson, Gerd; Söderman, Olle; Bonini, Massimo

    2008-09-11

    The thermodynamics and kinetics of formation of host-guest complexes between a series of bolaform surfactants of type C n Me 6 (2+)2Br (-) ( n = 8, 10, and 12) and alpha-cyclodextrin and beta-cyclodextrin were studied with the aid of isothermal titration calorimetry (ITC) at 298.15 and 308.20 K. The association constant, the enthalpy, and the entropy of formation were determined. The obtained thermodynamic parameters are compared with parameters for the micelle formation of a related cationic surfactant. The difference in magnitude and sign between the parameters of the alpha-CD and beta-CD complexes is discussed based on the curvature of the cavity of the CD. We suggest that the water molecules inside the alpha-CD cavity are not able to maintain their hydrogen bond network. Upon complex formation these water molecules are expelled and reform their hydrogen bond network. The situation is different in the larger beta-CD cavity where water has the possibility of a more extensive hydrogen bonding. The kinetics for alpha-CD is slow, associated with high activation energies for both association and dissociation of the complex. The rates increased with a decrease in the number of methylene groups in the hydrocarbon chain. The slow kinetics is argued to originate from the fact that the charged headgroup needs to be pushed through a relative nonpolar cavity. A comparison is made with the Born energy.

  15. Interaction of bolaform surfactants with p-sulfonatocalix[4]arene: the role of two positive charges in the binding.

    Science.gov (United States)

    Francisco, Vitor; Garcia-Rio, Luis

    2014-06-17

    The inclusion binding manners of bolaform surfactants of type C(n)R6(2+) 2Br(-) with different spacer lengths (n = 6, 12) and terminal headgroup volumes (R = methyl, ethyl) by p-sulfonatocalix[4]arene were studied. The combination of ITC parameters (binding constants and complexation enthalpy and entropy) and NMR chemical shifts and NOE cross-peaks obtained upon complexation allows us to propose different binding modes. The results point out that the spacer length has an influence on the binding stoichiometry. The bolaforms with larger spacer lengths between polar head groups enable the formation of 2:1 complexes in addition to 1:1, while with the shorter spacer they form only 1:1 complexes. On the other hand, the formation of 1:1 complexes is not affected by the headgroup volume or the spacer length of the bolaform. Unexpectedly, a complex binding mode was observed where both positive charged terminal groups of the bolaform are accommodated in the cavity of the calixarene. The inclusion of both terminal groups of the guests can be related to its own structure but also evidence the high flexibility of the calixarene.

  16. Comparative study on stability and coke deposition over supported Rh and FePO4 catalysts for oxy-bromination of methane

    Institute of Scientific and Technical Information of China (English)

    Ronghe; Lin; Yunjie; Ding; Runqin; Wang

    2014-01-01

    Rhodium- and iron phosphate-based catalysts are by far the most promising catalysts for oxy-bromination of methane(OBM) reaction. However, most literature reported either Rh- or FePO4-based catalysts, and the results were rarely studied in a uniform environmental condition. In this report, comparative study was conducted on silica- and silicon carbide-supported rhodium and iron phosphate catalysts with the main focuses on stability performance and coke deposition. The catalytic results demonstrated that the stability of both Rh- and FePO4-based catalysts was greatly influenced by the supports used, and silicon carbide-supported catalysts showed much better anti-coking ability as compared with silica-supported ones. Temperature-programmed oxidation over the used catalysts further indicated that the coke formation mechanisms were completely different between silica-supported rhodium and iron phosphate catalysts. While cokes might be caused by condensation of CH2Br2over supported iron phosphate, methane decomposition might be the reason for coke formation over silica-supported rhodium catalyst. These findings might pave the way for designing highly efficient and stable catalysts of the OBM reaction.

  17. High Quantum Yield Blue Emission from Lead-Free Inorganic Antimony Halide Perovskite Colloidal Quantum Dots.

    Science.gov (United States)

    Zhang, Jian; Yang, Ying; Deng, Hui; Farooq, Umar; Yang, Xiaokun; Khan, Jahangeer; Tang, Jiang; Song, Haisheng

    2017-09-26

    Colloidal quantum dots (QDs) of lead halide perovskite have recently received great attention owing to their remarkable performances in optoelectronic applications. However, their wide applications are hindered from toxic lead element, which is not environment- and consumer-friendly. Herein, we utilized heterovalent substitution of divalent lead (Pb(2+)) with trivalent antimony (Sb(3+)) to synthesize stable and brightly luminescent Cs3Sb2Br9 QDs. The lead-free, full-inorganic QDs were fabricated by a modified ligand-assisted reprecipitation strategy. A photoluminescence quantum yield (PLQY) was determined to be 46% at 410 nm, which was superior to that of other reported halide perovskite QDs. The PL enhancement mechanism was unraveled by surface composition derived quantum-well band structure and their large exciton binding energy. The Br-rich surface and the observed 530 meV exciton binding energy were proposed to guarantee the efficient radiative recombination. In addition, we can also tune the inorganic perovskite QD (Cs3Sb2X9) emission wavelength from 370 to 560 nm via anion exchange reactions. The developed full-inorganic lead-free Sb-perovskite QDs with high PLQY and stable emission promise great potential for efficient emission candidates.

  18. 210Po and major ions in drainage water from soil treated with various types of fertilizers.

    Science.gov (United States)

    Jiménez, Fernando; López, Raúl; Debán, Luis; Pardo, Rafael; García-Talavera, Marta

    2007-07-01

    The levels of (210)Po, nutrients (NH(4)(+), NO(3)(-), PO(4)(3 -)) and major ions (Na(+), K(+), Mg(2 +), Ca(2 +), F(-), NO(2 -), Br(-), Cl(-), SO(4)(2 -)) were determined, by means of lysimeter experiences, in drainage waters for agricultural soils untreated and treated with different types of fertilizers (animal manure, sewage sludge and NPK synthetic fertilizer) applied at several rates. Analytical determinations were performed by using alpha -spectrometry in the case of (210)Po, or Ion Exchange liquid chromatography for the other ionic species. Statistical uni and multivariate analysis of the results shown significant differences among lixiviates according to the different fertilizer treatments. Sewage sludge and manure applications resulted in similar compositions of lixiviates with low (210)Po levels, whereas synthetic fertilizers produced higher (210)Po concentrations and different concentration patterns of ionic species when applied at or above the recommended rates. All (210)Po levels were well below the limits proposed by the 2001/928/ Euratom Recommendation. The concentrations of the rest of the ionic species, exception made from NH(4)(+) and NO(3)(-), were also below the limits proposed by Spanish regulations.

  19. The Wendelstein three channel imager (3KK): alignment, commissioning, and first results

    Science.gov (United States)

    Lang-Bardl, F.; Bender, R.; Goessl, C.; Grupp, F.; Hess, H.-J.; Kaminski, J.; Hodapp, K.; Hopp, U.; Jacobson, S.; Kravcar, H.; Monna, A.; Mitsch, W.; Schlichter, J.; Wegner, M.

    2016-08-01

    The Ludwig-Maximilians-Universität München operates an astrophysical observatory on the summit of Mt. Wendelstein which was equipped with a modern 2m-class robotic telescope in 20111-3. One of the two Nasmyth ports is designed to deliver the excellent (efficiently support observations of targets of opportunities like Gamma-Ray-bursts or efficient photometric redshift determination of sources identified by surveys like PanSTARS, Planck (SZ) or eROSITA. The covered wavelength range is 340 nm to 2.3 microns. The camera provides standard broadband filters (Sloan, Y, J, H, Ks) and 5 narrowband filters (OI, Hα, SII, H2, Brλ). The narrowband filters will enable deep studies of star forming regions. We present the final design of the camera, the assembly and alignment procedure performed in the laboratory before we transported the instrument to the observatory. We also show first results of the achieved on sky performance concerning image quality and efficiency of the camera in the different filter passbands.

  20. Synthesis and structural characterization of five new copper (I) complexes with 1,10-phenanthroline and 1,4-bis(diphenylphosphino)butane(dppb)

    Science.gov (United States)

    Li, Jian-Bao; Fan, Wei-Wei; Min-Liu; Xiao, Ye-Lan; Jin, Qiong-Hua; Li, Zhong-Feng

    2015-04-01

    The mixture of copper(I) salts CuX (X = Cl, Br, SCN, CN, SO3CF3) and 1,10-phenanthroline (phen) reacts with 1,4-bis(diphenylphosphino)butane (dppb) to give dinuclear complexes [Cu2(dppb)(phen)2Cl2]ṡ4DMF (1), [Cu2(dppb)(phen)2Br2]ṡDMF (2), [Cu2(dppb)(phen)2(SCN)2] (3) and two 1D chain complexes {[Cu2(dppb)(phen)2(CN)2(H2O)]}nṡnH2O (4) and {[Cu2(dppb)(phen)2](SO3CF3)2}n (5), respectively. The structures of these compounds were investigated by elemental analysis, single-crystal X-ray diffraction, electronic absorption spectroscopy, fluorescence spectroscopy, 1H NMR and 31P NMR spectroscopy. Each Cu atom adopts a distorted tetrahedral configuration, and all the complexes are considerably air-stable in solid state and in solution. Detailed NMR studies have been performed to disclose the behavior of the prepared copper(I) complexes in solution. All the five complexes are bright green and cyan luminophores in a solid state at room temperature. This makes them potential candidates as cheap emitting materials for electroluminescent devices.

  1. Determination of Ion Concentrations and Heavy Metals in the Air Particulates of an Industrial Area

    Directory of Open Access Journals (Sweden)

    Ömer Işıldak

    2011-12-01

    Full Text Available This study deals with the determination of heavy metals, anions and cations in atmospheric aerosols at four heavily polluted sites in Samsun city, Turkey. The anions (Cl-, Br-, NO3- and NO2- and cations (Na+, K+ and NH4+ in the samples were determined by ion chromatography using a potentiometric detector with ion selective electrodes. Flame and graphite-furnace Atomic Absorption Spectrometer was used for the determination of Pb, Cu, Zn and Fe. The average values of Cl-, NO3-, NO2-, Br-, Na+, K+ and NH4+ concentrations in the samples were 4.58±1.30, 7.42±1.32, 0.86±0.10, 0.28±0.05, 0.77±0.13, 0.72±0.06, and 1.08±0.09 µg/m3 respectively. The average values of Zn, Cu, Fe and Pb concentrations in the samples were 2.32±0.21, 1.71±0.14, 2.29±0.18, and 2.46±0.22 µg/m3 respectively.

  2. Synthesis and Crystal Structure of 5-Methyl- 2-phenyl-4-[(2-p-bromophenylamino)- furylmethylene]-3(2H)-one

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yong; LI Jin-Zhou; ZHANG Heng-Qiang

    2008-01-01

    A novel 4-heterocyclic acylpyrazolone-based Schiff base compound 5-methyl- 2-phenyl-4-[(2-p-bromophenylamino)-furylmethylene]-3(2H)-one (C21H16N3O2Br) has been syn- thesized by the reaction of 1-phenyl-3-methyl-4-(α-furoyl)-pyrazolone-5 (HPMαFP) and p-bro- moaniline. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data: triclinic system, space group P(1), a = 9.0936(3), b = 9.8067(4), c = 11.6863(4) (A),α = 102.512(10), β = 90.9630(10), γ = 114.327(10)°, Mr = 422.28, Z = 2, F(000) = 428.0, V = 920.46(11) (A)3, Dc = 1.524 g/cm3, μ = 2.254mm-1, R = 0.0476 and wR = 0.1318 for 9389 independent reflections (Rint = 0.0122) and 3281 observed reflections (I > 2σ(I)). Structural analysis indicates that the compound exists in an amine-one form.

  3. MAPbI2.9-xBrxCl0.1 hybrid halide perovskites: Shedding light on the effect of chloride and bromide ions on structural and photoluminescence properties

    Science.gov (United States)

    Atourki, Lahoucine; Vega, Erika; Marí, Bernabé; Mollar, Miguel; Ait Ahsaine, Hassan; Bouabid, Khalid; Ihlal, Ahmed

    2016-12-01

    The optical and structural properties of CH3NH3PbI3 can be adjusted by introducing other extrinsic ions such as chloride and bromide. In this work, mixed bromide iodide lead perovskites with a 10% fraction of chloride were prepared from methylamine, lead nitrate and the corresponding hydro acid (X = I, Br, Cl). The effect of bromide and chloride incorporation on different properties of perovskite thin film was investigated. The Pawley fit method indicates the formation of the iodide halide MAPbI3 Pm-3 m cubic phase for x = 0 and the tetragonal P4/mmm phase for x ≥ 0.3. All deposited films showed a strong absorbance in the UV-vis range. The band gap values were estimated from absorbance measurements. It was found that the onset of the absorption edge for MAPbI2.9-xBrxCl0.1 thin film perovskites ranges between 1.60 and 1.80 eV. Moreover, it was found that both Cl and Br affect the PL emission of the mixed halide lead perovskite, the MAPbI2.9-xBrxCl0.1 films displayed intermediate values from 730 nm (MAPbI2.2Br0.7Cl0.1) to 770 nm (MAPbI2.6Br0.3Cl0.1).

  4. Removal of Acid Black 1 and Basic Red 2 from aqueous solutions by electrocoagulation/Moringa oleifera seed adsorption coupling in a batch system.

    Science.gov (United States)

    de Carvalho, Helder Pereira; Huang, Jiguo; Ni, Jiaheng; Zhao, Meixia; Yang, Xinyu; Wang, Xiansheng

    2015-01-01

    The removal of Acid Black 1 (AB1) and Basic Red 2 (BR2) from aqueous solutions via an electrocoagulation (EC)/Moringa oleifera seeds (MOS) adsorption coupling process by using aluminum and stainless steel electrode in a batch reactor is described in this study. The influences of the operational parameters, i.e. current density, MOS dosage, and dye initial concentration, on degree of color removal were studied, and the unit energy demand, the unit electrode material demand, and the charge loading were calculated and discussed. The amounts of adsorbent and energy consumption were considered as main criteria of process evaluation, and ideal conditions were chosen. The addition of an appropriate MOS dosage (0.6 g/L for AB1 and 5 g/L for BR2) resulted in faster decolorization of dyes especially at lower current densities and was simultaneously accompanied by a significant reduction in contact time compared to the conventional simple EC process. The coupling process achieved degree of removals above 99.3% and 94% for AB1 and BR2, respectively. The EC/MOS coupling technique could be recommended to replace the conventional simple EC because of its high degree of removal, short contact time, and low energy consumption.

  5. Probing organometallic reactions by time-resolved infrared spectroscopy in solution and in the solid state using quantum cascade lasers.

    Science.gov (United States)

    Calladine, James A; Horvath, Raphael; Davies, Andrew J; Wriglesworth, Alisdair; Sun, Xue-Zhong; George, Michael W

    2015-05-01

    The photochemistry and photophysics of metal carbonyl compounds (W(CO)6, Cp*Rh(CO)2 (Cp* = η(5)-C5Me5), and fac-[Re(CO)3(4,4'-bpy)2Br] [bpy = bipyridine]) have been examined on the nanosecond timescale using a time-resolved infrared spectrometer with an external cavity quantum cascade laser (QCL) as the infrared source. We show the photochemistry of W(CO)6 in alkane solution is easily monitored, and very sensitive measurements are possible with this approach, meaning it can monitor small transients with absorbance changes less than 10(-6) ΔOD. The C-H activation of Cp*Rh(CO)(C6H12) to form Cp*Rh(CO)(C6H11)H occurs within the first few tens of nanoseconds following photolysis, and we demonstrate that kinetics obtained following deconvolution are in excellent agreement with those measured using an ultrafast laser-based spectrometer. We also show that the high flux and tunability of QCLs makes them suited for solid-state and time-resolved measurements.

  6. Anion-π interaction in metal-organic networks formed by metal halides and tetracyanopyrazine

    Science.gov (United States)

    Rosokha, Sergiy V.; Kumar, Amar

    2017-06-01

    Co-crystallization of tetracyanopyrazine, TCP, with the tetraalkylammonium salts of linear [CuBr2]-, planar [PtCl4]2- or [Pt2Br6]2-, or octahedral [PtBr6]2- complexes resulted in formation of the alternating [MlXn]m-/TCP stacks separated by the Alk4N+ cations. These hybrid stacks showed multiple short contacts between halide ligands of the [MlXn]m- complexes and carbon atoms of the TCP acceptor indicating strong anion-π bonding between these species. It confirmed that the anion-π interaction is sufficiently strong to bring together such disparate components as ionic metal complexes and neutral aromatic molecules regardless of the geometry of the coordination compound. Structural features of the solid-state stacks and [MlXn]m-·TCP dyads resulted from the quantum-mechanical computations suggests that the molecular-orbital (weakly-covalent) component play an important role in association of the [MlXn]m- complexes with the TCP acceptor.

  7. Study of ammonium fluoride passivation time on CdZnTe bulk crystal wafers

    Energy Technology Data Exchange (ETDEWEB)

    Bensalah, H.; Crocco, J.; Carcelen, V.; Plaza, J.L.; Zheng, Q.; Dieguez, E. [Crystal Growth Laboratory, Departamento de Fisica de Materiales, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Marchini, L. [IMEM-CNR, Parma (Italy); Zanichelli, M. [Department of Physics, University of Parma (Italy); Dominguez, G.; Soriano, L. [Departamento de Fisica Aplicada and Instituto de Ciencias de Materiales Nicolas Cabrera, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

    2011-07-15

    The chemical etching and the passivation processes of CdZnTe wafers were studied. The treatment effects were tested through an X-Ray Photoelectron Spectroscopy (XPS) analysis and I-V measurement. The chemical etching in 2%Br-MeOH solution may effectively remove the damaged layer and improve the ohmic contact between CdZnTe wafer and Au electrodes making rich the surface with Te. After different etching times, the CdZnTe wafers were passivated with NH{sub 4}F/H{sub 2}O{sub 2}.CdZnTe wafer passivated immediately after etching showed the best passivation efficiency because the enriched Te on the surface was fully oxidized to TeO{sub 2}, which results in the thickest oxide layer, and the most stoichiometric surface. Also the surface leakage current was reduced in comparison with the sample passivated 24 h after etching. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Death associated protein kinases: molecular structure and brain injury.

    Science.gov (United States)

    Nair, Syam; Hagberg, Henrik; Krishnamurthy, Rajanikant; Thornton, Claire; Mallard, Carina

    2013-07-04

    Perinatal brain damage underlies an important share of motor and neurodevelopmental disabilities, such as cerebral palsy, cognitive impairment, visual dysfunction and epilepsy. Clinical, epidemiological, and experimental studies have revealed that factors such as inflammation, excitotoxicity and oxidative stress contribute considerably to both white and grey matter injury in the immature brain. A member of the death associated protein kinase (DAPk) family, DAPk1, has been implicated in cerebral ischemic damage, whereby DAPk1 potentiates NMDA receptor-mediated excitotoxicity through interaction with the NR2BR subunit. DAPk1 also mediate a range of activities from autophagy, membrane blebbing and DNA fragmentation ultimately leading to cell death. DAPk mRNA levels are particularly highly expressed in the developing brain and thus, we hypothesize that DAPk1 may play a role in perinatal brain injury. In addition to reviewing current knowledge, we present new aspects of the molecular structure of DAPk domains, and relate these findings to interacting partners of DAPk1, DAPk-regulation in NMDA-induced cerebral injury and novel approaches to blocking the injurious effects of DAPk1.

  9. Conductors with small Fermi energies and small gap energies

    Energy Technology Data Exchange (ETDEWEB)

    Thorn, R.J.

    1993-09-01

    If the Fermi energy is of the order of meV`s, the usual treatment of the density of free electrons is not valid, but use can be made of an averaged density of states that depends weakly on temperature, so that the temperature variation of the conductivity can be expressed by the equation: {sigma} {congruent} CT{sup (1-s)} 1n{l_brace}[(exp({beta}E{sub f}) + 1)/2][exp({minus}{beta}(E{sub g} {minus} E{sub f})) + 1)]{r_brace} in which E{sub f} is the Fermi energy, E{sub g} is the top of the energy gap for thermal activation, s is the exponent of the temperature-dependent scattering. This equation serves to define a class of solids consisting of a microcomposite with a narrow conduction band for which E{sub f} of the order of ceV`s or less and a thermal activated conduction for which E{sub g} is of the order of ceV`s. It describes quantitatively the conductivity, {sigma}(T;{Delta}, for YBa{sub 2}Cu{sub 3}O{sub 7-{Delta}} and {sigma}(T;p) as the hydrostatic pressure p is varied for {kappa}-(BEDT-TTF){sub 2}CuN(CN){sub 2}Br.

  10. Anion Exchange on Cationic Surfactant Micelles, and a Speciation Model for Estimating Anion Removal on Micelles during Ultrafiltration of Water.

    Science.gov (United States)

    Chen, Ming; Jafvert, Chad T

    2017-07-05

    Surfactant micelles combined with ultrafiltration can partially, or sometimes nearly completely, separate various ionic and nonionic pollutants from water. To this end, the selectivity of aqueous micelles composed of either cetyltrimethylammonium (CTA(+)) bromide or cetylpyridinium (CP(+)) chloride toward many environmentally relevant anions (IO3(-), F(-), Cl(-), HCO3(-), NO2(-), Br(-), NO3(-), H2PO4(-), HPO4(2-), SO4(2-), and CrO4(2-)) was investigated. Selectivity coefficients of CTA(+) micelles (with respect to Br(-)) and CP(+) micelle (with respect to Cl(-)) for these anions were evaluated using a simple thermodynamic ion exchange model. The sequence of anion affinity for the CTA(+) micelles and for the CP(+) micelles were the same, with decreasing affinity occurring in the order of: CrO4(2-) > SO4(2-) > HPO4(2-) > NO3(-) > Br(-) > NO2(-) > Cl(-) > HCO3(-) > H2PO4(-) ≈ F(-). From the associated component mass balance and ion exchange (i.e., mass action) equations, an overall speciation model was developed to predict the distribution of all anions between the aqueous and micellar pseudophase for complex ionic mixtures. Experimental results of both artificial and real surface waters were in good agreement to model predictions. Further, the results indicated that micelles combined with ultrafiltration may be a potential technology for nutrient and other pollutant removal from natural or effluent waters.

  11. PdMn and PdFe: New Materials for Temperature Measurement Near 2K

    Energy Technology Data Exchange (ETDEWEB)

    Aselage, T.L.; Duncan, R.V.; Klemme, B.J.; Sergatskov, D.A.; Adriaans, M.J.; Day, P.K.

    1999-02-01

    Interest in the critical dynamics of superfluid He in microgravity conditions has motivated the development of new high resolution thermometry technology for use in space experiments near 2K. The current material commonly used as the temperature sensing element for high resolution thermometers (HRTs) is copper ammonium bromide (Cu(NH{sub 4}){sub 2}Br{sub 4}2H{sub 2}O) or CAB, which undergoes a ferromagnetic phase transition at 1.8K. HRTs made from CAB have demonstrated low drift (<10fK/s) and a temperature resolution of 0.1nK. Unfortunately, paramagnetic salts such as CAB are difficult to prepare and handle, corrosive to most metals, and become dehydrated if kept under vacuum conditions at room temperature. We have developed a magnetic thermometer using dilute magnetic alloys of Mn or Fe dissolved in a pure Pd matrix. These metallic thermometers are easy to fabricate, chemically inert, and mechanically robust. Unlike salts, they may be directly soldered to the stage to be measured. Also, the Curie temperature can be varied by changing the concentration of Fe or Mn, making them available for use in a wide temperature range. Susceptibility measurements, as well as preliminary noise and drift measurements, show them to have sub-nK resolution with a drift of less than 10{sup {minus}13} K/s.

  12. Synthesis and structural investigation of mono- and polynuclear copper complexes of 4-ethyl-1-(pyridin-2-yl) thiosemicarbazide.

    Science.gov (United States)

    Hassanien, M M; Gabr, I M; Abdel-Rhman, M H; El-Asmy, A A

    2008-11-01

    The reaction between 2-hydrazinopyridine and ethylisothiocyanate produced 4-ethyl-1-(pyridin-2-yl) thiosemicarbazide (HEPTS). Its reaction with copper fluoride, chloride, bromide, acetate, nitrate, perchlorate, sulfate, carbonate, hydroxide and copper metal produced 15 Cu(II) complexes. The copper metal is easily oxidized in aqueous-ethanol solution of HEPTS giving [Cu2(EPTS)(H2O)3(OH)3]EtOH. Different complexes for the same anion were synthesized by controlling the heating time. Characterization by elemental, thermal, magnetic and spectral (electronic, IR, mass and ESR) studies showed the formation of mono-, di-, tri- and tetra nuclear complexes. The room temperature solid state ESR spectra of the complexes show an axial spectrum with dx2-y2 ground state, suggesting distorted tetragonal geometry around Cu(II) center. The kinetic and thermodynamic parameters for the different decomposition steps in the complexes were calculated. HEPTS and its Cu(II) complexes showed high activity against gram negative bacteria; [Cu3(EPTS)2(EtOH)2Br4] has more activity.

  13. PRX-08066, a novel 5-hydroxytryptamine receptor 2B antagonist, reduces monocrotaline-induced pulmonary arterial hypertension and right ventricular hypertrophy in rats.

    Science.gov (United States)

    Porvasnik, Stacy L; Germain, Sean; Embury, Jennifer; Gannon, Kimberley S; Jacques, Vincent; Murray, Justin; Byrne, Barry J; Shacham, Sharon; Al-Mousily, Faris

    2010-08-01

    Pulmonary arterial hypertension (PAH) is a life-threatening disease that results in right ventricular failure. 5-((4-(6-Chlorothieno[2,3-d]pyrimidin-4-ylamino)piperidin-1-yl)methyl)-2-fluorobenzonitrile monofumarate (PRX-08066) is a selective 5-hydroxytryptamine receptor 2B (5-HT2BR) antagonist that causes selective vasodilation of pulmonary arteries. In the current study, the effects of PRX-08066 were assessed by using the monocrotaline (MCT)-induced PAH rat model. Male rats received 40 mg/kg MCT or phosphate-buffered saline and were treated orally twice a day with vehicle or 50 or 100 mg/kg PRX-08066 for 5 weeks. Pulmonary and cardiac functions were evaluated by hemodynamics, heart weight, magnetic resonance imaging (MRI), pulmonary artery (PA) morphology, and histology. Cardiac MRI demonstrated that PRX-08066 (100 mg/kg) significantly (P PRX-08066 significantly reduced peak PA pressure at 50 and 100 mg/kg (P PRX-08066 therapy also significantly reduced right ventricle (RV)/body weight and RV/left ventricle + septum (P PRX-08066 (P PRX-08066 significantly attenuated the elevation in PA pressure and RV hypertrophy and maintained cardiac function. Pulmonary vascular remodeling was also diminished compared with MCT control rats. PRX-08066 prevents the severity of PAH in the MCT rat model.

  14. Synthesis and properties of the chain-like polymeric copper(Ⅱ)complexes bridged by bis(diphenylphosphino oxide)ethane

    Institute of Scientific and Technical Information of China (English)

    YANG, Rui-Na(杨瑞娜); HOU, Yi-Min(侯益民); HU, Xiao-Yuan(胡晓院); SUN, Yu-An(孙雨安); JIN, Dou-Man(金斗满)

    2000-01-01

    At room temperature, the chain-like polymeric copper(Ⅱ)complexes bridged by bis(diphenylphosphino oxide) ethane (dppeO2), [Cu(dppeO2)X2]n[X= Cl(1), Br(2)] have been prepared and characterized by elemental analysis, 31P NMR,TG-DTA X-ray analysis for [CuBr2(dppeO2)]n. The chain is composed of subunits containing tetrahedron coordinated copper(Ⅱ) atoms. The four-coordinated copper(Ⅱ)atom is ligated to another four-coordinated copper(Ⅱ) atom through dppeO2. The coordination sphere of copper(Ⅱ) atom is completed by two monodentate bromide and two oxygen atoms from bridging dppeO2. Crystal data are as follows: C26-H24CuP2Br2O2, 0.50 mm×0.40 mm×0.40 mm, monoclinic, space group: C2/c, λ=0.07107(Mo Kα), a=1.2286(2) mm, b =2.0555(8) nm, c = 1.0652(2) nm, β=97.366(9)°, V=2.668 nm3, Z=4, Dcalc=1.628g.cm-3,R =0.066; Rw= 0.091.

  15. Synthesis and structure of diorganotin dibromides, R2SnBr2 (R = 2,4,6-trimethylphenyl or 2,4,6-trimethylbenzyl): Hydrolysis of (2,4,6-Me3C6H2)2SnBr2

    Indian Academy of Sciences (India)

    Vadapalli Chandrasekhar; Ramalingam Thirumoorthi

    2010-09-01

    The reaction of SnBr4 with in situ generated 2,4,6-trimethylphenylmagnesium bromide afforded a mixture of (2,4,6-Me3C6H2)2SnBr2 (1) and (2,4,6-Me3C6H2)3SnBr (2) which could be separated from each other by their solubility differences in diethyl ether. On the other hand, the reaction of tin metal with 2,4,6-Me3C6H2CH2Br afforded (2,4,6-Me3C6H2CH2)2SnBr2 (3). Hydrolysis of the latter using triethylamine as the base afforded [{(2,4,6-Me3C6H2CH2)2Sn}2(-O)(Br)(-OH)]2.2CH2Cl2 (4) while the use of NaOH as the base afforded [{(2,4,6-Me3C6H2CH2)2Sn}2(-O)(OH)(-OH)]2.2CH2Cl2 (5). Compounds 4 and 5 are dimeric tetraorganodistannoxanes consisting of a central distannoxane (Sn2O2) motif.

  16. Geochemistry of marine sediments of the Brazilian Northeastern continental shelf

    Directory of Open Access Journals (Sweden)

    Fernanda Souza do Nascimento

    2010-01-01

    Full Text Available The marine sediment samples collected from the northeastern Brazilian continental shelf, at water depths between 20 and 80 m, consisted mainly of sands with an almost total absence of gravel and granules. Medium, coarse and very coarse sand grains are mostly composed of halimeda, lithothamnium, rodoliths and bioclastic sands with a carbonate content varying between 77 and 96 %. The chemistry in general shows a decreasing content of Ca (86.1 % >Si (6 % > Cl (3.6 % > Sr (0.8 % > K (0.66 % > S (0.62 % > Al (0.6 % > Na (0.55% > Mg (0.43 % > Fe (0.4 % > P (0.2 % > Br (0.04 % in the samples. There was no correlation between CaCO3 and chemical contents and grain size with depth and bio-components. With the exception of Sr of marine origin, all other elements (P, S, Br, Cl, Fe are of continental origin. The lithothamnium of some offshore samples shows higher CaCO3 content, while Mg and Na are present only in halimedas. Bioclastic sands contain no Br, and silt and clay fractions are rare and characterize samples closer to the coast. These marine bioclastic granulates are of very pure biogenic calcium carbonates and are thus highly to be recommended for economic purposes.Os granulados marinhos, da Plataforma Continental do nordeste brasileiro, coletados de profundidades entre 20 e 80 m, são predominantemente areias cascalhosas constituídas de halimedas, litotames, rodolitos e areias bioclásticas, cujos teores de carbonatos variam de 77 a 96 %. A concentração média geral de elementos químicos na ordem decrescente é Ca (86.1 % > Si (6 % > Cl (3.6 % > Sr (0.8 % > K (0.66 % > S (0.62 % > Al (0.6 % > Na (0.55 % > Mg (0.43 % > Fe (0.4 % > P (0.2 % > Br (0,04 %, independentemente da profundidade e tipo de bio-componente. Com exceção do Sr, que é de origem marinha, os demais elementos (P, S, Br, Cl, Fe são de origem continental. Elementos como Mg e Na foram restritos às halimedas em apenas duas amostras, enquanto Br não foi detectado nas areias

  17. Investigación de trihalometanos en agua potable del Estado Carabobo, Venezuela Trihalomethanes in the drinking water of Carabobo State, Venezuela

    Directory of Open Access Journals (Sweden)

    A. Sarmiento

    2003-04-01

    Full Text Available Objetivo: La desinfección del agua con cloro en las plantas de potabilización da lugar a la formación de trihalometanos (THM. Estos compuestos están asociados a efectos adversos para la salud. En este estudio se determinó la concentración de THM en el agua para consumo humano suministrada por las redes de distribución de los dos principales sistemas de potabilización de agua del Estado Carabobo, la planta Alejo Zuloaga y el embalse Pao-Cachinche que forman el Sistema Regional del Centro I (SRC-I y la planta Lucio Baldo Soules y el embalse Pao-La Balsa que forman el Sistema Regional del Centro II (SRC-II. Métodos: Se analizaron un total de 144 muestras recolectadas durante 6 muestreos que se realizaron durante los años 2000 y 2001. La concentración de THM se determinó por cromatografía de gases, mediante la técnica de headspace. Se determinaron las concentraciones para los siguientes THM: cloroformo (CHCl3, bromoformo (CHBr3, dibromoclorometano (CHBr2Cl y diclorobromometano (CHCl2Br. Resultados: La concentración de THM totales estuvo entre 47,84 y 93,23 μg/l. El CHCl3 fue el compuesto predominante, representando el 83% de total de THM para el SRC-I y el 82% en el SRC-II. Se encontró que las concentraciones de THM totales en el SRC-I (Red Baja y Red San Diego son significativamente superiores (p Objective: Disinfection of water with chlorine in water treatment plants leads to the formation of trihalomethanes (THMs. These compounds are associated with adverse health effects. The aim of this study was to analyze THM concentrations in the water provided for human consumption in the two main water treatment systems of Carabobo State: the Alejo Zuloaga plant and the Pao-Cachinche reservoir, which form the Central Regional System I (CRS I, and the Lucio Baldo Soules plant and the Pao-La Balsa reservoir, which form the Central Regional System II (CRS II. Methods: We analyzed 144 water samples collected in 6 samplings carried out in 2000

  18. Synthesis and characterization of salts containing the BrO(3)F(2)(-) anion; a rare example of a bromine(VII) species.

    Science.gov (United States)

    Lehmann, John F; Schrobilgen, Gary J

    2005-07-06

    The BrO(3)F(2)(-) anion has been prepared by reaction of BrO(3)F with the fluoride ion donors KF, RbF, CsF, [N(CH(3))(4)][F], and NOF. The BrO(3)F(2)(-) anion is only the fourth Br(VII) species to have been isolated in macroscopic quantities, and it is one of only three oxide fluorides that possess D(3)(h)() symmetry, the others being XeO(3)F(2) and OsO(3)F(2). The fluoride ion acceptor properties of BrO(3)F contrast with those of ClO(3)F, which does not react with the strong fluoride ion donor [N(CH(3))(4)][F] to form the analogous ClO(3)F(2)(-) salt. The single-crystal X-ray structures of [NO](2)[BrO(3)F(2)][F] and [N(CH(3))(4)][BrO(3)F(2)] confirm the D(3)(h)() symmetry of the BrO(3)F(2)(-) anion and provide accurate Br-O (1.593(3)-1.610(6) A) and Br-F (1.849(5)-1.827(4) A) bond lengths. The salt, [NO](2)[BrO(3)F(2)][F], is fully ordered, crystallizing in the monoclinic space group, C2/c, with a = 9.892(3) A, b = 12.862(4) A, c = 10.141(4) A, beta = 90.75(2) degrees , V = 12460(7) A(3), Z = 4, and R(1) = 0.0671 at -173 degrees C, whereas [N(CH(3))(4))][BrO(3)F(2)] exhibits a 2-fold disorder of the anion, crystallizing in the tetragonal space group, P4/nmm, with a = 8.5718(7) A, c = 5.8117(6) A, V = 427.02(7) A(3), Z = 2, and R(1) = 0.0314 at -173 degrees C. The (19)F chemical shift of [N(CH(3))(4))][BrO(3)F(2)] in CH(3)CN is 237.0 ppm and is more deshielded than those of the previously investigated Br(VII) species, BrO(3)F and BrF(6)(+). The vibrational frequencies of the BrO(3)F(2)(-) anion were determined by use of Raman and infrared spectroscopy and were assigned with the aid of electronic structure calculations and by analogy with the vibrational assignments reported for XeO(3)F(2) and OsO(3)F(2). The internal and symmetry force constants of BrO(3)F(2)(-) were determined by use of general valence force field and B-matrix methods, respectively, and are compared with those of XeO(3)F(2), OsO(3)F(2), and the unknown ClO(3)F(2)(-) anion. The instability of ClO(3

  19. Determination of anion and cation in leaching solution of imported smelting slag by reagent free ion chromatography%免试剂离子色谱法测定入境冶炼渣浸出液中阴阳离子

    Institute of Scientific and Technical Information of China (English)

    陈永欣; 曾雪灵; 黎香荣; 吕泽娥; 马丽方

    2012-01-01

    用免试剂离子色谱法对冶炼渣中阴、阳离子(F-,Cl-,NO2-,Br-,NO3 -,SO42 -,PO43-,Li+,Na+,NH4+,K+,Mg2+和Ca2+)进行了测定.阴离子分离条件:阴离子交换柱Ion Pac AS19,氢氧化钾溶液梯度淋洗,抑制电导检测,流速为1 mL/min;阳离子分离条件:阳离子交换柱Ion Pac CS16,甲基磺酸溶液梯度淋洗,抑制电导检测,流速为1.3 mL/min.同一天内的待测离子峰保留时间、峰高和峰面积的相对标准偏差分别小于0.35%,1.8%和1.1%,连续5天的待测离子峰保留时间、峰高和峰面积的相对标准偏差分别小于0.78%,2.4%和1.6%.被测离子的浓度与峰面积具有良好的线性,相关系数r=0.999 0~0.999 9,检出限低于20 μg/L.对入境氧化铁皮渣、钒渣、富锰渣浸出液中阴、阳离子进行测定,加标回收率在86%~110%之间.%The anion and cation (F- , Cl- , NO2- , Br- , NO3- , SO42- , PO43- , Li+ , Na+ , NH4 + , K+ , Mg2+ and Ca2+ ) in leaching solution of smelting slag were determined by reagent free ion chro-matography. The separation conditions of anion: cation exchange column Ion Pac AS19, gradient elu-tion with potassium hydroxide solution, suppressed conductance detection, flow rate of 1 mL/min; separation conditions of cation: anion exchange column Ion Pac CS16, gradient elution with methane-sulfonic acid solution, suppressed conductance detection, flow rate of 1. 3 mL/min. The relative standard deviations (RSDs) of retention time, peak height and peak area of testing ions within one day were less than 0. 35 %, 1.8 % and 1.1%, respectively. The RSDs of retention time, peak height and peak area of testing ions in continuous five days were less than 0. 78 %, 2. 4 % and 1.6%, respectively. The concentration of determined ions with its peak area had good linearity (r=0. 999 0 - 0. 999 9). The detection limit was lower than 20 μg/L. The anion and cation in leaching solution of imported scale slag, vanadium slag and manganese-rich slag were

  20. B═B and B≡E (E = N and o) multiple bonds in the coordination sphere of late transition metals.

    Science.gov (United States)

    Brand, Johannes; Braunschweig, Holger; Sen, Sakya S

    2014-01-21

    Because of their unusual structural and bonding motifs, multiply bonded boron compounds are fundamentally important to chemists, leading to enormous research interest. To access these compounds, researchers have introduced sterically demanding ligands that provide kinetic as well as electronic stability. A conceptually different approach to the synthesis of such compounds involves the use of an electron-rich, coordinatively unsaturated transition metal fragment. To isolate the plethora of borane, boryl, and borylene complexes, chemists have also used the coordination sphere of transition metals to stabilize reactive motifs in these molecules. In this Account, we summarize our results showing that increasingly synthetically challenging targets such as iminoboryl (B≡N), oxoboryl (B≡O), and diborene (B═B) fragments can be stabilized in the coordination sphere of late transition metals. This journey began with the isolation of two new iminoboryl ligands trans-[(Cy3P)2(Br)M(B≡N(SiMe3))] (M = Pd, Pt) attached to palladium and platinum fragments. The synthesis involved oxidative addition of the B-Br bond in (Me3Si)2N═BBr2 to [M(PCy3)2] (M = Pt, Pd) and the subsequent elimination of Me3SiBr at room temperature. Variation of the metal, the metal-bound coligands, and the substituent at the nitrogen atom afforded a series of analogous iminoboryl complexes. Following the same synthetic strategy, we also synthesized the first oxoboryl complex trans-[(Cy3P)2BrPt(BO)]. The labile bromide ligand adjacent to platinum makes the complex a viable candidate for further substitution reactions, which led to a number of new oxoboryl complexes. In addition to allowing us to isolate these fundamental compounds, the synthetic strategy is very convenient and minimizes byproducts. We also discuss the reaction chemistry of these types of compounds. In addition to facilitating the isolation of compounds with B≡E (E = N, O) triple bonds, the platinum fragment can also stabilize a

  1. About the photoionization of methyl bromide (CH{sub 3}Br). Photoelectron and photoionization mass spectrometric investigation

    Energy Technology Data Exchange (ETDEWEB)

    Locht, R. [Laboratoire de Dynamique Moleculaire, Departement de Chimie, Institut de Chimie, Bat. B6c, Universite de Liege, Sart-Tilman par B-4000 Liege 1 (Belgium)], E-mail: robert.locht@ulg.ac.be; Leyh, B. [Laboratoire de Dynamique Moleculaire, Departement de Chimie, Institut de Chimie, Bat. B6c, Universite de Liege, Sart-Tilman par B-4000 Liege 1 (Belgium); Dehareng, D. [Centre d' Ingenierie des Proteines, Institut de Chimie, Bat. B6a, Universite de Liege, Sart-Tilman par B-4000 Liege 1 (Belgium); Hottmann, K. [Institut fuer Chemie, Physikalische und Theoretische Chemie, Freie Universitaet Berlin, Takustrasse 3, D-14195 Berlin (Germany); Jochims, H.W. [Institut fuer Chemie, Physikalische und Theoretische Chemie, Freie Universitaet Berlin, Takustrasse 3, D-14195 Berlin (Germany); Baumgaertel, H. [Institut fuer Chemie, Physikalische und Theoretische Chemie, Freie Universitaet Berlin, Takustrasse 3, D-14195 Berlin (Germany)

    2006-04-21

    The threshold photoelectron (TPES) and the photoionization mass spectrometric study of CH{sub 3}Br in the 8-20eV photon energy range is presented. The interpretation and assignments are supported by ab initio calculations. The TPES shows several new discrete features in the Jahn-Teller split ground state X-bar {sup 2}E({sup 2}A{sup '}-{sup 2}A{sup '}') of CH{sub 3}Br{sup +}. An additional continuous band starts at about 11.8eV. These observations are both correlated with direct ionization and autoionizing transitions. This is supported by constant ion state (CIS) spectroscopy. A large enhancement of the transitions to the A-bar {sup 2}A and B-bar {sup 2}E states is ascribed to important autoionizing contributions. Based on the present calculations, the weak to very weak bands in the 17.5-22.0eV photon energy range were mainly assigned to 2a{sub 1}{sup -1} ionization and to double excitations described essentially by the 2e{sup -2}4a{sub 1}{sup 1} and 1e{sup -1}2e{sup -1}4a{sub 1}{sup 1} configurations. The photoionization mass spectrometric study allowed us to investigate in detail the ionization and dissociation of CH{sub 3}Br{sup +} leading to CH{sub 2}{sup +}, CH{sub 3}{sup +}, Br{sup +} and CH{sub 2}Br{sup +} from threshold up to 20eV photon energy. The experimental data are compared to ab initio dissociation energies. At the onset, the CH{sub 3}{sup +} and CH{sub 2}Br{sup +} fragment ion production is correlated with the ground state of CH{sub 3}Br{sup +} and both fragment ions have to appear through dissociative autoionization from the (3a{sub 1}{sup 1}/1e{sup 3})6s or 5s Rydberg state. This interpretation is supported by the photoabsorption spectrum measured recently in the same photon energy range. At higher energies, beside a likely direct (pre)dissociation of the A-bar {sup 2}A{sub 1} and B-bar {sup 2}E states of CH{sub 3}Br{sup +}, autoionization also contributes to the fragmentation in all decay channels. Avoided crossings in a manifold

  2. Effects of breed and harvest age on feed intake, growth, carcass traits, blood metabolites, and lipogenic gene expression in Boer and Kiko goats.

    Science.gov (United States)

    Solaiman, S; Min, B R; Gurung, N; Behrends, J; McElhenney, W

    2012-07-01

    The objectives of this experiment were to determine the effects of 2 different breeds (BR), Boer and Kiko, and 4 post-weaning harvest ages (HA; Days 0, 29, 56, and 85) on growth, carcass traits, blood metabolites, and lipogenic gene expression. Forty-eight goat (Capra hircus) kids (BW = 23.9 ± 1.50 kg; 3 to 4 mo) were used in a 2 × 4 factorial arrangement of treatments. Goats were stratified by BW within BR and randomly assigned to 4 HA. Kids were born between March 15 and April 7 to purebred does, and were represented by at least 3 purebred sires within each BR. They were fed a grain/hay (80:20) diet once per day. At designated HA, randomly pre-assigned goats (n = 6) from each BR were transported to the Meat Science Lab at Mississippi State University, Starkville, MS, and were harvested. There were no interactions (P > 0.10) between BR and HA. Boer tended (P = 0.08) to have greater initial BW, final BW (P = 0.05), and G/F ratio (P = 0.05). Although the 80:20 grain/hay diet was reinforced by adjusting DMI, both BR had similar total DMI, Boer kept that ratio, while Kiko consumed more (P = 0.001) hay (70:30, grain/hay) and had more (P = 0.001) DMI when expressed as g/kg BW. Boer tended to have greater transportation shrink (P = 0.07), HCW (P = 0.08), and cold carcass weights (CCW; P = 0.08), with greater (P = 0.001) carcass fat. No differences (P > 0.10) were observed in carcass shrink, dressing percentage, 12th rib fat thickness, and LM area between the 2 BR. When expressed as percentage empty BW, carcass bone was similar (P = 0.25), whereas muscle percentage (P = 0.02) was greater for Kiko and fat percentage was greater (P = 0.001) for Boer. Fat as a percentage of CCW remained relatively similar (P > 0.10) for both BR for the 2nd and 3rd HA. Differences were more evident (P = 0.01) at the 4th HA. Boer reached targeted harvest weight (29 kg) at the 3rd HA, while fat deposition continued (P = 0.01) during the 4th HA. Breed had no effect (P > 0.10) on meat color (L

  3. Parâmetros físico-químicos incomuns em água de abastecimento público de um município da região nordeste do Estado de São Paulo (Brasil | Unusual physico-chemical parameters in the public water supply of a town in the northeast of the São Paulo State (Brazil

    Directory of Open Access Journals (Sweden)

    Sergio Dovidauskas

    2017-02-01

    Full Text Available Amostras de águas de abastecimento público (n = 4347 de 88 municípios do nordeste do Estado de São Paulo (Brasil foram analisadas em 21 parâmetros físico-químicos: temperatura, condutividade (por condutimetria, cloro residual livre (colorimetria com N,N-dietil-p-fenilenodiamina, pH (potenciometria, cor aparente (espectrofotometria, turbidez (nefelometria, e concentrações de Li+, Na+, NH4+, K+, Ca2+, Mg2+, F-, ClO2-, BrO3-, Cl-, Br-, ClO3-, NO3-, PO43- e SO42- (cromatografia de íons. Os resultados foram submetidos à análise multivariada de dados. A análise de componentes principais das medianas de 12 variáveis (pH, condutividade, Li+, Na+, K+, Ca2+, Mg2+, Cl-, ClO3-, NO3-, PO43-, SO42- dos 88 municípios indicou Ibitinga como local com água de características físico-químicas únicas, caracterizada pelas concentrações relativas mais altas de sulfato, cloreto, lítio e sódio, e aos valores maiores de pH e condutividade. Em adição, Ibitinga foi o único município que apresentou sistematicamente brometo na composição da água. Uma segunda análise de componentes principais envolvendo as amostras de Ibitinga indicou uma amostra com concentrações mais altas de cloreto e sulfato, e quatro amostras nas quais a presença de nitrato foi característica. Análises de agrupamento hierárquico exibiram a formação dos mesmos grupos produzidos nas duas análises de componentes. A validação dos métodos cromatográficos também é apresentada. ================================================ Public water supply samples (n = 4347 from 88 municipalities in the northeast of the State of São Paulo (Brazil were analysed in 21 physico-chemical parameters: temperature, conductivity (by conductimetry, free residual chlorine (colorimetry with N,N-diethyl-p-phenylenediamine, pH (potentiometry, apparent color (spectrophotometry, turbidity (nephelometry, and concentrations of Li+, Na+, NH4+, K+, Ca2+, Mg2+, F-, ClO2-, BrO3-, Cl-, Br-, ClO3

  4. Competition entre supraconductivite et magnetisme au voisinage de la transition de Mott dans le conducteur organique quasi-bidimensionnel k-(BEDT-TTF)2copper[N(CN)2]bromine

    Science.gov (United States)

    Fournier, David

    Les conducteurs organiques quasi-bidimensionnels kappa-ET2X presentent d'importantes similitudes avec les SCHT telles qu'une phase isolant de Mott, un regime de pseudogap et un etat supraconducteur. L'etude de leurs proprietes apparait donc complementaire. Parmi les interrogations persistantes concernant la physique de ces systemes, l'origine du (ou des) processus exotique d'appariement, responsable de la supraconductivite est le sujet suscitant l'interet le plus marque dans la communaute. L'hypothese d'un mecanisme lie a la proximite d'un etat antiferromagnetique est privilegiee. Une etape importante dans la resolution de cette problematique est l'identification de la symetrie du parametre d'ordre. D'apres de nombreux travaux sur les systemes fortement correles, la sonde ultrasonore, de par sa sensibilite aux excitations de quasiparticule a basse temperature, est consideree comme particulierement adaptee a l'etude de cette propriete. Cependant, son emploi necessite l'utilisation d'un compose metallique a basse temperature et completement supraconducteur. Le compose metallique organique kappa-ET 2Cu[N(CN)2]Br presente toutes les caracteristiques necessaires a l'etude de cette propriete. En effet, il est situe loin de la transition du premier ordre de Mott et est completement supraconducteur. De facon surprenante, ce systeme semble se coupler fortement avec le reseau ce qui augmente significativement la sensibilite de cette sonde aux proprietes du gaz electronique. Cependant, des difficultes techniques importantes, liees a la nature intrinseque de ce materiau, doivent etre surmontees pour proceder a des mesures suivant differentes polarisations. La presente etude a profondement modifie notre comprehension de ce systeme. En effet, ces mesures ont permis de constater que le kappa-ET2Cu[N(CN)2]Br est un compose qui est situe en bordure de la zone de coexistence entre la supraconductivite et le magnetisme, ce qui constitue un resultat totalement inattendu. De plus, la

  5. Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity.

    Science.gov (United States)

    Sicilia, Violeta; Forniés, Juan; Casas, José Ma; Martín, Antonio; López, José A; Larraz, Carmen; Borja, Pilar; Ovejero, Carmen; Tordera, Daniel; Bolink, Henk

    2012-03-19

    The half-lantern compound [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)]·Me(2)CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC(7)H(4)NS(2)) and [Pt(bzq)(NCMe)(2)]ClO(4). The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)] is 2.910 (2) Å, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C···C distances being between 3.3 and 3.7 Å, which is indicative of significant π-π interactions. The reaction of 1 with halogens X(2) (X(2) = Cl(2), Br(2), or I(2)) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)X}(2)] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand μ-C(7)H(4)NS(2)-κN,S. The Pt-Pt distances (Pt-Pt = 2.6420(3) Å 2, 2.6435(4) Å 3, 2.6690(3) Å 4) are shorter than that in 1 because of the Pt-Pt bond formation. Time dependent-density functional theory (TD-DFT) studies performed on 1 show a formal bond order of 0 between the metal atoms, with the 6p(z) contribution diminishing the antibonding character of the highest occupied molecular orbital (HOMO) and being responsible for an attractive intermetallic interaction. A shortening of the Pt-Pt distance from 2.959 Å in the ground state S(0) to 2.760 Å in the optimized first excited state (T(1)) is consistent with an increase in the Pt-Pt bond order to 0.5. In agreement with TD-DFT calculations, the intense, structureless, red emission of 1 in the solid state and in solution can be mainly attributed to triplet metal-metal-to-ligand charge transfer ((3)MMLCT) [dσ*(Pt-Pt) → π*(bzq)] excited states. The high quantum yields of this emission measured in toluene (44%) and solid state (62%) at room temperature indicate

  6. Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

    Science.gov (United States)

    Nicovich, J. M.; Kreutter, K. D.; vanDijk, C. A.; Wine, P. H.

    1997-01-01

    Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the

  7. Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV alkoxide pincer complex

    Directory of Open Access Journals (Sweden)

    Jakub Pedziwiatr

    2017-02-01

    Full Text Available This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-bis[(diethyl etherlithium], [Li2Br2(C24H33N3(C4H10O2] (1 and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-1κ3N,N′,N′′;4κ3N,N′,N′′-tetra-μ-isopropanolato-1:2κ4O:O;3:4κ4O:O-diisopropanolato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N32(C3H7O6] or {[NHNNH]Ti(OiPr3(LiBr2}2 (2. Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O fragment bonded to them, with the Li atom adopting a distorted tetrahedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octahedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12/0.372 (12], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetrahedral coordination as in 1. The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4. The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N—H groups, no hydrogen bonding

  8. Effect of ocean acidification and elevated fCO2 on trace gas production by a Baltic Sea summer phytoplankton community

    Science.gov (United States)

    Webb, Alison L.; Leedham-Elvidge, Emma; Hughes, Claire; Hopkins, Frances E.; Malin, Gill; Bach, Lennart T.; Schulz, Kai; Crawfurd, Kate; Brussaard, Corina P. D.; Stuhr, Annegret; Riebesell, Ulf; Liss, Peter S.

    2016-08-01

    The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After

  9. Constraining the N2O5 UV absorption cross-section from spectroscopic trace gas measurements in the tropical mid-stratosphere

    Science.gov (United States)

    Kritten, L.; Butz, A.; Chipperfield, M. P.; Dorf, M.; Dhomse, S.; Hossaini, R.; Oelhaf, H.; Prados-Roman, C.; Wetzel, G.; Pfeilsticker, K.

    2014-02-01

    The absorption cross-section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in JPL-2011, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 +BrONO2 + HNO3) photochemistry. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding-Balloon) observations in similar air masses at nighttime, and all other relevant species from simulations of the SLIMCAT chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. In consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5 (λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

  10. Inhibition of catechol-O-methyl transferase (COMT) by tolcapone restores reductions in microtubule-associated protein 2 (MAP2) and synaptophysin (SYP) following exposure of neuronal cells to neurotropic HIV.

    Science.gov (United States)

    Lee, Ting Ting; Chana, Gursharan; Gorry, Paul R; Ellett, Anne; Bousman, Chad A; Churchill, Melissa J; Gray, Lachlan R; Everall, Ian P

    2015-10-01

    This investigation aimed to assess whether inhibition of cathecol-O-methyl transferase (COMT) by tolcapone could provide neuroprotection against HIV-associated neurodegenerative effects. This study was conducted based on a previous work, which showed that a single nucleotide polymorphism (SNP) at position 158 (val158met) in COMT, resulted in 40 % lower COMT activity. Importantly, this reduction confers a protective effect against HIV-associated neurocognitive disorders (HAND), which have been linked to HIV-associated brain changes. SH-SY5Y-differentiated neurons were exposed to macrophage-propagated HIV (neurotropic MACS2-Br strain) in the presence or absence of tolcapone for 6 days. RNA was extracted, and qPCR was performed using Qiagen RT2 custom array consisting of genes for neuronal and synaptic integrity, COMT and pro-inflammatory markers. Immunofluorescence was conducted to validate the gene expression changes at the protein level. Our findings demonstrated that HIV significantly increased the messenger RNA (mRNA) expression of COMT while reducing the expression of microtubule-associated protein 2 (MAP2) (p = 0.0015) and synaptophysin (SYP) (p = 0.012) compared to control. A concomitant exposure of tolcapone ameliorated the perturbed expression of MAP2 (p = 0.009) and COMT (p = 0.024) associated with HIV. Immunofluorescence revealed a trend reduction of SYP and MAP2 with exposure to HIV and that concomitant exposure of tolcapone increased SYP (p = 0.016) compared to HIV alone. Our findings demonstrated in vitro that inhibition of COMT can ameliorate HIV-associated neurodegenerative changes that resulted in the decreased expression of the structural and synaptic components MAP2 and SYP. As HIV-associated dendritic and synaptic damage are contributors to HAND, inhibition of COMT may represent a potential strategy for attenuating or preventing some of the symptoms of HAND.

  11. Crystal structure, phase transition and conductivity study of two new organic - inorganic hybrids: [(CH2)7(NH3)2]X2, X = Cl/Br

    Science.gov (United States)

    Mostafa, Mohga Farid; El-khiyami, Shimaa Said; Abd-Elal, Seham Kamal

    2017-01-01

    Two hybrids 1,7-heptanediammonium di-halide, [(C7H20N2]X2,X = Cl/Br crystallize in monoclinic P21/c, Z = 4. [(C7H20N2]Cl2: a = 4.7838 (2) Å, b = 16.9879 (8) Å, c = 13.9476 (8) Å, β = 97.773 (2)°, V = 1203.58(10) Å3, D = 1.137 g/cm3, λ = 0.71073 Å, R = 0.052 for 1055 reflections with I > 2σ(I), T = 298(2) K. [(C7H20N2]Br2: a = 4.7952 (10) Å, b = 16.9740 (5) Å, c = 13.9281 (5) Å, β = 97.793 (2)°, V = 1203.83(6) Å3, D = 1.612 g/cm3, λ = 0.71073 Å, R = 0.03 for 1959 reflections with I > 2σ(I) T = 298(2) K. Asymmetric unit cell of [(C7H20N2]X2,X = Cl/Br, each consist of one heptane-1,7-diammonium cation and two halide anions. The organic hydrocarbon layers pack in a stacked herring-bone manner, hydrogen bonded to the halide ions. Lattice potential energy is 1568.59 kJ/mol and 1560.78 kJ/mol, and cation molar volumes are 0.295 nm3 and 0.300 nm3 for chloride and bromide respectively. DTA confirmed chain melting transitions for both hybrids below T ∼ 340 K. Dielectric and ac conductivity measurements (290 340 K. Cross over from Jonscher's universal dielectric response at low temperatures T 340 K is observed. At high temperatures halide ion hopping in accordance with the jump relaxation model prevails.

  12. Far infrared and low frequency gas phase Raman spectra and conformational stability of the 1-halopropanes

    Science.gov (United States)

    Durig, J. R.; Godbey, S. E.; Sullivan, J. F.

    1984-06-01

    The far infrared (375-50 cm-1) and low frequency Raman (400-70 cm-1) spectra of the gaseous 1-halopropanes CH3CH2CH2F, CH3CH2CH2Cl, and CH3CH2CH2Br have been recorded and both the methyl and asymmetric torsional modes have been observed and assigned for both the gauche and trans conformers for all of these molecules. The asymmetric torsions for each molecule have several observed excited states which fall on the low frequency side of the fundamental. The asymmetric torsional potential functions have been calculated and, from these potential functions, the enthalpy differences between the high energy trans and low energy gauche conformers have been determined to be 122±10 cm-1 for the fluoride, 127±10 cm-1 for the chloride, and 37±10 cm-1 for the bromide. The trans and gauche methyl torsions have also been observed and assigned for the three 1-halopropanes. The resulting barriers in cm-1 are: 936±4 (trans), 986±9 (gauche) for 1-fluoropropane; 929±2 (trans), 1080±3 (gauche) for 1-chloropropane; and 841 (trans), 1016±8 (gauche) for 1-bromopropane. A complete vibrational assignment has also been made for the 1-fluoropropane molecule and, from the spectral data for the solid, it appears that there are two or more molecules per primitive cell. Attempts to obtain experimental values for the enthalpy differences in the gas phase were made and these results, as well as the determined potential functions, are discussed in relation to previous studies.

  13. Conformational and structural studies of 1-chloropropane and 1-bromopropane from temperature-dependant FT-IR spectra of rare gas solutions and ab initio calculations

    Science.gov (United States)

    Durig, J. R.; Zhu, X.; Shen, S.

    2001-08-01

    Variable temperature (-55 to -150°C) studies of the infrared spectra (3500-400 cm -1) of 1-chloropropane (CH 3CH 2CH 2Cl) and 1-bromopropane (CH 3CH 2CH 2Br) dissolved in liquid krypton and xenon, respectively, have been recorded. Utilizing two conformer pairs in krypton solution for chloride and three conformer pairs in xenon solution for bromide, enthalpy differences of 52±3 cm -1 (0.62±0.06 kJ/mol) and 72±7 cm -1 (0.86±0.08 kJ/mol) were obtained for the chloride and bromide, respectively, with the gauche form being the more stable conformer for both molecules. From these data, it is estimated that 28 and 26% of trans form are present at ambient temperature for the chloride and bromide, respectively. The conformation stabilities, harmonic force constants, fundamental frequencies, infrared intensities and Raman activities have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations for both halopropanes and these quantities have been compared to the experimental values when appropriate. The optimized geometries have also been obtained with several different ab initio basis sets with full electron correlation by the perturbation method up to MP2/6-311+G(2d,2p). The r0 structural parameters of both halopropanes have been obtained by combining the ab initio data with the previously reported microwave rotational constants for both conformers. The quantities are compared to the corresponding results for some similar molecules.

  14. A global model of tropospheric chlorine chemistry: Organic versus inorganic sources and impact on methane oxidation

    Science.gov (United States)

    Hossaini, Ryan; Chipperfield, Martyn P.; Saiz-Lopez, Alfonso; Fernandez, Rafael; Monks, Sarah; Feng, Wuhu; Brauer, Peter; Glasow, Roland

    2016-12-01

    Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by 2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea-salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub-ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1-5 × 104 atoms cm-3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to 4320 Gg Cl/yr, sustaining a background surface [Cl] of methane sink of 12-13 Tg CH4/yr due the CH4 + Cl reaction ( 2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for 10 to >20% of total boundary layer CH4 oxidation in some locations.

  15. Comparison of N-nitrosodimethylamine formation mechanisms from dimethylamine during chloramination and ozonation: A computational study

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yong Dong, E-mail: ydliu@bjut.edu.cn; Zhong, Rugang

    2017-01-05

    Highlights: • NDMA formation mechanisms from dimethylamine in chloramination/ozonation were reinvestigated by G4 method. • The reactivity order of halo-/hydroxyl-amines reacting with dimethylamine is NHCl{sub 2} ∼ NHBrCl > NH{sub 2}Cl >> NH{sub 2}OH. • Nitrene compound is an important intermediate to form NDMA in oxidation reaction. • Oxidation of unsymmetrical dimethylhydrazine by O{sub 2} is significantly less feasible compared to that by O{sub 3}. • The amines containing the second nitrogen source are potential NDMA precursors in ozonation. - Abstract: N-nitrosodimethylamine (NDMA) as a disinfection by-product has recently become the focus of considerable research interest due to its unusually high carcinogenicity. In this study, the formation mechanisms of NDMA from dimethylamine (DMA) during chloramination and ozonation were investigated by using the quantum chemical G4 method. The reactivity of haloamines and hydroxylamine reacting with DMA was found in the order: NHCl{sub 2} ∼ NHBrCl (Br{sup -}leaving) > NHBr{sub 2} > NH{sub 2}Cl ∼ NH{sub 2}Br >> NH{sub 2}OH. This offers a theoretical support for the experimentally proposed mechanism that dimethylamine reacts with NHCl{sub 2} rather than NH{sub 2}Cl to form chlorinated unsymmetrical dimethylhydrazine intermediate and the existence of bromochloramine in the presence of bromide during chloramination, and explains the observation that NDMA yield during ozonation is much lower than that during chloramination. Importantly, an N,N-dimethylaminonitrene was found to be a significant intermediate to form NDMA in oxidation reactions by molecular oxygen and ozone. Additionally, results suggest that the amines containing the second nitrogen source directly connecting or close to the N-(CH{sub 3}){sub 2} moiety are potential significant NDMA precursors upon ozonation. The findings of this study are helpful for expanding the knowledge of NDMA formation mechanism, and predicting potential NDMA precursors

  16. Hydrogen absorption and lithium ion conductivity in Li{sub 6}NBr{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Howard, M.A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Clemens, O. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Technical University of Darmstadt, Joint Research Laboratory Nanomaterials, Jovanka-Bontschits-Straße 2, 64287 Darmstadt (Germany); Karlsruhe Institute of Technology, Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Slater, P.R. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Anderson, P.A., E-mail: p.a.anderson@bham.ac.uk [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

    2015-10-05

    Highlights: • Li{sub 6}NBr{sub 3} was synthesized via solid state methods and hydrogenation attempted. • Hydrogenation of a lithium nitride halide was demonstrated for the first time. • Powder XRD and Raman spectroscopy showed that hydrogenation had gone to completion. • The ionic conductivities of Li{sub 6}NBr{sub 3} and Li{sub 3}N were compared through A.C. impedance spectroscopy. • The lower conductivity of Li{sub 6}NBr{sub 3} is consistent with its higher hydrogenation temperature. - Abstract: The reaction of lithium amide and imide with lithium halides to form new amide halide or imide halide phases has led to improved hydrogen desorption and absorption properties and, for the amides, lithium ion conductivities. Here we investigate the effect of bromide incorporation on the ionic conductivity and hydrogen absorption properties of lithium nitride. For the first time we show that it is possible for a lithium halide nitride, the cubic bromide nitride Li{sub 6}NBr{sub 3}, to take up hydrogen—a necessary condition for potential use as a reversible solid-state hydrogen storage material. Powder X-ray diffraction showed the formation of Li{sub 2}Br(NH{sub 2}) and LiBr, and Raman spectroscopy confirmed that only amide anions were present and that the hydrogen uptake reaction had gone to completion. The lithium ion conductivity of Li{sub 6}NBr{sub 3} at the hydrogenation temperature was found to be less than that of Li{sub 3}N, which may be a significant factor in the kinetics of the hydrogenation process.

  17. ENZYMATIC KINETICS OF CELLULASES ISOLATED FROM SOIL BACTE RIA OF DOON VALLEY , UTTARAKHAND

    Directory of Open Access Journals (Sweden)

    Vinit

    2015-05-01

    Full Text Available Cellulases refers to a suite of enzymes produced chiefly by fungi , bacteria , and protozoans that catalyze cellulolysis which is the hydrolysis of cellulose . Cellulose is the most abundant natural polymer on earth . It is the structural component of the plant cell walls which helps in the hydrolysis of 1, 4 - beta - D - glycosidic linkages in cellulose, lichenin and cereal beta - D - glucans . Cellulases are used for clarif ication of fruit juice, vegetable juice, roots, treatment of wine, extraction of oils and improving the quality of the bakery products . Eight soil samples were collected for cellulose preliminary screening from Gullarghati, Doon valley at different pH and temperatures, because maximum diversity was possible there as there was no interference by the humans . 110 colonies were isolated by the activity zone plate method containing CMC as a substrate using Congo red dye . Best twelve colonies were selected and ch ecked using DNS method at 540 A 0 . Four strains BR - 1, BR - 2, BR - 3 and BR - 4 were used on the basis of spectrophotometerically and characterized with the study of substrate . Maximum velocity (Vmax was observed for BR - 2 i . e . 170 units per mg protein with Km of 49 . 50mg/ml . Strain BR - 1 gave to pH optima at 4 . 5 and 6 . 5, strain BR - 2 gave maximum activity at 4 . 5 and 7 . 0 pH, BR - 3 strain gave maximum activity at pH 5 . 0 and 6 . 5 with the highest yield of cellulases w ere obtained at pH 4 . 5, 5 . 5 and 7 . 0 in bacterial s train BR - 4 . The results also shows the effect of temperature bacterial strain BR - 1, BR - 2 and BR - 4 with maximum cellulases activity at 45 0 C and bacterial strain BR - 3 maximum activity at 25 0 C .

  18. Laboratory investigations of the photochemical decay of alkylbromides trapped in ice

    Science.gov (United States)

    Schrems, Otto; Okaikwei, Bismark; Bluszcz, Thaddäus

    2014-05-01

    Photochemical reactions of atmospheric trace gases taking place at the surface of atmospheric ice particles and in bulk ice are important in tropospheric chemistry but also in polar and alpine snowpack chemistry. Consequently, the understanding of the uptake und incorporation of tropospheric 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. 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), methyl dibromide (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.

  19. A~tropical West Pacific OH minimum and implications for stratospheric composition

    Science.gov (United States)

    Rex, M.; Wohltmann, I.; Ridder, T.; Lehmann, R.; Rosenlof, K.; Wennberg, P.; Weisenstein, D.; Notholt, J.; Krüger, K.; Mohr, V.; Tegtmeier, S.

    2014-05-01

    Most of the short-lived biogenic and anthropogenic chemical species that are emitted into the atmosphere break down efficiently by reaction with OH and do not reach the stratosphere. Here we show the existence of a pronounced minimum in the tropospheric column of ozone over the West Pacific, the main source region for stratospheric air, and suggest a corresponding minimum of the tropospheric column of OH. This has the potential to amplify the impact of surface emissions on the stratospheric composition compared to the impact when assuming globally uniform OH conditions. Specifically, the role of emissions of biogenic halogenated species for the stratospheric halogen budget and the role of increasing emissions of SO2 in Southeast Asia or from minor volcanic eruptions for the increasing stratospheric aerosol loading need to be reassessed in light of these findings. This is also important since climate change will further modify OH abundances and emissions of halogenated species. Our study is based on ozone sonde measurements carried out during the TransBrom cruise with the RV Sonne roughly along 140-150° E in October 2009 and corroborating ozone and OH measurements from satellites, aircraft campaigns and FTIR instruments. Model calculations with the GEOS-Chem Chemistry and Transport Model (CTM) and the ATLAS CTM are used to simulate the tropospheric OH distribution over the West Pacific and the transport pathways to the stratosphere. The potential effect of the OH minimum on species transported into the stratosphere is shown via modeling the transport and chemistry of CH2Br2 and SO2.

  20. β-Resorcylic Acid, a Phytophenolic Compound, Reduces Campylobacter jejuni in Postharvest Poultry.

    Science.gov (United States)

    Wagle, B R; Arsi, K; Upadhyay, A; Shrestha, S; Venkitanarayanan, K; Donoghue, A M; Donoghue, D J

    2017-08-01

    Human Campylobacter infections, a leading foodborne illness globally, has been linked with the high prevalence of this bacterium on raw retail chicken products. Reduction of Campylobacter counts on poultry products would greatly reduce the risk of subsequent infections in humans. To this end, this study investigated the potential of the phytophenolic compound β-resorcylic acid (BR) to reduce Campylobacter counts on postharvest poultry (chicken skin or meat). Four trials in total, two each on thigh skin or breast meat, were conducted in which chicken skin or meat samples (2 ± 0.1 g; 10 samples per treatment) were inoculated with 50 μL (∼10(6) CFU per sample) of a cocktail of four wild strains of C. jejuni. After 30 min of attachment, inoculated samples were dipped in a 0, 0.5, 1, or 2% BR solution for 30 s immediately followed by vigorously vortexing the samples in Butterfield's phosphate diluent and plating the supernatant for Campylobacter enumeration. In addition, the effect of BR on the color of skin and meat samples was studied. Moreover, the change in the expression of survival and virulence genes of C. jejuni exposed to BR was evaluated. Data were analyzed by the PROC MIXED procedure of SAS (P 0.05). Real-time PCR results revealed that BR treatment down-regulated expression of select genes coding for motility (motA, motB) and attachment (cadF, ciaB) in the majority of C. jejuni strains. Stress response genes (sodB, katA) were upregulated in C. jejuni S-8 (P < 0.05). Overall, our results suggest that BR could be effectively used as antimicrobial dip treatment during poultry processing for reducing Campylobacter on chicken carcasses.

  1. Synthesis, characterization, and crystal structure of mercury(II) complex containing new phosphine oxide salt

    Science.gov (United States)

    Samiee, Sepideh; Kooti, Nadieh; Gable, Robert W.

    2017-02-01

    The reaction of new phosphonium-phosphine oxide salt [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]Br (1) with mercury(II) iodide in a methanolic solution yielded [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2[Hg2I5Br](2). These two compounds were fully characterized by elemental analysis, IR, 1H, 31P, and 13C NMR spectra. Crystal and molecular structure of 2 has been determined by means of X-ray diffraction. In mercury compound, the phosphine oxide salt is found as a counter ion letting the mercury(II) ion to bound halides to all four coordination sites and to give dimermercurate(II) ions as the structure-constructing species. The neighboring [P(O)Ph2(CH2)2PPh2CH2C(O)C6H4NO2]2+cations are joined together by intramolecular Csbnd H⋯O hydrogen bonds to give a 1-D chain structure along the crystallographic b-axis. The [Hg2I5Br]2-anions act as cross-linkers between neighbouring strands extending the supramolecular structure into 2D layers in (110) planes as well as balances the charge of the complex. The significant effects of Csbnd H⋯X (Xdbnd O, Br and I) and π⋯π aromatic interactions play a major role in the crystal packing of compound 2.

  2. Biogenic halocarbons from the Peruvian upwelling region as tropospheric halogen source

    Science.gov (United States)

    Hepach, Helmke; Quack, Birgit; Tegtmeier, Susann; Engel, Anja; Bracher, Astrid; Fuhlbrügge, Steffen; Galgani, Luisa; Atlas, Elliot L.; Lampel, Johannes; Frieß, Udo; Krüger, Kirstin

    2016-09-01

    Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L-1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L-1 and diiodomethane (CH2I2) of up to 32.4 pmol L-1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

  3. Electronic Structure of Rh(2)(&mgr;-CO)(CO)(2)(H(2)PCH(2)PH(2))(2). An Example of a Non-A-Frame Structure.

    Science.gov (United States)

    Bo, Carles; Costas, Miquel; Poblet, Josep M.; Rohmer, Marie-Mad.; Benard, Marc

    1996-05-22

    Calculations based on density functional theory (DFT) and Hartree-Fock configuration interaction (HF-CI) methodology have been carried out to investigate the rhodium-rhodium coupling in Rh(2)(CO)(2)(dppm)(2), 1 (dppm = Ph(2)PCH(2)PPh(2)) and in Rh(2)(&mgr;-CO)(CO)(2)(dppm)(2), 2. DFT geometries, obtained with the Dgauss program, are in good agreement with those determined from X-ray, but HF geometries, calculated using the same basis sets, yield bond distances systematically too long. Calculations indicate that the rhodium atoms in 1 are linked by a single bond. The insertion of a semibridging carbonyl between the two metal atoms leads to a shortening of the rhodium-rhodium distance and also to a noticeable weakening of the metal-metal interaction. Both effects, and also the stabilization of the HOMO of 2, are related to an observed change from square planar to tetrahedral of the ligand environment of the Rh atom proximal to the inserted CO. Both MO analysis and bond characterization from the topology of the charge density confirm the existence of a bonding interaction between the semibridging carbonyl and the distal rhodium atom. The electronic structures of the dicationic complex [Rh(2)(CO)(3)(dppm)(2)](2+) and of the A-frame-like, isoelectronic system Rh(2)Br(2)(&mgr;-CO) (dppm)(2) are also discussed. The electron deformation density is derived from 2 by means of several methodological approaches, namely, HF, HF-CI, DFT, and DFT + gradient corrections. The HF deformation density obtained in the plane containing the metals and the three CO ligands is discussed, as well as the "correlation density" obtained from the difference maps DFT - HF and CI - HF.

  4. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.

    2015-05-12

    The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2

  5. Synthesis, characterization and sorption properties of functionalized Cr-MIL-101-X (X=-F, -Cl, -Br, -CH3, -C6H4, -F2, -(CH3)2) materials

    Science.gov (United States)

    Buragohain, Amlan; Couck, Sarah; Van Der Voort, Pascal; Denayer, Joeri F. M.; Biswas, Shyam

    2016-06-01

    Four existing and three new functionalized chromium terephthalates having MIL-101 topology and denoted as Cr-MIL-101-X (existing ones with X=-F, 1-F; -Cl, 2-Cl; -Br, 3-Br; -CH3, 4-CH3; new ones with X=-C6H4, 5-C6H4; -F2, 6-F2, -(CH3)2, 7-(CH3)2) were synthesized under hydrothermal conditions. All the materials except 5-C6H4 could be prepared by a general synthetic route, in which the mixtures of CrO3, H2BDC-X (BDC=1,4-benzenedicarboxylate) linkers, conc. HCl and water with a molar ratio of 1:1:3.9:222.2 were reacted at 180 °C for 144 h. Compared to the 144 h of synthesis time, three of the compounds, namely 1-Cl, 2-Br and 5-C6H4, could be prepared in much shorter reaction times (12-18 h at 180-210 °C). The materials possess high thermal stability up to 270-300 °C in an air atmosphere. The activated compounds exhibit significant porosity (SBET range: 1273-2135 m2 g-1). At 0 °C and 1 bar, the CO2 adsorption capacities of the compounds fall in the 1.7-2.9 mmol g-1 range. Compounds 1-F and 6-F2 showed enhanced CO2 uptake values compared to parent Cr-MIL-101. The benzene adsorption capacities of the compounds lie in the range of 66.2-139.5 molecules per unit cell at 50 °C and p/p0=0.35. The increased benzene uptake value of 1-F compared to un-functionalized Cr-MIL-101 and 4-CH3 suggests that the fluorination has induced more hydrophobicity in Cr-MIL-101 as compared to the methylation.

  6. Thermodynamic Properties of κ-(BEDT-TTF2X Salts: Electron Correlations and Superconductivity

    Directory of Open Access Journals (Sweden)

    Yasuhiro Nakazawa

    2012-06-01

    Full Text Available Heat capacity measurements of κ-(BEDT-TTF2X (BEDT-TTF: Bis(ethylendithio tetrathiafulvalene, X: counteranions which are classified as two-dimensional (2D dimer-Mott system are reported. At first, we explain structural and electronic features originated from rigid dimerization in donor arrangement in 2D layers. The antiferromagnetic Mott insulating phase located at low-pressure region in the phase diagram shows vanishing γ electronic heat capacity coefficient in the heat capacity, which claims opening of a charge-gap in this insulating state. Then, a systematic change of the γ around the Mott boundary region is reported in relation to the glass freezing of ethylene dynamics. The thermodynamic parameters determined by ∆Cp/γTc of 10 K class superconductors, κ-(BEDT-TTF2Cu(NCS2 and κ-(BEDT-TTF2Cu[N(CN2]Br demonstrate that a rather large gap with a strong coupling character appears around the Fermi-surface. On the other hand, the low temperature heat capacity clearly shows a picture of nodal-gap structure due to an anisotropic pairing. The comparison with lower Tc compounds in the κ-type structure is also performed so as to discuss overall features of the κ-type superconductors. The heat capacity measurements of hole-doped systems containing mercury in the counteranions show an anomalous enhancement of γ, which is consistent with the T1−1 of NMR experiments etc. The results of heat capacity measurements under high pressures are also reported.

  7. Supplemental Thermal-Hydraulic Transient Analyses of BR2 in Support of Conversion to LEU Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Licht, J. [Argonne National Lab. (ANL), Argonne, IL (United States); Dionne, B. [Argonne National Lab. (ANL), Argonne, IL (United States); Sikik, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Van den Branden, G. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium); Koonen, E. [Belgian Nuclear Research Center (SCK-CEN), Mol (Belgium)

    2016-01-01

    Belgian Reactor 2 (BR2) is a research and test reactor located in Mol, Belgium and is primarily used for radioisotope production and materials testing. The Materials Management and Minimization (M3) Reactor Conversion Program of the National Nuclear Security Administration (NNSA) is supporting the conversion of the BR2 reactor from Highly Enriched Uranium (HEU) fuel to Low Enriched Uranium (LEU) fuel. The RELAP5/Mod 3.3 code has been used to perform transient thermal-hydraulic safety analyses of the BR2 reactor to support reactor conversion. A RELAP5 model of BR2 has been validated against select transient BR2 reactor experiments performed in 1963 by showing agreement with measured cladding temperatures. Following the validation, the RELAP5 model was then updated to represent the current use of the reactor; taking into account core configuration, neutronic parameters, trip settings, component changes, etc. Simulations of the 1963 experiments were repeated with this updated model to re-evaluate the boiling risks associated with the currently allowed maximum heat flux limit of 470 W/cm2 and temporary heat flux limit of 600 W/cm2. This document provides analysis of additional transient simulations that are required as part of a modern BR2 safety analysis report (SAR). The additional simulations included in this report are effect of pool temperature, reduced steady-state flow rate, in-pool loss of coolant accidents, and loss of external cooling. The simulations described in this document have been performed for both an HEU- and LEU-fueled core.

  8. Hunting liquid micro-pockets in snow and ice: Phase transition in salt solutions at the bulk and interface with X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Bartels-Rausch, Thorsten; Orlando, Fabrizio; Kong, Xiangrui; Waldner, Astrid; Artiglia, Luca; Ammann, Markus; Huthwelker, Thomas

    2016-04-01

    Sea salt, and in particular chloride, is an important reactant in the atmosphere. Chloride in air-borne sea salt aerosol is - once chemically converted to a molecular halogen (Cl2, BrCl) and released to the atmosphere - well known as important atmospheric reactant, driving large-scale changes to the atmospheric composition and in particular to ozone levels in remote areas, but also in coastal mega cities. Similar chemistry has been proposed for sea salt deposits in polar snow covers. A crucial factor determining the overall reactivity is the local physical environment of the chloride ion. For example, the reactivity of liquid aerosols decreases significantly upon crystallization. Surprisingly, the phases of NaCl-containing systems are still under debate, partially due to the limited availability of in situ measurements directly probing the local environment at the surface of frozen NaCl-water binary systems. Using core electron spectroscopy of the oxygen atoms in water, we previously showed that these systems follow the phase rules at the air-ice interface. This finding contrasts some earlier observations, where the presence of liquid below the eutectic point of bulk solutions was postulated. In the present study, we present new electron yield near-edge X-ray absorption fine structure spectroscopy (NEXAFS) data obtained at near-ambient pressures up to 20 mbar of NaCl frozen solutions. The method is sensitive to small changes in the local environment of the chlorine atom. The measurements were performed at the PHOENIX beamline at SLS. The study indicates frapant differences in the phases of NaCl - water mixtures at temperatures blow the freezing point for the surface of the ice vs. the bulk. This has significant impact on modelling chemical reactions in snow or ice and it's environmental consequences.

  9. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements from the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-02-01

    During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset of all halogen species relevant for the atmospheric budget of total organic bromine has been collected in the West Pacific region using the FALCON aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas cHromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CHBrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2 σ measurement uncertainties. In contrast to the suggestion that the Western Pacific could be a major source region for VSLS (Pyle et al., 2011), we found only slightly enhanced mixing ratios of brominated halogen source gases relative to the levels reported in Montzka et al. (2011) for other tropical regions. A budget for total organic bromine, including all four halons,CH3Br and the VSLS, is derived for the upper troposphere, the input region for the TTL and thus also for the stratosphere, compiled from the SHIVA dataset. With exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  10. Coexistence of charge order and antiferromagnetism in (TMTTF){sub 2}SbF{sub 6}: NMR study

    Energy Technology Data Exchange (ETDEWEB)

    Nomura, K., E-mail: knmr@phys.sci.hokudai.ac.jp; Yamamoto, M.; Matsunaga, N.; Hirose, S.; Shimohara, N.; Satoh, T.; Isome, T.; Liu, Y.; Kawamoto, A.

    2015-03-01

    The electronic state of (TMTTF){sub 2}SbF{sub 6} was investigated by the {sup 1}H and {sup 13}C NMR measurements. The temperature dependence of T{sub 1}{sup −1} in {sup 1}H NMR shows a sharp peak associated with the antiferromagnetic transition at T{sub AF}=6 K. The temperature dependence of T{sub 1}{sup −1} is described by the power law T{sup 2.4} below T{sub AF}. This suggests the nodal gapless spin wave excitation in antiferromagnetic phase. In {sup 13}C NMR, two sharp peaks at high temperature region, associated with the inner and the outer carbon sites in TMTTF dimer, split into four peaks below 150 K. It indicates that the charge disproportionation occurs. The degree of charge disproportionation Δρ is estimated as (0.25±0.09)e from the chemical shift difference. This value of Δρ is consistent with that obtained from the infrared spectroscopy. In the antiferromagnetic state (AFI), the observed line shape is well fitted by eight Lorentzian peaks. This suggests that the charge order with the same degree still remains in the AF state. From the line assignment, the AF staggered spin amplitude is obtained as 0.70 μ{sub B} and 0.24 μ{sub B} at the charge rich and the poor sites, respectively. These values corresponding to almost 1 μ{sub B} per dimer are quite different from 0.11 μ{sub B} of another AF (AFII) state in (TMTTF){sub 2}Br with effective higher pressure. As a result, it is understood that the antiferromagnetic staggered spin order is stabilized on the CO state in the AFI phase of (TMTTF){sub 2}SbF{sub 6}.

  11. NO2 Profile Retrieval using airborne multi axis UV-visible skylight absorption measurements over central Europe

    Directory of Open Access Journals (Sweden)

    I. Pundt

    2006-01-01

    Full Text Available A recent development in ground-based remote sensing of atmospheric constituents by UV/visible absorption measurements of scattered light is the simultaneous use of several directions with small elevation angles in addition to the traditional zenith-sky pointing. The different light paths through the atmosphere enable the vertical distribution of some atmospheric absorbers such as NO2, BrO or O3 to be retrieved. In this study, the amount of profile information that can be retrieved from such measurements on aircraft is investigated for the trace gas NO2. A Sensitivity study on synthetic data is performed for a combination of four lines of sight (LOS (0° (nadir, 88°, 92°, and 180° (zenith and three wavelength regions [center wavelengths: 362.5 nm, 437.5 nm, and 485.0 nm]. This investigation demonstrates the potential of this LOS/wavelengths setup to retrieve a significant amount of profile information from airborne multiaxis differential optical absorption spectrometer (AMAXDOAS measurements with a vertical resolution of 3.0 to 4.5 km in the lower troposphere and 2.0 to 3.5 km near flight altitude. Above 13 km the profile information content of AMAXDOAS measurements is sparse. Further, retrieved profiles with a significant amount (up to 3.2 ppbv of NO2 in the boundary layer over the Po-valley (Italy are presented. Airborne multiaxis measurements are thus a promising tool for atmospheric studies in the troposphere.

  12. NO2 Profile retrieval using airborne multi axis UV-visible skylight absorption measurements over central Europe

    Directory of Open Access Journals (Sweden)

    M. Bruns

    2006-01-01

    Full Text Available A recent development in ground-based remote sensing of atmospheric constituents by UV/visible absorption measurements of scattered light is the simultaneous use of several directions with small elevation angles in addition to the traditional zenith-sky pointing. The different light paths through the atmosphere enable the vertical distribution of some atmospheric absorbers such as NO2, BrO or O3 to be retrieved. In this study, the amount of profile information that can be retrieved from such measurements on aircraft is investigated for the trace gas NO2. A Sensitivity study on synthetic data is performed for a combination of four lines of sight (LOS (0°(nadir, 88°, 92°, and 180° (zenith and three wavelength regions [center wavelengths: 362.5 nm, 437.5 nm, and 485.0 nm]. The method used in this work is a combination of two previously established methods described in Petritoli et al. (2002 and Wang et al. (2004. The investigation presented here demonstrates the potential of this LOS/wavelengths setup to retrieve a significant amount of profile information from airborne multiax is differential optical absorption spectrometer (AMAXDOAS measurements with a vertical resolution of 3.0 to 4.5 km in the lower troposphere and 2.0 to 3.5 km near flight altitude. Above 13 km the profile information content of AMAXDOAS measurements is sparse. The retrieval algorithm used in this work is the AMAXDOAS profile retrievalalgorithm (APROVAL. Further, retrieved profiles with a significant amount (up to 3.2 ppbv of NO2 in the boundary layer over the Po-valley (Italy are presented. Airborne multiaxis measurements are thus a promising tool for atmospheric studies in the troposphere.

  13. Changes in Köppen-Geiger climate types under a future climate for Australia: hydrological implications

    Directory of Open Access Journals (Sweden)

    R. S. Crosbie

    2012-09-01

    Full Text Available The Köppen-Geiger climate classification has been used for over a century to delineate climate types across the globe. As it was developed to mimic the distribution of vegetation, it may provide a useful surrogate for making projections of the future distribution of vegetation, and hence resultant hydrological implications, under climate change scenarios. This paper developed projections of the Köppen-Geiger climate types covering the Australian continent for a 2030 and 2050 climate relative to a 1990 historical baseline climate using 17 Global Climate Models (GCMs and five global warming scenarios. At the highest level of classification for a +2.4 °C future climate (the upper limit projected for 2050 relative to the historical baseline, it was projected that the area of the continent covered by

    – tropical climate types would increase from 8.8% to 9.1%;
    – arid climate types would increase from 76.5% to 81.7%;
    – temperate climate types would decrease from 14.7% to 9.2%;<br> – cold climate types would decrease from 0.016% to 0.001%.

    Previous climate change impact studies on water resources in Australia have assumed a static vegetation distribution. If the change in projected climate types is used as a surrogate for a change in vegetation, then the major transition in climate from temperate to arid in parts of Australia under a drier future climate could cause indirect effects on water resources. A transition from annual cropping to perennial grassland would have a compounding effect on the projected reduction in recharge. In contrast, a transition from forest to grassland would have a mitigating effect on the projected reduction in runoff.

  14. Changes in Köppen-Geiger climate types under a future climate for Australia: hydrological implications

    Directory of Open Access Journals (Sweden)

    R. S. Crosbie

    2012-06-01

    Full Text Available The Köppen-Geiger climate classification has been used for over a century to delineate climate types across the globe. As it was developed to mimic the distribution of vegetation it may provide a useful surrogate for making projections of the future distribution of vegetation, and hence resultant hydrological implications, under climate change scenarios. This paper developed projections of the Köppen-Geiger climate types covering the Australian continent for a 2030 and 2050 climate relative to a 1990 historical baseline climate using 17 Global Climate Models (GCMs and five global warming scenarios. At the highest level of classification for a +2.4 °C future climate (the upper limit projected for 2050 relative to the historical baseline, it was projected that the area of the continent covered by:
    – Tropical climate types would increase from 8.8% to 9.1%
    – Arid climate types would increase from 76.5% to 81.7%
    – Temperate climate types would decrease from 14.7% to 9.2% <br> – Cold climate types would decrease from 0.016% to 0.001%.
    Previous climate change impact studies on water resources in Australia have assumed a static vegetation distribution. If the change in projected climate types is used as a surrogate for a change in vegetation, then the major transition in climate from Temperate to Arid in parts of Australia under a drier future climate could cause indirect effects on water resources. For a transition from annual cropping to perennial grassland this would have a compounding effect on the projected reduction in recharge. In contrast, a transition from forest to grassland would have a mitigating effect on the projected reduction in runoff.

  15. Preparation of a new polymeric ionic liquid-based monolith for stir cake sorptive extraction and its application in the extraction of inorganic anions.

    Science.gov (United States)

    Huang, Xiaojia; Chen, Linli; Yuan, Dongxing; Bi, Shangshang

    2012-07-27

    In this study, a novel stir cake sorptive extraction (SCSE) sorbent based on polymeric ionic liquid-based monolith (PILM) for the extraction of inorganic anions was prepared. In the presence of a porogen solvent containing 1-propanol and dimethylformamid, an ionic liquid, 1-ally-3-methylimidazolium chloride was used as monomer to copolymerize in situ with ethylene dimethacrylate to form PILM. The effect of preparation conditions such as ratio of functional monomer to cross-linker, content of porogenic solvent on the extraction efficiencies were investigated in detail. The PILM was characterized by elemental analysis, scanning electron microscopy, mercury intrusion porosimetry and infrared spectroscopy. In order to investigate the extraction capacity of PILM-SCSE for inorganic anions, the SCSE was combined with ion chromatography with conductivity detection, F(-), Cl(-), NO(2)(-), Br(-), NO(3)(-), PO(4)(3-) and SO(4)(2-) were selected as detected solutes. Several extractive parameters, including pH values in sample matrix, desorption solvent, extraction and desorption time were optimized. The results showed that under the optimum experimental conditions, low detection limits (S/N=3) and quantification limits (S/N=10) of the proposed method for the target anions were achieved within the range of 0.11-2.08 and 0.37-6.88 μg/L, respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction inorganic anions. Finally, the proposed method was successfully used to detect different water samples include commercial purified water, tab water and river water. Acceptable recoveries and satisfactory repeatability were obtained. To the best of our knowledge, this is the first to use polymeric ionic liquid to enrich inorganic anions.

  16. Theoretical exploration of pnicogen bond noncovalent interactions in HCHO· · · PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2) complexes

    Indian Academy of Sciences (India)

    Yan-Zhi Liu; Kun Yuan; Zhao Yuan; Yuan-Cheng Zhu; Xiang Zhao

    2015-10-01

    Pnicogen bond (ZB) is a new kind of intermolecular weak interaction, which would be an important strategy for the construction of supramolecular materials. In this paper, ab initio MP2/aug-cc-pvDZ calculations have been carried out to characterize the X-P ⋯ O ZB interactions between HCHO and PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2). The calculated interaction energies with basis set super-position error (BSSE) corrections in seven ZB complexes are between −7.51 and −20.36 kJ·mol−1. The relative stabilities of the seven complexes increase in the order: HCHO⋯ PH2CH3 < HCHO⋯ PH3 < HCHO⋯ PH2 C6H5 < HCHO⋯ PH2 Br < HCHO⋯ PH2 Cl < HCHO⋯ PH2F < HCHO⋯ PH2NO2. The natural bond orbital (NBO) and natural resonance theory (NRT) analysis were employed to investigate the electron behavior and nature of the ZBs. The natural bond orbital interactions in the ZBs are mainly LP1,2 (O) → * (P-X). The P-X (X= Br, Cl, F and NO2) are more suitable for acting as ZB donors than the P-X (X=H, CH3 and C6H5) groups. The electron density topology properties based on atoms-inmolecules (AIM) theory showed that the ZB interactions in the HCHO⋯ PH2X (X=Br, Cl, F and NO2) are stronger than those of HCHO⋯ PH2 X(X=CH3 , H and C6H5) complexes, indicating that the electron withdrawing of X benefits for the stability of ZB structure.

  17. Theoretical study of H-abstraction reactions from CH3Cl and CH3Br molecules by ClO and BrO radicals.

    Science.gov (United States)

    Canneaux, Sébastien; Hammaecher, Catherine; Cours, Thibaud; Louis, Florent; Ribaucour, Marc

    2012-05-03

    The rate constants of the H-abstraction reactions from CH(3)Cl and CH(3)Br molecules by ClO and BrO radicals have been estimated over the temperature range of 300-2500 K using four different levels of theory. Calculations of optimized geometrical parameters and vibrational frequencies are performed using B3LYP and MP2 methods combined with the cc-pVTZ basis set. Single-point energy calculations have been carried out with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (perturbatively) electron excitations CCSD(T) using the cc-pVTZ and cc-pVQZ basis sets. Canonical transition-state theory combined with an Eckart tunneling correction has been used to predict the rate constants as a function of temperature. In order to choose the appropriate levels of theory with chlorine- and bromine-containing species, the reference reaction Cl ((2)P(3/2)) + CH(3)Cl → HCl + CH(2)Cl (R(ref)) was first theoretically studied because its kinetic parameters are well-established from numerous experiments, evaluation data, and theoretical studies. The kinetic parameters of the reaction R(ref) have been determined accurately using the CCSD(T)/cc-pVQZ//MP2/cc-pVTZ level of theory. This level of theory has been used for the rate constant estimation of the reactions ClO + CH(3)Cl (R(1)), ClO + CH(3)Br (R(2)), BrO + CH(3)Cl (R(3)), and BrO + CH(3)Br (R(4)). Six-parameter Arrhenius expressions have been obtained by fitting to the computed rate constants of these four reactions (including cis and trans pathways) over the temperature range of 300-2500 K.

  18. Kinetic studies on the temperature dependence of the BrO + BrO reaction using laser flash photolysis.

    Science.gov (United States)

    Ferracci, Valerio; Hino, Kaori; Rowley, David M

    2011-05-07

    The BrO self-reaction, BrO + BrO → products (1), has been studied using laser flash photolysis coupled with UV absorption spectroscopy over the temperature range T = 266.5-321.6 K, under atmospheric pressure. BrO radicals were generated via laser photolysis of Br(2) in the presence of excess ozone. Both BrO and O(3) were monitored via UV absorption spectroscopy using charge-coupled device (CCD) detection. Simultaneous fitting to both temporal concentration traces allowed determination of the rate constant of the two channels of , BrO + BrO → 2Br + O(2) (1a); BrO + BrO → Br(2) + O(2) (1b), hence the calculation of the overall rate of and the branching ratio, α: k(1a)/cm(3) molecule(-1) s(-1) = (1.92 ± 1.54) × 10(-12) exp[(126 ± 214)/T], k(1b)/cm(3) molecule(-1) s(-1) = (3.4 ± 0.8) × 10(-13) exp[(181 ± 70)/T], k(1)/cm(3) molecule(-1) s(-1) = (2.3 ± 1.5) × 10(-12) exp(134 ± 185 /T) and α = k(1a)/k(1) = (0.84 ± 0.09) exp[(-7 ± 32)/T]. Errors are 1σ, statistical only. Results from this work show a weaker temperature dependence of the branching ratio for channel (1a) than that found in previous work, leading to values of α at temperatures typical of the Polar Boundary Layer higher than those reported by previous studies. This implies a shift of the partitioning between the two channels of the BrO self-reaction towards the bromine atom and hence directly ozone-depleting channel (1a). This journal is © the Owner Societies 2011

  19. Development and application of a sampling method for the determination of reactive halogen species in volcanic gas emissions

    Science.gov (United States)

    Rüdiger, Julian; Bobrowski, Nicole; Liotta, Marcello; Hoffmann, Thorsten

    2017-04-01

    Volcanoes are a potential large source of several reactive atmospheric trace gases including sulfur and halogen containing species. Besides the importance for atmospheric chemistry, the detailed knowledge of halogen chemistry in volcanic plumes can help to get insights into subsurface processes. In this study a gas diffusion denuder sampling method, using a 1,3,5-trimethoxybenzene (1,3,5-TMB) coating for the derivatization of reactive halogen species (RHS), was characterized by dilution chamber experiments. The coating proved to be suitable to collect selectively gaseous bromine species with oxidation states (OS) of +1 or 0 (such as Br2, BrCl, BrO(H) and BrONO2), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with reactive bromine species gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography mass spectrometry gives detection limits of 10 ng or less for Br2, Cl2, and I2. In 2015 the method was applied on volcanic gas plumes at Mt. Etna (Italy) giving reactive bromine mixing ratios from 0.8 ppbv to 7.0 ppbv. Total bromine mixing ratios of 4.7 ppbv to 27.5 ppbv were obtained by simultaneous alkaline trap sampling (by a Raschig-tube) followed by analysis with ion chromatography and inductively coupled plasma mass spectrometry. This leads to the first results of in-situ measured reactive bromine to total bromine ratios, spanning a range between 12±1 % and 36±2 %. Our finding is in an agreement with previous model studies, which imply values < 44 % for plume ages < 1 minute, which is consistent with the assumed plume age at the sampling sites.

  20. New radiometric dates for the Prehistory of Northwestern Iberia: Valdavara Cave (Becerreá, Lugo

    Directory of Open Access Journals (Sweden)

    Vaquero Rodríguez, Manuel

    2009-06-01

    Full Text Available The goal of this paper is to make known the first results of the excavations in Valdavara Cave (Becerreá, Lugo, paying special attention to the radiometric dating that places this cave among the few Galician sites with Upper Palaeolithic dates. During the excavation carried out in 2007, two archaeological locations were documented in the same karstic system (Valdavara 1 and Valdavara 2. The test pit initiated in Valdavara 1 allowed us to identify so far two stratigraphic units: an upper unit corresponding to Recent Prehistory and a lower unit (level 4 that yielded the Upper Palaeolithic dates. An assemblage of human remains from the Bronze Age was found in Valdavara 2.<br>
    El objetivo de este artículo es dar a conocer los primeros resultados de las excavaciones en la cueva de Valdavara (Becerreá, Lugo, prestando especial atención a las dataciones radiométricas que la sitúan entre los pocos yacimientos gallegos que han arrojado fechas correspondientes al Paleolítico Superior. La excavación realizada en el año 2007 permitió documentar dos localizaciones arqueológicas en el marco del mismo sistema cárstico (Valdavara 1 y Valdavara 2. El sondeo iniciado en Valdavara 1 ha permitido identificar hasta el momento dos conjuntos estratigráficos: un conjunto superior correspondiente a la Prehistoria reciente y un conjunto inferior (nivel 4 en el que se han obtenido las fechas del Paleolítico Superior final. En Valdavara 2 se encontró un conjunto de restos humanos de la Edad del Bronce.

  1. Syntheses of halogenated polyhedral phosphaboranes: crystal structure of conjuncto-3,3{sup '}-(closo-1,2-P{sub 2}B{sub 4}Br{sub 3}){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Keller, Willi [Institut fuer Chemie, Universitaet Hohenheim, Garbenstrasse 30, 70599, Stuttgart (Germany)

    2017-04-18

    Co-pyrolysis of B{sub 2}Br{sub 4} with PBr{sub 3} at 480 C gave, in addition to the main product closo-1,2-P{sub 2}B{sub 4}Br{sub 4}, conjuncto-3,3{sup '}-(1,2-P{sub 2}B{sub 4}Br{sub 3}){sub 2} (1) and the twelve-vertex closo-1,7-P{sub 2}B{sub 10}Br{sub 10} (2), both in low yields. X-ray structure determination for 1 [triclinic, space-group P1 with a = 7.220(2) Aa, b = 7.232(2) Aa, c = 8.5839(15) Aa, α = 97.213(15) , β = 96.81(2) , γ = 94.07(2) and Z = 1] confirmed that 1 adopts a structure consisting of two symmetrically boron-boron linked distorted octahedra with the bridging boron atoms in the 3,3{sup '}-positions and the phosphorus atoms in the 1,2-positions. The intercluster 2e/2c B-B bond length is 1.61(3) Aa. The shortest boron-boron bond within the cluster framework is 1.68(2) Aa located between the boron atoms antipodal to the phosphorus atoms. The icosahedral phosphaborane 2 was characterized by {sup 11}B-{sup 11}B COSY NMR spectroscopy showing cross peaks indicative for the isomer with the phosphorus atoms in 1,7-positions. Both the X-ray data of 1 and the NMR spectroscopic data of 1 and 2 give further evidence for the influence of an antipodal effect of heteroatoms to cross-cage boron atoms and, vice versa, of an additional shielding of the phosphorus atoms caused by B-Hal substitution at the boron positions trans to phosphorus. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Synthesis, characterization, and energetic properties of salts of the 1-cyanomethyl-1,1-dimethylhydrazinium cation.

    Science.gov (United States)

    Miró Sabaté, Carles; Delalu, Henri; Jeanneau, Erwann

    2012-05-01

    1,1-Dimethylhydrazine can be readily alkylated with bromoacetonitrile to form 1-cyanomethyl-1,1-dimethylhydrazinium bromide ([(CH(3))(2)N(CH(2)CN)NH(2)]Br, 1). The metathesis reaction of compound 1 led to the formation of a new family of energetic salts based on the [(CH(3))(2)N(CH(2)CN)NH(2)](+) cation and nitrate (2), perchlorate (3), azide (4), 5-aminotetrazolate ([H(2)N-CN(4)](-), 5), 5,5'-azobistetrazolate ([N(4)C-N=N-CN(4)](2-), 7), and picrate (8) anions. The new materials were characterized by elemental analysis, mass spectrometry, and (multinuclear) NMR and vibrational (infrared and Raman) spectroscopies. Additionally, the molecular structure of the [(CH(3))(2)N(CH(2)CN)NH(2)](+) cation in compounds 1, 3, and 8 and that of sodium 5,5'-azobistetrazolate octahydrate (NaZT·8H(2)O) were solved by X-ray diffraction techniques. The hydrogen-bonding networks found in the structure of salts 1, 3, 8, and NaZT·8H(2)O are described using graph-set analysis. The melting and decomposition points of the new compounds were determined by differential scanning calorimetry, and insight into their sensitivity towards impact, friction, and electrostatics was gained by submitting the materials to standard tests. Furthermore, we estimated some performance parameters of interest and predicted the decomposition gases formed upon decomposition of salts 2-8 and of mixtures with an oxidizer. The interesting thermal, sensitivity, and performance properties of some of the compounds described in this work make them attractive towards a prospective energetic application.

  3. Short-lived halocarbons efficient at influencing climate through ozone loss in the upper troposphere-lower stratosphere

    Science.gov (United States)

    Hossaini, Ryan; Chipperfield, Martyn; Montzka, Steven; Rap, Alex; Dhomse, Sandip; Feng, Wuhu

    2015-04-01

    Halogenated very short-lived substances (VSLS) of both natural and anthropogenic origin are a significant source of atmospheric bromine, chlorine and iodine. Due to relatively short atmospheric lifetimes (typically disproportionately large climate impact compared to other altitudes. Here we present chemical transport model simulations that quantify VSLS-driven ozone loss in the UTLS and infer the climate relevance of these ozone perturbations using a radiative transfer model. Our results indicate that through their impact on UTLS ozone, VSLS are efficient at influencing climate. We calculate a whole atmosphere global mean radiative effect (RE) of -0.20 (-0.16 to -0.23) Wm-2 from natural and anthropogenic VSLS-driven ozone loss, including a tropospheric contribution of -0.12 Wm-2. In the stratosphere, the RE due to ozone loss from natural bromine-containing VSLS (e.g. CHBr3, CH2Br2) is almost half of that from long-lived anthropogenic compounds (e.g. CFCs) and normalized by equivalent chlorine is ~4 times larger. We show that the anthropogenic chlorine-containing VSLS, not regulated by the Montreal Protocol, also contribute to ozone loss in the UTLS and that the atmospheric concentration of dichloromethane (CH2Cl2), the most abundant of these, is increasing rapidly. Finally, we present evidence that VSLS have made a small yet previously unrecognized contribution to the ozone-driven radiative forcing of climate since pre-industrial times of -0.02 (-0.01 to -0.03) Wm-2. Given the climate leverage that VSLS possess, future increases to their emissions, either through continued industrial or altered natural processes, may be important for future climate forcing.

  4. Inverse agonist histamine H3 receptor PET tracers labelled with carbon-11 or fluorine-18.

    Science.gov (United States)

    Hamill, Terence G; Sato, Nagaaki; Jitsuoka, Makoto; Tokita, Shigeru; Sanabria, Sandra; Eng, Waisi; Ryan, Christine; Krause, Stephen; Takenaga, Norihiro; Patel, Shil; Zeng, Zhizhen; Williams, David; Sur, Cyrille; Hargreaves, Richard; Burns, H Donald

    2009-12-01

    Two histamine H3 receptor (H3R) inverse agonist PET tracers have been synthesized and characterized in preclinical studies. Each tracer has high affinity for the histamine H3 receptor, has suitable lipophilicity, and neither is a substrate for the P-glycoprotein efflux pump. A common phenolic precursor was used to synthesize each tracer with high specific activity and radiochemical purity by an alkylation reaction using either [(11)C]MeI or [(18)F]FCD(2)Br. Autoradiographic studies in rhesus monkey and human brain slices showed that each tracer had a widespread distribution with high binding densities in frontal cortex, globus pallidus and striatum, and lower uptake in cerebellum. The specificity of this expression pattern was demonstrated by the blockade of the autoradiographic signal by either the H3R agonist R-alpha-methylhistamine or a histamine H3R inverse agonist. In vivo PET imaging studies in rhesus monkey showed rapid uptake of each tracer into the brain with the same distribution seen in the autoradiographic studies. Each tracer could be blocked by pretreatment with a histamine H3R inverse agonist giving a good specific signal. Comparison of the in vitro metabolism of each compound showed slower metabolism in human liver microsomes than in rhesus monkey liver microsomes, with each compound having a similar clearance rate in humans. The in vivo metabolism of 1b in rhesus monkey showed that at 60 min, approximately 35% of the circulating counts were due to the parent. These tracers are very promising candidates as clinical PET tracers to both study the histamine H3R system and measure receptor occupancy of H3R therapeutic compounds.

  5. Overview of the O3M SAF GOME-2 operational atmospheric composition and UV radiation data products and data availability

    Directory of Open Access Journals (Sweden)

    S. Hassinen

    2015-07-01

    Full Text Available The three GOME-2 instruments will provide unique and long data sets for atmospheric research and applications. The complete time period will be 2007–2022, including the period of ozone depletion as well as the beginning of ozone layer recovery. Besides ozone chemistry, the GOME-2 products are important e.g. for air quality studies, climate modeling, policy monitoring and hazard warnings. The heritage for GOME-2 is in the ERS/GOME and Envisat/SCIAMACHY instruments. The current Level 2 (L2 data cover a wide range of products such as trace gas columns (NO2, BrO, H2CO, H2O, SO2, tropospheric columns of NO2, total ozone columns and vertical ozone profiles in high and low spatial resolution, absorbing aerosol indices from the main science channels as well as from the polarization channels (AAI, AAI-PMD, Lambertian-equivalent reflectivity database, clear-sky and cloud-corrected UV indices and surface UV fields with different weightings and photolysis rates. The Ozone Monitoring and Atmospheric Composition Satellite Application Facility (O3M SAF processing and data dissemination is operational and running 24/7. Data quality is quarantined by the detailed review processes for the algorithms, validation of the products as well as by a continuous quality monitoring of the products and processing. This is an overview paper providing the O3M SAF project background, current status and future plans to utilization of the GOME-2 data. An important focus is the provision of summaries of the GOME-2 products including product principles and validation examples together with the product sample images. Furthermore, this paper collects the references to the detailed product algorithm and validation papers.

  6. Signatures of granular superconductivity and Josephson effects in macroscopic measurements: the case of new superconductors

    Directory of Open Access Journals (Sweden)

    S Senoussi

    2006-09-01

    Full Text Available   We report systematic investigations of the magnetic superconducting properties of the new superconducting materials (NS: New high temperature superconductors (HTS, Organic superconductors (OS, fullerenes, carbon nanotubes, MgB2 etc. We show that, contrary to conventional superconductors where the superconducting state can be coherent over several tenths of km, the macroscopic coherence range lc of the NS is often as short as 0.1 to 10 µm typically. As a consequence, the magnetic properties are dominated by granular-like effects as well as Josephson coupling between grains. Here, we concentrate on HTS ceramics and organic superconductors exclusively. In the first case we observe three distinct regimes: (i At very low field (H < 5 Oe to say all the grains are coupled via Josephson effect and lc can be considered as infinite. (2 At intermediate field (5 < H < 50 Oe, typically the grains are gradually decoupled by H and/or T. (iii At higher fields all the grains are decoupled and lc roughly coincides with the diameter of the metallurgical grains. The case of OS is more subtle and is connected with a kind of order-disorder transition that occurs in most of them. For instance, in this study, we exploit quenched disorder (after crossing such a transition in the -(BEDT-TTF2Cu[N(CN2]Br layered organic superconductor to get new insights on both the superconducting state (T £ 11.6 K and the glassy transition at Tg, by studying the superconducting properties as functions of annealing time and annealing temperature around the glassy transition. Our main result is that the data can be described by a percolation molecular cluster model in which the topology and the growth of the molecular clusters obey an Ising spin-glass-like model with Tg ≈ 80 K for the hydrogenated compound and Tg ≈ 55 K for the fully deuterated one.

  7. Highly fluorescent platinum(II) organometallic complexes of perylene and perylene monoimide, with Pt σ-bonded directly to the perylene core.

    Science.gov (United States)

    Lentijo, Sergio; Miguel, Jesús A; Espinet, Pablo

    2010-10-18

    3-Bromoperylene (BrPer) or N-(2,5-di-tert-butylphenyl)-9-bromo-perylene-3,4-dicarboximide (BrPMI) react with [Pt(PEt(3))(4)] to yield trans-[PtR(PEt(3))(2)Br] (R = Per, 1a; R = PMI, 1b). Neutral and cationic perylenyl complexes containing a Pt(PEt(3))X group have been prepared from 1a,b by substitution of the Br ligand by a variety of other ligands (NCS, CN, NO(3), CN(t)Bu, PyMe). The X-ray structures of trans-[PtR(PEt(3))(2)X] (R = Per, X = NCS (2a); R = PMI, X = NO(3) (4b); R = Per, X = CN(t)Bu (5a)) show that the perylenyl fragment remains nearly planar and is arranged almost orthogonal to the coordination plane: The three molecules appear as individual entities in the solid state, with no π-π stacking of perylenyl rings. Each platinum complex exhibits fluorescence associated to the perylene or PMI fragments with emission quantum yields, in solution at room temperature, in the range 0.30-0.80 and emission lifetimes ∼4 ns, but with significantly different emission maxima, by influence of the X ligands on Pt. The similarity of the overall luminescence spectra of these metalated complexes with the perylene or PMI strongly suggests a perylene-dominated intraligand π-π*emissive state, metal-perturbed by interaction of the platinum fragment mostly via polarization of the Ar-Pt bond.

  8. Synthesis and Crystal Structure of Bis((2-methoxy-mercaptomethyl-benzene)hexacarbonyldiiron) Complex

    Institute of Scientific and Technical Information of China (English)

    魏振宏; 游秀丽; 汤英; 肖知音

    2012-01-01

    The reaction of [Fe2S2(CO)6] with one equiv.of o-OCH3C6H4CH2Br under the re-duction of LiBHEt3 in dry THF afforded a tetranuclear cluster [(μ4-S){(μ-SCH2(o-OCH3)Ph)Fe2(CO)6}2](1).Complex 1 crystallizes in monoclinic,space group P21/n with a = 16.5623(6),b = 12.8265(5),c = 18.2702(7) ,β = 115.95(1)o,V = 3489.9(4) 3,Z = 4,μ = 1.87 mm-1,Dc = 1.709 Mg/m3,T = 296(2) K,C28H18Fe4O14S3,Mr = 898.03,F(000) = 1800,S = 1.10,R = 0.032 and wR = 0.058.Complex 1 consists of two diiron fragments possessing a {Fe2(CO)6} core.The two diiron units are bridged by an inorganic sulfide in a μ4-S binding mode and the sulfide is in a distorted tetrahedral geometry with the four iron atoms at each corner of the distorted tetrahedral.In its solid state,two types of non-classic intermolecular hydrogen bonding interactions plus a weak π-π stacking interaction led to a 2-D network.

  9. Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

    Science.gov (United States)

    Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

    2013-12-13

    A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained.

  10. Study of the micellization and micellar growth in pure alkanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide and MEGA10 surfactant solutions and their mixtures. Influence of the spacer on the enthalpy change accompanying sphere-to-rod transitions.

    Science.gov (United States)

    Martín, Victoria Isabel; Rodríguez, Amalia; Graciani, María del Mar; Robina, Inmaculada; Moyá, María Luisa

    2010-06-17

    The micellization and micellar growth in pure aqueous alkanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide, 12-s-12,2Br(-) (with s = 2,5,6,8,10,12), and N-decanoyl-N-methylglucamide MEGA10 solutions and their mixtures are investigated at 303 K. Application of different theoretical approaches to the binary mixtures shows a nonideal behavior. It also shows that the spacer length does not play an important role in the attractive interactions shown by the mixed systems. The sphere-to-rod morphological transition in the pure dimeric micellar solutions is studied at 303 K. From comparison of these results with those at 298 K the key role played by the spacer in the micellar growth is shown. The spacer length controls not only the surfactant concentration at which the morphological transition happens but also the sign of the enthalpy change accompanying the sphere-to-rod equilibrium. Spacers with an even number of methylenes show smaller C* values than those with an odd number of -CH(2)- units. An endothermic enthalpy change is found for even spacers whereas an exothermic enthalpy change is found for odd spacers. To the authors knowledge, this is the first time this experimental trend has been shown. Addition of MEGA10 diminishes the tendency of the aggregates to grow. An increment in the solution mole fraction of MEGA10 makes the formation of elongated micelles difficult. Microviscosity measurements provide additional information about the influence of the MEGA10 content on the sphere-to-rod transition.

  11. CARIBIC observations of short-lived halocarbons and carbonyl sulphide over Asia

    Science.gov (United States)

    Leedham, E.; Wisher, A.; Oram, D.; Baker, A. K.; Brenninkmeijer, C. A.

    2013-12-01

    The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com) aims to investigate the spatial and temporal distribution of a wide-range of compounds, including those of marine origin/influence, via ~monthly flights to collect in situ data and whole air samples aboard a commercial Lufthansa aircraft. CARIBIC measures up to an altitude of 12 km, allowing the influence of marine compounds on the upper troposphere/lower stratosphere (UTLS) to be explored. In particular, CARIBIC is a useful tool for exploring the impact of very short lived halocarbons (e.g. CH2Br2, CHBr3), whose impact on stratospheric ozone is dependent on convective uplift to the UTLS, a process which is not yet fully quantified. As part of the suite of CARIBIC measurements, whole air samples are analysed at the University of East Anglia (UEA) via gas chromatography mass spectrometry for carbonyl sulphide (OCS) and up to 40 halocarbons (accounting for virtually 100% of organic chlorine, bromine and iodine in the UTLS). Here we present an overview of short-lived halocarbons and OCS measured by CARIBIC. We focus on two regions of particular interest. (1) measurements made in 2012 over the tropical west Pacific to link with UEA measurements made during the SHIVA campaign. (2) measurements made during a collection of flights over India in 2008. Flights over India investigated the impact of monsoon circulation on the distribution of these compounds; for example, elevated concentrations of OCS were seen in CARIBIC samples taken over India during the summer monsoon (July - September). These flights, along with a wider range of flights over Asia (from Frankfurt to Guangzhou, Manila, Bangkok and Kuala Lumpur) can provide unique information on the influence of tropical convection and monsoon circulation on halocarbon and OCS transport within this region.

  12. Effect of adenosine on the supramolecular architecture and activity of 5-fluorouracil

    Science.gov (United States)

    Singh, Udai P.; Kashyap, Sujata; Singh, Hari Ji; Mishra, Bhupesh Kumar; Roy, Partha; Chakraborty, Ajanta

    2012-04-01

    The reactions of adenosine (Ad) with 5-halouracils (5XU where X = F for 1, Cl for 2, Br for 3 and I for 4) resulted in the formation of co-crystals 1-4 in monoclinic with P21 space group. Despite of great variation in the halo substituent at the 5th position of the uracil, each structure contains the same number and same type of non-covalent interactions i.e., primary N-H⋯N, N-H⋯O, O-H⋯N, O-H⋯O hydrogen bonds and secondary C-H⋯O and X⋯O interactions within these motifs as well as with neighboring molecules. As compared to Ad the size of cavity increases in co-crystal 1 to accommodate the 5FU as a guest. With the variation of halogen from fluoro to iodo on the uracil, the orientation of the molecules remains the same with a slight difference in the dihedral angle in all the co-crystals 1-4. This study demonstrates that hydrogen-bonded interactions between adenosine and halouracils provide a supramolecular assembly to these co-crystals. Computational studies illustrate that the size of the halo substituents on uracil has no effect on the hydrogen bond interaction energy. It further reveals that the orientation of molecules remain same in both solid phase as well as in the gaseous phase. The antitumor and DNA cleavage activity studies show that the antitumor activity of 5-fluorouracil against MCF-7 breast cancer decreases in the presence of adenosine.

  13. Network Analysis of Sequence-Function Relationships and Exploration of Sequence Space of TEM β-Lactamases.

    Science.gov (United States)

    Zeil, Catharina; Widmann, Michael; Fademrecht, Silvia; Vogel, Constantin; Pleiss, Jürgen

    2016-05-01

    The Lactamase Engineering Database (www.LacED.uni-stuttgart.de) was developed to facilitate the classification and analysis of TEM β-lactamases. The current version contains 474 TEM variants. Two hundred fifty-nine variants form a large scale-free network of highly connected point mutants. The network was divided into three subnetworks which were enriched by single phenotypes: one network with predominantly 2be and two networks with 2br phenotypes. Fifteen positions were found to be highly variable, contributing to the majority of the observed variants. Since it is expected that a considerable fraction of the theoretical sequence space is functional, the currently sequenced 474 variants represent only the tip of the iceberg of functional TEM β-lactamase variants which form a huge natural reservoir of highly interconnected variants. Almost 50% of the variants are part of a quartet. Thus, two single mutations that result in functional enzymes can be combined into a functional protein. Most of these quartets consist of the same phenotype, or the mutations are additive with respect to the phenotype. By predicting quartets from triplets, 3,916 unknown variants were constructed. Eighty-seven variants complement multiple quartets and therefore have a high probability of being functional. The construction of a TEM β-lactamase network and subsequent analyses by clustering and quartet prediction are valuable tools to gain new insights into the viable sequence space of TEM β-lactamases and to predict their phenotype. The highly connected sequence space of TEM β-lactamases is ideally suited to network analysis and demonstrates the strengths of network analysis over tree reconstruction methods.

  14. [Preparation of an agglomerated ion chromatographic stationary phase with 2,3-ionene and its application in SO4(2-) analysis].

    Science.gov (United States)

    Wang, Muhua; Liu, Junwei; Huang, Zhongping; Zhang, Jiajie; Zhu, Yan

    2015-07-01

    The poly-electrolyte cation functional group of 2,3-ionene was synthesized with tetramethyl ethylenediamine and 1,3-dibromopropane as the raw materials. Multiporous polystyrene-divinylbenzene microsphere particles (PS-DVB) were produced by swelling method with polystyrene as seeds and sulfonated. Then the 2,3-ionene was bonded on the sulfonated multi-porous polystyrene-divinylbenzene microsphere particles by agglomeration to get the agglomerative ion-exchange stationary phase. After optimizing the synthetic conditions, the new stationary phase was characterized by the techniques including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The chromatographic column was packed by slurry method and applied in the analysis of SO4(2-) with a conductivity detector. SO4(2-) and other six common anions including F-, Cl-, NO2(-), Br-, NO3(-), PO4(3-), were separated and analyzed rapidly on the self-regulating chromatographic column within 8 min. The linear range was from 0.5 to 50 mg/L with correlation coefficient (r) of 0.9992. The LOD was 0.04 mg/L with S/N of 3. The relative standard deviations (RSDs, n = 6) were 2.4% and 3.1% for the peak area and retention time, respectively. The recoveries were between 99.2% and 101.8%. The retention times of SO4(2-) did not change significantly after long time use of the self-regulating chromatographic column. The self-regulating chromatographic column is suitable for the detection of SO4(2-) in complex matrix samples.

  15. Effects of nitrate supplementation via beetroot juice on contracting rat skeletal muscle microvascular oxygen pressure dynamics

    Science.gov (United States)

    Ferguson, Scott K.; Hirai, Daniel M.; Copp, Steven W.; Holdsworth, Clark T.; Allen, Jason D.; Jones, Andrew M.; Musch, Timothy I.; Poole, David C.

    2013-01-01

    NO3− supplementation via beetroot juice (BR) augments exercising skeletal muscle blood flow subsequent to its reduction to NO2− then NO. We tested the hypothesis that enhanced vascular control following BR would elevate the skeletal muscle O2 delivery/O2 utilization ratio (microvascular PO2, PmvO2) and raise the PmvO2 during the rest-contractions transition. Rats were administered BR (~0.8 mmol/kg/day, n=10) or water (control, n=10) for 5 days. PmvO2 was measured during 180 s of electrically-induced (1 Hz) twitch spinotrapezius muscle contractions. There were no changes in resting or contracting steady-state PmvO2. However, BR slowed the PmvO2 fall following contractions onset such that time to reach 63% of the initial PmvO2 fall increased (MRT1; control: 16.8±1.9, BR: 24.4±2.7 s, p<0.05) and there was a slower relative rate of PmvO2 fall (Δ1PmvO2/τ1; control: 1.9±0.3, BR: 1.2±0.2 mmHg/s, p<0.05). Despite no significant changes in contracting steady state PmvO2, BR supplementation elevated the O2 driving pressure during the crucial rest-contractions transients thereby providing a potential mechanism by which BR supplementation may improve metabolic control. PMID:23584049

  16. Mixed-Halide CH3 NH3 PbI3-x Xx (X=Cl, Br, I) Perovskites: Vapor-Assisted Solution Deposition and Application as Solar Cell Absorbers.

    Science.gov (United States)

    Sedighi, Rahime; Tajabadi, Fariba; Shahbazi, Saeed; Gholipour, Somayeh; Taghavinia, Nima

    2016-08-01

    There have been recent reports on the formation of single-halide perovskites, CH3 NH3 PbX3 (X=Cl, Br, I), by means of vapor-assisted solution processing. Herein, the successful formation of mixed-halide perovskites (CH3 NH3 PbI3-x Xx ) by means of a vapor-assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3 NH3 X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3 NH3 PbI3-x Clx , the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3 NH3 PbI3 (with trace Cl) and CH3 NH3 PbCl3 with a ratio of about 2:1. In the case of CH3 NH3 PbI3-x Brx , single-phase CH3 NH3 PbI2 Br is formed in a considerably shorter reaction time than that of CH3 NH3 PbI3 . The mesostructured perovskite solar cells based on CH3 NH3 PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3 NH3 PbI3-x Clx and CH3 NH3 PbI3-x Brx the best recorded efficiencies are 11.6 and 10.5 %, respectively.

  17. Estimation of steady-state and transcient power distributions for the RELAP analyses of the 1963 loss-of-flow and loss-of-pressure tests at BR2.

    Energy Technology Data Exchange (ETDEWEB)

    Dionne, B.; Tzanos, C. P. (Nuclear Engineering Division)

    2011-05-23

    To support the safety analyses required for the conversion of the Belgian Reactor 2 (BR2) from highly-enriched uranium (HEU) to low-enriched uranium (LEU) fuel, the simulation of a number of loss-of-flow tests, with or without loss of pressure, has been undertaken. These tests were performed at BR2 in 1963 and used instrumented fuel assemblies (FAs) with thermocouples (TC) imbedded in the cladding as well as probes to measure the FAs power on the basis of their coolant temperature rise. The availability of experimental data for these tests offers an opportunity to better establish the credibility of the RELAP5-3D model and methodology used in the conversion analysis. In order to support the HEU to LEU conversion safety analyses of the BR2 reactor, RELAP simulations of a number of loss-of-flow/loss-of-pressure tests have been undertaken. Preliminary analyses showed that the conservative power distributions used historically in the BR2 RELAP model resulted in a significant overestimation of the peak cladding temperature during the transient. Therefore, it was concluded that better estimates of the steady-state and decay power distributions were needed to accurately predict the cladding temperatures measured during the tests and establish the credibility of the RELAP model and methodology. The new approach ('best estimate' methodology) uses the MCNP5, ORIGEN-2 and BERYL codes to obtain steady-state and decay power distributions for the BR2 core during the tests A/400/1, C/600/3 and F/400/1. This methodology can be easily extended to simulate any BR2 core configuration. Comparisons with measured peak cladding temperatures showed a much better agreement when power distributions obtained with the new methodology are used.

  18. Weakly coordinating anions: crystallographic and NQR studies of halogen-metal bonding in silver, thallium, sodium, and potassium halomethanesulfonates.

    Science.gov (United States)

    Wulfsberg, Gary; Parks, Katherine D; Rutherford, Richard; Jackson, Debra Jones; Jones, Frank E; Derrick, Dana; Ilsley, William; Strauss, Steven H; Miller, Susie M; Anderson, Oren P; Babushkina, T A; Gushchin, S I; Kravchenko, E A; Morgunov, V G

    2002-04-22

    35Cl, (79,81)Br, and (127)I NQR (nuclear quadrupole resonance) spectroscopy in conjunction with X-ray crystallography is potentially one of the best ways of characterizing secondary bonding of metal cations such as Ag(+) to halogen donor atoms on the surfaces of very weakly coordinating anions. We have determined the X-ray crystal structure of Ag(O(3)SCH(2)Cl) (a = 13.241(3) A; b = 7.544(2) A; c = 4.925(2) A; orthorhombic; space group Pnma; Z = 4) and compared it with the known structure of Ag(O(3)SCH(2)Br) (Charbonnier, F.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B 1978, 34, 3598-3601). The halogen atom in each is apical (three-coordinate), being weakly coordinated to two silver ions. (127)I NQR studies on Ag(O(3)SCH(2)I) show the expected NQR consequences of three-coordination of iodine: substantially reduced NQR frequencies nu(1) and nu(2) and a fairly small NQR asymmetry parameter eta. The reduction of the halogen NQR frequency of the coordinating halogen atom in Ag(O(3)SCH(2)X) becomes more substantial in the series X = Cl < Br < I, indicating that the coordination to Ag(+) strengthens in this series, as expected from hard-soft acid-base principles. The numbers of electrons donated by the organic iodine atom to Ag(+) have been estimated; these indicate that the bonding to the cation is weak but not insignificant. We have not found any evidence for the bonding of these organohalogen atoms to another soft-acid metal ion, thallium. A scheme for recycling of thallium halide wastes is included.

  19. Anion exchangers with branched functional ion exchange layers of different hydrophilicity for ion chromatography.

    Science.gov (United States)

    Shchukina, O I; Zatirakha, A V; Smolenkov, A D; Nesterenko, P N; Shpigun, O A

    2015-08-21

    Novel polystyrene-divinylbenzene (PS-DVB) based anion exchangers differing from each other in the structure of the branched functional ion exchange layer are prepared to investigate the role of linker and functional site on ion exchange selectivity. The proposed method of synthesis includes the obtaining of aminated PS-DVB particles by means of their acylation with following reductive amination with methylamine. Further modification of the obtained secondary aminogroups is provided by the alkylation with either 1,4-butanediol diglycidyl ether (1,4-BDDGE) or resorcinol diglycidyl ether (RDGE), which form the linkers of different hydrophobicity, and amination of terminal epoxide rings with trimethylamine (TMA), dimethylethanolamine (DMEA), methyldiethanolamine (MDEA) or triethanolamine (TEA). The variation of the structure and hydrophobicity of the linker and terminal quaternary ammonium sites in the functional layer allows the alteration of selectivity and separation efficiency of the obtained adsorbents. The ion exchange selectivity and separation efficiency of the anion exchangers are evaluated using the model mixtures of anions (F(-), HCOO(-), Cl(-), NO2(-), Br(-), NO3(-), HPO4(2-) and SO4(2-)) in potassium hydroxide eluents. The adsorbents show the decrease of selectivity with increasing the hydrophilicity of the terminal functional site. The anion exchangers having more flexible and hydrophilic 1,4-BDDGE linker provide smaller separation factors for most of the analytes as compared with RDGE-containing adsorbents with the same terminal ion exchange sites, but are characterized with higher column efficiencies and better peak symmetry for polarizable anions. In case of 1,4-BDDGE-modified anion exchangers of the particle size of 3.3μm functionalized with DMEA and MDEA the calculated values of column efficiencies for polarizable NO3(-) and Br(-) are up to 49,000 and 53,000N/m, respectively, which is almost twice higher than the values obtained for the RDGE

  20. Pushing the limits: detecting H2 emission from faint bipolar planetary nebulae in the IPHAS sample

    Science.gov (United States)

    Ramos-Larios, G.; Guerrero, M. A.; Sabin, L.; Santamaría, E.

    2017-09-01

    We have obtained deep narrowband images in the near-infrared H2 λ2.122 μm emission line for a sample of 15 faint Isaac Newton Telescope Photometric H α Survey (IPHAS) bipolar planetary nebulae (PNe) to search for molecular material. H2 emission is found in most of them (14 out of 15), mostly associated with rings at their equatorial regions and with their bipolar lobes. These detections add to the high occurrence of H2 emission among bipolar PNe reported in previous works, resulting from the large reservoir of molecular material in these sources and the suitable excitation conditions for H2 emission. The correlation between detailed bipolar morphology and H2 luminosity is also confirmed: bipolar PNe with broad equatorial rings (R-BPNe) have almost no continuum emission, are H2 brighter and have larger H2/Br γ line ratio than bipolar PNe with pinched equatorial waists (W-BPNe). The origin of this dichotomy is unclear. The larger size and age of R-BPNe are consistent with shock excitation of H2, whereas ultraviolet pumping is most likely the excitation mechanism in the smaller and younger W-BPNe, which would explain their lower H2 luminosity. Although both types of bipolar PNe seem to proceed from the same progenitor population, this does not imply that R-BPNe descend from W-BPNe. Otherwise, we note that some of the H2-weak bipolar PNe harbor post-common envelope binary systems and symbiotic stars. Finally, we suggest that the long-living H2 emission from R-BPNe arises from a discrete distribution of compact knots embedded within the ionized gas at the equatorial region.

  1. The role of nuclear localization signal in parvovirus life cycle.

    Science.gov (United States)

    Liu, Peng; Chen, Shun; Wang, Mingshu; Cheng, Anchun

    2017-04-14

    Parvoviruses are small, non-enveloped viruses with an approximately 5.0 kb, single-stranded DNA genome. Usually, the parvovirus capsid gene contains one or more nuclear localization signals (NLSs), which are required for guiding the virus particle into the nucleus through the nuclear pore. However, several classical NLSs (cNLSs) and non-classical NLSs (ncNLSs) have been identified in non-structural genes, and the ncNLSs can also target non-structural proteins into the nucleus. In this review, we have summarized recent research findings on parvovirus NLSs. The capsid protein of the adeno-associated virus has four potential nuclear localization sequences, named basic region 1 (BR), BR2, BR3 and BR4. BR3 was identified as an NLS by fusing it with green fluorescent protein. Moreover, BR3 and BR4 are required for infectivity and virion assembly. In Protoparvovirus, the canine parvovirus has a common cNLS located in the VP1 unique region, similar to parvovirus minute virus of mice (MVM) and porcine parvovirus. Moreover, an ncNLS is found in the C-terminal region of MVM VP1/2. Parvovirus B19 also contains an ncNLS in the C-terminal region of VP1/2, which is essential for the nuclear transport of VP1/VP2. Approximately 1 or 2 cNLSs and 1 ncNLS have been reported in the non-structural protein of bocaviruses. Understanding the role of the NLS in the process of parvovirus infection and its mechanism of nuclear transport will contribute to the development of therapeutic vaccines and novel antiviral medicines.

  2. Energetics, molecular electronic structure, and spectroscopy of forming Group IIA dihalide complexes

    Science.gov (United States)

    Devore, T. C.; Gole, J. L.

    1999-02-01

    Multiple-collision relaxed (helium) chemiluminescence and laser-induced fluorescent spectroscopy have been used to demonstrate the highly efficient collisional stabilization of electronically excited Group IIA dihalide collision complexes formed in M (Ca,Sr)+X 2 (XY) (Cl 2, Br 2, ICl, IBr, I 2) reactive encounters. The first discrete emission spectra for the CaCl 2, CaBr 2, SrCl 2, SrBr 2, and SrICl dihalides are observed and evaluated; however, the low-pressure `continuous' chemiluminescent emission observed for forming barium dihalide (BaX 2) complexes is quenched under these experimental conditions. The reactions of the Group IIA metals with molecular fluorine do not readily produce the corresponding dihalide. While the lowest-lying observed dihalide visible transition is, as predicted, found to result in an extended progression in a dihalide complex bending mode (SrCl 2), the observed progression suggests the presence of a residual halogen (Cl-Cl) bond. Two higher-lying transitions are dominated by a vibrational mode structure corresponding to progressions in the symmetric stretching mode or, for nominally forbidden electronic transitions, odd quanta of the asymmetric stretching mode. Some evidence for sequence structure associated with the dihalide bending mode is also obtained. These observations are consistent with complex formation as it is coupled with a modified valence electron structure (correlation diagram) associated with the highly ionic nature of the dihalides. The bonding in the Group IIA dihalides (and their complexes), whose atomization energies are more than twice the metal monohalide bond energy, strongly influences the evaluation of energetics and the determination of monohalide bond energies from chemiluminescent processes. Discrepancies between those bond strengths determined by mass spectrometry and chemiluminescence are discussed with a focus on energy partitioning in dihalide complex formation and its influence on chemical vapor

  3. Synthesis and characterization of neutral and anionic carbonyl derivatives of palladium(II).

    Science.gov (United States)

    Ara, Irene; Forniés, Juan; Martín, Antonio; Martín, L Francisco; Menjón, Babil; Miedes, Helvia

    2010-08-21

    The action of CO on the solvento-complexes cis-[PdR2(thf)2] [R = C6F5 (1), C6Cl5 (2)] at low temperature gives cis-[PdR2(CO)2] [R = C6F5 (3), C6Cl5 (4)] in good yield by simple replacement of the highly labile thf molecules. These are rare cases of Pd(II) dicarbonyl compounds, whose characterization relies on spectroscopic and analytic data. The crystal structure of the square-planar platinum homologue cis-[Pt(C6Cl5)2(CO)2] is also presented. CO can split the double bridging-system in the dinuclear species [{PdR2}2(mu-X)2]2- giving the homologous series of anionic monocarbonyl Pd(II) derivatives with formula [cis-PdR2X(CO)]- (5-10: R = C6F5, C6Cl5; X = Cl, Br, I), which were isolated (except for the R = C6F5 and X = I) and suitably characterized. Characterization includes the crystal and molecular structure of [PPh3Me][cis-Pd(C6F5)2Br(CO)] (6'). The anionic species [NBu4][cis-Pd(C6F5)2Cl(CO)] (5) reacts with neutral cis-[Pd(C6F5)2(CO)2] (3) under CO extrusion, affording the dinuclear derivative [NBu4][{Pd(C6F5)2(CO)}2(mu-Cl)] (11), which contains a single unsupported halide bridge (X-ray diffraction). Complex 11 can be considered as modelling a possible intermediate step in intermolecular CO substitution reactions that are easily undergone by Pd(II) halo carbonyl species.

  4. Emission of atmospherically significant halocarbons by naturally occurring and farmed tropical macroalgae

    Directory of Open Access Journals (Sweden)

    E. C. Leedham

    2013-06-01

    Full Text Available Current estimates of global halocarbon emissions highlight the tropical coastal environment as an important source of very short-lived (VSL biogenic halocarbons to the troposphere and stratosphere, due to a combination of assumed high primary productivity in tropical coastal waters and the prevalence of deep convective transport, potentially capable of rapidly lifting surface emissions to the upper troposphere/lower stratosphere. However, despite this perceived importance, direct measurements of tropical coastal biogenic halocarbon emissions, notably from macroalgae (seaweeds, have not been made. In light of this, we provide the first dedicated study of halocarbon production by a range of 15 common tropical macroalgal species and compare these results to those from previous studies of polar and temperate macroalgae. Variation between species was substantial; CHBr3 production rates, measured at the end of a 24 h incubation, varied from 1.4 to 1129 pmol g FW−1 h−1 (FW = fresh weight of sample. We used our laboratory-determined emission rates to estimate emissions of CHBr3 and CH2Br2 (the two dominant VSL precursors of stratospheric bromine from the coastlines of Malaysia and elsewhere in South East Asia (SEA. We compare these values to previous top-down model estimates of emissions from these regions and, by using several emission scenarios, we calculate an annual CHBr3 emission of 40 (6–224 Mmol Br−1 yr, a value that is lower than previous estimates. The contribution of tropical aquaculture to current emission budgets is also considered. Whilst the current aquaculture contribution to halocarbon emissions in this regional is small, the potential exists for substantial increases in aquaculture to make a significant contribution to regional halocarbon budgets.

  5. Inhibition of Catechol-O-methyl Transferase (COMT) by Tolcapone Restores Reductions in Microtubule-associated Protein 2 (MAP2) and Synaptophysin (SYP) Following Exposure of Neuronal Cells to Neurotropic HIV

    Science.gov (United States)

    Lee, Ting Ting; Chana, Gursharan; Gorry, Paul R.; Ellett, Anne; Bousman, Chad A.; Churchill, Melissa J.; Gray, Lachlan R.; Everall, Ian P.

    2015-01-01

    This investigation aimed to assess whether inhibition of cathecol-O-methyl transferase (COMT) by Tolcapone could provide neuroprotection against HIV-associated neurodegenerative effects. This study was conducted based on previous work, which showed that a single nucleotide polymorphism (SNP) at position 158 (val158met) in COMT, resulted in 40% lower COMT activity. Importantly, this reduction confers a protective effect against HIV-associated neurocognitive disorders (HAND), which have been linked to HIV-associated brain changes. SH-SY5Y differentiated neurons were exposed to macrophage-propagated HIV (neurotropic MACS2-Br strain) in the presence or absence of Tolcapone for 6 days. RNA was extracted and qPCR was performed using Qiagen RT2-custom-array consisting of genes for neuronal and synaptic integrity, COMT and pro-inflammatory markers. Immunofluorescence was conducted to validate the gene expression changes at the protein level. Our findings demonstrated that HIV significantly increased the mRNA expression of COMT while reduced the expression of microtubule-associated protein 2 (MAP2) (p=0.0015) and synaptophysin (SYP) (p=0.012) compared to control. A concomitant exposure of Tolcapone ameliorated the perturbed expression of MAP2 (p=0.009) and COMT (p=0.024) associated with HIV. Immunofluorescence revealed a trend reduction of SYP and MAP2 with exposure to HIV, and that concomitant exposure of Tolcapone increased SYP (p=0.016) compared to HIV alone. Our findings demonstrated in vitro that inhibition of COMT can ameliorate HIV-associated neurodegenerative changes that resulted in the decreased expression of the structural and synaptic components MAP2 and SYP. As HIV-associated dendritic and synaptic damage are contributors to HAND, inhibition of COMT may represent a potential strategy for attenuating or preventing some of the symptoms of HAND. PMID:26037113

  6. Rational Synthesis and Investigation of Porous Metal-Organic Framework Materials from a Preorganized Heterometallic Carboxylate Building Block.

    Science.gov (United States)

    Sapianik, Aleksandr A; Zorina-Tikhonova, Ekaterina N; Kiskin, Mikhail A; Samsonenko, Denis G; Kovalenko, Konstantin A; Sidorov, Alexey A; Eremenko, Igor L; Dybtsev, Danil N; Blake, Alexander J; Argent, Stephen P; Schröder, Martin; Fedin, Vladimir P

    2017-02-06

    The tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (1, where piv(-) = pivalate and py = pyridine) has been successfully employed as a presynthesized node for the construction of four porous metal-organic frameworks (MOFs) [Li2Zn2(R-bdc)3(bpy)]·solv (2-R, R-bdc(2-); R = H, Br, NH2, NO2) by reaction with 4,4'-bipyridine (bpy) and terephthalate anionic linkers. The [Li2Zn2] node is retained in the products, representing a rare example of the rational step-by-step design of isoreticular MOFs based on complex heterometallic building units. The permanent porosity of the activated frameworks was confirmed by gas adsorption isotherm measurements (N2, CO2, CH4). Three compounds, 2-H, 2-Br, and 2-NH2 (but not 2-NO2), feature extensive hysteresis between the adsorption and desorption curves in the N2 isotherms at low pressures. The substituents R decorate the inner surface and also control the aperture of the channels, the volume of the micropores, and the overall surface area, thus affecting both the gas uptake and adsorption selectivity. The highest CO2 absorption at ambient conditions (105 cm(3)·g(-1) or 21 wt % at 273 K and 1 bar for 2-NO2) is above the average values for microporous MOFs. The photoluminescent properties of the prototypic 2-H as well as the corresponding host-guest compounds with various aromatic molecules (benzene, toluene, anisole, and nitrobenzene) were systematically investigated. We discovered a rather complex pattern in the emission response of this material depending on the wavelength of excitation as well as the nature of the guest molecules. On the basis of the crystal structure of 2-H, a mechanism for these luminescent properties is proposed and discussed.

  7. Syntheses, reactions, and structures of dioxycarbene complexes of rhenium

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, G.L.; Kim, S.; Jacobson, R.A.; Angelici, R.J.

    1987-06-03

    The cyclic dioxycarbene complex Re(CO)4Br(COCH2CH2O) (I) reacts with PPh3 to give initially fac-Re(CO)3(PPh3)Br(COCH2CH2O) (II) and upon further reaction Re(CO)2(PPh3)2Br(COCH2CH2O) (II). The reaction of I with the diphosphines Ph2P(CH2)/sub n/PPh2 (n = 1,2) gives the diphosphine-bridged complexes (Re(CO)3Br(COCH2CH2O))2(Ph2P(CH2)/sub n/PPh2) (IV, n = 1; V, n = 2). The structures of I and V were established by X-ray diffraction studies. The crystals of I are orthorhombic, space group Pbca, with a = 11.764 (2) A, b = 17.579 (4) A, c = 10.658 (2) A, and Z = 8, while those of V are triclinic, space group P anti I, with a = 11.160 (2) A, b = 11.369 (3) A, c = 10.090 (3) A, = 111.58 (3), US = 95.40 (2), el = 92.78 (2), Z = 1, and two acetones ((CH3)2CO) of crystallization. The dimethyldithiocarbamate ion, S2CN(CH3)2, reacts with I to remove in effect ethylene oxide form the carbene ligand, giving Gr(CO)5Br and HOCH2CH2SC(=S)N(CH3)2.

  8. Homogeneous catalysts supported on soluble polymers: biphasic Suzuki-Miyaura coupling of aryl chlorides using phase-tagged palladium-phosphine catalysts.

    Science.gov (United States)

    an der Heiden, Markus; Plenio, Herbert

    2004-04-02

    The Suzuki-Miyaura coupling of aryl chlorides and PhB(OH)(2) under biphasic conditions (DMSO/heptane) can be performed in almost quantitative yields over several cycles by means of polymeric Pd catalysts with soluble polyethylene glycol phase tags. Three sterically demanding and electron-rich phosphines 1-CH(2)Br,4-CH(2)P(1-Ad)(2)-C(6)H(4), and 2-PCy(2),2'-OH-biphenyl, and 2-PtBu(2),2'-OH-biphenyl were covalently bonded to 2000 Dalton MeOPEG-OH. The catalysts, which were formed in situ from Na(2)[PdCl(4)], the respective polymeric phosphine, KF/K(3)PO(4), and PhB(OH)(2), efficiently couple aryl chlorides at 80 degrees C at 0.5 mol % loading, resulting in a >90 % yield of the respective biphenyl derivatives. The use of polar phase tags allows the efficient recovery of palladium-phosphine catalysts by simple phase separation of the catalyst-containing DMSO solution and the product-containing n-heptane phase. The high activity (TOF) of the catalyst remains almost constant over more than five reaction cycles, which involve the catalytic reaction, separation of the product phase from the catalyst phase, and addition of new reactants to initiate the next cycle. The Buchwald type biphenyl phosphines form the most active Pd catalysts, which are 1.3-2.8 times more active than catalysts derived from diadamantyl-benzylphosphine, but appear to be less robust in the recycling experiments. There is no apparent leaching of the catalyst into the heptane solution (<0.05 %), as evidenced by spectrophotometric measurements, and contamination of the product with Pd is avoided.

  9. Molecular analysis of the Adh region of the genome of Drosophila melanogaster.

    Science.gov (United States)

    Chia, W; Karp, R; McGill, S; Ashburner, M

    1985-12-20

    A small region of the genome of Drosophila melanogaster has been cloned in a series of overlapping phage. A length of 165 X 10(3) base-pairs of contiguous DNA that spans polytene chromosome region 35A4 to 35B1 and includes the structural gene for alcohol dehydrogenase (Adh) as well as at least two other genes, outspread (osp) and no-ocelli (noc), has been characterized by mapping chromosome aberrations to the DNA. The relationship between osp and Adh is surprising: of nine osp alleles associated with chromosome breakpoints, five map distal (i.e. 5') to Adh and four map proximal (i.e. 3') to this gene. None affects the expression of Adh. As defined by these and other breakpoints, the osp gene spans at least 52 X 10(3) base-pairs and overlaps the Adh gene. The noc gene, as defined by the mapping of nearly 30 breakpoints, is at least 50 X 10(3) base-pairs in size. Alleles of noc and noc- deletions show either of two kinds of interaction with the recessive lethality of l(2)br29ScoR+1, a lethal that maps immediately distal to noc. One class of noc allele is viable when heterozygous with ScoR+1, while the other class is lethal or semi-lethal. Both classes, however, are homozygous or hemizygous viable. The locations of these two classes of noc allele on the DNA fall into two clusters, with those that are viable with ScoR+1 located proximal to those that are not. The physical boundary between these classes lies at a site just distal to that of the breakpoint of the inversion associated with ScoR+1 itself.

  10. Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

    Science.gov (United States)

    Hung, Ching-Cheh

    1994-01-01

    Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

  11. Colorimetric chemosensor of symmetrical benzoylthiourea derivatives as for detection of Cu2+ in aqueous solution

    Science.gov (United States)

    Hamedan, N. A.; Hasan, S.; Zaki, H. M.; Alias, N. Z.

    2017-02-01

    A novel receptor, designed with a combination of oxygen (O), nitrogen (N) and sulfur (S) -binding sites for metal ions was synthesized. Ortho (A), meta (B) and para (C) bearing benzoyl thiourea were designed and synthesized with triamine group to apply as colorimetric chemosensors for detection of Cu2+. The structure was confirmed by characterized the compound using Elemental analysis, Fourier Infrared (FTIR) and proton Nuclear Magnetic Resonance (1H NMR) spectroscopy. Functional groups of C=O, N-H, C=N and C=S were found at 1677 cm-1, 3240 cm-1, 1591 cm-1, 1024 cm-1 respectively while 1H NMR shows peaks of alkane (CH2), benzene (Ar-H), CONH, CSNH at 3.68 – 4.14, 7.16 – 7.86, 8.74, and 9.2 respectively. Elemental analysis for A, B and C C20H21N5O2S2Br2 found was compatible with the expected theoretical calculation. For an application, all of these three sensors showed excellent colorimetric specific selectivity and high sensitivity for Cu2+ in acetonitrile/water binary solutions, so only A was selected for further studies towards sensitivity. When Cu2+ was added to the solution of A, a dramatic color change from yellow to green, while other cations Fe2+, Zn2+, Ni2+, Co2+, Cr3+ and Mn2+ did not interfere with the recognition process for Cu2+. The detection limit of the sensor C toward Cu2+ was 1.15 x 10-5 M, which is less sensitive that sensor A and B with a detection limit of 6.2 x 10-6 M and 1.5 x 10-6 M respectively. This indicated that the sensor A and B might be useful as an efficient chemical sensor.

  12. Similarities between the Binding Sites of SB-206553 at Serotonin Type 2 and Alpha7 Acetylcholine Nicotinic Receptors: Rationale for Its Polypharmacological Profile.

    Directory of Open Access Journals (Sweden)

    Patricia Möller-Acuña

    Full Text Available Evidence from systems biology indicates that promiscuous drugs, i.e. those that act simultaneously at various protein targets, are clinically better in terms of efficacy, than those that act in a more selective fashion. This has generated a new trend in drug development called polypharmacology. However, the rational design of promiscuous compounds is a difficult task, particularly when the drugs are aimed to act at receptors with diverse structure, function and endogenous ligand. In the present work, using docking and molecular dynamics methodologies, we established the most probable binding sites of SB-206553, a drug originally described as a competitive antagonist of serotonin type 2B/2C metabotropic receptors (5-HT2B/2CRs and more recently as a positive allosteric modulator of the ionotropic α7 nicotinic acetylcholine receptor (nAChR. To this end, we employed the crystal structures of the 5-HT2BR and acetylcholine binding protein as templates to build homology models of the 5-HT2CR and α7 nAChR, respectively. Then, using a statistical algorithm, the similarity between these binding sites was determined. Our analysis showed that the most plausible binding sites for SB-206553 at 5-HT2Rs and α7 nAChR are remarkably similar, both in size and chemical nature of the amino acid residues lining these pockets, thus providing a rationale to explain its affinity towards both receptor types. Finally, using a computational tool for multiple binding site alignment, we determined a consensus binding site, which should be useful for the rational design of novel compounds acting simultaneously at these two types of highly different protein targets.

  13. Non-invasive quantification of endogenous root auxin transport using an integrated flux microsensor technique.

    Science.gov (United States)

    McLamore, Eric S; Diggs, Alfred; Calvo Marzal, Percy; Shi, Jin; Blakeslee, Joshua J; Peer, Wendy A; Murphy, Angus S; Porterfield, D Marshall

    2010-09-01

    Indole-3-acetic acid (IAA) is a primary phytohormone that regulates multiple aspects of plant development. Because polar transport of IAA is an essential determinant of organogenesis and dynamic tropic growth, methods to monitor IAA movement in vivo are in demand. A self-referencing electrochemical microsensor was optimized to non-invasively measure endogenous IAA flux near the surface of Zea mays roots without the addition of exogenous IAA. Enhanced sensor surface modification, decoupling of acquired signals, and integrated flux analyses were combined to provide direct, real time quantification of endogenous IAA movement in B73 maize inbred and brachytic2 (br2) auxin transport mutant roots. BR2 is localized in epidermal and hypodermal tissues at the root apex. br2 roots exhibit reduced shootward IAA transport at the root apex in radiotracer experiments and reduced gravitropic growth. IAA flux data indicates that maximal transport occurs in the distal elongation zone of maize roots, and net transport in/out of br2 roots was decreased compared to B73. Integration of short term real time flux data in this zone revealed oscillatory patterns, with B73 exhibiting shorter oscillatory periods and greater amplitude than br2. IAA efflux and influx were inhibited using 1-N-naphthylphthalamic acid (NPA), and 2-naphthoxyacetic acid (NOA), respectively. A simple harmonic oscillation model of these data produced a correlation between modeled and measured values of 0.70 for B73 and 0.69 for br2. These results indicate that this technique is useful for real-time IAA transport monitoring in surface tissues and that this approach can be performed simultaneously with current live imaging techniques.

  14. Emission of atmospherically significant halocarbons by naturally occurring and farmed tropical macroalgae

    Science.gov (United States)

    Leedham, E. C.; Hughes, C.; Keng, F. S. L.; Phang, S.-M.; Malin, G.; Sturges, W. T.

    2013-06-01

    Current estimates of global halocarbon emissions highlight the tropical coastal environment as an important source of very short-lived (VSL) biogenic halocarbons to the troposphere and stratosphere, due to a combination of assumed high primary productivity in tropical coastal waters and the prevalence of deep convective transport, potentially capable of rapidly lifting surface emissions to the upper troposphere/lower stratosphere. However, despite this perceived importance, direct measurements of tropical coastal biogenic halocarbon emissions, notably from macroalgae (seaweeds), have not been made. In light of this, we provide the first dedicated study of halocarbon production by a range of 15 common tropical macroalgal species and compare these results to those from previous studies of polar and temperate macroalgae. Variation between species was substantial; CHBr3 production rates, measured at the end of a 24 h incubation, varied from 1.4 to 1129 pmol g FW-1 h-1 (FW = fresh weight of sample). We used our laboratory-determined emission rates to estimate emissions of CHBr3 and CH2Br2 (the two dominant VSL precursors of stratospheric bromine) from the coastlines of Malaysia and elsewhere in South East Asia (SEA). We compare these values to previous top-down model estimates of emissions from these regions and, by using several emission scenarios, we calculate an annual CHBr3 emission of 40 (6-224 Mmol Br-1 yr), a value that is lower than previous estimates. The contribution of tropical aquaculture to current emission budgets is also considered. Whilst the current aquaculture contribution to halocarbon emissions in this regional is small, the potential exists for substantial increases in aquaculture to make a significant contribution to regional halocarbon budgets.

  15. Biosorption studies on waste cotton seed for cationic dyes sequestration: equilibrium and thermodynamics

    Science.gov (United States)

    Sivarajasekar, N.; Baskar, R.; Ragu, T.; Sarika, K.; Preethi, N.; Radhika, T.

    2017-07-01

    The immature Gossypium hirsutum seeds—an agricultural waste was converted into a novel adsorbent and its effectiveness for cationic dyes removal was discussed in this study. Characterization revealed that sulfuric acid activated waste Gossypium hirsutum seed (WGSAB) contains surface area 496 m2 g-1. The ability of WGSAB to adsorb basic red 2 (BR2) and basic violet 3 (BV3) from aqueous solutions has been studied. Batch adsorption studies were carried out at different initial dye concentrations (100-300 mg l-1), contact time (1-5 h), pH (2-12) and temperature (293-323 K) to understand the adsorption mechanism. Adsorption data were modeled using Langmuir, Freundlich and Toth adsorption isotherms. Equilibrium data of the adsorption process fitted very well to the Toth model for both dyes. The Langmuir maximum adsorption capacity was 66.69 mg g-1 for BV3 and 50.11 mg g-1 for BR2 at optimum conditions. The near unity value of Toth isotherm constant (BR2: 0.999 and BV3: 1.0) indicates that WGSAB surface is heterogeneous in nature. The maximum adsorption capacity predicted by Toth isotherm of BV3 (66.699 mg g-1) is higher than BR2 (50.310 mg g-1). The kinetic investigation revealed that the BR2 and BV3 were chemisorbed on WGSAB surface following Avrami fractional order kinetics. Further, the fractional order and rate constant values are almost similar for every concentration in both the dyes. The thermodynamic parameters such as Δ H 0, Δ S 0 and Δ G 0 were evaluated. The dye adsorption process was found to be spontaneous and endothermic for the two dyes. Regeneration of WGSAB exhausted by the two dyes could be possible via acetic acid as elutant.

  16. Visible-light-Mediated TiO2 photocatalysis of fluoroquinolone antibacterial agents.

    Science.gov (United States)

    Paul, Tias; Miller, Penney L; Strathmann, Timothy J

    2007-07-01

    This study reports on the photocatalytic transformation of fluoroquinolone antibacterial agents (ciprofloxacin, enrofloxacin, norfloxacin, and flumequine) in aqueous titanium dioxide (TiO2) suspensions irradiated with ultraviolet (UV; lambda > 324 nm) or visible light (lambda > 400, > 420, or > 450 nm). Visible-light-mediated fluoroquinolone degradation is unexpected from direct photolysis or established TiO2 band gap photoexcitation mechanisms, which both require UV light. Visible-light-mediated photocatalysis requires an appropriate conduction band electron acceptor (e.g., O2, BrO3-), but is not dependent upon hydroxyl radical, superoxide, or other reactive oxygen species generated upon TiO2 band gap excitation. The process slows considerably when fluoroquinolone adsorption is inhibited. Whereas fluoroquinolone decomposition in UV-irradiated TiO2 suspensions is accompanied by mineralization, no changes in dissolved organic carbon occur during visible-light-photocatalyzed degradation. Results are consistent with a proposed charge-transfer mechanism initiated by photoexcitation of surface-complexed fluoroquinolone molecules. Complexation to the TiO2 surface causes a red shift in the fluoroquinolone absorption spectrum (via ligand-to-metal charge transfer), enabling photoexcitation by visible light. Fluoroquinolone oxidation then occurs by electron transfer into the TiO2 conduction band, which delivers the electron to an adsorbed electron acceptor. The lack of organic carbon mineralization indicates formation of stable organic byproducts that are resistant to further degradation by visible light. In UV-irradiated TiO2 suspensions, the charge-transfer mechanism acts in parallel with the semiconductor band gap photoexcitation mechanism.

  17. Análisis de la localización, dinámica intracelular y producción de 02 - por el sistema NADPH oxidasa de las células fagocíticas

    Directory of Open Access Journals (Sweden)

    Pablo Patiño

    2001-04-01

    Full Text Available

    El sistema NADPH oxidasa, un sistema encargado de producir
    anión superóxido (O2 - en las células fagocíticas, está formado por las proteínas: gp91 phox, p22 phox, p47 phox, p67 phox, p40 phox y la proteína Rac. Las células COS-7, una línea celular de riñón de simio, que expresa endógenamente Rac1, y que por transfección estable expresan gp91 phox, p47 phox y p22 phox, pueden ser cotransfectadas adicionalmente con vectores episomales pGFP-N3, pEGFP-C1 y pCDNA3.1zeo(+ que contengan el cDNA tipo silvestre y mutante de la proteína p67 phox obtenidos por mutagénesis sitio-dirigida. Estos vectores contienen el gen de la proteína verde fluorescente (GFP, útil para explorar la localización intracelular y la dinámica de los componentes del sistema oxidasa. Después de la cotransfección, se estimulan las células con PMA y se determina la producción de O2<br />- y la señal de fluorescencia generada por GFP de forma directa en células vivas por microscopía confocal.

     

     

  18. Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand

    Science.gov (United States)

    Ouyang, Xing-Mei; Li, Zhen-Wu; Okamura, Taka-aki; Li, Yi-Zhi; Sun, Wei-Yin; Tang, Wen-Xia; Ueyama, Norikazu

    2004-01-01

    A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag 2( L)( L')](ClO 4) 2 ( 1) [ L'=1,6-bis(4-imidazol-1'-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L' together with AgClO 4·H 2O. It is interesting that the open-chain tetradentate ligand L' only served as a bidentate ligand to bridge the Ag 2L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu 2( L)( μ-SO 4) 2]·3H 2O·3MeOH ( 2) is formed by sulfate bridges between the neighboring Cu 2L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni 2( L)(H 2O) 4(SO 4) 2] ( 3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd 2( L)( μ-Cl) 2Cl 2]·2H 2O ( 4) and [Cd 2( L)( μ-Br) 2Br 2] ( 5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.

  19. Reactivity of BrCl, Br₂, BrOCl, Br₂O, and HOBr toward dimethenamid in solutions of bromide + aqueous free chlorine.

    Science.gov (United States)

    Sivey, John D; Arey, J Samuel; Tentscher, Peter R; Roberts, A Lynn

    2013-02-01

    HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br(2), BrOCl, and Br(2)O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr](T)), [Cl(-)], and [FAC](o)) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr](T) ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on [HOBr](T) implicates Br(2)O as an active brominating agent. That bromination rates increased with increasing [Cl(-)], [FAC](o) (at constant [HOBr](T)), and excess bromide (where [Br(-)](o)>[FAC](o)) implicate BrCl, BrOCl, and Br(2), respectively, as brominating agents. As equilibrium constants for the formation of Br(2)O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr ≪ Br(2)O water and wastewater chlorination.

  20. Moessbauer spectroscopic study on inorganic compounds. Pt. 2

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Masashi; Kitazawa, Takafumi; Nanba, Hiroshi; Yoshinaga, Tomohiro; Nakajima, Norio; Sumisawa, Yasuhiro; Takeda, Masuo [Toho Univ., Funabashi, Chiba (Japan). Faculty of Science; Sawahata, Hiroyuki; Ito, Yasuo

    1998-01-01

    {sup 166}Er and {sup 127}I Moessbauer spectra were observed. {sup 166}Er Moessbauer spectrum of Er metal and 9 compounds were measured by {sup 166}Ho/Y{sub 0.6}Ho{sub 0.4}H{sub 2} source at 12K and the parameters such as e{sup 2}qQ(mm s{sup -1}), Heff(T) and {tau}(ns) were determined. The relaxation time of ErCl{sub 3}{center_dot}6H{sub 2}O was 0.7ns, long, but that of ErCl{sub 3} was 10 ps, short time. {sup 127}I Moessbauer spectrum of PhI(O{sub 2}CR){sub 2} (R=CH{sub 3}, CHF{sub 2}, CH{sub 2}Cl, CHCl{sub 2}, CCl{sub 3}, CH{sub 2}Br, CHBr{sub 2} and CBr{sub 3}) were observed and compared with that of R`{sub 3}Sb(O{sub 2}CR){sub 2} was similar to that of PhI(O{sub 2}CR){sub 2}. The correlation coefficient between e{sup 2}qQ({sup 127}I) and Mulliken population of carboxylic hydrogen atom of R{sub 2}CO{sub 2}H was -0.87. The relation between the hypervalent bond of O-I-O and that of O-Sb-0 was shown by the equation: e{sup 2}qQ({sup 121}Sb)/mm s{sup -1} = -47.2 + 1.32 e{sup 2}qQ({sup 127}I)/mm s{sup -1}. Hypervalent iodine complex such as (PhI(py){sub 2}){sup 2+} salt and E-Sb-I (E=O, I, N and C) were studied, too. (S.Y.)

  1. Synthesis, Crystal Structure and Catalytic Behavior of 1-Ethyl-3-benyl-imidazolyl Tetranuclear N-Heterocyclic Carbene Silver Bromide

    Institute of Scientific and Technical Information of China (English)

    WANG Zhi-Guo; SU Zhi-Xian; BIAN Qing-Quan; LIU Si-Man; LIU Ting

    2012-01-01

    The title complex [Ag(carbene)2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P with a = 10.1597(10), b =11.0646(11), c = 13.0245(14) , α = 102.230(2), β = 90.606, γ = 113.9250(10)o, V = 1300.3(2) 3, Mr = 748.06, Z = 2, Dc = 1.911 g/cm3, μ(MoKα) = 4.60 mm-1 and F(000) = 728. The structure was refined to R = 0.0316 and wR = 0.0835 for 3744 observed reflections with I 〉 2σ(I). The title compound crystallizes as a centrosymmetric tetranuclear compound. One half of the molecule comprises the asymmetric unit of the structure. The Ag(1) atom is nearly linear or T-shaped when the Ag(1)-Ag(2) interaction is taken into consideration, which is bi-coordinated by two carbene carbon atoms. The Ag(2) atom adopts tetrahedral geometry. The catalytic behavior of the title complex has been investigated, and the results indicate it has a highly catalytic activation for L-lactide polymerization.

  2. Ductility in a new low nickel stainless steel for reinforced concrete

    Directory of Open Access Journals (Sweden)

    Cobo, A.

    2011-12-01

    Full Text Available This paper discusses the stress-strain curves for a new low nickel stainless steel, a conventional AISI 304 stainless steel and a carbon steel commonly used in reinforced concrete structures. Ductility was studied in terms of ultimate tensile strength (fmax, elastic limit (fy and total elongation at maximum force [ultimate strain; uniform elongation] (εmax. The three materials were assessed with internationally accepted criteria, such as plastic rotational capacity, necking region and the toughness index (total energy absorbed at uniform elongation. The findings were compared to the properties of three types of conventional reinforcing steel: 500SD, 500N and 500H (EC-2.<br>
    En este trabajo se presentan los diagramas tensióndeformación de un nuevo acero inoxidable con bajo contenido en níquel, un inoxidable convencional AISI 304 y un acero al carbono de uso común en estructuras de hormigón armado. Dicha ductilidad se ha estudiado determinando la tensión máxima (fmax, la tensión en el límite elástico (fy y la deformación bajo carga máxima (εmax. Los tres materiales se han evaluado utilizando criterios aceptados internacionalmente, como son el índice p (capacidad de rotación plástica, el índice A* (área plástica de endurecimiento y el índice de tenacidad Id (energía total absorbida en el punto de alargamiento bajo carga máxima, los resultados obtenidos se han comparado con los aceros convencionales de armaduras 500SD, 500N y 500H (EC-2.

  3. Reactive bromine chemistry in Mt. Etna's volcanic plume: the influence of total Br, high temperature processing, aerosol loading and plume-air mixing

    Directory of Open Access Journals (Sweden)

    T. J. Roberts

    2014-03-01

    Full Text Available Volcanic emissions present a source of reactive halogens to the troposphere, through rapid plume chemistry that converts the emitted HBr to more reactive forms such as BrO. The nature of this process is poorly quantified, yet is of interest to understand volcanic impacts on the troposphere, and infer volcanic activity from volcanic gas measurements (i.e. BrO / SO2 ratios. Recent observations from Etna report an initial increase and subsequent plateau or decline in BrO / SO2 ratios with distance downwind. We present daytime PlumeChem model simulations that reproduce and explain the reported trend in BrO / SO2 at Etna including the initial rise and subsequent plateau. Through suites of model simulations we also investigate the influences of volcanic aerosol loading, bromine emission, and plume-air mixing rate on the downwind plume chemistry. Emitted volcanic HBr is converted into reactive bromine by autocatalytic bromine chemistry cycles whose onset is accelerated by the model high-temperature initialisation. These rapid chemistry cycles also impact the reactive bromine speciation through inter-conversion of Br, Br2, BrO, BrONO2, BrCl, HOBr. Formation of BrNO2 is also discussed. We predict a new evolution of Br-speciation in the plume, with BrO, Br2, Br and HBr as the main plume species in the near downwind plume whilst BrO, and HOBr are present in significant quantities further downwind (where BrONO2 and BrCl also make up a minor fraction. The initial rise in BrO / SO2 occurs as ozone is entrained into the plume whose reaction with Br promotes net formation of BrO. Aerosol has a modest impact on BrO / SO2 near-downwind (2 occurs as entrainment of oxidants HO2 and NO2 promotes net formation of HOBr and BrONO2, whilst the plume dispersion dilutes volcanic aerosol so slows the heterogeneous loss rates of these species. A higher volcanic aerosol loading enhances BrO / SO2 in the (> 6 km downwind plume. Simulations assuming low/medium and high Etna

  4. Oxidative treatment of bromide-containing waters: formation of bromine and its reactions with inorganic and organic compounds--a critical review.

    Science.gov (United States)

    Heeb, Michèle B; Criquet, Justine; Zimmermann-Steffens, Saskia G; von Gunten, Urs

    2014-01-01

    Bromide (Br(-)) is present in all water sources at concentrations ranging from ≈ 10 to >1000 μg L(-1) in fresh waters and about 67 mg L(-1) in seawater. During oxidative water treatment bromide is oxidized to hypobromous acid/hypobromite (HOBr/OBr(-)) and other bromine species. A systematic and critical literature review has been conducted on the reactivity of HOBr/OBr(-) and other bromine species with inorganic and organic compounds, including micropollutants. The speciation of bromine in the absence and presence of chloride and chlorine has been calculated and it could be shown that HOBr/OBr(-) are the dominant species in fresh waters. In ocean waters, other bromine species such as Br2, BrCl, and Br2O gain importance and may have to be considered under certain conditions. HOBr reacts fast with many inorganic compounds such as ammonia, iodide, sulfite, nitrite, cyanide and thiocyanide with apparent second-order rate constants in the order of 10(4)-10(9)M(-1)s(-1) at pH 7. No rate constants for the reactions with Fe(II) and As(III) are available. Mn(II) oxidation by bromine is controlled by a Mn(III,IV) oxide-catalyzed process involving Br2O and BrCl. Bromine shows a very high reactivity toward phenolic groups (apparent second-order rate constants kapp ≈ 10(3)-10(5)M(-1)s(-1) at pH 7), amines and sulfamides (kapp ≈ 10(5)-10(6)M(-1)s(-1) at pH 7) and S-containing compounds (kapp ≈ 10(5)-10(7)M(-1)s(-1) at pH 7). For phenolic moieties, it is possible to derive second-order rate constants with a Hammett-σ-based QSAR approach with [Formula in text]. A negative slope is typical for electrophilic substitution reactions. In general, kapp of bromine reactions at pH 7 are up to three orders of magnitude greater than for chlorine. In the case of amines, these rate constants are even higher than for ozone. Model calculations show that depending on the bromide concentration and the pH, the high reactivity of bromine may outweigh the reactions of chlorine during

  5. The radical trap in atom transfer radical polymerization need not be thermodynamically stable. A study of the MoX(3)(PMe(3))(3) catalysts.

    Science.gov (United States)

    Maria, Sébastien; Stoffelbach, François; Mata, José; Daran, Jean-Claude; Richard, Philippe; Poli, Rinaldo

    2005-04-27

    The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order Cl MoX(4)(PMe(3))(3) for X = Cl and Br. On the other hand, I(-) is more easily oxidized than the MoI(3)(PMe(3))(3) complex; thus, the putative MoI(4)(PMe(3))(3) complex is redox unstable. Electrochemical studies of MoI(3)(PMe(3))(3) in the presence of X(-) (X = Cl or Br) reveal the occurrence of facile halide-exchange processes, leading to the conclusion that the MoI(3)X(PMe(3))(3) products are also redox unstable. The oxidation of MoX(3)(PMe(3))(3) with (1)/(2)Br(2) yields MoX(3)Br(PMe(3))(3) (X = Cl, Br), whose molecular nature is confirmed by single-crystal X-ray analyses. On the other hand, the oxidation of MoI(3)(PMe(3))(3) by I(2) slowly yields a tetraiodomolybdate(III) salt of iodotrimethylphosphonium, [Me(3)PI][MoI(4)(PMe(3))(3)], as confirmed by an X-ray study. This product has no controlling ability in radical polymerization. The redox instability of MoI(3)X(PMe(3))(3) can be reconciled with its involvement as a radical trapping species in the MoI(3)(PMe(3))(3)-catalyzed ATRP, given the second-order nature of its decomposition rate.

  6. A metal-free organic-inorganic aqueous flow battery

    Science.gov (United States)

    Huskinson, Brian; Marshak, Michael P.; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R.; Galvin, Cooper J.; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G.; Aziz, Michael J.

    2014-01-01

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br- redox couple, yields a peak galvanic power density exceeding 0.6Wcm-2 at 1.3Acm-2. Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and

  7. Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible.

    Science.gov (United States)

    Le Grognec, E; Claverie, J; Poli, R

    2001-10-03

    Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (AIBN). This arises from the generation of a putative Mo(IV) alkyl species from the AIBN-generated radical addition to the Mo(III) compound. The controlled nature of the polymerizations is indicated by linear M(n) progression with the conversion in all cases and moderate polydispersity indices (PDIs). Controlled polymerization of styrene is also given by compounds 3 and 4 in combination with alkyl bromides. These complexes then operate by the ATRP mechanism, again in accord with the theoretical predictions. Controlled character is revealed by linear increase of M(n) versus conversion, low PDIs, a stop-and-go experiment, and (1)H NMR and MALDI-TOF analyses of the polymer end groups. The same controlled polymerization is given by a "reverse" ATRP experiment, starting from AIBN and CpMo(PMe(3))(2)Cl(2)Br, 5. On the other hand, when compound 1 or 2 is used in combination with an alkyl bromide (as for an ATRP experiment), the isolated polystyrene shows by M(n), (1)H NMR, and MALDI-TOF analyses that catalytic chain transfer (CCT) radical polymerization takes place in this case. Kinetics simulations underscore the conditions regulating the radical polymerization mechanism and the living character of the polymerization. The complexes herein described are ineffective at controlling the

  8. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements of brominated hydrocarbons in the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, Stephan; Bönisch, Harald; Keber, Timo; Oram, Dave; Mills, Graham; Engel, Andreas

    2014-05-01

    Halogenated hydrocarbons play a major role as precursors for stratospheric ozone depletion. Released from the surface in the troposphere, the halocarbons reach the stratosphere via transport through the tropical tropopause layer. The contribution of the so called very short lived species (VSLS), having atmospheric lifetimes of less than half a year as sources gases for stratospheric bromine is significant. Source gas observations of long-lived bromine compounds and VSLS have so far not been able to explain the amount of bromine derived in the stratosphere from observations of BrO and modeling of the ratio of BrO to total bromine. Due to the short lifetimes and the high atmospheric variability, the representativeness of the available observations of VSLS source gases remains unclear, as these may vary with region and display seasonal variability. During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset with over 700 samples of ambient air of all halogen species relevant for the atmospheric budget of total organic bromine (long lived halocarbons: H-1301, H-1211, H-1202, H-2402 and CH3Br, very short lived substances: CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CHBrCl) have been collected from onboard the FALCON aircraft in the West Pacific region. Measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia. We will present the datasets, compare these to other observation, derive a bromine budget for the West Pacific and derive an estimate of the amount of bromine from VSLS reaching the stratosphere. Using the mean mixing ratios in the upper troposphere of the halocarbons mentioned above, the calculated budget of the total organic

  9. Atmospheric test of the J(BrONO2)/kBrO+NO2 ratio: implications for total stratospheric Bry and bromine-mediated ozone loss

    Science.gov (United States)

    Kreycy, S.; Camy-Peyret, C.; Chipperfield, M. P.; Dorf, M.; Feng, W.; Hossaini, R.; Kritten, L.; Werner, B.; Pfeilsticker, K.

    2013-07-01

    We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220 ± 5 K an overall 1.7 (+0.4 -0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH2Br2, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum -0.8%), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation

  10. Coinage metal complexes with bridging hybrid phosphine-NHC ligands: synthesis of di- and tetra-nuclear complexes.

    Science.gov (United States)

    Simler, Thomas; Braunstein, Pierre; Danopoulos, Andreas A

    2016-03-28

    A series of P-NHC-type hybrid ligands containing both PR2 and N-heterocyclic carbene (NHC) donors on meta-bis-substituted phenylene backbones, L(Cy), L(tBu) and L(Ph) (R = Cy, tBu, Ph, respectively), was accessed through a modular synthesis from a common precursor, and their coordination chemistry with coinage metals was explored and compared. Metallation of L(Ph)·n(HBr) (n = 1, 2) with Ag2O gave the pseudo-cubane [Ag4Br4(L(Ph))2], isostructural to [Ag4Br4(L(R))2] (R = Cy, tBu) (T. Simler, P. Braunstein and A. A. Danopoulos, Angew. Chem., Int. Ed., 2015, 54, 13691), whereas metallation of ·HBF4 (R = Ph, tBu) led to the dinuclear complexes [Ag2(L(R))2](BF4)2 which, in the solid state, feature heteroleptic Ag centres and a 'head-to-tail' (HT) arrangement of the bridging ligands. In solution, interconversion with the homoleptic 'head-to-head' (HH) isomers is facilitated by ligand fluxionality. 'Head-to-tail' [Cu2Br2(L(R))2] (R = Cy, tBu) dinuclear complexes were obtained from L(R)·HBr and [Cu5(Mes)5], Mes = 2,4,6-trimethylphenyl, which also feature bridging ligands and heteroleptic Cu centres. Although the various ligands L(R)l ed to structurally analogous complexes for R = Cy, tBu and Ph, the rates of dynamic processes occurring in solution are dependent on R, with faster rates for R = Ph. Transmetallation of both NHC and P donor groups from [Ag4Br4(L(tBu))2] to AuI by reaction with [AuCl(THT)] (THT = tetrahydrothiophene) led to L(tBu) transfer and to the dinuclear complex [Au2Cl2L(tBu)] with one L(tBu) ligand bridging the two Au centres. Except for the silver pseudo-cubanes, all other complexes do not exhibit metallophilic interactions.

  11. Constraining the N2O5 UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere

    Science.gov (United States)

    Kritten, L.; Butz, A.; Chipperfield, M. P.; Dorf, M.; Dhomse, S.; Hossaini, R.; Oelhaf, H.; Prados-Roman, C.; Wetzel, G.; Pfeilsticker, K.

    2014-09-01

    The absorption cross section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding - Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200-260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260-350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5(λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2-0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.

  12. Thiosemicarbazone Cu(II) and Zn(II) complexes as potential anticancer agents: syntheses, crystal structure, DNA cleavage, cytotoxicity and apoptosis induction activity.

    Science.gov (United States)

    Shao, Jia; Ma, Zhong-Ying; Li, Ang; Liu, Ya-Hong; Xie, Cheng-Zhi; Qiang, Zhao-Yan; Xu, Jing-Yuan

    2014-07-01

    Four novel thiosemicarbazone metal complexes, [Cu(Am4M)(OAc)]·H2O (1), [Zn(HAm4M)Cl2] (2), [Zn2(Am4M)2Br2] (3) and [Zn2(Am4M)2(OAc)2]·2MeOH (4) [HAm4M=(Z)-2-(amino(pyridin-2-yl)methylene)-N-methylhydrazinecarbothioamide], have been synthesized and characterized by X-ray crystallography, elemental analysis, ESI-MS and IR. X-ray analysis revealed that complexes 1 and 2 are mononuclear, which possess residual coordination sites for Cu(II) ion in 1 and good leaving groups (Cl(-)) for Zn(II) ion in 2. Both 3 and 4 displayed dinuclear units, in which the metal atoms are doubly bridged by S atoms of two Am4M(-) ligands in 3 and by two acetate ions in bi- and mono-dentate forms, respectively, in 4. Their antiproliferative activities on human epithelial cervical cancer cell line (HeLa), human liver hepatocellular carcinoma cell line (HepG-2) and human gastric cancer cell line (SGC-7901) were screened. Inspiringly, IC50 value (11.2±0.9 μM) of complex 1 against HepG-2 cells was nearly 0.5 fold of that against human hepatic cell lines LO2, showing a lower toxicity to human liver cells. Additionally, it displayed a stronger inhibition on the viability of HepG-2 cells than cisplatin (IC50=25±3.1 μM), suggesting complex 1 might be a potential high efficient antitumor agent. Furthermore, fluorescence microscopic observation and flow cytometric analysis revealed that complex 1 could significantly suppress HepG-2 cell viability and induce apoptosis. Several indexes, such as DNA cleavage, reactive oxygen species (ROS) generation, comet assay and cell cycle analysis indicated that the antitumor mechanism of complex 1 on HepG-2 cells might be via ROS-triggered apoptosis pathway. Copyright © 2014. Published by Elsevier Inc.

  13. A metal-free organic-inorganic aqueous flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  14. Scanning mutagenesis in a yeast system delineates the role of the NPxxY(x)(5,6)F motif and helix 8 of the adenosine A(2B) receptor in G protein coupling.

    Science.gov (United States)

    Liu, Rongfang; Nahon, Dennis; le Roy, Beau; Lenselink, Eelke B; IJzerman, Adriaan P

    2015-06-15

    The adenosine receptor subfamily includes four subtypes: the A1, A2A, A2B and A3 receptors, which all belong to the superfamily of G protein-coupled receptors (GPCRs). The adenosine A2B receptor is the least investigated of the adenosine receptors, and the molecular mechanisms of its activation have hardly been explored. We used a single-GPCR-one-G protein yeast screening method in combination with mutagenesis studies, molecular modeling and bio-informatics to investigate the importance of the different amino acid residues of the NPxxY(x)6F motif and helix 8 in the human adenosine A2B receptor (hA2BR) activation. A scanning mutagenesis protocol was employed, yielding 11 single mutations and one double mutation of the NPxxY(x)6F motif and 16 single mutations of helix 8. The amino acid residues P287(7.50), Y290(7.53), R293(7.56) and I304(8.57) were found to be essential, since mutation of these amino acid residues to alanine led to a complete loss of function. Western blot analysis showed that mutant receptor R293(7.56)A was not expressed, whereas the other proteins were. Amino acid residues that are also important in receptor activation are: N286(7.49), V289(7.52), Y292(7.55), N294(8.47), F297(8.50), R298(8.51), H302(8.55) and R307(8.60). The mutation Y290(7.53)F lost 50% of efficacy, while F297(8.50)A behaved similar to wild type receptor. The double mutation, Y290(7.53)F/F297(8.50)Y, lost around 70% of efficacy and displayed a lower potency for the reference agonist 5'-(N-ethylcarboxamido)adenosine (NECA). This study provides new insight into the molecular interplay and impact of TM7 and helix 8 for hA2B receptor activation, which may be extrapolated to other adenosine receptors and possibly to other GPCRs.

  15. New methodology for Ozone Depletion Potentials of short-lived compounds: n-Propyl bromide as an example

    Science.gov (United States)

    Wuebbles, Donald J.; Patten, Kenneth O.; Johnson, Matthew T.; Kotamarthi, Rao

    2001-07-01

    A number of the compounds proposed as replacements for substances controlled under the Montreal Protocol have extremely short atmospheric lifetimes, on the order of days to a few months. An important example is n-propyl bromide (also referred to as 1-bromopropane, CH2BrCH2CH3 or simplified as 1-C3H7Br or nPB). This compound, useful as a solvent, has an atmospheric lifetime of less than 20 days due to its reaction with hydroxyl. Because nPB contains bromine, any amount reaching the stratosphere has the potential to affect concentrations of stratospheric ozone. The definition of Ozone Depletion Potentials (ODP) needs to be modified for such short-lived compounds to account for the location and timing of emissions. It is not adequate to treat these chemicals as if they were uniformly emitted at all latitudes and longitudes as normally done for longer-lived gases. Thus, for short-lived compounds, policymakers will need a table of ODP values instead of the single value generally provided in past studies. This study uses the MOZART2 three-dimensional chemical-transport model in combination with studies with our less computationally expensive two-dimensional model to examine potential effects of nPB on stratospheric ozone. Multiple facets of this study examine key questions regarding the amount of bromine reaching the stratosphere following emission of nPB. Our most significant findings from this study for the purposes of short-lived replacement compound ozone effects are summarized as follows. The degradation of nPB produces a significant quantity of bromoacetone which increases the amount of bromine transported to the stratosphere due to nPB. However, much of that effect is not due to bromoacetone itself, but instead to inorganic bromine which is produced from tropospheric oxidation of nPB, bromoacetone, and other degradation products and is transported above the dry and wet deposition processes of the model. The MOZART2 nPB results indicate a minimal correction of the

  16. C-Functionalized, air- and water-stable 9,10-dihydro-9,10-diboraanthracenes: efficient blue to red emitting luminophores.

    Science.gov (United States)

    Reus, Christian; Weidlich, Sabine; Bolte, Michael; Lerner, Hans-Wolfram; Wagner, Matthias

    2013-08-28

    9,10-Dihydro-9,10-diboraanthracene (DBA) provides a versatile scaffold for the development of boron-doped organic luminophores. Symmetrically C-halogenated DBAs are obtained through the condensation of 4-bromo-1,2-bis(trimethylsilyl)benzene or 4,5-dichloro-1,2-bis(trimethylsilyl)benzene with BBr3 in hexane. Unsymmetrically C-halogenated DBAs are formed via an electrophilic solvent activation reaction if the synthesis is carried out in o-xylene. Mechanistic insight has been achieved by in situ NMR spectroscopy, which revealed C-halogenated 1,2-bis(dibromoboryl)benzenes to be the key intermediates. Treatment of the primary 9,10-dibromo-DBAs with MesMgBr yields air- and water-stable C-halogenated 9,10-dimesityl-DBAs (2-Br-6,7-Me2-DBA(Mes)2; 2,6-Br2-DBA(Mes)2; 2,3-Cl2-6,7-Me2-DBA(Mes)2; 2,3,6,7-Cl4-DBA(Mes)2). Subsequent Stille-type C-C-coupling reactions give access to corresponding phenyl, 2-thienyl, and p-N,N-diphenylaminophenyl derivatives, which act as highly emissive donor-acceptor dyads or donor-acceptor-donor triads both in solution and in the solid state. 2-Thienyl was chosen as a model substituent to show that already a variation of the number and/or the positional distribution of the donor groups suffices to tune the emission wavelength of the resulting benchtop stable compounds from 469 nm (blue) to 540 nm (green). A further shift of the fluorescence maximum to 594 nm (red) can be achieved by switching from 2-thienyl to p-aminophenyl groups. A comparison of the optoelectronic properties of selected C-substituted DBA(Mes)2 derivatives with those of the isostructural anthracene analogues unveiled the following: (i) The DBA core is a much better electron acceptor. (ii) The emission colors of DBAs fall in the visible range of the spectrum (blue to orange), while anthracenes emit exclusively in the near-ultraviolet to blue wavelength regime. (iii) DBAs show significantly higher solid-state quantum yields.

  17. Investigation of the Oxidation Reaction of O3 with Bromide Ion in Aqueous Solution%水溶液中臭氧和溴离子的反应研究

    Institute of Scientific and Technical Information of China (English)

    俞潇婷; 张家辉; 潘循皙; 张仁熙; 侯惠奇

    2012-01-01

    The reaction mechanism of O3 with bromide ion in aqueous solution was studied by ion chromatography and UV-Vis spectrometry instruments.Ion chromatography analysis showed that only 10% of Br-which was oxidized by ozone was formed into bromate ion.The results demonstrated that the final products of the oxidation reaction were identified as Br2 and Br-3 except for BrO-3.The formation of Br-3 which was yielded from the reaction of Br2 with Br-was the major process in the reaction of Br-attacked by O3.The characteristic absorption spectrum of Br-3 with an absorption peak at 260 nm was also investigated.The results may provide helpful information about the mechanism of the oxidation reaction of Br-with O3 and fate of Br-or its derivatives in the environment by the oxidation processes.%为探明O3氧化Br-的反应机制,采用离子色谱、PDA紫外-可见光度仪研究了水中Br-被O3氧化的反应过程.离子色谱分析表明,被氧化的Br-中只有约10%被O3氧化成BrO3-.进一步研究表明,除了生成BrO3-外,Br-被O3氧化过程中还产生了Br2,Br2又与溶液中存在的Br-结合形成Br3-,并首次得到了Br3-的吸收光谱,测得Br3-的最大吸收峰λmax为260 nm,提出了Br-与O3的基元反应.该研究补充和完善了O3氧化Br-的反应机制,也为O3处理含Br-水时Br-的归趋提供了有益信息.

  18. Atmospheric test of the J(BrONO2/kBrO+NO2 ratio: implications for total stratospheric Bry and bromine-mediated ozone loss

    Directory of Open Access Journals (Sweden)

    B. Werner

    2012-10-01

    Full Text Available We report on time-dependent O3, NO2 and BrO profile measurements taken in the stratosphere by limb observations of scattered skylight at high-latitudes during autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicates that, the measurements can be used to constrain the ratio J(BrONO2/kBrO+NO2, for which overall a 1.69 ± 0.04 larger ratio is found than indicated by the most recent JPL compilation (Sander et al., 2011. Sensitivity studies reveal the major reasons likely to be (1 a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2 a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011. Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry estimated from stratospheric BrO measurements at high NOx loadings, since the J(BrONO2/kBrO+NO2 ratio largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This brings estimates of total stratospheric bromine inferred from organic source gas measurements (i.e. CH3Br, the halons, CH2Br2, CHBr3, ... into closer agreement with estimates based on BrO observations (inorganic method. The consequences for stratospheric ozone due to the revised J(BrONO2/kBrO+NO2 ratio are small (maximum −0.8%, since at high NOx (for which most Bry assessments are made an overestimated Bry using the inorganic method would in return almost cancel out with the amount of reactive bromine calculated in the photochemical models.

  19. Acylmethyl(aryl)tellurium(IV,II) derivatives: intramolecular secondary bonding and steric rigidity.

    Science.gov (United States)

    Chauhan, Ashok K S; Singh, Puspendra; Srivastava, Ramesh C; Duthie, Andrew; Voda, Andreea

    2008-08-14

    Electrophilic substitution of acylmethanes (methyl ketones), RCOCH3 (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl3 (Ar = 1-C10H7, Np, A; 2,4,6-Me3C6H2, Mes, B; 4-MeOC6H4, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH2)ArTeCl2. Reduction of the dichlorides, gives tellurides, (i-PrCOCH2)ArTe, 1A-1C, which give the corresponding dihalides, (i-PrCOCH2)ArTeX2 (X = Cl, 1Aa-1Ca; Br, 1Ab-1Cb; I, 1Ac-1Cc) when reacted in situ with SO2Cl2, Br2 or I2. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar2Te2 except in the case of (i-PrCOCH2)MesTe (1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate 1H and 13C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te-C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one 125Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1cA and 1Cc which are indicative of the presence of intramolecular Te...O secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te-C(mesityl) bond axis. Intermolecular C-HO...O H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.

  20. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.