WorldWideScience

Sample records for carbon complexes

  1. Carbon dioxide transport over complex terrain

    OpenAIRE

    Sun, RC

    2004-01-01

    The nocturnal transport of carbon dioxide over complex terrain was investigated. The high carbon dioxide under very stable conditions flows to local low-ground. The regional drainage flow dominates the carbon dioxide transport at the 6 m above the ground and carbon dioxide was transported to the regional low ground. The results show that the local drainage flow was sensitive to turbulent mixing associated with local wind shear.

  2. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-07-14

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  3. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Loring, John S.; Chen, Jeffrey; Benezeth, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-06-16

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  4. Study of new complexes of uranium and comba radical. I.- Complexes defective in sodium carbonate

    International Nuclear Information System (INIS)

    Some complexes formed in presence of defect of sodium carbonate with respect to the stoichiometric ratio (U): (C03) = 1:3 are studied. This ratio corresponds to the main complex which is responsible for the uranium extraction with CDMBAC organic solutions and from U(VI) aqueous solutions with an excess of sodium carbonate. (Author) 10 refs

  5. Complexity of carbon market from multi-scale entropy analysis

    Science.gov (United States)

    Fan, Xinghua; Li, Shasha; Tian, Lixin

    2016-06-01

    Complexity of carbon market is the consequence of economic dynamics and extreme social political events in global carbon markets. The multi-scale entropy can measure the long-term structures in the daily price return time series. By using multi-scale entropy analysis, we explore the complexity of carbon market and mean reversion trend of daily price return. The logarithmic difference of data Dec16 from August 6, 2010 to May 22, 2015 is selected as the sample. The entropy is higher in small time scale, while lower in large. The dependence of the entropy on the time scale reveals the mean reversion of carbon prices return in the long run. A relatively great fluctuation over some short time period indicates that the complexity of carbon market evolves consistently with economic development track and the events of international climate conferences.

  6. Carbon footprint of building products and assembled constructional complexes

    OpenAIRE

    Petrović, Klemen

    2015-01-01

    Greenhouse gases are becoming bigger and bigger polluter of our planet. Carbon dioxide represents the largest part of greenhouse gases (70 %), because of that we represent carbon footprint with CO2 equivalent (CO2-e). We will compare assembled construction complexes and their carbon footprint in this graduation thesis. At first we will explain what greenhouse gases are and how they are formed. Then we will present some of the studies that research field of materials in constructio...

  7. Lanthanide carbonate-phosphate complexes of different ligands

    International Nuclear Information System (INIS)

    Previously undescribed carbonate-phosphate complexes of lanthanides (Ln) have been derived. Their optical and luminescent properties have been stUdied. It is shown that the lanthanide ions may form in solutions highly charged anions preferably corresponding to formulas: [NdCO3(PO4)3]8-, [HoCO3(PO4)3]8- and [Er(CO3)2(PO4)]10-. The stability constants (Ksub(st)) of the resulting heteroligand complexes have been determined. A new version of the luminescent method of determining the composition of carbonate-phosphate complexes of Eu is suggested

  8. Spontaneous Resolution and Carbonation of Chiral Benzyllithium Complexes

    DEFF Research Database (Denmark)

    Lennartson, Anders; Sundberg, Jonas; Wiklund, Tove; Hilmersson, Göran; Håkansson, Mikael

    2010-01-01

    CO2, but the bulk product was racemic. It is unclear whether the lack of selectivity originates during crystallisation or carbonation. In order to investigate this, similar complexes displaying Si or S atoms in the α-position were prepared and structurally characterized: [Li(tmsb)(tmpda)] (tmsb = 1...

  9. Adsorptive preconcentration of rareearth oxine complexes onto activated carbon

    International Nuclear Information System (INIS)

    This paper describes a method for the determination of traces of rare earth using energy dispersive x-ray fluorescence spectrometry (EDXRF) after preconcentration of their oxine complexes onto activated carbon. Various parameters that influence adsorptive preconcentration of rare earth onto activated carbon viz. pH, amounts of activated carbon and oxine, time of stirring and aqueous phase volume were systematically studied. A numerical method based on simple least square procedure using fifth order polynomial with 25 consecutive values was developed for smoothing and differentiation of EDXRF data which was previously digitized and averaged. First order derivative EDXRF in conjunction with adsorptive preconcentration on activated carbon enables one to determine as low as 10 ppb of each individual rare earth elements

  10. Excitation transfer and luminescence in porphyrin-carbon nanotube complexes

    CERN Document Server

    Magadur, G; Alain-Rizzo, V; Voisin, C; Roussignol, Ph; Deleporte, E; Delaire, J A

    2007-01-01

    Functionalization of carbon nanotubes with hydrosoluble porphyrins (TPPS) is achieved by "$\\pi$-stacking". The porphyrin/nanotube interaction is studied by means of optical absorption, photoluminescence and photoluminescence excitation spectroscopies. The main absorption line of the porphyrins adsorbed on nanotubes exhibits a 120 meV red shift, which we ascribe to a flattening of the molecule in order to optimize $\\pi-\\pi$ interactions. The porphyrin-nanotube complex shows a strong quenching of the TPPS emission while the photoluminescence intensity of the nanotubes is enhanced when the excitation laser is in resonance with the porphyrin absorption band. This reveals an efficient excitation transfer from the TPPS to the carbon nanotube.

  11. Excitation transfer and luminescence in porphyrin-carbon nanotube complexes

    OpenAIRE

    Magadur, Gurvan; Lauret, Jean-Sébastien; Alain-Rizzo, Valérie; C. Voisin; Roussignol, Ph.; Deleporte, Emmanuelle; Delaire, Jacques,

    2007-01-01

    Functionalization of carbon nanotubes with hydrosoluble porphyrins (TPPS) is achieved by "$\\pi$-stacking". The porphyrin/nanotube interaction is studied by means of optical absorption, photoluminescence and photoluminescence excitation spectroscopies. The main absorption line of the porphyrins adsorbed on nanotubes exhibits a 120 meV red shift, which we ascribe to a flattening of the molecule in order to optimize $\\pi-\\pi$ interactions. The porphyrin-nanotube complex shows a strong quenching ...

  12. High-temperature carbonates in the Stillwater Complex, Montana, USA

    Science.gov (United States)

    Aird, H. M.; Boudreau, A. E.

    2012-12-01

    The processes involved in the petrogenesis of the sulphide-hosted platinum-group-element (PGE) deposits of the Stillwater Complex are controversial, with theories ranging from the purely magmatic to those involving an aqueous fluid. To further constrain these models, we have been examining the trace phase assemblages in rocks away from the ore zones. High-temperature carbonates have been observed in association with sulphide minerals below the platiniferous J-M Reef of the Stillwater Complex. The carbonate assemblage consists of dolomite with exsolved calcite and is found in contact with sulphide minerals: chalcopyrite and pyrrhotite in the Peridotite Zone; and pyrrhotite with pentlandite, pyrite and chalcopyrite in Gabbronorite I of the Lower Banded Series. The minimal silicate alteration and the lack of greenschist minerals in association with the mineral assemblage are consistent with a high-temperature origin for the carbonates. The calcite-dolomite geothermometer [1] yields a minimum formation temperature of ~900°C for the unmixed assemblages. A reaction rim surrounds the carbonate-sulphide assemblages, showing an alteration of the host orthopyroxene to a more Ca-enriched, Fe-depleted composition. This is consistent with diffusive exchange between carbonates and pyroxenes at high temperatures, mediated by an aqueous fluid. The highly variable molar MnO/FeO ratios in both the high-temperature carbonates and their associated altered pyroxene rims also imply their interaction with a fluid. The carbonate assemblages are consistent with Stillwater fluid inclusion studies [2], showing that fluids comprising coexisting Cl-rich brine and carbonic fluid were trapped in pegmatitic quartz at 700-715°C, some of which also contained "accidental" calcite inclusions. The high Cl-content of apatite [3] found below the platiniferous J-M Reef is further evidence that a Cl-rich fluid was migrating through the rocks beneath the Reef. Carbonates have been shown to be stabilized

  13. Carbon-13 NMR characterization of actinyl(VI) carbonate complexes in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Clark, D.L.; Hobart, D.E.; Palmer, P.D. [Los Alamos National Lab., NM (United States); Sullivan, J.C. [Argonne National Lab., IL (United States); Stout, B.E. [Cincinnati Univ., OH (United States). Dept. of Chemistry

    1992-07-01

    The uranyl(VI) carbonate system has been re-examined using {sup 13}C NMR of 99.9% {sup 13}C-enriched U{sup VI}O{sub 2} ({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} in millimolar concentrations. By careful control of carbonate ion concentration, we have confirmed the existence of the trimer, and observed dynamic equilibrium between the monomer and the timer. In addition, the ligand exchange reaction between free and coordinated carbonate on Pu{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} and Am{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} systems has been examined by variable temperature {sup 13}C NMR line-broadening techniques {sup 13}C NMR line-broadening techniques. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was written to allow for experimental determination of ligand exchange parameters for paramagnetic actinide complexes. Preliminary Eyring analysis has provided activation parameters of {Delta}G{sup {double_dagger}}{sub 295} = 56 kJ/M, {Delta}H{sup {double_dagger}} = 38 kJ/M, and {Delta}S{sup {double_dagger}} = {minus}60 J/M-K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl (VI) carbonate complex self-exchange reaction. Experiments for determination of the activation parameters for the americium (VI) carbonate system are in progress.

  14. Building complex carbon skeletons with ethynyl[2.2]paracyclophanes

    OpenAIRE

    Ina Dix; Lidija Bondarenko; Jones, Peter G; Thomas Oeser; Henning Hopf

    2014-01-01

    Ethynyl[2.2]paracyclophanes are shown to be useful substrates for the preparation of complex, highly unsaturated carbon frameworks. Thus both the pseudo-geminal- 2 and the pseudo-ortho-diethynylcyclophane 4 can be dimerized by Glaser coupling to the respective dimers 9/10 and 11/12. Whereas the former isomer pair could not be separated so far, the latter provided the pure diastereomers after extensive column chromatography/recrystallization. Isomer 11 is chiral and could be separated on a col...

  15. Reduction of uranyl carbonate and hydroxyl complexes and neptunyl carbonate complexes studied with chemical-electrochemical methods and rixs spectroscopy

    International Nuclear Information System (INIS)

    Sweden and Finland plan to dispose of spent fuel from commercial nuclear power plants in deep underground repositories sited in granitic rocks. The fuel assemblies will be placed in canisters consisting of an outer corrosion-resistant copper shell with an inner cast iron insert that gives mechanical strength and reduces void space in the canister. The canister will be placed in a disposal borehole lined with compacted bentonite blocks. After sealing of the borehole, groundwater seepage will saturate the bentonite. The water flow path and transport mechanism between the host rock and the canister will be via diffusion through the swollen bentonite. Any oxygen trapped in the repository will be consumed by reaction with the host rock, pyrite in the bentonite and through microbial activity, giving long-term conditions with low redox potentials. Under these conditions, uranium dioxide - the matrix of unirradiated fuel - is a stable phase. This reducing near-field environment can upset by radiolysis of water caused by the radioactivity of the fuel, which after a few hundred years will be primarily alpha activity. Radiolysis of water produces equal amounts of oxidising and reducing species, but the reducing species produced by alpha radiolysis is molecular hydrogen, which is expected to be far less reactive than the produced oxidising species, H2O2. Alpha radiolysis could create locally oxidising conditions close to the fuel surface and oxidise the U(IV) in the uranium dioxide fuel to the more soluble U(VI) oxidation state. Furthermore, the solubility of U(VI) is enhanced in the presence of bicarbonate/carbonate by the formation of strong anionic uranyl carbonate complexes. This increase in solubility can amount to 4 to 5 orders of magnitude depending on the composition of the groundwater in contact with the fuel. The other tetravalent actinides in the fuel, Np and Pu, also have higher solubilities when oxidised beyond 4+ to neptunyl and plutonyl species. Once these

  16. Carbonate complexation of Np(IV) in alkaline solutions

    International Nuclear Information System (INIS)

    Reliable thermodynamic data for actinide (IV) have been required. The solubility of Np(IV) in carbonate media was studied for determination of thermodynamic data. The concentration of dissolved Np(IV) was measured with ionic strengths from 0.5 to 2.9 M (M ≡ mol·dm-3), hydrogen-ion concentration exponent (pHc = -log[H+]) from 8 to 13 and with the total carbonate concentration (CT) from 5x10-3 M to 7x10-1 M by an oversaturation method. It was found that the solubility of Np(IV) decreased with increasing pHc and increased with increasing CT. On the basis of analysis of the solubility data, the dominant aqueous species of Np(IV) were expected to be Np(CO3)44-, Np(CO3)2(OH)22- and Np(CO3)2(OH)44- in the present study. The apparent equilibrium constants of the carbonate and carbonatohydroxo complexes were obtained in the respective ionic strength and the equilibrium constants at the zero ionic strength were extrapolated. The obtained equilibrium constants supported the literature values strongly, and contributed to improve the reliability of the thermodynamic data. (author)

  17. Complexation of europium(III) with carbonate ions in groundwater

    International Nuclear Information System (INIS)

    The equilibrium extraction behavior of Eu(III) studied in chloroform solutions containing 1-nitroso-2-naphthol (HA), either alone or combined with 2,2'-dipyridyl, 1,10-phenanthroline (phen), or trioctylphosphine oxide (TOPO) shows that the metal ion is extracted as either EuA3, EuA3.2,2'-dipyridyl, EuA3.phen, or EuA32TOPO, respectively. The synergic effect of phen or TOPO on the extraction of EU(III) with 1-nitrose-2-naphthol is more pronounced over that of 2,2'-dipyridyl. The carbonate complexation of EU(III) has been studied in 1.0 M ionic strength solutions at pH 8.0-9.0 and 250C using the synergic extraction system of 1-nitroso-2-naphthol and phen. The following complexes have been identified: EuCo+3, Eu(CO3)-2, Eu(CO3)3-3, and Eu(CO3)5-4; the results suggest that the first two species predominate at carbonate concentrations and pH similar to those found in most groundwaters. The formation constants of these species have been calculated at zero ionic strength using both SIT and ion pairing models

  18. Carbon and oxygen isotopic composition of the carbonates from the Jacupiranga and Catalao I carbonatite complexes, Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Morikiyo, Toshiro (Shinshu Univ., Matsumoto, Nagano (Japan). Faculty of Science); Hirano, Hideo; Matsuhisa, Yukihiro

    1990-11-01

    Carbon and oxygen isotope compositions were measured for carbonates from the Jacupiranga and Catalao I carbonatite complexes in Brazil. The {delta}{sup 13}C values of the Jacupiranga carbonates are uniform, ranging from -6.4 to -5.6 per mille with the average of -6.07 per mille. Except for one sample, the {delta}{sup 18}O values of the carbonates are between 7.1 and 8.1 per mille, and the average value is 7.6 per mille. The isotopic compositions of the Jacupiranga carbonates represent the value of primary igneous carbonatite. The {delta}{sup 13}C values of dolomites are about 0.5 per mille higher than those of calcites. The {delta}{sup 13}C values of carbonates from the Catalao I complex range from -6.8 to -5.2 per mille with the average of -5.83 per mille. Those values are similar to the values of the Jacupiranga carbonates. However, oxygen isotopic compositions of the Catalao I carbonates show a wide range of 8.4 to 22.3 per mille. Carbonates with the lowest {delta}{sup 18}O values in the complex are considered to represent the igneous stage. Carbonates with extremely high {delta}{sup 18}O values of about 22 per mille are considered to have precipitated from low-temperature hydrothermal fluids. The group of intermediate {delta}{sup 18}O values indicates a variable degree of contamination by the {delta}{sup 18}O-rich hydrothermal carbonates. The contribution of secondary stage hydrothermal carbonates seems to be significant in the Catalao I complex as compared with the Jacupiranga complex. The development of a network structure in the Catalao I complex may have enhanced the circulation of the later stage hydrothermal fluids. (author).

  19. Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

    Science.gov (United States)

    Amundsen, H. E. F.; Benning, L.; Blake, D. F.; Fogel, M.; Ming, D.; Skidmore, M.; Steele, A.

    2011-01-01

    The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

  20. Fixation of atmospheric carbon dioxide by a cadmium(II) macrocyclic complex.

    Science.gov (United States)

    Janzen, Daron E; Botros, Maikel E; VanDerveer, Donald G; Grant, Gregory J

    2007-12-01

    A crystal structure showing an unusual trinuclear Cd(II) cluster bridged in mu3 fashion by a carbonate ligand is reported. The carbonate ion is formed by fixation of atmospheric carbon dioxide from the corresponding cadmium mononuclear complex containing an aza crown ether. PMID:18271488

  1. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 250C. Possible structures of complexes in solution are discussed

  2. Thermodynamic and electrochemical properties of some rare earth cryptates and related complexes in propylene carbonate

    International Nuclear Information System (INIS)

    The stability of trivalent lanthanide complexes with [1]-cryptand 22 and [2]-cryptands 222 and 211 and also tris (3.6- dioxa heptyl) amine (TDHA) is studied in propylene carbonate solution by potentiometry with Ag+ as an auxiliary cation. Complexation enthalpies and entropies are determined for other complexes of some trivalent lanthanides (La, Er, Pr and Eu) with ligands 222, 221, 211, 22, 21, 18C6 and TDHA. [1]- and [2]- crytands are complexing agents more powerful than TDHA and crown-ethers 15C6 and 18C6. For ligands containing nitrogen complexe stability increase with RE atomic number but decrease for crown-ethers. In propylene carbonate complexes are stabilized by enthalpic effects, entropic contribution is variable. Polarographic reduction of samarium cryptate with ligand 222, 221 and 22 in propylene carbonate is reversible as in more solvating solvents water and methanol. Mixed complexes are formed with chlorides and this cryptate system is more difficult to reduce

  3. Scandium-bearing carbonates of the Tarr albitite complex, southeast Sinai

    Science.gov (United States)

    Bogoch, Ron; Eldad, Hannah; Yaacov, Nathan

    1984-04-01

    Unusually high Sc-concentrations (30 to 150 ppm) were found in the carbonate minerals (dolomite, breunnerite, calcite) of the Tarr albitite complex. Scandium is probably part of the carbonate crystal structure substituting for (Mg, Fe 2+). Scandium is considered to have originated from a source of mantle-affinity, thus supporting an earlier suggestion that the Tarr albitite complex is related to an ophiolite at depth.

  4. Preliminary results on the hydrolysis and carbonate complexation of dioxoplutonium(V)

    International Nuclear Information System (INIS)

    The hydrolysis and carbonate complexation reactions of dioxoplutonium (V) were studied in near neutral aqueous systems. These experiments involved the addition of hydroxide or carbonate to Pu(V) in a perchorate medium. Change in the electronic adsorption spectra provided information about the chemical properties of Pu(V). The results indicate the Pu(V) does not hydrolyze below pH 7.15. In the carbonate complexation studies, log β11 was measured to be 4.4 +- 0.7. 5 figs., 3 tabs

  5. Anoxic carbon degradation in Arctic sediments: Microbial transformations of complex substrates

    DEFF Research Database (Denmark)

    Arnosti, Carol; Finke, Niko; Larsen, Ole;

    2005-01-01

    Complex substrates are degraded in anoxic sediments by the concerted activities of diverse microbial communities. To explore the effects of substrate complexity on carbon transformations in permanently cold anoxic sediments, four substrates—Spirulina cells, Isochrysis cells, and soluble high...... of carbon degradation diverged, with an additional 43%, 32%, 33%, and 8% of Isochrysis, Iso-Ex, Spirulina, and Spir-Ex carbon respired to CO2 over the next 750 h of incubation. Somewhat surprisingly, the soluble, carbohydrate-rich extracts did not prove to be more labile substrates than the whole...... cells from which they were derived. Although Spirulina and Iso-Ex differed in physical and chemical characteristics (solid/soluble, C/N ratio, lipid and carbohydrate content), nearly identical quantities of carbon were respired to CO2. In contrast, only 15% of Spir-Ex carbon was respired, despite the...

  6. COMPLEX COMPOST AND CIRCULATION OF NITROGEN AND CARBON AT THE AGROLANDSCAPE SYSTEMS

    OpenAIRE

    Belyuchenko I. S.

    2014-01-01

    Complex compost includes all elements of the periodic table and is valuable due to the complexity of its system. Among the elements forming a chemical composition of the complex compost we can identify two most important, which are distinguishing a specific character of the interaction with each other and defining the basic processes to ensure vegetation of living system - nitrogen and carbon. Nitrogen determines the rate of energy and connects with living forms of organic matter; it is inclu...

  7. Measurement of solubilities for rhodium complexes and phosphine ligands in supercritical carbon dioxide

    OpenAIRE

    Shimoyama, Yusuke; Sonoda, Masanori; Miyazaki, Kaoru; Higashi, Hidenori; Iwai, Yoshio; ARAI, Yasuhiko

    2008-01-01

    The solubilities of phosphine ligands and rhodium (Rh) complexes in supercritical carbon dioxide were measured with Fourier transform infrared (FT-IR) spectroscopy at 320 and 333 K and several pressures. Triphenylphosphine (TPP) and tris(p-trifluoromethylphenyl)-phosphine (TTFMPP) were selected as ligands for the Rh complex. The solubilities of the fluorinated ligands and complexes were compared with those of the non-fluorinated compounds. The solubilities of ligand increased up to 10 times b...

  8. Ultrasonic tomography of complex shaped carbon fiber composites

    OpenAIRE

    Zhvyrblya Vadim; Filippov German; Sedanova Elizaveta; Salchak Yana

    2016-01-01

    Non-destructive quality assurance of complex shaped objects is one of the major challenges in the variety of industrial areas. Robot-assisted ultrasound tomography is one of the common methods used for this purpose. This study proposes a tomography based on the preliminary received 3-D reconstruction results. The obtained experimental details represent the applicability of the suggested method to ensure effective quality control.

  9. Ultrasonic tomography of complex shaped carbon fiber composites

    Directory of Open Access Journals (Sweden)

    Zhvyrblya Vadim

    2016-01-01

    Full Text Available Non-destructive quality assurance of complex shaped objects is one of the major challenges in the variety of industrial areas. Robot-assisted ultrasound tomography is one of the common methods used for this purpose. This study proposes a tomography based on the preliminary received 3-D reconstruction results. The obtained experimental details represent the applicability of the suggested method to ensure effective quality control.

  10. Electrochemical study of copper-aminopurine complexes at carbon electrodes

    Czech Academy of Sciences Publication Activity Database

    Jelen, František; Hasoň, Stanislav; Kouřilová, Alena; Trnková, L.

    Alghero, 2008. s. 103. [6th International Copper Meeting, Copper and Related Metals in Biology. 11.10.2008-15.10.2008, Alghero] R&D Projects: GA AV ČR(CZ) IAA100040602; GA AV ČR(CZ) IAA400040804; GA AV ČR(CZ) KAN200040651; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : aminopurines * elimination voltammetry * copper complexes Subject RIV: BO - Biophysics

  11. Investigation of different-ligand complexes of holmium and erbium with NTA and carbonate ion

    International Nuclear Information System (INIS)

    Found out have been the optimum conditions for the formation of the lantanides (Ln) multiligand complexes with the nitriletriacetic acid (NTA) and the carbonate-ion. It has been established that the components correlation in complex compounds is equal to 1:1:1. Computed have been the values of the oscillator forces of the absorption bands, that conform to the ''supersensitive'' migration of the multiligand complexes, It is shown that the increment in the oscillator forces, the induced entering of one carbonate-ion into the Ln-NTA complex molecule conforms to about 1/4 of the oscillator forces increment during the migration from the aquo ion to the [Ln(CO3)4]5- complex carbonaceous ion

  12. Immobilisation of Alkylamine-Functionalised Osmium Redox Complex on Glassy Carbon using Electrochemical Oxidation

    International Nuclear Information System (INIS)

    The electrochemical oxidation of alkylamines provides a method for modification of carbon, and other surfaces via formation of a radical amine that reacts with the surface. Direct electrochemical oxidation of an alkylamine functional group of a redox complex provides a simple route to preparation of a redox active layer on carbon surfaces. Here we report on oxidation of an osmium redox complex, containing an alkylamine ligand distal to the metal co-ordination site, on carbon electrodes to directly produce a redox active film on the surface. The presence of the redox-active layer of osmium complexes is confirmed by cyclic voltammetry and X-Ray photoelectron spectroscopy. The average surface coverage of the attached film upon electrolysis of an [Os(2,2′-bipyridine)2(4-aminomethylpyridine)Cl].PF6 complex is 0.84 (± 0.3) × 10−10 moles cm−2, demonstrating that coverages close to that predicted for a close-packed monolayer of complex is attained. The bioelectrocatalytic activity of the modified electrode was evaluated for oxidation of glucose in presence of glucose oxidase in solution. Hence, electrochemical coupling of alkylamine functionalised osmium redox complexes provides a simple and efficient methodology for obtaining redox active monolayers on carbon surfaces with potential applications to biosensor and biofuel cell device development

  13. COMPLEX COMPOST AND CIRCULATION OF NITROGEN AND CARBON AT THE AGROLANDSCAPE SYSTEMS

    Directory of Open Access Journals (Sweden)

    Belyuchenko I. S.

    2014-03-01

    Full Text Available Complex compost includes all elements of the periodic table and is valuable due to the complexity of its system. Among the elements forming a chemical composition of the complex compost we can identify two most important, which are distinguishing a specific character of the interaction with each other and defining the basic processes to ensure vegetation of living system - nitrogen and carbon. Nitrogen determines the rate of energy and connects with living forms of organic matter; it is included as the part of protein and is a major element in determining the productivity of ecosystems. At the cycle of carbon its organic forms and carbon dioxide take a part, presenting the main factors of the processes of respiration and photosynthesis

  14. Talc-carbonate alteration of ultramafic rocks within the Leka Ophiolite Complex, Central Norway

    Science.gov (United States)

    Bjerga, A.; Konopásek, J.; Pedersen, R. B.

    2015-06-01

    Petrographic and geochemical analyses of partly and completely serpentinized and carbonated peridotites within the ultramafic section of the Leka Ophiolite Complex have been used to elucidate the evolution of alterations and identify possible fluid sources. The alterations show no evidence for any major deformation and are located along low-angle structures that were formed in a late stage of the structural evolution of the ophiolite complex. Modeling of mineral equilibria in the SiO2-MgO-FeO-Fe2O3-CaO-H2O ± CO2 system has been utilized to constrain the conditions during serpentinization and carbonation. The partly altered peridotites consist of the mineral assemblage olivine-clinopyroxene-serpentine-magnetite-brucite and formed at temperatures Talc-carbonate rocks formed by the breakdown of the serpentine in the previously formed serpentinite rock at temperatures talc-magnesite-magnetite-dolomite. Carbon isotope values determined for dolomite from crosscutting carbonate lenses within the talc-carbonate rock yield δ13C values of ~- 5 indicative of a mantle source for the carbon required for the carbonation. Oxygen isotope values δSMOW18O of ~ 10.8-11.3‰ together with initial 87Sr/86Sri = 400Ma values of 0.7029 and 0.7063, suggest dehydration of rocks with mantle affinity as a source for the fluids. Based on analytical results and field observations we propose that the formation of the talc- and carbonate-bearing alteration zones is caused by the focused infiltration of fluids that originated at the bottom of already partly serpentinized ophiolite complex during extension-driven burial at the late stage of the Caledonian orogeny.

  15. Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3)

    International Nuclear Information System (INIS)

    Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An3+ and Ln3+ cations. The study of the solubility of double carbonates (AlkLn(CO3)2,xH2O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO3)45- whereas the heaviest (Eu and Dy) form Ln(CO3)33- in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO3)45- while Dy to Lu form Ln(CO3)33-. Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO3)33- complex, specially with Cs+. Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)

  16. ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite

    Science.gov (United States)

    Bargar, J.R.; Kubicki, J.D.; Reitmeyer, R.; Davis, J.A.

    2005-01-01

    The speciation of carbonate adsorbed to hematite in air-equilibrated aqueous solutions has been studied using ATR-FTIR spectroscopy. Samples were measured over a range of pH conditions, at 0.1 M NaCl and at low ionic strength, and in H2O and D2O solutions to permit a multispecies analysis of the data. Second-derivative analyses and fits to the spectra indicate the presence of two major and two minor surface-bound carbonate species. The two major complexes coexist at near-neutral pH and low ionic strength. One of these two complexes is relatively sensitive to ionic strength, being displaced at 0.1 M NaCl, whereas the other is not. Comparison of experimental to DFT/MO-calculated frequencies suggest these two major species to be (a) a monodentate binuclear inner-sphere carbonate surface complex, and (b) a fully or partially solvated carbonate (CO32-) species that is symmetry broken and appears to reside in the structured vicinal water layers at the hematite-water interface, retained by hydrogen bonding and/or other forces. Minor carbonate complexes include diffuse layer CO32- and an unidentified inner-sphere species. Both of the dominant species observed here are likely to be significant controls of the surface charge and sorptive properties of Fe-oxides. Copyright ?? 2005 Elsevier Ltd.

  17. Chemical behaviour of Pu and Am: Hydrolysis reaction in brine solutions, carbonate complexation, α-radiolysis, humate complexation and speciation

    International Nuclear Information System (INIS)

    The chemical behaviour of transuranic elements (Pu and Am) has been investigated in saline solution of different NaCl concentrations in the near neutral pH range. Important reactions considered are hydrolysis, carbonate complexation, redox reaction, alpha-radiolysis, colloid generation and humate complexation. Hydrolysis reactions are studied for Pu(VI) in 3.6 M NaCl and for Am(III) in 0.1 M and 0.6 M NaCl solution, whereas carbonate complexation of Pu(IV) and Am(III) is investigated in HCO3-/CO32- solution of varying pH. Consequences of alpha-radiolysis in NaCl solution are thoroughly analysed as for the Eh change due to Cl- oxidation and the oxidation of Pu(IV) and Am(III). In groundwaters colloid generation of Am(III), particularly pseudocolloids, is characterized and correlated with the concentration of humic substances. Humate complexation under discussion deals mainly with the stabilization of Am(III) in a given groundwater through its colloid generation. (orig.)

  18. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    Science.gov (United States)

    Iyer, Vivekanantan S.; Vollhardt, K. Peter C.

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  19. Range of engineering-geological properties for some carbonate rock complexes for Balkan peninsula

    International Nuclear Information System (INIS)

    The Carbonate Rock masses are a geological media with extremely complex states and properties, which has a certain influences on the mechanical and hydraulic behavior during construction and exploitation of engineering structures. Practical aspects of the problem analysis arise from the fact that the areas of Bosnia and Herzegovina, Macedonia and the entire Balkans is characterized by presence of wide areas covered with carbonate complexes, where large number of complex engineering structures have been, or shall be constructed in the future. In this context, their engineering-geological modeling is still a practical and scientific challenge. The analysis of engineering- geological properties is one of the main steps in forming of analytical and geotechnical models for complex rock structures. This article gives a data about the range for these properties, according to the results from an extensive investigation program. Some original correlations and testing results are given and they are compared with some published relations from the world. (Author)

  20. Complexes of carbon nanotubes with oligonucleotides in thin Langmuir-Blodgett films to detect electrochemically hybridization

    Science.gov (United States)

    Egorov, A. S.; Egorova, V. P.; Krylova, H. V.; Lipnevich, I. V.; Orekhovskaya, T. I.; Veligura, A. A.; Govorov, M. I.; Shulitsky, B. G.

    2014-10-01

    Self-assembled complexes consisting of thin multi-walled carbon nanotubes (MWCNTs) and DNA-oligonucleotides which are able to a cooperative binding to complementary oligonucleotides have been investigated. It was establised a high-performance charge transport in nanostructured Langmuir-Blodgett complexes thin MWCNTs/DNA. A method to electrochemically detect DNA hybridization on the self-organized structures has been proposed.

  1. Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes.

    Science.gov (United States)

    Huang, Kewei; Saha, Avishek; Dirian, Konstantin; Jiang, Chengmin; Chu, Pin-Lei E; Tour, James M; Guldi, Dirk M; Martí, Angel A

    2016-07-21

    Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs. PMID:27353007

  2. Formation of oxygen complexes in controlled atmosphere at surface of doped glassy carbon

    Indian Academy of Sciences (India)

    Aleksandra A Perić-Grujić; Tatjana M Vasiljević; Olivera M Nešković; Miomir V Veljković; Zoran V Laušević; Mila D Laušević

    2006-10-01

    The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the samples was cleaned under vacuum up to 1273 K. Specific functional groups, subsequently formed under dry CO2 or O2 atmosphere on the surface of boron-doped and phosphorus-doped glassy carbon samples, were examined using the temperature-programmed desorption method combined with mass spectrometric analysis. Characterization of surface properties of undoped and doped samples has shown that in the presence of either boron or phosphorus heteroatoms, a lower amount of oxygen complexes formed after CO2 exposure, while, typically, higher amount of oxygen complexes formed after O2 exposure. It has been concluded that the surface of undoped glassy carbon has a greater affinity towards CO2, while in the presence of either boron or phosphorus heteroatoms, the glassy carbon surface affinity becomes greater towards O2, under experimental conditions.

  3. Study of IV B elements carbonate complexes 1. Stability constant of thorium (IV) pentacarbonate complex

    International Nuclear Information System (INIS)

    A method for the solvent extraction of thorium (IV) by chelation and neutronic activation analysis, allows the determination of stability constant of thorium (IV) pentacarbonate complexe at an ionic strength of 1.0 and 2.5: log β = 26.2 ± 0.2 and 26.3 ± 0.2. 10 refs

  4. Human carbonic anhydrase II as a host for piano-stool complexes bearing a sulfonamide anchor.

    Science.gov (United States)

    Monnard, Fabien W; Heinisch, Tillmann; Nogueira, Elisa S; Schirmer, Tilman; Ward, Thomas R

    2011-08-01

    d(6)-piano-stool complexes bearing an arylsulfonamide anchor display sub-micromolar affinity towards human Carbonic Anhydrase II (hCA II). The 1.3 Å resolution X-ray crystal structure of [(η(6)-C(6)Me(6))Ru(bispy 3)Cl](+)⊂ hCA II highlights the nature of the host-guest interactions. PMID:21706094

  5. Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • We have determined thermodynamic stabilities of Fe(III)-carbonate species. • We have determined the effect of those species on the solubility of ferrihydrite. • Results. • Highlight the importance of two Fe(III)-carbonate: FeOHCO3 and Fe(CO3)33−. - Abstract: The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO2 varying between (0.982–98.154 kPa) at 25 °C. The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO3 and Fe(CO3)33−, with formation constants log*β°1,1,1 = 10.76 ± 0.38 and log β°1,0,3 = 24.24 ± 0.42, respectively. The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO2 and at T = (25 ± 1) °C, as log*Ks,0 = 1.19 ± 0.41. The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO2-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers

  6. PALADYN, a comprehensive land surface-vegetation-carbon cycle model of intermediate complexity

    Science.gov (United States)

    Willeit, Matteo; Ganopolski, Andrey

    2016-04-01

    PALADYN is presented, a new comprehensive and computationally efficient land surface-vegetation-carbon cycle model designed to be used in Earth system models of intermediate complexity for long-term simulations and paleoclimate studies. The model treats in a consistent manner the interaction between atmosphere, terrestrial vegetation and soil through the fluxes of energy, water and carbon. Energy, water and carbon are conserved. The model explicitly treats permafrost, both in physical processes and as important carbon pool. The model distinguishes 9 surface types of which 5 are different vegetation types, bare soil, land ice, lake and ocean shelf. Including the ocean shelf allows to treat continuous changes in sea level and shelf area associated with glacial cycles. Over each surface type the model solves the surface energy balance and computes the fluxes of sensible, latent and ground heat and upward shortwave and longwave radiation. It includes a single snow layer. The soil model distinguishes between three different macro surface types which have their own soil column: vegetation and bare soil, ice sheet and ocean shelf. The soil is vertically discretized into 5 layers where prognostic equations for temperature, water and carbon are consistently solved. Phase changes of water in the soil are explicitly considered. A surface hydrology module computes precipitation interception by vegetation, surface runoff and soil infiltration. The soil water equation is based on Darcy's law. Given soil water content, the wetland fraction is computed based on a topographic index. Photosynthesis is computed using a light use efficiency model. Carbon assimilation by vegetation is coupled to the transpiration of water through stomatal conductance. The model includes a dynamic vegetation module with 5 plant functional types competing for the gridcell share with their respective net primary productivity. Each macro surface type has its own carbon pools represented by a litter, a fast

  7. Extraction of cobalt ion from textile using a complexing macromolecular surfactant in supercritical carbon dioxide

    International Nuclear Information System (INIS)

    Cobalt ion under the form of cobalt nitrate is removed from a textile lab coat using supercritical carbon dioxide extraction. The process involves a macromolecular additive of well-defined architecture, acting both as a surfactant and a complexing agent. The extraction efficiency of cobalt reaches 66% when using a poly(1,1,2,2-tetrahydroperfluoro-decyl-acrylate-co-vinyl-benzylphosphonic diacid) gradient copolymer in the presence of water at 160 bar and 40 C. The synergy of the two additives, namely the copolymer and water which are useless if used separately, is pointed out. The potential of the supercritical carbon dioxide process using complexing macromolecular surfactant lies in the ability to modulate the complexing unit as a function of the metal as well as the architecture of the surface-active agent for applications ranging for instance from nuclear decontamination to the recovery of strategic metals. (authors)

  8. Carbon 13 nuclear magnetic resonance spectroscopy of cobalt(III) complexes with flexible tetraamine ligands

    Energy Technology Data Exchange (ETDEWEB)

    Brubaker, G.R.; Johnson, D.W.

    1983-10-01

    Carbon 13 NMR was found to be an extremely sensitive probe of the stereochemistry of this series of diamagnetic ''Werner'' complexes. Our interpretation is based upon two parameters, the donation of electron density to the metal and the steric perturbation required for coordination. The different symmetry of the complexes often permits determination of stereochemistry from the electronic spectrum. In addition, other methods including vibrational spectroscopy and proton NMR, have been used with some success to determine stereochemistry. These methods suffer, however, from a lack of sensitivity, especially in complexes with unsymmetrical ligands. In the course of continuing study of the stereochemistry of six coordinate transition metal complexes, we have investigated a large variety of cobalt(III) complexes with various tetraamine ligands.

  9. Complex formation during dissolution of metal oxides in molten alkali carbonates

    DEFF Research Database (Denmark)

    Li, Qingfeng; Borup, Flemming; Petrushina, Irina;

    1999-01-01

    as the partial pressure of carbon dioxide varies. By combination of solubility and electromotive force measurements, a model is constructed assuming the dissolution involves complex formation. The possible species for lead are proposed to be [Pb(CO3)(2)](-2) and/or [Pb(CO3)(3)](-4). A similar complex......Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe2O3,and Bi2O3 in molten Li/K carbonates have been measured at 650 degrees C under...... carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe2O3 and Bi2O3 remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution...

  10. Deriving a CO2-permselective carbon membrane from a multilayered matrix of polyion complexes.

    Science.gov (United States)

    Chen, Xinwei; Khoo, Kian Guan; Kim, Min Woo; Hong, Liang

    2014-07-01

    A multilayered assembly consisting of polyion complexes was developed over porous ceramic as a unique precursor for a carbon membrane (CM). This specific layer was attained through in situ polymerization of N-methylpyrrole (mPy) over a prime coating layer of poly(4-styrenesulfonic acid) (PSSA) with an embedded oxidant on the ceramic surface. Extensive ion-pair complexation between the sulfonic acid groups of PSSA and the tertiary amine groups of the resulting poly(N-methylpyrrole) (PmPy) sustains this assembly layer. Incorporating cetyltrimethylammonium bromide (CTAB) into the PSSA is critical in facilitating the infiltration of mPy into the PSSA layer and promoting interfacial contact between the two polymers. Upon pyrolysis, the precursor coating was collectively converted into a carbon composite matrix. Such copyrolysis restrains the grain sizes of the carbonized PmPy, thereby halting defects in the resultant carbonaceous matrix. The gas separation performances of the CMs obtained at various graphitization temperatures showed that the least graphitized carbon matrix exhibited the best selectivity of CO2/CH4 = 167 with a CO2 permeability of 7.19 Barrer. This specific feature is attributed to both imine and imide pendant groups that function as selective adsorption sites for CO2 in the carbon skeleton. PMID:24905039

  11. Probing the complex ion structure in liquid carbon at 100 GPa.

    Science.gov (United States)

    Kraus, D; Vorberger, J; Gericke, D O; Bagnoud, V; Blažević, A; Cayzac, W; Frank, A; Gregori, G; Ortner, A; Otten, A; Roth, F; Schaumann, G; Schumacher, D; Siegenthaler, K; Wagner, F; Wünsch, K; Roth, M

    2013-12-20

    We present the first direct experimental test of the complex ion structure in liquid carbon at pressures around 100 GPa, using spectrally resolved x-ray scattering from shock-compressed graphite samples. Our results confirm the structure predicted by ab initio quantum simulations and demonstrate the importance of chemical bonds at extreme conditions similar to those found in the interiors of giant planets. The evidence presented here thus provides a firmer ground for modeling the evolution and current structure of carbon-bearing icy giants like Neptune, Uranus, and a number of extrasolar planets. PMID:24483747

  12. Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

    Directory of Open Access Journals (Sweden)

    Jha Prashant

    2009-08-01

    Full Text Available Abstract Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI, U(V, U(IV, U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG, and U-2-Keto-3-doxyoctanoate (KDO with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI to U(IV is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V- and U(IV-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI and U(IV rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids.

  13. EXAFS investigations of earth-alkaline metal uranyl tri-carbonate complexes

    International Nuclear Information System (INIS)

    Carbonate and bicarbonate are the common anions found in significant concentrations in many natural waters, and are exceptionally strong complexation agents for actinide ions. Seepage, flooding and mining waters from the uranium mining area in the south-east of Germany (Saxony and Thuringia) contain relatively high amounts of magnesium, calcium, carbonate and sulphate ions. In these waters the pH values range from 7.0 to 8.0 and the uranium content is about 0.02 mmol/L where magnesium, calcium and carbonate concentrations are 11.6 mmol/L, 6.9 mmol/L and 3.9 mmol/L, respectively. The existence of the natural complexes Ca2UO2(CO3)3(aq) and Mg2UO2(CO3)3(aq) were recently able to be confirmed by spectroscopic measurements. We performed extended X-ray absorption fine structure (EXAFS) measurements at the uranium LIII-edge to study the structures of these complexes. The results obtained from these complex solutions are compared with those from the corresponding EXAFS and XRD data related to the secondary minerals of uranium, liebigite, Ca2[UO2(CO3)3] . 10 H2O and bayleyite, Mg2[UO2(CO3)3]-10 H2O and they are in good agreement. (authors)

  14. Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.

    Science.gov (United States)

    Williams, B S; Goldberg, K I

    2001-03-21

    The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

  15. Joint Optimal Production Planning for Complex Supply Chains Constrained by Carbon Emission Abatement Policies

    Directory of Open Access Journals (Sweden)

    Longfei He

    2014-01-01

    Full Text Available We focus on the joint production planning of complex supply chains facing stochastic demands and being constrained by carbon emission reduction policies. We pick two typical carbon emission reduction policies to research how emission regulation influences the profit and carbon footprint of a typical supply chain. We use the input-output model to capture the interrelated demand link between an arbitrary pair of two nodes in scenarios without or with carbon emission constraints. We design optimization algorithm to obtain joint optimal production quantities combination for maximizing overall profit under regulatory policies, respectively. Furthermore, numerical studies by featuring exponentially distributed demand compare systemwide performances in various scenarios. We build the “carbon emission elasticity of profit (CEEP” index as a metric to evaluate the impact of regulatory policies on both chainwide emissions and profit. Our results manifest that by facilitating the mandatory emission cap in proper installation within the network one can balance well effective emission reduction and associated acceptable profit loss. The outcome that CEEP index when implementing Carbon emission tax is elastic implies that the scale of profit loss is greater than that of emission reduction, which shows that this policy is less effective than mandatory cap from industry standpoint at least.

  16. Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha M.

    2012-01-01

    relatively inert carbonaceous dust from the ISM into the vital organic precursors to life such as amino acids and sugars intimately mixed with dust and ice in primitive planetesimals. Since the number of carbon atoms entering the Solar Nebula as dust exceeds the number of atoms entering the nebula as oxide grains. the formation of large quantities of complex organic molecules may represent the largest single chemical cycle in the nebula.

  17. Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes

    Science.gov (United States)

    Huang, Kewei; Saha, Avishek; Dirian, Konstantin; Jiang, Chengmin; Chu, Pin-Lei E.; Tour, James M.; Guldi, Dirk M.; Martí, Angel A.

    2016-07-01

    Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs.Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs

  18. Mitochondrial gamma carbonic anhydrases are required for complex I assembly and plant reproductive development.

    Science.gov (United States)

    Fromm, Steffanie; Braun, Hans-Peter; Peterhansel, Christoph

    2016-07-01

    Complex I of the mitochondrial electron transport chain (mETC) in plants contains an extra domain that is made up from proteins homologous to prokaryotic gamma-carbonic anhydrases (γCA). This domain has been suggested to participate in complex I assembly or to support transport of mitochondrial CO2 to the chloroplast. Here, we generated mutants lacking CA1 and CA2 - two out of three CA proteins in Arabidopsis thaliana. Double mutants were characterized at the developmental and physiological levels. Furthermore, the composition and activity of the mETC were determined, and mutated CA versions were used for complementation assays. Embryo development of double mutants was strongly delayed and seed development stopped before maturation. Mutant plants could only be rescued on sucrose media, showed severe stress symptoms and never produced viable seeds. By contrast, callus cultures were only slightly affected in growth. Complex I was undetectable in the double mutants, but complex II and complex IV were upregulated concomitant with increased oxygen consumption in mitochondrial respiration. Ectopic expression of inactive CA variants was sufficient to complement the mutant phenotype. Data indicate that CA proteins are structurally required for complex I assembly and that reproductive development is dependent on the presence of complex I. PMID:26889912

  19. Nature of Non-Fickian Solute Transport in Complex Heterogeneous Porous Media - Carbonates

    Science.gov (United States)

    Bijeljic, B.; Mostaghimi, P.; Blunt, M. J.

    2011-12-01

    Despite the range of significant practical applications of solute transport, including the long-term fate of nuclear waste repositories, secure storage of CO2 and improved oil recovery, even the qualitative behavior of most rocks is uncertain: vast carbonate sedimentary basins contain more than half the world's current oil reserves yet experimental data on transport in carbonates is scant. The relationship between pore structure, velocity field and transport remains unknown, particularly for heterogeneous carbonates. We simulate solute transport through 3D μ-CT images of different rock samples, representing geological media of increasing pore-scale complexity: a sandpack, a Berea sandstone and a Portland limestone. A finite-difference Stokes solver is employed to compute the flow field and transport particles semi-analytically along streamlines to represent advection with a random motion to model diffusion. We predict the propagators measured on similar cores in Nuclear Magnetic Resonance (NMR) experiments. Dispersion coefficient dependence on Peclet number is shown to have different scaling for complex carbonates. The behavior is explained using continuous time random walks with a truncated power-law distribution of travel times: transport is qualitatively different for the complex limestone compared to the sandstone or sandpack, with long tailing, an almost immobile peak concentration and a very slow approach to asymptotic dispersion. We demonstrate the different nature of non-Fickian transport in carbonates by analyzing the transit time probabilities ψ(τ) of traveling between two neighboring voxels for Portland carbonate that show an approximately power-law dependence of travel times ψ(τ) ~ τ -1-β with a slope corresponding to β = 0.7, as shown in Fig.1. The comparison with ψ(τ) of the sandpack and Berea sandstone for Pe = ∝ indicates quantitatively different generic behavior, as the sandpack and sandstone have slope corresponding to β = 1.8 (two

  20. Hydroxyl, water, ammonia, carbon monoxide and neutral carbon towards the Sgr A complex

    CERN Document Server

    Karlsson, Roland; Hjalmarson, Åke; Winnberg, Anders; Fathi, Kambiz; Frisk, Urban; Olberg, Michael

    2013-01-01

    We observed OH, H$_2$O, HN$_3$, C$^{18}$O, and C$_I$ towards the +50 km/s cloud (M-0.02-0.07), the CND and the +20 km/s (M-0.13-0.08) cloud in the Sgr A complex with the VLA, Odin and SEST. Strong OH absorption, H$_2$O emission and absorption lines were seen at all three positions. Strong C$^{18}$O emissions were seen towards the +50 and +20 km/s clouds. The CND is rich in H$_2$O and OH, and these abundances are considerably higher than in the surrounding clouds, indicating that shocks, star formation and clump collisions prevail in those objects. A comparison with the literature reveals that it is likely that PDR chemistry including grain surface reactions, and perhaps also the influences of shocks has led to the observed abundances of the observed molecular species studied here. In the redward high-velocity line wings of both the +50 and +20 km/s clouds and the CND, the very high H$_2$O abundances are suggested to be caused by the combined action of shock desorption from icy grain mantles and high-temperatu...

  1. Highly fluorous complexes of ruthenium and osmium and their solubility in supercritical carbon dioxide.

    Science.gov (United States)

    Berven, Bradley M; Koutsantonis, George A; Skelton, Brian W; Trengove, Robert D; White, Allan H

    2009-12-21

    A series of ruthenium and osmium complexes containing highly fluorous diphosphine ligands (F)P(wedge)P(F) = (F(13)C(6)C(6)H(4)-p)(2)P(CH(2))(2)P(p-C(6)H(4)C(6)F(13))(2) (dfppe) and (F(13)C(6)C(6)H(4)-p)(2)P(CH(2))(3)P(p-C(6)H(4)C(6)F(13))(2) (dfppp) has been prepared. The fluorous diphosphine ligands incorporate four C(6)F(13) "fluoro-ponytails", and these have been effective in solubilizing the complexes in supercritical carbon dioxide (scCO(2)). Precise solubility measurements in scCO(2) were performed for some of the complexes. The new complexes [MX(2)((F)P(wedge)P(F))(2)] and [MX((F)P(wedge)P(F))(eta-C(5)H(5))], M = Ru, Os, X = Cl, Br, have been characterized by a number of spectroscopic techniques and their electrochemical properties measured, three of the ruthenium complexes also being characterized by single-crystal X-ray studies. The noncovalent interactions observed in the X-ray structures have been analyzed by the Hirshfeld surface approach, putting them on a more solid footing. The fluorinated complexes show significantly different solvation properties from those of the analogous unfluorinated compounds, particularly with respect to their behavior in common organic solvents and their good scCO(2) solubility. PMID:19938863

  2. Complex resistivity spectra in relation to multiscale pore geometry in carbonates and mixed-siliciclastic rocks

    Science.gov (United States)

    Norbisrath, Jan Henrik

    Carbonate rocks are known to have complex and heterogeneous pore structures, which result from their biogenic origin and strong affinity for diagenetic processes that change their pore structure after burial. The combination of sheer endless variations of precursor biogenic material, depositional environments, and diagenetic effects results in rocks that are interesting to study but intricate to understand. Many schemes to categorize the diversity of carbonate rocks are in use today; most are based on the macropore structure and qualitative thin-section analysis. Many studies, however, acknowledge that micropores have a significant influence on the macroscopic petrophysical rock properties, which are essential to determine reservoir quality. Micropores are, by definition, smaller than the thickness of a thin-section (cementation factors (m) in rocks with such microporosity type. The BIB-SEM method is also used on a dataset of mixed carbonate-siliciclastic (mudrock) samples with high kerogen and pyrite content. Results show that the nanopore geometry here has little influence on cementation factors, and instead porosity is the main control on m in mudrocks. Cementation factors are crucial for estimates of oil-in-place and water saturation in a wireline application, and a slight change of (assumed) cementation factor can change the interpreter's evaluation from dry hole to discovery. Therefore, accurate determination of cementation factors is a critical task in formation evaluation, similar to accurate estimates of permeability. To achieve this goal, this dissertation utilizes a new approach of using complex resistivity spectra (CRS) to assess the pore geometry and its resulting electrical and fluid flow properties. Specifically, frequency dispersion of complex resistivity in the kHz range is used as input for a new model to predict cementation factor and permeability in a wide variety of core plug samples. The underlying concept that relates CRS to flow properties

  3. Adsorption of some metal complexes derived from acetyl acetone on activated carbon and purolite S-930

    Directory of Open Access Journals (Sweden)

    Salam A.H. Al-Ameri

    2014-12-01

    Full Text Available A new Schiff base (HL derived from condensation of p-anisidine and acetyl acetone has been prepared and used as a chelating ligand to prepare Cr(III, Mn(II, Co(II, Ni(II and Cu(II complexes. The study of the nature of these complexes formed in ethanol solution following the mole ratio method (2:1, L:M gave results which were compared successfully with these obtained from isolated solid state studies. These studies revealed that the complexes having square planner geometry of the type (ML2, M = Co(II, Ni(II and Cu(II, and octahedral geometry of the type [CrIIIL2(H2O2]Cl and [MNIIL2(H2O2]. The adsorption studies of three complexes Cr(III, Mn(II, and Co(II on activated carbon, H and Na-forms of purolite S-930 resin show high adsorption percentage for Cr(III on purolite S-930 due to ion exchange interaction compared with high adsorption of neutral Mn(II, Co(II complexes on activated charcoal. Linear plot of log Qe versus log Ce showed that the adsorption isotherm of these three complexes on activated carbon, H and Na-forms of purolite S-930 surface obeys Freundlich isotherm and was similar to S-curve type according to Giles classification which investigates heterogeneous adsorption. The regression values indicate that the adsorption data for these complexes fitted well within the Freundlich isothermal plots for the concentration studied. The accuracy and precision of the concentration measurements of these complexes were determined by preparing standard laboratory samples, the results show relative error ranging from ±1.08 to 5.31, ±1.04 to 4.82 and ±0.28 to 3.09 and the relative standard deviation did not exceed ±6.23, ±2.77 and ±4.38% for A1, A2 and A3 complexes, respectively.

  4. Preparation of Carbon Nanotubes by the Catalysis of Polymer Metal Complex on Porous Al203 Matrix

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ At present, synthesis of carbon nanotubes (CNTs) is normally conducted on a vapor-to-solid interface at ca. 500-3500℃ via various vapor phase methods, such as are discharge, laser ablation, catalytic pyrolysis and chemical vapor deposition, etc.1-2 Recently, channel materials (such as channels of alumina and of AlPO4-5 zeolite) 3 have been utilized as solid-state templates to grow CNTs inside the channel. Here we described a novel method to prepare the carbon nanotubes based on the decomposition of C2H2 gas on the Co-Ni catalyst anchored by polymer complex on the porous A12O3 matrix. The degree of graphitization of synthesized CNTs and catalysts are of great interest.

  5. Preparation of Carbon Nanotubes by the Catalysis of Polymer Metal Complex on Porous Al203 Matrix

    Institute of Scientific and Technical Information of China (English)

    SHI; YanLi

    2001-01-01

    At present, synthesis of carbon nanotubes (CNTs) is normally conducted on a vapor-to-solid interface at ca. 500-3500℃ via various vapor phase methods, such as are discharge, laser ablation, catalytic pyrolysis and chemical vapor deposition, etc.1-2 Recently, channel materials (such as channels of alumina and of AlPO4-5 zeolite) 3 have been utilized as solid-state templates to grow CNTs inside the channel. Here we described a novel method to prepare the carbon nanotubes based on the decomposition of C2H2 gas on the Co-Ni catalyst anchored by polymer complex on the porous A12O3 matrix. The degree of graphitization of synthesized CNTs and catalysts are of great interest.  ……

  6. Optical approaches to examining the dynamics of dissolved organic carbon in optically complex inland waters

    International Nuclear Information System (INIS)

    Optical approaches were developed to examine the relationship between the optically active and the optically inactive fractions of dissolved organic carbon in inland waters. A multiple linear regression model was developed on the basis of an extensive dataset from Taihu Lake, and validated employing data from another large shallow eutrophic lake (Chaohu Lake) in southern China. The model was used to estimate the concentration of dissolved organic matter (n = 191) using the absorption characteristics of its chromophoric fraction with a high correlation coefficient (R2 = 0.62) and a low root mean squared error (RMSE = 9.67%). This intra-ecosystem validity allows us to improve our understanding of carbon dynamics using optical remote sensing approaches for these optically complex lakes, where multiple sources and sinks of dissolved organic matter were present. (letter)

  7. A Ni-Fe Layered Double Hydroxide-Carbon Nanotube Complex for Water Oxidation

    CERN Document Server

    Gong, Ming; Wang, Hailiang; Liang, Yongye; Wu, Justin Zachary; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

    2013-01-01

    Highly active, durable and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions including water splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel iron layered double hydroxide nanoplates on mildly oxidized multi-walled carbon nanotubes. Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-layered double hydroxide. The nanoplates were covalently attached to a network of nanotubes, affording excellent electrical wiring to the nanoplates. The ultra-thin Ni-Fe layered double hydroxide nanoplates/carbon nanotube complex was found to exhibit unusually high electro-catalytic activity and stability for oxygen evolution and outperformed commercial precious metal Ir catalysts.

  8. Synergistic strengthening of polyelectrolyte complex membranes by functionalized carbon nanotubes and metal ions.

    Science.gov (United States)

    Liu, Tao; An, Quan-Fu; Zhao, Qiang; Wu, Jia-Kai; Song, Yi-Hu; Zhu, Bao-Ku; Gao, Cong-Jie

    2015-01-01

    Hydrophilic polymers have garnered much attention due to their critical roles in various applications such as molecular separation membranes, bio-interfaces, and surface engineering. However, a long-standing problem is that their mechanical properties usually deteriorate at high relative humidity (RH). Through the simultaneous incorporation of functionalized carbon nanotubes and copper ions (Cu(2+)), this study introduces a facile method to fabricate high strength polyelectrolyte complex nanohybrid membranes resistant to high RH (90%). For example, the tensile strength of the nanohybrid membranes is 55 MPa at 90% RH (80% of the original value at 30% RH). These results are explained by copper ions depressing the swelling degree of the membrane, and functionalized carbon nanotubes promoting stress transfer between the polymer matrix and them. The nanohybrid membranes are efficient in separating water/alcohol mixtures containing relatively high water content (up to 30 wt%), whereas common hydrophilic polymer membranes usually suffer from excessive swelling under this condition. PMID:25586650

  9. Charge transport and optical properties of the complexes of indigo wrapped over carbon nanotubes.

    Science.gov (United States)

    Joshi, Ankita; Ramachandran, C N

    2016-05-18

    A new molecular system comprising the non-covalently functionalized complexes of single walled (6,6) carbon nanotubes (SWCNTs) of finite length with indigo is proposed based on the dispersion-corrected density functional theory calculations. In the complexes viz. the dyad and triad, indigo is wrapped over carbon nanotubes in the ratio of 1 : 1 and 2 : 1, respectively. A comprehensive study of stabilization energy, ionization energy, electron affinity, the energy gap between the highest occupied and lowest unoccupied molecular orbitals (ΔELUMO-HOMO), and absorption spectra unravels the structure-property relationship of the complexes. The energy gap of ∼1 eV between the HOMO and the LUMO of the complexes suggests that they can be semiconductive. The energy levels of the frontier molecular orbitals of indigo and CNT suggest the possibility of the photoinduced charge transfer between them. Using the charge hopping rate based on Marcus theory, a hole mobility as high as 8.77 cm(2) V(-1) s(-1) is obtained for the dyad. For both the dyad and triad, a higher value of hole mobility than electron mobility is observed, thereby suggesting them to be useful for p-type semiconductor devices. The time-dependent density functional theory (TD-DFT) calculations predict that the absorption of indigo-CNT complexes occurs in the visible and the near-infrared regions finding applications in organic light emitting diodes (OLEDs). Furthermore, the effects of the length and the capping of CNTs as well as the orientation of indigo over the CNTs on the charge transport properties are also discussed. PMID:27156536

  10. Heterologous Production of an Energy-Conserving Carbon Monoxide Dehydrogenase Complex in the Hyperthermophile Pyrococcus furiosus.

    Science.gov (United States)

    Schut, Gerrit J; Lipscomb, Gina L; Nguyen, Diep M N; Kelly, Robert M; Adams, Michael W W

    2016-01-01

    Carbon monoxide (CO) is an important intermediate in anaerobic carbon fixation pathways in acetogenesis and methanogenesis. In addition, some anaerobes can utilize CO as an energy source. In the hyperthermophilic archaeon Thermococcus onnurineus, which grows optimally at 80°C, CO oxidation and energy conservation is accomplished by a respiratory complex encoded by a 16-gene cluster containing a CO dehydrogenase, a membrane-bound [NiFe]-hydrogenase and a Na(+)/H(+) antiporter module. This complex oxidizes CO, evolves CO2 and H2, and generates a Na(+) motive force that is used to conserve energy by a Na(+)-dependent ATP synthase. Herein we used a bacterial artificial chromosome to insert the 13.2 kb gene cluster encoding the CO-oxidizing respiratory complex of T. onnurineus into the genome of the heterotrophic archaeon, Pyrococcus furiosus, which grows optimally at 100°C. P. furiosus is normally unable to utilize CO, however, the recombinant strain readily oxidized CO and generated H2 at 80°C. Moreover, CO also served as an energy source and allowed the P. furiosus strain to grow with a limiting concentration of sugar or with peptides as the carbon source. Moreover, CO oxidation by P. furiosus was also coupled to the re-utilization, presumably for biosynthesis, of acetate generated by fermentation. The functional transfer of CO utilization between Thermococcus and Pyrococcus species demonstrated herein is representative of the horizontal gene transfer of an environmentally relevant metabolic capability. The transfer of CO utilizing, hydrogen-producing genetic modules also has applications for biohydrogen production and a CO-based industrial platform for various thermophilic organisms. PMID:26858706

  11. Migration of dissolved organic carbon in biochars and biochar-mineral complexes

    OpenAIRE

    Yun Lin; Paul Munroe; Stephen Joseph; Rita Henderson

    2012-01-01

    The objective of this work was to determine the contribution of dissolved organic carbon (DOC) from a biochar mineral complex (BMC), so as to better understand the interactions between DOC, biochar, clay, and minerals during thermal treatment, and the effects of BMC on amended soils. The BMC was prepared by heating a mixture of a H3PO4-treated saligna biochar from Acacia saligna, clays, other minerals, and chicken manure. The BMC was applied to a sandy loam soil in Western Australia, where wh...

  12. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    International Nuclear Information System (INIS)

    Organic aerosols comprise approximately 30% by mass of the total fine particulate matter present in urban atmospheres. The chemical composition of such aerosols is complex and reflects input from multiple sources of primary emissions to the atmosphere, as well as from secondary production of carbonaceous aerosol species via photochemical reactions. To identify discrete sources of fine carbonaceous particles in urban atmospheres, analytical methods must reconcile both bulk chemical and molecular properties of the total carbonaceous aerosol fraction. This paper presents an overview of the analytical protocol developed and used in a study of the major sources of fine carbon particles emitted to an urban atmosphere. 23 refs., 1 fig., 2 tabs

  13. Carbon monoxide migratory insertion - A comparison of cationic and neutral palladium(II) complexes

    International Nuclear Information System (INIS)

    With the use of ANSTO's resources and expertise and with support from AINSE, we have carried out extensive computer modelling on the mechanism of the palladium catalysed carbonylation reaction, a process which is used industrially in the conversion of carbon monoxide into biodegradable polymers. In this project, experimental and theoretical work has focussed on using Pd(II) complexes containing pyridine carboxylate ligands (NC5H4COO) to explore the fundamental mechanistic steps. The results for subsequent steps in the catalytic cycle are presented and their implication for the design of more efficient catalysts are discussed

  14. The Complex Relationship between Metals and Carbonic Anhydrase: New Insights and Perspectives

    OpenAIRE

    Maria Giulia Lionetto; Roberto Caricato; Maria Elena Giordano; Trifone Schettino

    2016-01-01

    Carbonic anhydrase is a ubiquitous metalloenzyme, which catalyzes the reversible hydration of CO2 to HCO3 − and H+. Metals play a key role in the bioactivity of this metalloenzyme, although their relationships with CA have not been completely clarified to date. The aim of this review is to explore the complexity and multi-aspect nature of these relationships, since metals can be cofactors of CA, but also inhibitors of CA activity and modulators of CA expression. Moreover, this work analyzes n...

  15. Laser-induced synthesis of a nanostructured polymer-like metal-carbon complexes

    Science.gov (United States)

    Arakelian, S.; Kutrovskaya, S.; Kucherik, A.; Osipov, A.; Povolotckaia, A.; Povolotskiy, A.; Manshina, A.

    2016-04-01

    Synthesis of nanotructured metal-carbon materials by laser irradiation is an actual branch of laser physics and nanotechnology. Laser sources with different pulse duration allow changing the heating rate with realization of different transition scenarios and synthesis materials with various physical properties. We study the process of the formation of nanostructured metal-clusters and complexes using laser irradiation of colloidal systems which were consisted of carbon micro- nanoparticles and nanoparticles of noble metals. For carbon nanoparticles synthesis we use the method of laser ablation in liquid. For the realization of different regimes of laser surface modification of the target (glassycarbon and shungite) and the formation of micro- nanoparticles in a liquid the YAG:Nd laser with a pulse duration from 0.5 ms up to 20 ms (pulse energy up to 50J) was applied. We have used the CW-laser with moderate intensity in liquid (water or ethanol) for nanoparticle of noble metals synthesis. Thus, colloidal systems were obtained by using CW-laser with λ = 1.06 μm, I ~ 105-6 W/cm2, and t = 10 min. The average size of resulting particles was approximately about 10 to 100 nm. The nanoparticle obtaining was provided in the colloidal solution with different laser parameters. In this work we have investigated the mechanism of the metal-carbon cluster formation during the process of irradiation of colloidal system which were consisted of separate carbon, silver and gold nanoparticles. This system was irradiated by nanosecond laser (100 ns) with average power up to 50W.

  16. Synthesis of the Multinuclear Cobaloxime Complexes via Click Chemistry as Catalysts for the Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides

    Indian Academy of Sciences (India)

    Ahmet Kilic; Armagan Keles; Emine Aytar; Mustafa Durgun; Mahmut Ulusoy

    2015-09-01

    In this study, the structurally similar multinuclear cobaloxime complexes based on dioxime ligands were synthesized and characterized as trinuclear complexes with respect to varied axial groups. The multinuclear cobaloxime complexes were characterized by 1H, 13C-NMR, FT-IR, UV-Vis, LC-MS spectra, melting point and magnetic susceptibility measurements. These multinuclear cobaloxime complexes have been successfully applied to the synthesis of cyclic carbonates from CO2 and epoxides under optimized conditions and with-out using any solvent. All multinuclear cobaloxime complexes obtained by click chemistry are good catalysts for the cycloaddition of CO2 to different epoxides in the presence of pyridine as a co-catalyst. Additionally, the effects of epoxides, bases, temperature, pressure, and time on the yield of cyclic carbonates were investigated.

  17. Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes

    Science.gov (United States)

    Gupta, Ayush; Blakemore, James D.; Brunschwig, Bruce S.; Gray, Harry B.

    2016-03-01

    We report the synthesis and surface immobilization of two new pyrene-appended molecular metal complexes: a ruthenium tris(bipyridyl) complex (1) and a bipyridyl complex of [Cp*Ir] (2) (Cp*  =  pentamethylcyclopentadienyl). X-ray photoelectron spectroscopy confirmed successful immobilization on high surface area carbon electrodes, with the expected elemental ratios for the desired compounds. Electrochemical data collected in acetonitrile solution revealed a reversible reduction of 1 near  -1.4 V, and reduction of 2 near  -0.75 V. The noncovalent immobilization, driven by association of the appended pyrene groups with the surface, was sufficiently stable to enable studies of the molecular electrochemistry. Electroactive surface coverage of 1 was diminished by only 27% over three hours soaking in electrolyte solution as measured by cyclic voltammetry. The electrochemical response of 2 resembled its soluble analogues, and suggested that ligand exchange occurred on the surface. Together, the results demonstrate that noncovalent immobilization routes are suitable for obtaining fundamental understanding of immobilized metal complexes and their reductive electrochemical properties.

  18. Immobilization and electrochemical properties of ruthenium and iridium complexes on carbon electrodes

    International Nuclear Information System (INIS)

    We report the synthesis and surface immobilization of two new pyrene-appended molecular metal complexes: a ruthenium tris(bipyridyl) complex (1) and a bipyridyl complex of [Cp*Ir] (2) (Cp*  =  pentamethylcyclopentadienyl). X-ray photoelectron spectroscopy confirmed successful immobilization on high surface area carbon electrodes, with the expected elemental ratios for the desired compounds. Electrochemical data collected in acetonitrile solution revealed a reversible reduction of 1 near  −1.4 V, and reduction of 2 near  −0.75 V. The noncovalent immobilization, driven by association of the appended pyrene groups with the surface, was sufficiently stable to enable studies of the molecular electrochemistry. Electroactive surface coverage of 1 was diminished by only 27% over three hours soaking in electrolyte solution as measured by cyclic voltammetry. The electrochemical response of 2 resembled its soluble analogues, and suggested that ligand exchange occurred on the surface. Together, the results demonstrate that noncovalent immobilization routes are suitable for obtaining fundamental understanding of immobilized metal complexes and their reductive electrochemical properties. (paper)

  19. Complex formation in the ternary U(VI)-F-L system (L = carbonate, oxalate and picolinate)

    International Nuclear Information System (INIS)

    The formation of ternary complexes and their equilibrium constants, in the system U(VI)-F--L, where L is one of the ligands picolinate, oxalate or carbonate have been investigated by potentiometric titrations using both F- and H- selective electrodes. The experimental results indicated that very stable ternary complexes are formed with the composition UO2LFq, q = 1 to 3, and UO2L2F for L = picolinate and oxalate. These complexes have a pentagonal bipyramid coordination geometry, with the five exchangeable donor atoms in a plane perpendicular to the linear UO2-group. The equilibrium constants have been determined at 25 C in a 1.00 M NaClO4 ionic medium. The equilibrium constants for the stepwise addition of F- to UO2L to form UO2LFq, q = 1 to 3, and to UO2L2 to form UO2L2F indicates that the prior coordination of L to U(VI) has a fairly small effect on the subsequent bonding of fluoride, except for a statistical effect determined by the number of available coordination sites. These results indicates that ternary complexes might be important for the speciation and transport of hexavalent actinides in ground and surface water systems. (orig.)

  20. Temperature and ionic strength influences on actinide(VI)/(V) redox potentials for carbonate limiting complexes

    International Nuclear Information System (INIS)

    Actinide behaviour was studied in two limiting aqueous solutions: acidic and carbonate. Cyclic voltametry was validated with well-known U redox system. SIT was used to account for I influence. Taylor's series expansions to the second order were used to account for T influence. Redox potentials of actinide couples had previously been measured in non complexing media. The above data treatments give standard values for redox potential E0, for the corresponding entropy ΔS0, enthalpy ΔH0 and heat capacity ΔCp0 changes, and also for the corresponding excess values (i.e. the variation of these thermodynamic constants with ionic strength). This methodology was here used in carbonate media to measure the potential of the redox couple PuO2(CO3)34-/PuO2(CO3)35- from 5 to 70 degC and from I = 0.5 to 4.5 M in Na2CO3, NaClO4 media. Experimental details and full results are given for Pu. Only final results are given for Np. Previous and/or published data for U and Am are discussed. E and ΔS variations with T or I were enough to be measured. The values obtained for the fitted SIT coefficients Δε, and for ΔS and ΔCp are similar for U, Np and Pu redox reactions. Using this analogy for Am missing data is discussed. β3V/β3VI formation constant ratio of the carbonate limiting complexes were deduced from the potential shift from complexing to non complexing media for the Actinide(VI)/Actinide(V) redox couples. β3V(U and Pu) and β3VI(Np) were finally proposed using published β3VI(U and Pu) and β3V(Np). For Am, this data treatment was used to discuss the AmO22+/ AmO2+ redox potential

  1. Complexation or uranyl ion. II. Complexation of uranyl ion in the VP-IAp anion exchanger phase during sorption from carbonate media

    International Nuclear Information System (INIS)

    The complicated process of increased uranium sorption from carbonate medium by the strongly basic anion exchanger VP-1Ap after additional treatment with alkaline solution was studied by IR spectroscopy. The process is related to the formation of certain complex forms of uranyl, differing in degree of polymerization, in which polynuclear forms predominate

  2. Hydrogen bonded complexes of cyanuric acid with pyridine and guanidinium carbonate

    Indian Academy of Sciences (India)

    K Sivashankar

    2000-12-01

    Hydrogen bonded complexes of cyanuric acid (CA) with pyridine, [C3N3H3O3:C5H5N], 1, and guanidinium carbonate [C3H2N3][C(NH2)3], 2, have been prepared at room temperature and characterized by single-crystal X-ray diffraction. Structure of 1 shows pyridine molecules substituting the inter-tape hydrogen bond in CA by N-H…N and C-H…O hydrogen bonds. The structure reveals CA-pyridine hydrogen-bonded single helices held together by dimeric N-H…O hydrogen bonding between CA molecules. In 2, the CA tapes, resembling a sine wave interact with the guanidinium cations through N-H…O and N-H…N hydrogen bonds forming guanidinium cyanurate sheets.

  3. Thermal decomposition and Moessbauer analysis of two iron hydroxy-carbonate complexes

    International Nuclear Information System (INIS)

    Full text:The two iron hydroxy carbonate complexes (NH4)2Fe2(OH)4(CO3)2.H2O and (NH4)4Fe2(OH)4(CO3)3.3H2O were prepared by the method of Dvoak and Feitknecht. Moessbauer spectra of the first sample at room temperature and 81K showed principally a ferric doublet with a small quadrupole splitting while spectra of the second sample showed a broad ferric doublet with a large mean quadrupole splitting of 1mm/s. Parameters for both spectra were characteristic of distorted octahedral coordination to oxygens. Thermal gravimetric analysis of both samples up to 750 K showed several fractions corresponding to the loss of the more volatile components

  4. Asteroseismology of GD358 with complex core carbon and oxygen abundance profiles

    Science.gov (United States)

    Kim, Agnes; Provencal, Judith

    2015-08-01

    GD358 is the brightest (mv = 13.7) and best studied helium atmosphere white dwarf pulsator. We present an analysis based on over 1000 hours of observations spanning 2007-2014 as well as archival data going back to 1982. Each modern season of observations was obtained as part of multisite Whole Earth Telescope campaigns (WET). The WET allows continuous coverage of targets over the course of days to weeks. From the complete data set, we identify a total of 27 independent frequencies and fit 15 of them as m=0 modes in our asteroseismic analysis of GD358. As an upgrade to previous analyses of the star, we include complex carbon and oxygen core abundance profiles derived and parameterized from stellar evolution calculations.

  5. Organometallic Complexes Anchored to Conductive Carbon for Electrocatalytic Oxidation of Methane at Low Temperature.

    Science.gov (United States)

    Joglekar, Madhura; Nguyen, Vinh; Pylypenko, Svitlana; Ngo, Chilan; Li, Quanning; O'Reilly, Matthew E; Gray, Tristan S; Hubbard, William A; Gunnoe, T Brent; Herring, Andrew M; Trewyn, Brian G

    2016-01-13

    Low-temperature direct methane fuel cells (DMEFCs) offer the opportunity to substantially improve the efficiency of energy production from natural gas. This study focuses on the development of well-defined platinum organometallic complexes covalently anchored to ordered mesoporous carbon (OMC) for electrochemical oxidation of methane in a proton exchange membrane fuel cell at 80 °C. A maximum normalized power of 403 μW/mg Pt was obtained, which was 5 times higher than the power obtained from a modern commercial catalyst and 2 orders of magnitude greater than that from a Pt black catalyst. The observed differences in catalytic activities for oxidation of methane are linked to the chemistry of the tethered catalysts, determined by X-ray photoelectron spectroscopy. The chemistry/activity relationships demonstrate a tangible path for the design of electrocatalytic systems for C-H bond activation that afford superior performance in DMEFC for potential commercial applications. PMID:26492385

  6. Modification of multiwall carbon nanotubes with ruthenium(II) terpyridine complex

    Energy Technology Data Exchange (ETDEWEB)

    Li Huayang [Clark Atlanta University, Chemistry Department (United States); Wu Jie [Georgia Institute of Technology, School of Materials Science and Engineering (United States); Jeilani, Yassin A. [Spelman College, Department of Chemistry (United States); Ingram, Conrad W.; Harruna, Issifu I., E-mail: iharruna@cau.edu [Clark Atlanta University, Chemistry Department (United States)

    2012-06-15

    Multiwall carbon nanotubes (MWCNTs, 1-3 {mu}M in length and 20-25 nm in diameter) were initially functionalized with a 2,2 Prime :6 Prime 2 Double-Prime -terpyridine-chelated ruthenium(II) complex by covalent amidation. The resulting functionalized ruthenium MWCNTs (RuMWCNTs, 1-2 {mu}M in length and 10-20 nm in diameter) were characterized by thermogravimetric analysis, X-ray photoelectronic spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM). Thermogravimetric experiments of RuMWCNTs show that the functional group coverage of terpyridine-rutheniun-terpyridine (tpy-Ru-tpy) is 0.7036 mmol/1.0 g carbon. The XPS results show N1s and Ru3d{sup 5/5} signals, confirming the presence of tpy-Ru-tpy groups on the surface of MWCNTs. The FTIR spectra of the RuMWCNTs display the typical stretching mode of the carboxyl group (amide I) and a combination of amide N-H and C-N stretching mode (amide II). The Raman D- and G-line peak intensity ratio of RuMWCNTs (ID/IG 2.21) exceeds that of pristine MWCNTs (ID/IG 1.93), suggesting covalent bonding of tpy-Ru-tpy to MWCNTs and supporting the disruption of the graphitic integrity due to the proposed covalent functionalization. High-resolution SEM images confirm that tpy-Ru-tpy moieties are interconnected or attached as aggregated structures (100-200-nm range) on the surfaces of the carbon nanotubes after functionalization. The electrical property of RuMWCNTs depicts higher resistance (10.10 M Ohm-Sign ) than that of OX-MWCNTs (15.38 k Ohm-Sign ).

  7. 28-Homobrassinolide Modulate Antenna Complexes and Carbon Skeleton of Brassica juncea L. under Temperature Stress

    Directory of Open Access Journals (Sweden)

    Harpreet Kaur

    2014-08-01

    Full Text Available The aim of present study was to explore the ameliorative impact of 28-homoBL on morpho-physiological attributes, photosynthetic pigments and sugars of Brassica juncea L. exposed to oxidative stress caused by extreme temperatures (4 and 44 °C. For this, experiments were carried out at the Plant Physiology Laboratory, Department of Botany, Punjabi University, Patiala. Effect of different degrees of temperature (4 and 44 °C taking 24 °C as control was studied. 28-homoBL (10-6, 10-9 and 10-12M primed and unprimed seeds of B. juncea L. in terms of antenna complexes and end products of photosynthesis that is total carbohydrates and total soluble sugars was investigated. All concentrations of 28-homoBL used in present study showed different effects on morphology and light quenching pigments. All concentrations of 28-homoBL showed promoting effect on growth and light quenching pigments. The carbon makeup ameliorated positively in stressed and non-stressed components of photosynthetic machinery and 10-9 M 28-homoBL showed best results. In conclusion 28-homoBL showed great potential in protecting the reaction centre of photosynthetic machinery from oxidative stress caused by extreme low and high temperatures but in very dose dependent manner and thus modulate the carbon skeleton of the plant.

  8. Migration of dissolved organic carbon in biochars and biochar-mineral complexes

    Directory of Open Access Journals (Sweden)

    Yun Lin

    2012-05-01

    Full Text Available The objective of this work was to determine the contribution of dissolved organic carbon (DOC from a biochar mineral complex (BMC, so as to better understand the interactions between DOC, biochar, clay, and minerals during thermal treatment, and the effects of BMC on amended soils. The BMC was prepared by heating a mixture of a H3PO4-treated saligna biochar from Acacia saligna, clays, other minerals, and chicken manure. The BMC was applied to a sandy loam soil in Western Australia, where wheat was grown. Liquid chromatography-organic carbon detection (LC-OCD tests were carried out on water extracts from the untreated biochar, the BMC, the BMC-amended soil, and on a control soil to measure the DOC concentration. LC-OCD tests provide a fingerprint of the DOC, which allows the fractions of DOC to be determined. Thermal processing enhanced the reaction of the A. saligna biochar with manure, clays and minerals, and affected the distribution of the DOC fractions. Notably, the process leads to immobilization of hydrophobic DOC and to an increase in the concentration of low-molecular-weight neutrals in the BMC. The application of the BMC to soil increases the DOC in the amended soil, especially the biopolymer fraction.

  9. Nitrogen-doped carbon nanofoam derived from amino acid chelate complex for supercapacitor applications

    Science.gov (United States)

    Ramakrishnan, Prakash; Shanmugam, Sangaraju

    2016-06-01

    We report a novel strategy to fabricate the nitrogen-doped mesoporous carbon nanofoam structures (N-MCNF), derived from magnesium amino acid chelate complex (Mg-acc-complex) for its application towards high performance supercapacitor (SCs) system. A series of N-MCNF with well-connected carbon nanofoam structure have been developed by varying the synthesis temperature. The fabricated N-MCNF material possesses a high surface area (1564 m2 g-1) and pore volume (1.767 cm3 g-1) with nitrogen content of 3.42 wt%. A prototypical coin cell type symmetric N-MCNF SC device has been assembled with 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIMBF4] ionic liquid electrolyte, and evaluated for SCs studies. The N-MCNF with high textural properties delivers unprecedented SC performance, such as high specific capacitance (204 Fg-1 at 0.25 Ag-1, 25 °C), high energy density (63.4 Wh kg-1), high power density (35.9 kW kg-1) and long-term cycle life (32,500 cycles). Significantly, N-MCNF materials exhibited high power rate performance, at 500 mV-1 (115 Fg-1) and 25 Ag-1 (166 Fg-1) owing to the uniform mesopore size distribution (∼4 nm). The N-MCNF SC device delivered maximum energy densities of 83.4 and 93.3 Wh kg-1 at 60 °C and 90 °C, respectively. Such outstanding N-MCNF SC device is successfully demonstrated in solar energy harvester applications.

  10. Unique chemical properties of metal-carbon bonds in metal-carboranyl and metal-carboryne complexes

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The metal-carbon bonds in metal-carboranyl and metal-carboryne complexes behave very differently from those in classical organometallic complexes. The unique electronic and steric properties of ico-sahedral carboranyl moiety make the M-C bond in metal-carboranyl complexes inert toward unsaturated molecules, and on the other hand, the sterically demanding carborane cage can induce unexpected C-C coupling reactions. The M-C bonds in metal-carboryne complexes are, however, active toward various kinds of unsaturated molecules and the reactivity patterns are dependent upon the electronic configurations of the metal ions. This account provides an overview of our recent work in this area.

  11. Complexes of Imidazole with Poly(ethylene glycol) as a Corrosion Inhibitor for Carbon Steel in Sulphuric Acid

    Science.gov (United States)

    Salimi, Saeed; Nasr-Esfahani, Mojtaba; Umoren, Saviour A.; Saebnoori, Ehsan

    2015-12-01

    The inhibiting action of polyethylene glycol and imidazole (PEG/IMZ)) complexes prepared by a simple deprotonation procedure on carbon steel corrosion in 0.5 mol/L sulphuric acid was evaluated using the weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques complemented by surface analysis using scanning electron microscopy. The inhibiting effect of the PEG/IMZ complexes on carbon steel corrosion was compared with the non-complex forms. Results obtained show that PEG/IMZ complex is a very effective corrosion inhibitor of carbon steel in the acid environment. The inhibition efficiency increased with the increase in the temperature and also with increasing percentage of imidazole in the complex. Corrosion inhibition occurs by virtue of adsorption of PEG/IMZ complexes on the steel surface which was found to follow the Temkin adsorption isotherm model. The PEG/IMZ complexes function as a mixed-type inhibitor. Results from all the methods employed are in a reasonably good agreement.

  12. Rotational Spectrum and Structure of the 1,1-Difluoroethylene···Carbon Dioxide Complex.

    Science.gov (United States)

    Anderton, Ashley M; Peebles, Rebecca A; Peebles, Sean A

    2016-01-21

    Rotational spectra for five isotopologues of the 1:1 weak complex between 1,1-difluoroethylene (H2C═CF2) and carbon dioxide (CO2) have been measured using 480 MHz bandwidth chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy between 5.5 and 18.5 GHz. The observed structure of the complex is planar, with the CO2 aligned roughly parallel to the C═C bond, and experimental structural parameters derived from rotational constants are consistent with the most stable geometry predicted by basis set superposition error and zero point energy corrected ab initio geometry optimizations at the MP2/6-311++G(2d,2p) level. Comparisons with the recently characterized vinyl fluoride···carbon dioxide complex reveal slightly longer intermolecular distances in the present complex, but very similar binding energies. PMID:26745797

  13. Climate and carbon cycle variations in the 20th and 21st centuries in a model of intermediate complexity

    Science.gov (United States)

    Eliseev, A. V.; Mokhov, I. I.; Karpenko, A. A.

    2007-02-01

    The climate model of intermediate complexity developed at the Oboukhov Institute of Atmospheric Physics, Russian Academy of Sciences (IAP RAS CM), has been supplemented by a zero-dimensional carbon cycle model. With the carbon dioxide emissions prescribed for the second half of the 19th century and for the 20th century, the model satisfactorily reproduces characteristics of the carbon cycle over this period. However, with continued anthropogenic CO2 emissions (SRES scenarios A1B, A2, B1, and B2), the climate-carbon cycle feedback in the model leads to an additional atmospheric CO2 increase (in comparison with the case where the influence of climate changes on the carbon exchange between the atmosphere and the underlying surface is disregarded). This additional increase is varied in the range 67 90 ppmv depending on the scenario and is mainly due to the dynamics of soil carbon storage. The climate-carbon cycle feedback parameter varies nonmonotonically with time. Positions of its extremes separate characteristic periods of the change in the intensity of anthropogenic emissions and of climate variations. By the end of the 21st century, depending on the emission scenario, the carbon dioxide concentration is expected to increase to 615 875 ppmv and the global temperature will rise by 2.4 3.4 K relative to the preindustrial value. In the 20th 21st centuries, a general growth of the buildup of carbon dioxide in the atmosphere and ocean and its reduction in terrestrial ecosystems can be expected. In general, by the end of the 21st century, the more aggressive emission scenarios are characterized by a smaller climate-carbon cycle feedback parameter, a lower sensitivity of climate to a single increase in the atmospheric concentration of carbon dioxide, a larger fraction of anthropogenic emissions stored in the atmosphere and the ocean, and a smaller fraction of emissions in terrestrial ecosystems.

  14. THE INFLUENCE OF THE COMPLEX CHEMICAL ADDITIVE CONTAINING THE STRUCTURED CARBON NANOMATERIAL ON PROPERTIES OF CEMENT

    Directory of Open Access Journals (Sweden)

    O. Yu. Sheyda

    2015-01-01

    Full Text Available The paper presents results of investigations on influence of domestic complex chemical additive containing structured carbon nanomaterial and characterized by a combination effect (curing acceleration and plasticizing on cement and cement stone properties. The purpose of the investigations, on the one hand, has been to confirm efficacy of УКД-1additive from the perspective for increasing the rate of gain, strength growth of cement concrete and additive influence on setting time with the purpose to preserve molding properties of concrete mixes in time, and on the other hand, that is to assess “mechanism” of the УКД-1 additive action in the cement concrete. The research results have revealed regularities in changes due to the additive of water requirements and time period of the cement setting. The reqularities are considered as a pre-requisite for relevant changes in molding properties of the concrete mixes. The paper also experimentally substantiates the possibility to decrease temperature of cement concrete heating with the УДК-1 additive. It has been done with the purpose to save energy resources under production conditions. In addition to this the paper proves the efficiency of the additive which is expressed in strength increase of cement stone up to 20–40 % in the rated age (28 days that is considered as a basis for strength growth of cement concrete. The paper confirms a hypothesis on physical nature of this phenomenon because the X-ray phase analysis method has shown that there are no changes in morphology of portland cement hydration products under the action of the additive agent containing a structured carbon nanomaterial. Results of theoretical and experimental investigations on УКД-1 additive efficiency have been proved by industrial approbation while fabricating precast concrete products and construction of monolithic structures under plant industrial conditions (Minsk, SS “Stroyprogress” JSC MAPID and on

  15. Trace element geochemistry of Amba Dongar carbonatite complex, India: Evidence for fractional crystallization and silicate-carbonate melt immiscibility

    Indian Academy of Sciences (India)

    Jyotiranjan S Ray; P N Shukla

    2004-12-01

    Carbonatites are believed to have crystallized either from mantle-derived primary carbonate magmas or from secondary melts derived from carbonated silicate magmas through liquid immiscibility or from residual melts of fractional crystallization of silicate magmas. Although the observed coexistence of carbonatites and alkaline silicate rocks in most complexes, their coeval emplacement in many, and overlapping initial 87Sr/86Sr and 143Nd/144Nd ratios are supportive of their cogenesis; there have been few efforts to devise a quantitative method to identify the magmatic processes. In the present study we have made an attempt to accomplish this by modeling the trace element contents of carbonatites and coeval alkaline silicate rocks of Amba Dongar complex, India. Trace element data suggest that the carbonatites and alkaline silicate rocks of this complex are products of fractional crystallization of two separate parental melts. Using the available silicate melt-carbonate melt partition coefficients for various trace elements, and the observed data from carbonatites, we have tried to simulate trace element distribution pattern for the parental silicate melt. The results of the modeling not only support the hypothesis of silicate-carbonate melt immiscibility for the evolution of Amba Dongar but also establish a procedure to test the above hypothesis in such complexes.

  16. Degraded tropical rain forests possess valuable carbon storage opportunities in a complex, forested landscape.

    Science.gov (United States)

    Alamgir, Mohammed; Campbell, Mason J; Turton, Stephen M; Pert, Petina L; Edwards, Will; Laurance, William F

    2016-01-01

    Tropical forests are major contributors to the terrestrial global carbon pool, but this pool is being reduced via deforestation and forest degradation. Relatively few studies have assessed carbon storage in degraded tropical forests. We sampled 37,000 m(2) of intact rainforest, degraded rainforest and sclerophyll forest across the greater Wet Tropics bioregion of northeast Australia. We compared aboveground biomass and carbon storage of the three forest types, and the effects of forest structural attributes and environmental factors that influence carbon storage. Some degraded forests were found to store much less aboveground carbon than intact rainforests, whereas others sites had similar carbon storage to primary forest. Sclerophyll forests had lower carbon storage, comparable to the most heavily degraded rainforests. Our findings indicate that under certain situations, degraded forest may store as much carbon as intact rainforests. Strategic rehabilitation of degraded forests could enhance regional carbon storage and have positive benefits for tropical biodiversity. PMID:27435389

  17. Formation and annealing of metastable (interstitial oxygen)-(interstitial carbon) complexes in n- and p-type silicon

    CERN Document Server

    Makarenko, L F; Lastovskii, S B; Murin, L I; Moll, M; Pintilie, I

    2014-01-01

    It is shown experimentally that, in contrast to the stable configuration of (interstitial carbon)-(interstitial oxygen) complexes (CiOi), the corresponding metastable configuration (CiOi{*}) cannot be found in n-Si based structures by the method of capacitance spectroscopy. The rates of transformation CiOi{*} -> CiOi are practically the same for both n- and p-Si with a concentration of charge carriers of no higher than 10(13) cm(-3). It is established that the probabilities of the simultaneous formation of stable and metastable configurations of the complex under study in the case of the addition of an atom of interstitial carbon to an atom of interstitial oxygen is close to 50\\%. This is caused by the orientation dependence of the interaction potential of an atom of interstitial oxygen with an interstitial carbon atom, which diffuses to this oxygen atom.

  18. Complex frictional behaviour of clay-bearing carbonate faults revealed by integrated field and experimental investigation

    Science.gov (United States)

    Bullock, R. J.; De Paola, N.; Holdsworth, R.

    2013-12-01

    Seismicity in the Northern Apennines of Italy nucleates in and propagates through a complex carbonate multilayer sequence, comprising limestones with regular marl interbeds. Observations from the Gubbio fault (1984, Ms = 5.2) indicate that earthquake displacement is localized within narrow principal slip zones, characterized by cataclasites, gouges and calcite veins, and containing up to 50% phyllosilicate. Due to their predominantly velocity-strengthening nature, phyllosilicates are often considered to promote aseismic behaviour during the inter-seismic and post-seismic (afterslip) periods, and may act as barriers to rupture propagation in the upper crust. To assess the effect of clay content on the frictional behaviour and microstructural evolution of carbonate faults during earthquake propagation, we performed high-velocity friction (HVF) experiments, using a rotary-shear apparatus, on end-member gouges of calcite (Cal), montmorillonite (Mont) and mixed-layer illite-smectite (I/S), and on 50:50 and 80:20 mixtures of Cal+Mont and Cal+I/S. Experiments were conducted at room temperature, 1.3 m/s slip rate and 9 MPa normal load. Each sample was run under dry and water-saturated conditions, and experiments terminated both at peak friction (μp) and steady-state friction (μss) for comparison of microstructures at contrasting strength stages. Results for the dry gouges are in-line with previous HVF experiments: all samples attain a peak in friction at the onset of slip, ranging from 0.59 (Mont) to 0.72 (Cal), followed by a dramatic decrease in strength within the first ~0.5 m, after which friction maintains a constant μss value, ranging from 0.15 (Cal) to 0.22 (Mont). Frictional behaviour of the wet gouges is very different: clay-bearing samples typically do not exhibit a peak in friction; steady-state behaviour is attained immediately at the onset of sliding with friction coefficient values as low as 0.05. In summary, when dry, calcite controls the strength of the

  19. Evolution of multi-mineral formation evaluation using LWD data in complex carbonates offshore Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Ferraris, Paolo; Borovskaya, Irina [Schlumberger, Houston, TX (United States)

    2012-07-01

    Petrophysical Formation Evaluation using Logging While Drilling (LWD) measurements is a new requisite when drilling in carbonates reservoirs offshore Brazil. These reservoirs are difficult to characterize due to an unusual mixture of the minerals constituting the matrix and affecting rock texture. As wells are getting deeper and more expensive, an early identification of the drilled targets potential is necessary for valuable decisions. Brazil operators have been especially demanding towards service providers, pushing for development of suitable services able to positively identify and quantify not only the presence of hydrocarbons but also their flowing capability. In addition to the standard gamma ray / resistivity / porosity and density measurements, three new measurements have proven to be critical to evaluate complex carbonate formations: Nuclear Magnetic Resonance (NMR), Spectroscopy and Capture Cross-Section (sigma). Under appropriate logging conditions, NMR data provides lithology independent porosity, bound and free fluids fractions, reservoir texture and permeability. Capture Spectroscopy allows assessment of mineral composition in terms of calcite, dolomite, quartz and clay fractions, and in addition highlights presence of other heavier minerals. Finally, sigma allows performing a volumetric formation evaluation without requiring custom optimization of the classical exponents used in all forms of resistivity saturation equations. All these new measurements are inherently statistical and if provided by wireline after drilling the well they may result in significant usage of rig time. When acquired simultaneously while drilling they have three very clear advantages: 1) no extra rig time, 2) improved statistics due to long formation exposure (drilling these carbonates is a slow process and rate of penetration (ROP) rarely exceeds 10 m/hr), 3) less invasion effect and better hole condition. This paper describes the development of two LWD tools performing the

  20. New concepts for understanding the effect of complex pore structures on petrophysical properties of carbonate rocks

    International Nuclear Information System (INIS)

    Important reservoir properties such as porosity or permeability controlling reservoir storativity and productivity are critically influenced by pore space characteristics, which cannot be reduced on a purely volumetric effect. Pore size, pore shape and interface effects exert the strongest influence and the relationships between these properties are not well understood yet. Por e space properties are especially complex in carbonate rocks, where diverse pore types and pore geometries, as well as complicate d pore structures (different scales, shapes and connectivities) exist. In this study, experimental investigations combining different measurement techniques and results of model calculations for carbonate reservoir rocks were used to achieve a better understanding of parameters controlling electrical and hydraulic conductivity (permeability). A modified Archie relationship for water-saturated carbonate rocks has been developed, considering electrically relevant pore types (interparticle, fracture and connected vug porosity; i.e. effective porosity) and separate vugs, which contribute only marginally to electrical conductivity . Central to this concept is the application of two Archie exponents: Exponent m related to connected porosity and exponent m* related to total porosity. Regressions for calculation of exponent m and effective porosity from total porosity and resistivity data have been established for a partitioning of total porosity derived from porosity logs into interparticle, fracture and separate vug porosity. New capillary type pore models have been developed for interparticle porosity covering curved and cone-shaped pore geometries. They numerically explain the influence of pore body and pore throat radius on all considered properties (porosity, specific surface, permeability, electrical resistivity) for “non-cylindrical” pore channels. Model equations deliver three essential results: (1) The mostly empirically formulated influences of pore shape

  1. Controlling the Adsorption of Ruthenium Complexes on Carbon Surfaces through Noncovalent Bonding with Pyrene Anchors: An Electrochemical Study.

    Science.gov (United States)

    Kohmoto, Mayuko; Ozawa, Hiroaki; Yang, Li; Hagio, Toshihiro; Matsunaga, Mariko; Haga, Masa-Aki

    2016-05-01

    Surface modifications of carbon nanomaterials, such as graphene or carbon nanotubes, through noncovalent π-π interactions between π-conjugated carbon surfaces and pyrene anchors have received much attention on account of the applications of these materials in organic electronic and sensor devices. Despite the rapidly expanding use of pyrene anchors, little is known about the number of pyrene groups required in order to achieve a stable attachment of molecules on nanocarbon surfaces. So far, systematic studies on such surface modifications through adsorption isotherms and desorption behavior of molecules still remain scarce. In this study, we have investigated the effect of the number of pyrene anchors in redox-active Ru complexes on their adsorption on carbon nanomaterials through noncovalent π-π interactions. The Ru(II/III) couple was used as a redox marker in order to determine the surface coverage on nanocarbon surfaces such as highly oriented pyrolytic graphite (HOPG), single-walled carbon nanotubes (SWCNTs), and multiwalled carbon nanotubes (MWCNTs). The amount of surface coverage as well as the kinetic stability of the Ru complexes was thereby observed to be directly proportional to the number of pyrene groups present in the ligands. The desorption rate from HOPG electrode increased in the order Ru-1 with eight pyrene groups (k = 2.0 × 10(-5) s(-1)) compounds having more than two and/or optimally four pyrene groups revealed a stable adsorption on the nanocarbon surfaces. The heterogeneous electron transfer rate between the Ru complex, Ru-2, and the carbon nanomaterials increased in the order SWCNTs (kET = 1.3 s(-1)) < MWCNTs (ϕ = 5-9 nm) (kET = 4.0 s(-1)) < MWCNTs (ϕ = 110-170 nm) (kET = 14.9 s(-1)) < HOPG (kET = 110 s(-1)). PMID:27065057

  2. Simplifying the complexity of a coupled carbon turnover and pesticide degradation model

    Science.gov (United States)

    Marschmann, Gianna; Erhardt, André H.; Pagel, Holger; Kügler, Philipp; Streck, Thilo

    2016-04-01

    The mechanistic one-dimensional model PECCAD (PEsticide degradation Coupled to CArbon turnover in the Detritusphere; Pagel et al. 2014, Biogeochemistry 117, 185-204) has been developed as a tool to elucidate regulation mechanisms of pesticide degradation in soil. A feature of this model is that it integrates functional traits of microorganisms, identifiable by molecular tools, and physicochemical processes such as transport and sorption that control substrate availability. Predicting the behavior of microbially active interfaces demands a fundamental understanding of factors controlling their dynamics. Concepts from dynamical systems theory allow us to study general properties of the model such as its qualitative behavior, intrinsic timescales and dynamic stability: Using a Latin hypercube method we sampled the parameter space for physically realistic steady states of the PECCAD ODE system and set up a numerical continuation and bifurcation problem with the open-source toolbox MatCont in order to obtain a complete classification of the dynamical system's behaviour. Bifurcation analysis reveals an equilibrium state of the system entirely controlled by fungal kinetic parameters. The equilibrium is generally unstable in response to small perturbations except for a small band in parameter space where the pesticide pool is stable. Time scale separation is a phenomenon that occurs in almost every complex open physical system. Motivated by the notion of "initial-stage" and "late-stage" decomposers and the concept of r-, K- or L-selected microbial life strategies, we test the applicability of geometric singular perturbation theory to identify fast and slow time scales of PECCAD. Revealing a generic fast-slow structure would greatly simplify the analysis of complex models of organic matter turnover by reducing the number of unknowns and parameters and providing a systematic mathematical framework for studying their properties.

  3. Carbon Nanotubes, Nanocrystal Forms, and Complex Nanoparticle Aggregates in common fuel-gas combustion sources and the ambient air

    International Nuclear Information System (INIS)

    Aggregated multiwall carbon nanotubes (with diameters ranging from ∼3 to 30nm) and related carbon nanocrystal forms ranging in size from 0.4 to 2 μm (average diameter) have been collected in the combustion streams for methane/air, natural gas/air, and propane gas/air flames using a thermal precipitator. Individual particle aggregates were collected on carbon/formvar-coated 3mm nickel grids and examined in a transmission electron microscope, utilizing bright-field imaging, selected-area electron diffraction analysis, and energy-dispersive X-ray spectrometry techniques. The natural gas and propane gas sources were domestic (kitchen) stoves, and similar particle aggregates collected in the outdoor air were correspondingly identified as carbon nanocrystal aggregates and sometimes more complex aggregates of silica nanocrystals intermixed with the carbon nanotubes and other carbon nanocrystals. Finally, and in light of the potential for methane-series gas burning as major sources of carbon nanocrystal aggregates in both the indoor and outdoor air, data for natural gas consumption and corresponding asthma deaths and incidence are examined with a degree of speculation regarding any significance in the correlations

  4. Evidence of different stoichiometries for the limiting carbonate complexes of lanthanides(3); Mise en evidence d'un changement de stoechiometrie du complexe carbonate limite au sein de la serie des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Philippini, V

    2007-12-15

    Two stoichiometries have been proposed by different laboratories to interpret measurements on the limiting carbonate complexes of An{sup 3+} and Ln{sup 3+} cations. The study of the solubility of double carbonates (AlkLn(CO{sub 3}){sub 2},xH{sub 2}O) in concentrated carbonate solutions at room temperature and high ionic strengths has shown that on the one hand the lightest lanthanides (La and Nd) form Ln(CO{sub 3}){sub 4}{sup 5-} whereas the heaviest (Eu and Dy) form Ln(CO{sub 3}){sub 3}{sup 3-} in the studied chemical conditions, and on the other hand, that the kinetics of precipitation of double carbonates depends on the alkali metal and the lanthanide ions. The existence of two stoichiometries for the limiting carbonate complexes was confirmed by capillary electrophoresis hyphenated to an inductively coupled plasma mass spectrometer (CE-ICP-MS), used to extend the study to the whole series of lanthanides (except Ce, Pm and Yb). Two behaviours have been put forward comparing the electrophoretic mobilities: La to Tb form Ln(CO{sub 3}){sub 4}{sup 5-} while Dy to Lu form Ln(CO{sub 3}){sub 3}{sup 3-}. Measurements by time resolved laser fluorescence spectroscopy (TRLFS) on Eu(III) indicate small variations of the geometry of Eu(CO{sub 3}){sub 3}{sup 3-} complex, specially with Cs{sup +}. Although analogies are currently used among the 4f-block trivalent elements, different aqueous speciations are evidenced in concentrated carbonate solutions across the lanthanide series. (author)

  5. Structures of murine carbonic anhydrase IV and human carbonic anhydrase II complexed with brinzolamide: molecular basis of isozyme-drug discrimination.

    OpenAIRE

    Stams, T.; Y. Chen; Boriack-Sjodin, P. A.; Hurt, J. D.; Liao, J; May, J. A.; Dean, T.; Laipis, P; Silverman, D. N.; Christianson, D. W.

    1998-01-01

    Carbonic anhydrase IV (CAIV) is a membrane-associated enzyme anchored to plasma membrane surfaces by a phosphatidylinositol glycan linkage. We have determined the 2.8-angstroms resolution crystal structure of a truncated, soluble form of recombinant murine CAIV. We have also determined the structure of its complex with a drug used for glaucoma therapy, the sulfonamide inhibitor brinzolamide (Azopt). The overall structure of murine CAIV is generally similar to that of human CAIV; however, some...

  6. The role of the carbon-silicon complex in eliminating deep ultraviolet absorption in AlN

    Science.gov (United States)

    Gaddy, Benjamin E.; Bryan, Zachary; Bryan, Isaac; Xie, Jinqiao; Dalmau, Rafael; Moody, Baxter; Kumagai, Yoshinao; Nagashima, Toru; Kubota, Yuki; Kinoshita, Toru; Koukitu, Akinori; Kirste, Ronny; Sitar, Zlatko; Collazo, Ramón; Irving, Douglas L.

    2014-05-01

    Co-doping AlN crystals with Si is found to suppress the unwanted 4.7 eV (265 nm) deep ultraviolet absorption associated with isolated carbon acceptors common in materials grown by physical vapor transport. Density functional theory calculations with hybrid functionals demonstrate that silicon forms a stable nearest-neighbor defect complex with carbon. This complex is predicted to absorb at 5.5 eV and emit at or above 4.3 eV. Absorption and photoluminescence measurements of co-doped samples confirm the presence of the predicted CN-SiAl complex absorption and emission peaks and significant reduction of the 4.7 eV absorption. Other sources of deep ultraviolet absorption in AlN are also discussed.

  7. Unexpected carbon-oxygen bond cleavage of THF promoted by guanidinate titanium complex/lithium diisopropylamide: Synthesis and crystal structure

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yong; WANG Mei; YAO Yingming; SHEN Qi

    2005-01-01

    An unexpected carbon-oxygen bond cleavage of THF (THF = tetrahydrofuran) promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2iNC(NCy)2]Li (Cy = cyclohexyl) formed in situ reacted with TiCl4(THF)2 in a 2:1 molar ratio to produce the guanidinate titanium chloride [Pr2iNC(NCy)2]2TiCl2 (1) in good yield. The reaction of [Pr2iNC(NCy)2]2TiCl2 with lithium diisopropylamide in THF afforded an unexpected [Pr2iNC(NCy)2]2Ti(OBun)2 (2), which was formed by the cleavage of carbon-oxygen bond of THF. Complexes 1 and 2 were fully characterized by elemental analysis, NMR and IR spectroscopies, and X-ray crystal structure determination for complex 2.

  8. Competitive surface complexation reactions of sulfate and natural organic carbon on soil

    International Nuclear Information System (INIS)

    The ecological implications of subsurface SO42- loading on nutrient cation leaching, acidification, and the destruction of concrete containers used to store low-level radioactive waste, has been thoroughly addressed. Processes favoring SO42- adsorption by the subsurface matrix tend to alleviate these adverse ecological conditions and this has been investigated to a lesser extent. In this study, the adsorption of SO42 onto several soil types with indigenous SO42- and organic carbon removed, was measured as a function of pH in the presence and absence of added natural organic matter (NOM). Sulfate adsorption was strongly pH dependent and the presence of >2 mg L-1 NOM resulted in a consistent decrease in sulfate adsorption over the pH range 4.5 to 8. The tendency of these soils to adsorb SO42- was related to their large quantity of Fe-oxides and the presence of kaolinite in the 42- was related to their large quantity of Fe-oxides and the presence of kaolinite in the 42- onto positive or neutral surface sites (XOH + H+ + SO42- = XSO4- + H2O) as a inner-sphere complex proved successful in describing the adsorption of sulfate under the experimental conditions. The estimated value of the intrinsic equilibrium constant (K) for the above reaction was of the order 1010 suggesting strong sulfate adsorption. Estimated K values were found to be unaffected by the presence of added NOM. 57 refs., 3 figs., 3 tabs

  9. Preparation, characterization and cytotoxicity of carbon nanotube-chitosan-phycocyanin complex

    Science.gov (United States)

    Liao, Xiaoxia; Zhang, Xuewu

    2012-01-01

    Photodynamic therapy (PDT) or photothermal therapy (PTT) using nanomaterials has shown great prospect for cancer treatment. Phycocyanin (PC) is a photoharvesting pigment and is also an attractive candidate for PDT. The multiwalled carbon nanotube (MWNT) is a potent candidate for PTT due to its extraordinary photo-to-thermal energy conversion efficiency upon excitation with near-infrared (NIR) light. To date, although MWNT-CS complexes have been well studied, no report about the reconjugation of MWNT-CS with phycocyanin is available in the literature. Here, by using water-soluble chitosan (CS), we prepared and characterized a novel biomaterial, MWNT-CS-PC, with the potential for PDT and PTT. The cytotoxicity experiments found that MWNT-CS-PC exhibited cell growth inhibition activity. Moreover, with irradiation of NIR light (808 nm) or visible light (532 nm), the photoinduced cytotoxicity was indeed enhanced. These results suggest that MWNT-CS-PC may potentially serve as a future photodynamic and photothermal therapy for cancer.

  10. Preparation, characterization and cytotoxicity of carbon nanotube–chitosan–phycocyanin complex

    International Nuclear Information System (INIS)

    Photodynamic therapy (PDT) or photothermal therapy (PTT) using nanomaterials has shown great prospect for cancer treatment. Phycocyanin (PC) is a photoharvesting pigment and is also an attractive candidate for PDT. The multiwalled carbon nanotube (MWNT) is a potent candidate for PTT due to its extraordinary photo-to-thermal energy conversion efficiency upon excitation with near-infrared (NIR) light. To date, although MWNT–CS complexes have been well studied, no report about the reconjugation of MWNT–CS with phycocyanin is available in the literature. Here, by using water-soluble chitosan (CS), we prepared and characterized a novel biomaterial, MWNT–CS–PC, with the potential for PDT and PTT. The cytotoxicity experiments found that MWNT–CS–PC exhibited cell growth inhibition activity. Moreover, with irradiation of NIR light (808 nm) or visible light (532 nm), the photoinduced cytotoxicity was indeed enhanced. These results suggest that MWNT–CS–PC may potentially serve as a future photodynamic and photothermal therapy for cancer. (paper)

  11. Thermodynamic Complexing of Monocyclopentadienylferrum (II) Intercalates with Double-Walled Carbon Nanotubes.

    Science.gov (United States)

    Мykhailenko, О V; Prylutskyy, Yu I; Кomarov, І V; Strungar, А V

    2016-12-01

    By employing the methods of molecular mechanics, semi-empirical quantum-chemical РМ3 and Monte-Carlo, the positioning of monocyclopentadienylferrum (II) molecules in double-walled (5,5)@(10,10) carbon nanotubes (CNT) depending on their concentration and temperature has been studied. The molecules have been found out to form stable bonds with CNT walls, with a tendency between intercalate stability and the CNT structure. The temperature growth (over ~500 K) causes gradual bond ruining followed by extrusion of interwall intercalate. Further temperature increase up to 600-700 K is characterised with intercalate external surface desorption, stabilising the whole system and keeping the interwall intercalate only. The CNT's UV-spectrum (5,5)@(10,10) depending on the intercalate concentration and association constant of the "double-walled CNT-intercalate" system have been calculated. A combination of unique optical, electrical and magnetic behaviour of cyclopentadienyl complexes with their ability to form high-stable intercalate with CNT opens a prospect of their applying in nanotechnology. PMID:26951128

  12. Charge Transfer Complex Role in the Formation of Chlorobenzene in the γ-Irradiated Carbon Tetrachloride - Benzene System

    International Nuclear Information System (INIS)

    The formation of carbon tetrachloride-benzene charge transfer complex was confirmed by UV and NMR spectrometric studies. A change in UV spectrum of benzene is observed upon addition of carbon tetrachloride. The appearance of new bands supports the formation of charge transfer complex. NMR study shows that benzene proton chemical shift depends on the CCI4-C6H6 molar ratio. This observation is another criterion for the formation of benzene - carbon tetrachloride charge transfer complex. Job's Continuous Variation method indicates that a 2:1 CCI4-C6H6 charge transfer complex(2:1 CTC) could be formed. The association constants (K2:1) of this 2:1 CTC was found to be 0.0197 M-2 .The maximum concentration of 2:1 CTC was found at about 33% benzene mole percent. The maximum yield of chlorobenzene was obtained, also, upon radiolysis of CCI4-C6H6 samples at 2:1 molar ratio (33% benzene mole percent). Therefore, it could be concluded that 2:1 CTC participates in thc formation of chlorobenzene upon radiolysis of benzene - carbon tetrachloride system.This conclusion was supported by the dependence of the chlorobenzene yield of γ-irradiated 2: 1 carbon tetrachloride - benzene system on irradiation time according to third order kinetic equation with a very good linearity (R2 = 0.9977). Accordingly, the rate constant for the chlorobenzene formation under this condition, was found to be ∼ 5.5 x 10-7 L2 .moI-2.h-1. We propose a radiation chemical mechanism in which the 2: 1 CTC plays a role in the formation of chlorobenzene

  13. Clay:organic-carbon and organic carbon as determinants of the soil physical properties: reassessment of the Complexed Organic Carbon concept

    Science.gov (United States)

    Matter, Adrien; Johannes, Alice; Boivin, Pascal

    2016-04-01

    Soil Organic Carbon (SOC) is well known to largely determine the soil physical properties and fertility. Total porosity, structural porosity, aeration, structural stability among others are reported to increase linearly with increasing SOC in most studies. Is there an optimal SOC content as target in soil management, or is there no limit in physical fertility improvement with SOC? Dexter et al. (2008) investigated the relation between clay:SOC ratio and the physical properties of soils from different databases. They observed that the R2 of the relation between SOC and the physical properties were maximized when considering the SOC fraction limited to a clay:SOC ratio of 10. They concluded that this fraction of the SOC was complexed, and that the additional SOC was not influencing the physical properties as strongly as the complexed one. In this study, we reassessed this approach, on a database of 180 undisturbed soil samples collected from cambiluvisols of the Swiss Plateau, on an area of 2400 km2, and from different soil uses. The physical properties were obtained with Shrinkage Analysis, which involved the parameters used in Dexter et al., 2008. We used the same method, but detected biases in the statistical approach, which was, therefore, adapted. We showed that the relation between the bulk density and SOC was changing with the score of visual evaluation of the structure (VESS) (Ball et al., 2007). Therefore, we also worked only on the "good" structures according to VESS. All shrinkage parameters were linearly correlated to SOC regardless of the clay:SOC ratio, with R2 ranging from 0.45 to 0.8. Contrarily to Dexter et al. (2008), we did not observed an optimum in the R2 of the relation when considering a SOC fraction based on the clay:SOC ratio. R2 was increasing until a Clay:SOC of about 7, where it reached, and kept, its maximum value. The land use factor was not significant. The major difference with the former study is that we worked on the same soil group

  14. Ruthenium-bipyridine complexes bearing fullerene or carbon nanotubes: synthesis and impact of different carbon-based ligands on the resulting products.

    Science.gov (United States)

    Wu, Zhen-yi; Huang, Rong-bin; Xie, Su-yuan; Zheng, Lan-sun

    2011-09-01

    This paper discusses the synthesis of two carbon-based pyridine ligands of fullerene pyrrolidine pyridine (C(60)-py) and multi-walled carbon nanotube pyrrolidine pyridine (MWCNT-py) via 1,3-dipolar cycloaddition. The two complexes, C(60)-Ru and MWCNT-Ru, were synthesized by ligand substitution in the presence of NH(4)PF(6), and Ru(II)(bpy)(2)Cl(2) was used as a reaction precursor. Both complexes were characterized by mass spectroscopy (MS), elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy (IR), ultraviolet/visible spectroscopy (UV-VIS) spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and cyclic voltammetry (CV). The results showed that the substitution way of C(60)-py is different from that of MWCNT-py. The C(60)-py and a NH(3) replaced a Cl(-) and a bipyridine in Ru(II)(bpy)(2)Cl(2) to produce a five-coordinate complex of [Ru(bpy)(NH(3))(C(60)-py)Cl]PF(6), whereas MWCNT-py replaced a Cl(-) to generate a six-coordinate complex of [Ru(bpy)(2)(MWCNT-py)Cl]PF(6). The cyclic voltammetry study showed that the electron-withdrawing ability was different for C(60) and MWCNT. The C(60) showed a relatively stronger electron-withdrawing effect with respect to MWCNT. PMID:21769337

  15. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah, E-mail: absalimi@uok.ac.i [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); Mahdioun, Monierosadat; Noorbakhsh, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Abdolmaleki, Amir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156/83111 (Iran, Islamic Republic of); Ghavami, Raoof [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2011-03-30

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20-100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1-12). The surface coverages and heterogeneous electron transfer rate constants (k{sub s}) of immobilized Mn-complex were approximately 1.58 x 10{sup -10} mole cm{sup -2} and 48.84 s{sup -1}. The modified electrode showed excellent electrocatalytic activity toward H{sub 2}O{sub 2} reduction. Detection limit, sensitivity, linear concentration range and k{sub cat} for H{sub 2}O{sub 2} were, 0.2 {mu}M and 692 nA {mu}M{sup -1} cm{sup -2}, 1 {mu}M to 1.5 mM and 7.96({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1}, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.

  16. Single-Walled Carbon Nanotube Dynamics in Simple and Complex Media

    Science.gov (United States)

    Fakhri, Nikta

    Understanding the dynamics of single-walled carbon nanotubes (SWNTs) in simple and complex environments is crucial for establishing potential application of nanotube architectures for materials and biosciences. In this thesis we employ the visualization and analysis tools to image and quantify and the Brownian bending and diffusion of SWNTs in different media in order to understand and eventually to tailor nanotube mobility in confined environments. We image Brownian bending dynamics of SWNTs in water using Near-infrared (NIR) fluorescence microscopy. The bending stiffness of each chirality-assigned SWNT is extracted from the variance of the curvature fluctuations. Relaxation times of the bending fluctuations are measured from the autocorrelation of SWNT shapes. We find that the bending stiffness scales as the cube of the nanotube diameter, in agreement with an elastic continuum model. The measured shape relaxation times are in excellent agreement with the semiflexible chain model, showing that SWNTs may truly be considered as the ideal model semiflexible filaments. The motion of stiff objects in crowded environments has been investigated for more than three decades in polymer science and biophysics; yet, theory and experiments have not established whether a minute amount of flexibility affects the mobility of stiff slender filaments. We image the Brownian motion of SWNTs in a network by NIR fluorescence microscopy. We show direct evidence of SWNTs reptating in the network, and confirm that their small flexibility enhances significantly their rotational diffusion. Our results establish the reptation dynamics of stiff filaments and provide a framework to tailor SWNTs mobility in confined media. By varying SWNT surface modifications, we can selectively tune the sensitivity of the carbon nanotubes to the different physical properties of the porous media for sensing applications, We introduce a simple procedure for dispersion of SWNTs in aqueous solutions using

  17. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. PMID:24128453

  18. Reconstruction of Holocene carbon dynamics in a large boreal peatland complex, southern Finland

    Science.gov (United States)

    Mathijssen, Paul J. H.; Väliranta, Minna; Korrensalo, Aino; Alekseychik, Pavel; Vesala, Timo; Rinne, Janne; Tuittila, Eeva-Stiina

    2016-06-01

    Holocene peatland development and associated carbon (C) dynamics were reconstructed for a southern boreal Finnish peatland complex with fen and bog areas. In order to assess the role of local factors and long-term allogenic climate forcing in peatland development patterns, we studied a total of 18 peat cores and reconstructed vertical peat growth and lateral peat area expansion rates, the C accumulation rate (CAR), past vegetation composition and past methane (CH4) fluxes. We combined fossil plant data with measured contemporary CH4 flux - vegetation relationship data to reconstruct CH4 fluxes over time. When these reconstructions were added to the CAR estimations, a more complete picture of Holocene-scale C dynamics was achieved. Basal peat ages showed that expansion of the peat area was rapid between 11,000 and 8000 cal. BP, but decreased during the dry mid-Holocene and is probably currently limited by basal topography. A similar pattern was observed for peat growth and CAR in the fen core, whereas in the bog core CAR increased after ombrotrophication, i.e. after 4400 cal. BP. The effect of fire on vegetation and CAR was more conspicuous at the bog site than at the fen site. The CH4 flux reconstructions showed that during the Holocene CH4 emissions at the fen site decreased from 19 ± 15 to 16 ± 8 g CH4 m-2 yr-1 and at the bog site from 20 ± 15 to 14 ± 8 g CH4 m-2 yr-1. Our results suggest that a combination of changing climate, fire events and local conditions have modified the autogenic peatland development and C dynamics.

  19. Efficient transformation of mammalian cells using DNA interpolyelectrolyte complexes with carbon chain polycations.

    Science.gov (United States)

    Kabanov, A V; Astafieva, I V; Maksimova, I V; Lukanidin, E M; Georgiev, G P; Kabanov, V A

    1993-01-01

    A new method for mammalian cell transformation is proposed which is based on incorporation of plasmids into interpolyelectrolyte complexes (IPECs) with carbon chain polycations. The method is illustrated by examples of pRSV CAT and p beta-Gal plasmid IPECs with poly(N-ethyl-4-vinylpyridinium bromide) (C2PVP) and poly(N-ethyl-4-vinylpyridinium)-poly(N-cetyl-4-vinylpyridinium+ ++) bromides random copolymer (C16PVP). These IPECs are produced spontaneously due to formation of a cooperative system of interchain electrostatic bonds after mixing DNA and polycation solutions. The interaction of IPEC with normal mouse fibroblasts NIH 3T3, human T-lymphoma "Jurkat", and Mardin Darby canine kidney cells has been studied. The data obtained has revealed that plasmid incorporation into IPECs significantly enhances both DNA adsorption on the plasma membrane and DNA uptake into a cell. The in vitro transformation of NIH 3T3 cells was monitored by a standard cloramphenicol acetyltransferase (CAT) assay (pRSV CAT plasmid) and by detection of beta-galactosidase (beta-Gal) expression using 4-methylumbeliferril beta-D-galactopyranoside as a substrate (p beta-Gal plasmid). In both cases it has been proved that IPEC-incorporated plasmids possess an ability for efficient cell transformation. The transforming activity of IPECs depends on their composition and polycation chemical structure. Under optimal conditions the efficiency of cell transformation with IPECs is several fold higher than that observed during standard calcium phosphate precipitation. The mechanism of the phenomenon observed is discussed.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8305514

  20. Basin-scale Modeling of Geological Carbon Sequestration: Model Complexity, Injection Scenario and Sensitivity Analysis

    Science.gov (United States)

    Huang, X.; Bandilla, K.; Celia, M. A.; Bachu, S.

    2013-12-01

    Geological carbon sequestration can significantly contribute to climate-change mitigation only if it is deployed at a very large scale. This means that injection scenarios must occur, and be analyzed, at the basin scale. Various mathematical models of different complexity may be used to assess the fate of injected CO2 and/or resident brine. These models span the range from multi-dimensional, multi-phase numerical simulators to simple single-phase analytical solutions. In this study, we consider a range of models, all based on vertically-integrated governing equations, to predict the basin-scale pressure response to specific injection scenarios. The Canadian section of the Basal Aquifer is used as a test site to compare the different modeling approaches. The model domain covers an area of approximately 811,000 km2, and the total injection rate is 63 Mt/yr, corresponding to 9 locations where large point sources have been identified. Predicted areas of critical pressure exceedance are used as a comparison metric among the different modeling approaches. Comparison of the results shows that single-phase numerical models may be good enough to predict the pressure response over a large aquifer; however, a simple superposition of semi-analytical or analytical solutions is not sufficiently accurate because spatial variability of formation properties plays an important role in the problem, and these variations are not captured properly with simple superposition. We consider two different injection scenarios: injection at the source locations and injection at locations with more suitable aquifer properties. Results indicate that in formations with significant spatial variability of properties, strong variations in injectivity among the different source locations can be expected, leading to the need to transport the captured CO2 to suitable injection locations, thereby necessitating development of a pipeline network. We also consider the sensitivity of porosity and

  1. Model complexity in carbon sequestration:A design of experiment and response surface uncertainty analysis

    Science.gov (United States)

    Zhang, Y.; Li, S.

    2014-12-01

    Geologic carbon sequestration (GCS) is proposed for the Nugget Sandstone in Moxa Arch, a regional saline aquifer with a large storage potential. For a proposed storage site, this study builds a suite of increasingly complex conceptual "geologic" model families, using subsets of the site characterization data: a homogeneous model family, a stationary petrophysical model family, a stationary facies model family with sub-facies petrophysical variability, and a non-stationary facies model family (with sub-facies variability) conditioned to soft data. These families, representing alternative conceptual site models built with increasing data, were simulated with the same CO2 injection test (50 years at 1/10 Mt per year), followed by 2950 years of monitoring. Using the Design of Experiment, an efficient sensitivity analysis (SA) is conducted for all families, systematically varying uncertain input parameters. Results are compared among the families to identify parameters that have 1st order impact on predicting the CO2 storage ratio (SR) at both end of injection and end of monitoring. At this site, geologic modeling factors do not significantly influence the short-term prediction of the storage ratio, although they become important over monitoring time, but only for those families where such factors are accounted for. Based on the SA, a response surface analysis is conducted to generate prediction envelopes of the storage ratio, which are compared among the families at both times. Results suggest a large uncertainty in the predicted storage ratio given the uncertainties in model parameters and modeling choices: SR varies from 5-60% (end of injection) to 18-100% (end of monitoring), although its variation among the model families is relatively minor. Moreover, long-term leakage risk is considered small at the proposed site. In the lowest-SR scenarios, all families predict gravity-stable supercritical CO2 migrating toward the bottom of the aquifer. In the highest

  2. Reconstruction of Holocene carbon dynamics in a large boreal peatland complex, southern Finland

    Science.gov (United States)

    Mathijssen, Paul J. H.; Väliranta, Minna; Korrensalo, Aino; Alekseychik, Pavel; Vesala, Timo; Rinne, Janne; Tuittila, Eeva-Stiina

    2016-06-01

    Holocene peatland development and associated carbon (C) dynamics were reconstructed for a southern boreal Finnish peatland complex with fen and bog areas. In order to assess the role of local factors and long-term allogenic climate forcing in peatland development patterns, we studied a total of 18 peat cores and reconstructed vertical peat growth and lateral peat area expansion rates, the C accumulation rate (CAR), past vegetation composition and past methane (CH4) fluxes. We combined fossil plant data with measured contemporary CH4 flux - vegetation relationship data to reconstruct CH4 fluxes over time. When these reconstructions were added to the CAR estimations, a more complete picture of Holocene-scale C dynamics was achieved. Basal peat ages showed that expansion of the peat area was rapid between 11,000 and 8000 cal. BP, but decreased during the dry mid-Holocene and is probably currently limited by basal topography. A similar pattern was observed for peat growth and CAR in the fen core, whereas in the bog core CAR increased after ombrotrophication, i.e. after 4400 cal. BP. The effect of fire on vegetation and CAR was more conspicuous at the bog site than at the fen site. The CH4 flux reconstructions showed that during the Holocene CH4 emissions at the fen site decreased from 19 ± 15 to 16 ± 8 g CH4 m-2 yr-1 and at the bog site from 20 ± 15 to 14 ± 8 g CH4 m-2 yr-1. Our results suggest that a combination of changing climate, fire events and local conditions have modified the autogenic peatland development and C dynamics.

  3. Complexity

    CERN Document Server

    Gershenson, Carlos

    2011-01-01

    The term complexity derives etymologically from the Latin plexus, which means interwoven. Intuitively, this implies that something complex is composed by elements that are difficult to separate. This difficulty arises from the relevant interactions that take place between components. This lack of separability is at odds with the classical scientific method - which has been used since the times of Galileo, Newton, Descartes, and Laplace - and has also influenced philosophy and engineering. In recent decades, the scientific study of complexity and complex systems has proposed a paradigm shift in science and philosophy, proposing novel methods that take into account relevant interactions.

  4. Bifacial dye-sensitized solar cells from covalent-bonded polyaniline-multiwalled carbon nanotube complex counter electrodes

    Science.gov (United States)

    Zhang, Huihui; He, Benlin; Tang, Qunwei; Yu, Liangmin

    2015-02-01

    Exploration of cost-effective counter electrodes (CEs) and enhancement of power conversion efficiency have been two persistent objectives for dye-sensitized solar cells (DSSCs). In the current work, polyaniline-multiwalled carbon nanotube (PANi-MWCNT) complexes are synthesized by a reflux method and employed as CE materials for bifacial DSSCs. Owing to the high optical transparency of PANi-MWCNT complex CE, the incident light from rear side can compensate for the incident light from TiO2 anode. The charge-transfer ability and electrochemical behaviors demonstrate the potential utilization of PANi-MWCNT complex CEs in robust bifacial DSSCs. The electrochemical properties as well as photovoltaic performances are optimized by adjusting MWCNT dosages. A maximum power conversion efficiency of 9.24% is recorded from the bifacial DSSC employing PANi-8 wt‰ MWCNT complex CE for both irradiation, which is better than 8.08% from pure PANi CE.

  5. Thermodynamics and speciation: Carbonate complexation of Am(III) and speciation of actinides by pulsed laser spectroscopies

    International Nuclear Information System (INIS)

    The report includes the carbonate complexation of Am(III) and speciation of actinides by pulsed laser spectroscopies. Part A describes the carbonate complexation behaviour of Am3+ in aqueous solution under 1% CO2 partial pressure, investigated by solubility and spectroscopic experiments. The average constants determined by the two methods are: log Ksp (Am2(CO3)3)=-29.7 ± 0.6, log β1=6.3 ± 0.3 and log β2 = 9.7 ± 0.6. Part B presents speciation capabilities of three different pulsed laser spectroscopies: laser-induced photoacoustic spectroscopy (LPAS), time-resolved laser-induced fluorescence spectroscopy (TRLFS) and photoacoustic detection of light scattering (PALS). Examples for the speciation of Am(III) and Cm(III) in different aquatic media are presented. (orig.)

  6. Carbon-13 magnetic relaxation rates or iron (III) complexes of some biogenic amines and parent compounds in aqueous solutions

    International Nuclear Information System (INIS)

    Spin-lattice relaxation rates (R1) from naturally occuring C-13 F.T. N.M.R. spectra of some catecholamines and parent compounds with Iron(III) at pD = 4 were determined in order to elucidate the molecular mechanism underlying their association in aqueous solutions. Complexation was observed only for catecholic ligands. The R1 values were used to calculate iron-carbon scaled distances, and two complexation models were proposed where the catecholic function binds Fe(III) in the first and second coordination spheres respectively. The latter case was shown to be the consistent with the molecular geometries. (orig.)

  7. Electrosorption of Os(III)-complex at single-wall carbon nanotubes immobilized on a glassy carbon electrode: Application to nanomolar detection of bromate, periodate and iodate

    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; Kavosi, Begard [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Department of Chemistry, Arak University, P.O. Box, 38156-879 Arak (Iran, Islamic Republic of); Babaei, Ali [Department of Chemistry, Arak University, P.O. Box, 38156-879 Arak (Iran, Islamic Republic of); Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2008-06-16

    A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl{sub 2}).ClO{sub 4}, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage ({gamma}) and charge transfer rate constant (k{sub s}) of the immobilized Os-complex on SWCNTs were 3.07 x 10{sup -9} mol cm{sup -2}, 5.5 ({+-}0.2) s{sup -1}, 2.94 x 10{sup -9} mol cm{sup -2}, 7.3 ({+-}0.3) s{sup -1} at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO{sub 3}{sup -}, IO{sub 3}{sup -} and IO{sub 4}{sup -} in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 ({+-}0.2) x 10{sup 3}, 7.32 ({+-}0.2) x 10{sup 3} and 1.75 ({+-}0.2) x 10{sup 3} M{sup -1} s {sup -1}, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.

  8. CALCIUM CARBONATE REDUCES IRON ABSORPTION FROM IRON SULFATE, BUT NOT WHEN IRON IS PRESENTED AS AN ORGANIC COMPLEX

    Directory of Open Access Journals (Sweden)

    E. C. CONCEI�O

    2008-09-01

    Full Text Available

    Experimental and epidemiological evidences have demonstrated that calcium inhibits iron absorption; calcium carbonate being one of the most effective calcium sources to reduce iron absorption from dietary origin or from iron sulfate. In the present work, the short-term effect of calcium from calcium carbonate on iron absorption was studied in rats, using different iron compounds (monosodium ferric EDTA, iron-bys-glicine, iron peptide complex with iron sulfate as a control. Eighty (80 animals were divided into groups of 10 animals each with homogeneous weight. After 18h fast, the animals received by gavage 5 mL of a dispersion containing one of the iron compounds (1mg Fe/kg body weight, concomitantly or not with calcium carbonate at a molar ratio of 150:1 (Ca/Fe. Two hours after the administration, the animals were sacrificed and blood was collected for serum iron determination (iron transfer rate from intestinal lumen to blood compartment. Additionally, the intestines were collected for soluble iron determination (available iron. The results demonstrated that calcium ion from calcium carbonate inhibits the iron absorption from iron sulfate, but not from organic iron (di- or trivalent complexes.

  9. DIFFERENTIAL INHIBITION OF MITOCHONDRIAL RESPIRATORY COMPLEXES BY INHALATION OF COMBUSTION SMOKE AND CARBON MONOXIDE, IN VIVO, IN THE RAT BRAIN

    OpenAIRE

    Lee, Heung M; Hallberg, Lance M.; Greeley, George H.; Englander, Ella W.

    2010-01-01

    Combustion smoke contains gases and particulates, which act via hypoxia and cytotoxicity producing mechanisms to injure cells and tissues. While carbon monoxide (CO) is the major toxicant in smoke, its toxicity is exacerbated in presence of other compounds. Here, we examined modulations of mitochondrial and cytosolic energy metabolism by inhalation of combustion smoke versus CO, in vivo, in the rat brain. Measurements revealed reduced activities of respiratory complexes, with greater inhibiti...

  10. Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates

    Science.gov (United States)

    Wolf, Stephan E.; Müller, Lars; Barrea, Raul; Kampf, Christopher J.; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten; Emmerling, Franziska; Tremel, Wolfgang

    2011-03-01

    During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. Electronic supplementary information (ESI) available: (S1 and S5) TEM at higher magnifications and of crystallizations conducted at pH = 6.0, 9.0 and 11.3; (S2) sketch of a spreading liquid particle on a TEM grid; (S3) wide-angle scattering of BaCO3 and CdCO3; (S4 and S6-S9) ESI-MS spectra of a solution of carbon dioxide and of bicarbonates of Sr, Ba, Pb, Mn and Cd. See DOI: 10.1039/c0nr00761g

  11. Novel in situ multiharmonic EQCM-D approach to characterize complex carbon pore architectures for capacitive deionization of brackish water

    International Nuclear Information System (INIS)

    Multiharmonic analysis by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D) is introduced as an excellent tool for quantitative studying electrosorption of ions from aqueous solution in mesoporous (BP-880) or mixed micro-mesoporous (BP-2000) carbon electrodes. Finding the optimal conditions for gravimetric analysis of the ionic content in the charged carbon electrodes, we propose a novel approach to modeling the charge-dependent gravimetric characteristics by incorporation of Gouy-Chapman-Stern electric double layer model for ions electrosorption into meso- and micro-mesoporous carbon electrodes. All three parameters of the gravimetric equation evaluated by fitting it to the experimental mass changes curves were validated using supplementary nitrogen gas sorption analysis and complementing atomic force microscopy. Important overlap between gravimetric EQCM-D analysis of the ionic content of porous carbon electrodes and the classical capacitive deionization models has been established. The necessity and usefulness of non-gravimetric EQCM-D characterizations of complex carbon architectures, providing insight into their unique viscoelastic behavior and porous structure changes, have been discussed in detail. (paper)

  12. Novel in situ multiharmonic EQCM-D approach to characterize complex carbon pore architectures for capacitive deionization of brackish water.

    Science.gov (United States)

    Shpigel, Netanel; Levi, Mikhael D; Sigalov, Sergey; Aurbach, Doron; Daikhin, Leonid; Presser, Volker

    2016-03-23

    Multiharmonic analysis by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D) is introduced as an excellent tool for quantitative studying electrosorption of ions from aqueous solution in mesoporous (BP-880) or mixed micro-mesoporous (BP-2000) carbon electrodes. Finding the optimal conditions for gravimetric analysis of the ionic content in the charged carbon electrodes, we propose a novel approach to modeling the charge-dependent gravimetric characteristics by incorporation of Gouy-Chapman-Stern electric double layer model for ions electrosorption into meso- and micro-mesoporous carbon electrodes. All three parameters of the gravimetric equation evaluated by fitting it to the experimental mass changes curves were validated using supplementary nitrogen gas sorption analysis and complementing atomic force microscopy. Important overlap between gravimetric EQCM-D analysis of the ionic content of porous carbon electrodes and the classical capacitive deionization models has been established. The necessity and usefulness of non-gravimetric EQCM-D characterizations of complex carbon architectures, providing insight into their unique viscoelastic behavior and porous structure changes, have been discussed in detail. PMID:26902741

  13. Conformations of dimethyl carbonate and its complexes with water: A matrix isolation infrared and ab initio study

    Science.gov (United States)

    Kar, Bishnu Prasad; Ramanathan, N.; Sundararajan, K.; Viswanathan, K. S.

    2012-09-01

    Conformations of dimethyl carbonate (DMC) were studied using matrix isolation infrared spectroscopy. Infrared spectra of DMC trapped in inert gas matrixes, using an effusive source at 298 and 423 K, showed evidence of both the ground state (cis-cis), and higher energy (cis-trans) conformers. Experiments were also performed using a supersonic jet source to deposit the matrix, to look for conformational cooling in the expansion process. The structures and vibrational frequencies of these conformers were computed at the B3LYP/6-31++G** level of theory. Natural bond orbital analyses were performed to understand the role of the delocalization interactions in conformational preferences. Complexes of DMC with H2O were also studied. A 1:1 DMC-H2O complex was identified in the matrix isolation experiments, where the carbonyl oxygen of DMC served as the proton acceptor for the hydrogen bonded complex. This observation was corroborated by computations performed on the complex at the B3LYP/6-31++G** level. Our computations also indicated another minimum, corresponding to an alkoxy bonded DMC-H2O complex, which was less exothermic; however, this complex was not identified in our experiments. Atoms-in-molecules theory was also performed to understand the nature of the intermolecular interaction in the DMC-H2O complex.

  14. Carbon-water Cycling in the Critical Zone: Understanding Ecosystem Process Variability Across Complex Terrain

    Energy Technology Data Exchange (ETDEWEB)

    Barnard, Holly [Univ. of Colorado, Boulder, CO (United States); Brooks, Paul [Univ. of Utah, Salt Lake City, UT (United States); Univ. of Arizona, Tucson, AZ (United States)

    2016-06-16

    One of the largest knowledge gaps in environmental science is the ability to understand and predict how ecosystems will respond to future climate variability. The links between vegetation, hydrology, and climate that control carbon sequestration in plant biomass and soils remain poorly understood. Soil respiration is the second largest carbon flux of terrestrial ecosystems, yet there is no consensus on how respiration will change as water availability and temperature co-vary. To address this knowledge gap, we use the variation in soil development and topography across an elevation and climate gradient on the Front Range of Colorado to conduct a natural experiment that enables us to examine the co-evolution of soil carbon, vegetation, hydrology, and climate in an accessible field laboratory. The goal of this project is to further our ability to combine plant water availability, carbon flux and storage, and topographically driven hydrometrics into a watershed scale predictive model of carbon balance. We hypothesize: (i) landscape structure and hydrology are important controls on soil respiration as a result of spatial variability in both physical and biological drivers: (ii) variation in rates of soil respiration during the growing season is due to corresponding shifts in belowground carbon inputs from vegetation; and (iii) aboveground carbon storage (biomass) and species composition are directly correlated with soil moisture and therefore, can be directly related to subsurface drainage patterns.

  15. Carbon, hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos, Greece

    Science.gov (United States)

    Rye, R.O.; Schuiling, R.D.; Rye, D.M.; Jansen, J.B.H.

    1976-01-01

    At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700??C. The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The ??18O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated ??18OH2O values of the metamorphic fluids in the schist-rich zones decrease from about 15??? in the lower grades to an average of about 8.5??? in the migmatite. The ??D values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated ??DH2O values for the metamorphic fluid decrease from -5??? in the glaucophane zone to an average of about -70??? in the migmatite. The ??D values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend. The??18O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The ??D values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism. Detailed data on 20 marble units show systematic variations of ??18O values which depend upon metamorphic grade. Below the 540??C isograd very steep ??18O gradients at the margins and large ??18O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540??C isograd lower ??18O values occur in

  16. Functional characterization of mutants affected in the carbonic anhydrase domain of the respiratory complex I in Arabidopsis thaliana.

    Science.gov (United States)

    Soto, Débora; Córdoba, Juan Pablo; Villarreal, Fernando; Bartoli, Carlos; Schmitz, Jessica; Maurino, Veronica G; Braun, Hans Peter; Pagnussat, Gabriela C; Zabaleta, Eduardo

    2015-09-01

    The NADH-ubiquinone oxidoreductase complex (complex I) (EC 1.6.5.3) is the main entrance site of electrons into the respiratory chain. In a variety of eukaryotic organisms, except animals and fungi (Opisthokonta), it contains an extra domain comprising trimers of putative γ-carbonic anhydrases, named the CA domain, which has been proposed to be essential for assembly of complex I. However, its physiological role in plants is not fully understood. Here, we report that Arabidopsis mutants defective in two CA subunits show an altered photorespiratory phenotype. Mutants grown in ambient air show growth retardation compared to wild-type plants, a feature that is reversed by cultivating plants in a high-CO2 atmosphere. Moreover, under photorespiratory conditions, carbon assimilation is diminished and glycine accumulates, suggesting an imbalance with respect to photorespiration. Additionally, transcript levels of specific CA subunits are reduced in plants grown under non-photorespiratory conditions. Taken together, these results suggest that the CA domain of plant complex I contributes to sustaining efficient photosynthesis under ambient (photorespiratory) conditions. PMID:26148112

  17. The coupling of carbon dioxide and epoxides by phenanthroline derivatives containing different Cu(II) complexes as catalyst

    Science.gov (United States)

    Kilic, Ahmet; Palali, Ahmet Arif; Durgun, Mustafa; Tasci, Zeynep; Ulusoy, Mahmut

    2013-09-01

    A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2‧,3‧-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV-Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.

  18. Stability constants important to the understanding of plutonium in environmental waters, hydroxy and carbonate complexation of PuO2+

    International Nuclear Information System (INIS)

    The formation constants for the reactions PuO2+ + H2O = PuO2(OH) + H+ and PuO2+ + CO32 = PuO2(CO3)- were determined in aqueous sodium perchlorate solutions by laser-induced photoacoustic spectroscopy. The molar absorptivity of the PuO2+ band at 569 nm decreased with increasing hydroxide concentration. Similarly, spectral changes occurred between 540 and 580 nm as the carbonate concentration was increased. The absorption data were analyzed by the non-linear least-squares program SQUAD to yield complexation constants. Using the specific ion interaction theory, both complexation constants were extrapolated to zero ionic strength. These thermodynamic complexation constants were combined with the oxidation-reduction potentials of Pu to obtain Eh versus pH diagrams. 120 refs., 35 figs., 12 tabs

  19. Two different carbon-hydrogen complexes in silicon with closely spaced energy levels

    Science.gov (United States)

    Stübner, R.; Kolkovsky, Vl.; Weber, J.

    2015-08-01

    An acceptor and a single donor state of carbon-hydrogen defects (CHA and CHB) are observed by Laplace deep level transient spectroscopy at 90 K. CHA appears directly after hydrogenation by wet chemical etching or hydrogen plasma treatment, whereas CHB can be observed only after a successive annealing under reverse bias at about 320 K. The activation enthalpies of these states are 0.16 eV for CHA and 0.14 eV for CHB. Our results reconcile previous controversial experimental results. We attribute CHA to the configuration where substitutional carbon binds a hydrogen atom on a bond centered position between carbon and the neighboring silicon and CHB to another carbon-hydrogen defect.

  20. Two different carbon-hydrogen complexes in silicon with closely spaced energy levels

    International Nuclear Information System (INIS)

    An acceptor and a single donor state of carbon-hydrogen defects (CHA and CHB) are observed by Laplace deep level transient spectroscopy at 90 K. CHA appears directly after hydrogenation by wet chemical etching or hydrogen plasma treatment, whereas CHB can be observed only after a successive annealing under reverse bias at about 320 K. The activation enthalpies of these states are 0.16 eV for CHA and 0.14 eV for CHB. Our results reconcile previous controversial experimental results. We attribute CHA to the configuration where substitutional carbon binds a hydrogen atom on a bond centered position between carbon and the neighboring silicon and CHB to another carbon-hydrogen defect

  1. The Myriophyllum spicatum L. -epiphyte complex: A study of the community carbon metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Godmaire, H.

    1988-01-01

    The kinetics of extracellular organic carbon (EOC) released by Myriophyllum spicatum L. were investigated and the importance of EOC release to epiphytic heterotrophs was determined. EOC released by colonized Myriophyllum leaves was positively related to the dissolved inorganic carbon (DIC) concentration of the external medium and to photosynthetic activity. Maximum rate of release occurred during the exponential phase of growth. In short-term incubation (1-6 h), {sup 14}C-EOC accounted for 0.2-0.4% of carbon photoassimilation. {sup 14}C-EOC consisted primarily of low molecular weight products. The {sup 14}C-technique seriously underestimated the release rate compared to direct measurement of EOC which gave values of approximately 2.2% of carbon photoassimilation. During a diurnal cycle, the EOC release rate increased in the afternoon as photosynthesis decreased, and reached 2.8% of the carbon photoassimilation at the end of the light period. Axenic plants were characterized by lower growth rates and lower EOC release rates than colonized plants. The amount of EOC released during the day by colonized plants was 2.0 to 4.5 fold greater than the utilized by epiphytic heterotrophs. Therefore, EOC released by Myriophyllum may constitute a significant source of carbon for attached and surrounding heterotrophic organisms.

  2. The distribution and amount of carbon in the largest peatland complex in Amazonia

    Science.gov (United States)

    Draper, Frederick C.; Roucoux, Katherine H.; Lawson, Ian T.; Mitchard, Edward T. A.; Honorio Coronado, Euridice N.; Lähteenoja, Outi; Torres Montenegro, Luis; Valderrama Sandoval, Elvis; Zaráte, Ricardo; Baker, Timothy R.

    2014-12-01

    Peatlands in Amazonian Peru are known to store large quantities of carbon, but there is high uncertainty in the spatial extent and total carbon stocks of these ecosystems. Here, we use a multi-sensor (Landsat, ALOS PALSAR and SRTM) remote sensing approach, together with field data including 24 forest census plots and 218 peat thickness measurements, to map the distribution of peatland vegetation types and calculate the combined above- and below-ground carbon stock of peatland ecosystems in the Pastaza-Marañon foreland basin in Peru. We find that peatlands cover 35 600 ± 2133 km2 and contain 3.14 (0.44-8.15) Pg C. Variation in peat thickness and bulk density are the most important sources of uncertainty in these values. One particular ecosystem type, peatland pole forest, is found to be the most carbon-dense ecosystem yet identified in Amazonia (1391 ± 710 Mg C ha-1). The novel approach of combining optical and radar remote sensing with above- and below-ground carbon inventories is recommended for developing regional carbon estimates for tropical peatlands globally. Finally, we suggest that Amazonian peatlands should be a priority for research and conservation before the developing regional infrastructure causes an acceleration in the exploitation and degradation of these ecosystems.

  3. The distribution and amount of carbon in the largest peatland complex in Amazonia

    International Nuclear Information System (INIS)

    Peatlands in Amazonian Peru are known to store large quantities of carbon, but there is high uncertainty in the spatial extent and total carbon stocks of these ecosystems. Here, we use a multi-sensor (Landsat, ALOS PALSAR and SRTM) remote sensing approach, together with field data including 24 forest census plots and 218 peat thickness measurements, to map the distribution of peatland vegetation types and calculate the combined above- and below-ground carbon stock of peatland ecosystems in the Pastaza-Marañon foreland basin in Peru. We find that peatlands cover 35 600 ± 2133 km2 and contain 3.14 (0.44–8.15) Pg C. Variation in peat thickness and bulk density are the most important sources of uncertainty in these values. One particular ecosystem type, peatland pole forest, is found to be the most carbon-dense ecosystem yet identified in Amazonia (1391 ± 710 Mg C ha−1). The novel approach of combining optical and radar remote sensing with above- and below-ground carbon inventories is recommended for developing regional carbon estimates for tropical peatlands globally. Finally, we suggest that Amazonian peatlands should be a priority for research and conservation before the developing regional infrastructure causes an acceleration in the exploitation and degradation of these ecosystems. (letter)

  4. Electrocatalytic and simultaneous determination of isoproterenol, uric acid and folic acid at molybdenum (VI) complex-carbon nanotube paste electrode

    Energy Technology Data Exchange (ETDEWEB)

    Beitollahi, Hadi, E-mail: h.beitollahi@yahoo.com [Environment Department, Research Institute of Environmental Sciences, International Center for Science, High Technology and Environmental Sciences, Kerman (Iran, Islamic Republic of); Sheikhshoaie, Iran [Department of Chemistry, Faculty of Science, Shahid Bahonar University of Kerman, Kerman 76175-133 (Iran, Islamic Republic of)

    2011-11-30

    Highlights: > A molybdenum (VI) complex-carbon nanotube paste electrode have been fabricated. > This electrode reduced the oxidation potential of isoproterenol by about 175 mV. > It resolved the voltammetric waves of isoproterenol, uric acid and folic acid. - Abstract: This paper describes the development, electrochemical characterization and utilization of a novel modified molybdenum (VI) complex-carbon nanotube paste electrode for the electrocatalytic determination of isoproterenol (IP). The electrochemical profile of the proposed modified electrode was analyzed by cyclic voltammetry (CV) that showed a shift of the oxidation peak potential of IP at 175 mV to less positive value, compared with an unmodified carbon paste electrode. Differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS) at pH 7.0 was performed to determine IP in the range from 0.7 to 600.0 {mu}M, with a detection limit of 35.0 nM. Then the modified electrode was used to determine IP in an excess of uric acid (UA) and folic acid (FA) by DPV. Finally, this method was used for the determination of IP in some real samples.

  5. Synthesis and evaluation of multi-wall carbon nanotube–paclitaxel complex as an anti-cancer agent

    Science.gov (United States)

    Ghasemvand, Fariba; Biazar, Esmaeil; Tavakolifard, Sara; Khaledian, Mohammad; Rahmanzadeh, Saeid; Momenzadeh, Daruosh; Afroosheh, Roshanak; Zarkalami, Faezeh; Shabannezhad, Marjan; Hesami Tackallou, Saeed; Massoudi, Nilofar; Heidari Keshel, Saeed

    2016-01-01

    Aim: The aim of this study was to design multi-walled carbon nanotubes (MWCNTs) loaded with paclitaxel (PTX) anti-cancer drug and investigate its anti-cancerous efficacy of human gastric cancer. Background: Carbon nanotubes (CNTs) represent a novel nano-materials applied in various fields such as drug delivery due to their unique chemical properties and high drug loading. Patients and methods: In this study, multi-walled carbon nanotubes (MWCNTs) pre-functionalized covalently with a paclitaxel (PTX) as an anti-cancer drug and evaluated by different analyses including, scanning electron microscope (SEM), particle size analyzer and cellular analyses. Results: A well conjugated of anti-cancer drug on the carbon nanotube surfaces was shown. This study demonstrates that the MWCN-PTX complex is a potentially useful system for delivery of anti-cancer drugs. The flow cytometry, CFU and MTT assay results have disclosed that MWCNT/PTXs might promote apoptosis in MKN-45 gastric adenocarcinoma cell line. Conclusion: According to results, our simple method can be designed a candidate material for chemotherapy. It has presented a few bio-related applications including, their successful use as a nano-carriers for drug transport. PMID:27458512

  6. Chemical behaviour of plutonium in natural, aquatic systems: Hydrolysis, carbonate complexation and redox reactions

    International Nuclear Information System (INIS)

    In order to clear up the geochemical behaviour of plutonium and its migration mechanisms in groundwater, hydrolysis, redox behaviour, compound formation in carbonate solutions and colloid formation were examined in groundwater conditions, i.e. at pH values between 5 and 8 and at redox potentials of between -300 and +700 mV. Solubility measurements, spectroscopic processes (UV, VIS, IR spectroscopy and laser induced photoacoustic spectroscopy) and electrochemical processes (cyclic voltammetry, differential pulse polarography) are used as methods of investigation. The hydrolysis constants of Pu IV and Pu VI and the solubility product of Pu (OH)4 were determined and hydrolysis products of divalent and trivalent type are described. From solubility experiments, the stability constants for Pu (IV) carbonate compounds and the solubility product for the carbonate system of stable bodies of Pu (OH)2 CO3 were calculated. Using absorption spectroscopy, the disproportionate kinetics of Pu (V) in carbonate was determined at various pH values. A slow, but continuous, reduction in Pu (VI) was found in carbonate solution, which was derived from radiolytic effects. The speed of this auto-reduction was determined, depending on various experimental parameters. (orig./RB)

  7. Theory of complex fluids in the warm-dense-matter regime, and application to phase-transitions in liquid carbon

    CERN Document Server

    Dharma-wardana, M W C

    2016-01-01

    Using data from recent laser-shock experiments and related density-functional molecular-dynamics simulations on carbon, we demonstrate that the ionic structures predicted within the neutral-pseudo-atom approach for a complex liquid in the warm-dense matter regime are in good agreement with available data, even where transient covalent bonding dominates ionic correlations. Evidence for an unusual phase transition of a liquid $\\to$ vapor with an abrupt decrease in ionization occurring simultaneously is presented. Here a covalently-bonded metallic-liquid, i.e., carbon of density 1.0 g/cm$^3$, transits to a disordered mono-atomic fluid at 7 eV. Other transitions where the mean ionization $Z$ drops abruptly are also uncovered

  8. Carbon as a source for yellow luminescence in GaN: Isolated C{sub N} defect or its complexes

    Energy Technology Data Exchange (ETDEWEB)

    Christenson, Sayre G.; Xie, Weiyu; Sun, Y. Y., E-mail: suny4@rpi.edu; Zhang, S. B., E-mail: zhangs9@rpi.edu [Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States)

    2015-10-07

    We study three carbon defects in GaN, isolated C{sub N} and its two complexes with donors C{sub N}–O{sub N}, and C{sub N}–Si{sub Ga}, as a cause of the yellow luminescence using accurate hybrid density functional calculation, which includes the semi-core Ga 3d electrons as valence electrons and uses a larger 300-atom supercell. We show that the isolated C{sub N} defect yields good agreement with experiment on the photoluminescence (PL) peak position, zero-phonon line, and thermodynamic defect transition level. We find that the defect state of the complexes that is involved in the PL process is the same as that of the C{sub N} defect. The role of the positively charged donors (O{sub N} or Si{sub Ga}) next to C{sub N} is to blue-shift the PL peak. Therefore, the complexes cannot be responsible for the same PL peak as isolated C{sub N}. Our detailed balance analysis further suggests that under thermal equilibrium at typical growth temperature, the concentration of isolated C{sub N} defect is orders of magnitude higher than the defect complexes, which is a result of the small binding energy in these complexes.

  9. Carbon as a source for yellow luminescence in GaN: Isolated CN defect or its complexes

    International Nuclear Information System (INIS)

    We study three carbon defects in GaN, isolated CN and its two complexes with donors CN–ON, and CN–SiGa, as a cause of the yellow luminescence using accurate hybrid density functional calculation, which includes the semi-core Ga 3d electrons as valence electrons and uses a larger 300-atom supercell. We show that the isolated CN defect yields good agreement with experiment on the photoluminescence (PL) peak position, zero-phonon line, and thermodynamic defect transition level. We find that the defect state of the complexes that is involved in the PL process is the same as that of the CN defect. The role of the positively charged donors (ON or SiGa) next to CN is to blue-shift the PL peak. Therefore, the complexes cannot be responsible for the same PL peak as isolated CN. Our detailed balance analysis further suggests that under thermal equilibrium at typical growth temperature, the concentration of isolated CN defect is orders of magnitude higher than the defect complexes, which is a result of the small binding energy in these complexes

  10. Bimetallic nickel complexes for selective CO2 carbon capture and sequestration.

    Science.gov (United States)

    Möller, F; Merz, K; Herrmann, C; Apfel, U-P

    2016-01-21

    Herein we report a dinickel azacryptand complex that enables fast, selective, and tight CO2 binding from air. Exploiting the affinity of the cavitand towards azides, CO2 release was observed. Despite the stability of the azido complex, UV irradiation under atmospheric conditions proved to be a suitable pathway for N3(-) replacement by CO2. PMID:26666316

  11. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO2) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO2, an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  12. Kinetics of the Removal of Chromium Complex Dye from Aqueous Solutions Using Activated Carbons and Polymeric Adsorbent

    OpenAIRE

    Eglė Kazlauskienė; Danutė Kaušpėdienė

    2011-01-01

    The kinetics of the removal of chromium complex dye (Lanasyn Navy M-DNL) from aqueous solutions using polymeric adsorbent Macronet MN 200 (MN 200) as an alternative option for activated carbon Norit RB 0.8 CC (AC) was studied in the batch system. The residual colour of dye solution treated with AC or MN 200 strongly depends on solution pH with lower values at acidic pH when a positively charged surface net is favourable for the adsorption of the dye anion. The removal of dye using MN 200 was ...

  13. THE ACTIVATION OF CARBON OXIDES BY LOW VALENT GROUP IV AND THORIUM COMPLEXES

    OpenAIRE

    Zoe Button

    2012-01-01

    Following discoveries in our laboratory that mixed-ring uranium(III) complexes reductively couple CO to produce new C-C bonds and transform this small molecule into potentially useful small organic things, further research has taken place into the synthesis, characterisation and reactivity of the zirconium, hafnium and thorium analogues. The first part of this thesis describes the preparation of the novel zirconium(IV) and hafnium(IV) mixed-sandwich chloride complexes using sterically demandi...

  14. Cobalt(III) complexes of [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane. Report of an inert, chelate hydrogen carbonate ion

    DEFF Research Database (Denmark)

    Broge, Louise; Søtofte, Inger; Olsen, Carl Erik; Springborg, Johan

    2001-01-01

    .H2O (3a). The coordination geometry around the cobalt(III) ion is a distorted octahedron with the inorganic ligands at cis-positions. Complex 2 is the second example of a cobalt(III) complex for which the X-ray structure,sfiows a chelate binding mode of the hydrogen carbonate entity. The pK(a) value...

  15. Zirconium Hydride Complex Supported by a Tetradentate Carbon-Centered Tripodal Tris(aryloxide) Ligand: Synthesis, Structure, and Reactivity.

    Science.gov (United States)

    Nakanishi, Yusuke; Ishida, Yutaka; Kawaguchi, Hiroyuki

    2016-04-18

    A dizirconium trihydride complex supported by a tetradentate carbon-centered tris(aryloxide) ligand [{Na(dme)}3{(O3C)Zr}2(μ-H)3] (2; [O3C] = [(3,5-(t)Bu2-2-O-C6H2)3C](4-)) was prepared by reacting [(O3C)Zr(thf)3] (1) with NaBHEt3 in toluene. Exposure of 2 in THF to CO2 (1 atm) resulted in facile insertion of CO2 into Zr-H bonds, yielding a formate complex [{Na(thf)2}3{(O3C)Zr}2(μ-O2CH)3] (3). Treatment of 2 with P4 in toluene led to formation of [Na(thf)5][{Na(thf)2}2{(O3C)Zr}2(μ-P3)] (4) and PH3, in which hydrogenation of P4 took place. Complex 2 reacted with Me3SiN3 to afford an azide-bridged cyclotrimer [{Na(thf)2}{(O3C)ZrN3(thf)}]3 (5) with concomitant liberation of Me3SiH. The molecular structures of these complexes 2-5 have been determined by X-ray diffraction analyses. PMID:27045559

  16. Complex forest dynamics indicate potential for slowing carbon accumulation in the southeastern United States

    OpenAIRE

    John W. Coulston; Wear, David N.; Vose, James M.

    2015-01-01

    Over the past century forest regrowth in Europe and North America expanded forest carbon (C) sinks and offset C emissions but future C accumulation is uncertain. Policy makers need insights into forest C dynamics as they anticipate emissions futures and goals. We used land use and forest inventory data to estimate how forest C dynamics have changed in the southeastern United States and attribute changes to land use, management, and disturbance causes. From 2007-2012, forests yielded a net sin...

  17. Closo-Carborane-metal complexes containing metal-carbon and metal-boron sigma-bonds

    International Nuclear Information System (INIS)

    This paper examines the metal derivatives of the closo-carboranes formed through carborane carbon-metal and carborane boron-metal bonds. In order to provide a better perspective of the closo-carborane-metal compounds the authors include derivatives containing carboranyl groups bonded to boron and silicon, which are normally classified as nonmetals. The structures, nomenclature system, and general preparative methods of the closo-carboranes are examined

  18. Structural studies of β-carbonic anhydrase from the green alga Coccomyxa: inhibitor complexes with anions and acetazolamide.

    Directory of Open Access Journals (Sweden)

    Shenghua Huang

    Full Text Available The β-class carbonic anhydrases (β-CAs are widely distributed among lower eukaryotes, prokaryotes, archaea, and plants. Like all CAs, the β-enzymes catalyze an important physiological reaction, namely the interconversion between carbon dioxide and bicarbonate. In plants the enzyme plays an important role in carbon fixation and metabolism. To further explore the structure-function relationship of β-CA, we have determined the crystal structures of the photoautotroph unicellular green alga Coccomyxa β-CA in complex with five different inhibitors: acetazolamide, thiocyanate, azide, iodide, and phosphate ions. The tetrameric Coccomyxa β-CA structure is similar to other β-CAs but it has a 15 amino acid extension in the C-terminal end, which stabilizes the tetramer by strengthening the interface. Four of the five inhibitors bind in a manner similar to what is found in complexes with α-type CAs. Iodide ions, however, make contact to the zinc ion via a zinc-bound water molecule or hydroxide ion--a type of binding mode not previously observed in any CA. Binding of inhibitors to Coccomyxa β-CA is mediated by side-chain movements of the conserved residue Tyr-88, extending the width of the active site cavity with 1.5-1.8 Å. Structural analysis and comparisons with other α- and β-class members suggest a catalytic mechanism in which the movements of Tyr-88 are important for the CO(2-HCO(3(- interconversion, whereas a structurally conserved water molecule that bridges residues Tyr-88 and Gln-38, seems important for proton transfer, linking water molecules from the zinc-bound water to His-92 and buffer molecules.

  19. Structural studies of β-carbonic anhydrase from the green alga Coccomyxa: inhibitor complexes with anions and acetazolamide.

    Science.gov (United States)

    Huang, Shenghua; Hainzl, Tobias; Grundström, Christin; Forsman, Cecilia; Samuelsson, Göran; Sauer-Eriksson, A Elisabeth

    2011-01-01

    The β-class carbonic anhydrases (β-CAs) are widely distributed among lower eukaryotes, prokaryotes, archaea, and plants. Like all CAs, the β-enzymes catalyze an important physiological reaction, namely the interconversion between carbon dioxide and bicarbonate. In plants the enzyme plays an important role in carbon fixation and metabolism. To further explore the structure-function relationship of β-CA, we have determined the crystal structures of the photoautotroph unicellular green alga Coccomyxa β-CA in complex with five different inhibitors: acetazolamide, thiocyanate, azide, iodide, and phosphate ions. The tetrameric Coccomyxa β-CA structure is similar to other β-CAs but it has a 15 amino acid extension in the C-terminal end, which stabilizes the tetramer by strengthening the interface. Four of the five inhibitors bind in a manner similar to what is found in complexes with α-type CAs. Iodide ions, however, make contact to the zinc ion via a zinc-bound water molecule or hydroxide ion--a type of binding mode not previously observed in any CA. Binding of inhibitors to Coccomyxa β-CA is mediated by side-chain movements of the conserved residue Tyr-88, extending the width of the active site cavity with 1.5-1.8 Å. Structural analysis and comparisons with other α- and β-class members suggest a catalytic mechanism in which the movements of Tyr-88 are important for the CO(2)-HCO(3)(-) interconversion, whereas a structurally conserved water molecule that bridges residues Tyr-88 and Gln-38, seems important for proton transfer, linking water molecules from the zinc-bound water to His-92 and buffer molecules. PMID:22162771

  20. Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)]− anionic complex

    International Nuclear Information System (INIS)

    The [Co(Pyridine)(CO2)]− anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO2 binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO2)]− in which a central cobalt atom is bound to pyridine and CO2 moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO2 to be bound within the anionic complex by 1.4 eV

  1. X-ray film chamber with carbon target of Tien-Shan complex array

    International Nuclear Information System (INIS)

    X-ray films were exposed inside the ionization calorimeter under 74g/sq cm of carbon and 5 cm of lead. The X-ray film chamber area is 35 sq. m. Moving X-ray films were used, 50% of the events, which yield incidence time, were identified with corresponding extensive air showers (EAS). For such events the size spectrum of associated EAS was derived. Two methods of energy measurement using X-ray films and ionization calorimeter were compared. The energy transfer from selected hadrons to electromagnetic components is illustrated. It is found that in cascades with high energy release into electromagnetic components the hadron component is practically absent

  2. Complex forest dynamics indicate potential for slowing carbon accumulation in the southeastern United States

    Science.gov (United States)

    Coulston, John W.; Wear, David N.; Vose, James M.

    2015-01-01

    Over the past century forest regrowth in Europe and North America expanded forest carbon (C) sinks and offset C emissions but future C accumulation is uncertain. Policy makers need insights into forest C dynamics as they anticipate emissions futures and goals. We used land use and forest inventory data to estimate how forest C dynamics have changed in the southeastern United States and attribute changes to land use, management, and disturbance causes. From 2007-2012, forests yielded a net sink of C because of net land use change (+6.48 Tg C yr-1) and net biomass accumulation (+75.4 Tg C yr-1). Forests disturbed by weather, insect/disease, and fire show dampened yet positive forest C changes (+1.56, +1.4, +5.48 Tg C yr-1, respectively). Forest cutting caused net decreases in C (-76.7 Tg C yr-1) but was offset by forest growth (+143.77 Tg C yr-1). Forest growth rates depend on age or stage of development and projected C stock changes indicate a gradual slowing of carbon accumulation with anticipated forest aging (a reduction of 9.5% over the next five years). Additionally, small shifts in land use transitions consistent with economic futures resulted in a 40.6% decrease in C accumulation.

  3. Compositions of magmas and carbonate silicate liquid immiscibility in the Vulture alkaline igneous complex, Italy

    Science.gov (United States)

    Solovova, I. P.; Girnis, A. V.; Kogarko, L. N.; Kononkova, N. N.; Stoppa, F.; Rosatelli, G.

    2005-11-01

    This paper presents a study of melt and fluid inclusions in minerals of an olivine-leucite phonolitic nephelinite bomb from the Monticchio Lake Formation, Vulture. The rock contains 50 vol.% clinopyroxene, 12% leucite, 10% alkali feldspars, 8% hauyne/sodalite, 7.5% nepheline, 4.5% apatite, 3.2% olivine, 2% opaques, 2.6% plagioclase, and < 1% amphibole. We distinguished three generations of clinopyroxene differing in composition and morphology. All the phenocrysts bear primary and secondary melt and fluid inclusions, which recorded successive stages of melt evolution. The most primitive melts were found in the most magnesian olivine and the earliest clinopyroxene phenocrysts. The melts are near primary mantle liquids and are rich in Ca, Mg and incompatible and volatile elements. Thermometric experiments with the melt inclusions suggested that melt crystallization began at temperatures of about 1200 °C. Because of the partial leakage of all primary fluid inclusions, the pressure of crystallization is constrained only to minimum of 3.5 kbar. Combined silicate-carbonate melt inclusions were found in apatite phenocrysts. They are indicative of carbonate-silicate liquid immiscibility, which occurred during magma evolution. Large hydrous secondary melt inclusions were found in olivine and clinopyroxene. The inclusions in the phenocrysts recorded an open-system magma evolution during its rise towards the surface including crystallization, degassing, oxidation, and liquid immiscibility processes.

  4. End-labeling of peptide nucleic acid with osmium complex. Voltammetry at carbon and mercury electrodes

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Trefulka, Mojmír; Fojta, Miroslav

    2009-01-01

    Roč. 11, č. 2 (2009), s. 359-362. ISSN 1388-2481 R&D Projects: GA AV ČR(CZ) KAN400310651; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : peptide nucleic acid end-labeling * osmium tetroxide complexes * electroactive labels Subject RIV: BO - Biophysics Impact factor: 4.243, year: 2009

  5. Iron(0) Aminocarbene Complexes Bearing Heterocyclic Substituent on Carbene Carbon Atom: Electrochemistry and Reactivity

    Czech Academy of Sciences Publication Activity Database

    Hoskovcová, I.; Zvěřinová, R.; Dvořák, D.; Záliš, Stanislav; Ludvík, Jiří

    Lausanne: International Society of Electrochemistry, 2008, 080898-080898. [Annual Meeting of the International Society of Electrochemistry /59./. Seville (ES), 07.09.2008-12.09.2008] R&D Projects: GA AV ČR IAA400400813 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrochemistry * reactivity * iron aminocarbene complexes Subject RIV: CG - Electrochemistry http://www.uco.es/electroquimica-rseq/Circular_Seville08.pdf

  6. Adatom complexes and self-healing mechanisms on graphene and single-wall carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Tsetseris, Leonidas [ORNL; Pantelides, Sokrates T [ORNL

    2009-01-01

    Point defects play a role in the functionalization, chemical activation, carrier transport, and nano-engineering of graphitic systems. Here, we use first-principles calculations to describe several processes that alter the properties of graphene and single-wall carbon nanotubes (SWCNTs) in the presence of self-interstitials (SI's). We find that, while two or four SI's are stabilized in hillock-like structures that stay idle unless the system is heated to very high temperatures, clustering of three C adatoms leads to the formation of mobile protrusions on graphene and large enough SWCNTs. For different SI concentrations and SWCNT size, the interplay between mobile and immobile species may favor one of the two competing processes, self-healing or formation of adatom superstructures.

  7. Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

    Energy Technology Data Exchange (ETDEWEB)

    Thoi, VanSara; Kornienko, Nick; Margarit, C; Yang, Peidong; Chang, Christopher

    2013-06-07

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  8. Chiral Cobalt(III) Complexes as Bifunctional Brønsted Acid-Lewis Base Catalysts for the Preparation of Cyclic Organic Carbonates.

    Science.gov (United States)

    Rulev, Yuri A; Larionov, Vladimir A; Lokutova, Anastasia V; Moskalenko, Margarita A; Lependina, Ol'ga L; Maleev, Victor I; North, Michael; Belokon, Yuri N

    2016-01-01

    Stereochemically inert cationic cobalt(III) complexes were shown to be one-component catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide at 50 °C and 5 MPa carbon dioxide pressure. The optimal catalyst possessed an iodide counter anion and could be recycled. A catalytic cycle is proposed in which the ligand of the cobalt complexes acts as a hydrogen-bond donor, activating the epoxide towards ring opening by the halide anion and activating the carbon dioxide for subsequent reaction with the halo-alkoxide. No kinetic resolution was observed when terminal epoxides were used as substrates, but chalcone oxide underwent kinetic resolution. PMID:26663897

  9. A geochemical constraint on the formation process of a manganese carbonate nodule in the siliceous mudstone of the Jurassic accretionary complex in the Mino Belt, Japan

    Science.gov (United States)

    Nakada, Ryoichi; Shirai, Taka'aki; Takahashi, Satoshi; Suzuki, Noritoshi; Ogawa, Kazuhiro; Takahashi, Yoshio

    2014-12-01

    Manganese (Mn) carbonate nodules, which differ from seafloor Mn nodules mainly composed of MnO2, are occasionally embedded in the form of a lens shape in the Jurassic accretionary complexes, such as the Mino Belt in Japan. The interpretation of the formation process of Mn carbonate is still controversial, particularly concerning whether the Mn carbonate was formed primarily or secondarily. In this study, a fresh Mn carbonate nodule incorporated into the red siliceous mudstone was collected for geochemical and sedimentological analysis. The optical observation of thin sections indicates that the Mn carbonate nodules are composed of abraded grains of rhodochrosite spherule with radiolarians and are sedimentary embedded in siliceous mudstone. Microfossil radiolarians from the Mn carbonate nodules and the host red siliceous mudstone are dated as the Bajocian, but the radiolarians in the nodules are somewhat older than those in the host red siliceous mudstone. Geochemical analysis using the X-ray absorption near-edge structure on Ce indicates the dominance of trivalent Ce at present, despite the observation of a positive Ce anomaly in the PAAS-normalized REE pattern of Mn carbonate. The REE adsorption experiment on synthesized MnCO3 does not show any distinctive positive Ce anomaly, and a thermodynamic calculation suggests the possible coexistence of rhodochrosite and spontaneous oxidation of Ce. A leaching experiment that can selectively decompose the carbonate phase demonstrated no Ce anomaly in the carbonate phase of the Mn carbonate and a poor contribution to the bulk REE concentration. The carbon isotope data of Mn carbonate nodule implied the dominance of inorganic marine carbonate origin with small contribution of organic decomposition. The most plausible account of all of the observational and geochemical results is that the rhodochrosite grains were primarily formed on the depositional site and subsequently transferred to a different site, where siliceous

  10. Characterization of Carbon-Rich Phases in a Complex Microstructure of a Commercial X80 Pipeline Steel

    Science.gov (United States)

    Morales, E. V.; Bott, I. S.; Silva, R. A.; Morales, A. M.; de Souza, L. F. G.

    2016-05-01

    The wide use of the term M/A constituent conceals many complexities about shape, size, and composition. This work uses metallographic techniques and transmission electron microscopy to characterize the entire microstructure development which is observed during continuous cooling in a commercial X80 pipeline steel. A general model is presented which allows calculating the volume fractions of martensite and retained austenite, as well as their compositions in these carbon-rich phases of the M/A constituent for this commercial pipeline steel. This approach takes into account the allotriomorphic ferrite formation and the massive alloyed carbide precipitation before the acicular ferrite formation. Two morphologies (in the film and blocky forms) of the M/A constituent were registered. The calculated M/A volume fraction resulted in agreement with the fraction of this constituent experimentally obtained through the optical microscopy observations. This allowed the justification of the very small volumetric fraction of the M/A constituent with the film morphology.

  11. Kinetics of the Removal of Chromium Complex Dye from Aqueous Solutions Using Activated Carbons and Polymeric Adsorbent

    Directory of Open Access Journals (Sweden)

    Eglė Kazlauskienė

    2011-04-01

    Full Text Available The kinetics of the removal of chromium complex dye (Lanasyn Navy M-DNL from aqueous solutions using polymeric adsorbent Macronet MN 200 (MN 200 as an alternative option for activated carbon Norit RB 0.8 CC (AC was studied in the batch system. The residual colour of dye solution treated with AC or MN 200 strongly depends on solution pH with lower values at acidic pH when a positively charged surface net is favourable for the adsorption of the dye anion. The removal of dye using MN 200 was found relatively higher than that using AC. The pseudo-second order and intraparticle diffusion models agreed well with experimental data. The parameters of these models were studied as a function of temperature and adsorbent nature.Article in Lithuanian

  12. Actinide-to-carbon bonds in Cp2An(alkyl)2, -(butadiene), -(metallacyclopentadiene), and -(cyclobutadiene) complexes

    International Nuclear Information System (INIS)

    The electronic structure of actinide bis(cyclopentadienyl)dialkyl, -butadiene, -metallacyclopentadiene, and -cyclobutadiene complexes is examined. Some Cp*2Th(alkyl)2 complexes display an interesting structural deformation in which a Th-C-C(alkyl) angle (α) opens up considerably. A molecular orbital analysis of Cp2Th(C2H5)2 traces the deformation to the characteristic shape of the d/sub σ/ fragment orbital of Cp2Th(C2H5)+. The potential energy curve for the ethyl pivoting was found to be very soft, with a shallow minimum at α ∼ 1600. Nonrigidity of the ethyl orientation indicates that not only an α hydrogen but also a β hydrogen can come close to Th without a loss of Th-C bond strength; the discussion should provide a theoretical basis for understanding important aspects of C-H activation chemistry involving actinide centers. The Cp2An(s-cis-C4H6) complex was calculated to be 0.74 eV (Th) or 0.42 eV (U) more stable than its s-trans-C4H6 isomer, in contrast to the analogous Cp2Zr(C4H6) complex where the stability of the two geometrical isomers was well-balanced. The σ2,π character of the s-cis-C4H6 coordination to An is somewhat less pronounced than that in the Zr congener, in harmony with the X-ray structures, while highly negative charges are accumulated on the s-cis-C4H6 terminal carbons

  13. Sedimentology of a Mid-Late Ordovician carbonate mud-mound complex from the Kathmandu nappe in Central Nepal

    Science.gov (United States)

    Pas, Damien; Da Silva, Anne-Christine; Dhital, Megh Raj; Boulvain, Frédéric

    2011-08-01

    This sedimentological study of the Godavari quarry is the first relating to the Palaeozoic Tethyan sedimentary rocks of the Katmandu nappe (Central Nepal). Sedimentological analyses led to the identification of six microfacies belonging to a large carbonate mud-mound complex, which can be divided into mound, flank and off-mound main depositional settings. Identification of two dasycladaceans ( Dasyporell a cf. silurica ( Stolley, 1893) and Vermiporella sp.) in the mound facies gives a Mid-Late Ordovician age to this newly discovered Godavari carbonate mud-mound, which makes this mound one of the oldest ever described in the Asian continent. The mound microfacies are characterized by a high micritic content, the presence of stromatactis and the prevalence of red coloured sediments (the red pigmentation probably being related to organic precipitation of iron). The flank microfacies are characterized by a higher crinoid and argillaceous content and the presence of bio- and lithoclasts concentrated in argillaceous lenses. Finally, the off-mound microfacies show very few bioclasts and a high argillaceous content. Palaeoenvionmental interpretation of microfacies, in terms of bathymetry, leads us to infer that the Godavari mud-mound started to grow in a deep environment setting below the photic and wave action zones and that it evolved to occupy a location below the fair weather wave base. Cementation of cavities within the mound facies underlines a typical transition from a marine to a burial diagenetic environment characterized by: (1) a radiaxial non luminescent feroan calcite cement (marine) showing a bright orange luminescent band in its middle part; (2) a bright zoned orange fringe of automorphic feroan calcite (meteoric phreatic); (3) a dull orange xenomorphic feroan calcite cement in the centre of cavities (burial) and (4) a saddle dolomite within the centre of larger cavities. The faunal assemblage (diversity and relative proportion) of the Godavari mound facies

  14. Luminescent blooming of dendronic carbon nanotubes through ion-pairing interactions with an Eu(III) complex.

    Science.gov (United States)

    Maggini, Laura; Toma, Francesca Maria; Feruglio, Luigi; Malicka, Joanna M; Da Ros, Tatiana; Armaroli, Nicola; Prato, Maurizio; Bonifazi, Davide

    2012-05-01

    A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with a second-generation polyamidoamine (PAMAM) dendron, presenting four terminal amino groups per grafted aryl moiety. These reactive functions were alkylated to obtain a positively charged polycationic dendron/carbon nanotube system (d-MWCNTs⋅Cl), which eventually underwent anion exchange reaction with a negatively charged and highly luminescent Eu(III) complex ([EuL(4)]⋅NEt(4), in which L = (2-naphtoyltrifluoroacetonate)). This process afforded the target material d-MWCNTs⋅[EuL(4)], in which MWCNTs are combined with red-emitting Eu(III) centers through electrostatic interactions with the dendronic branches. Characterization of the novel MWCNT materials was accomplished by means of TGA and TEM, whereas d-MWCNTs⋅Cl and d-MWCNTs⋅ [EuL(4)] further underwent XPS, SEM and Raman analyses. These studies demonstrate the integrity of the luminescent [EuL(4)](-) center in the luminescent hybrid, the massive load of the cationic binding sites, and the virtually complete anion-exchange into the final hybrid material. The occurrence of the ion-pairing interaction with MWCNTs was unambiguously demonstrated through DOSY NMR diffusion studies. Photophysical investigations show that MWCNTs⋅[EuL(4)] is a highly soluble and brightly luminescent red hybrid material in which MWCNTs act as photochemically inert scaffolds with negligible UV/Vis absorption, compared with the grafted Eu complex, and with no quenching activity. The high dispersibility of MWCNTs⋅[EuL(4)] in a polymer matrix makes it a promising luminophore for applications in material science. PMID:22488679

  15. Electrocatalytic oxidation of some amino acids on a nickel-curcumin complex modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Majdi, S. [Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of); Jabbari, A. [Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran (Iran, Islamic Republic of)]. E-mail: jabbari@kntu.ac.ir; Heli, H. [Institute of Biochemistry and Biophysics, University of Tehran, Tehran (Iran, Islamic Republic of); Moosavi-Movahedi, A.A. [Institute of Biochemistry and Biophysics, University of Tehran, Tehran (Iran, Islamic Republic of)

    2007-04-01

    This study investigated the electrocatalytic oxidation of alanine, L-arginine, L-phenylalanine, L-lysine and glycine on poly-Ni(II)-curcumin film (curcumin: 1,7-bis [4-hydroxy-3-methoxy phenyl]-1,6-heptadiene-3,5-dione) electrodeposited on a glassy carbon electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of amino acids the anodic peak current of low valence nickel species increased, followed by a decrease in the corresponding cathodic current. This indicates that amino acids were oxidized on the redox mediator which was immobilized on the electrode surface via an electrocatalytic mechanism. Using Laviron's equation, the values of {alpha} and k {sub s} for the immobilized redox species were determined as 0.43 {+-} 0.03 and 2.47 {+-} 0.02 x 10{sup 6} s{sup -1}, respectively. The rate constant, the electron transfer coefficient and the diffusion coefficients involved in the electrocatalytic oxidation of amino acids were determined.

  16. Conformational Mobility of GOx Coenzyme Complex on Single-Wall Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Yu Kang

    2008-12-01

    Full Text Available A critical issue in bioelectrochemical applications that use electrodes modified by Single Wall Carbon Nanotubes (SWCNTs is to ensure high activity of the catalytic site of an immobilized enzyme protein interacting with nanomaterials. Since Flavin Adenine Dinucleotide (FAD, a coenzyme of glucose oxidase (GOx, is the active center of the catalytic site, conformation of which could determine the activity of enzyme, it is important to understand the dynamic mechanism of its conformational mobility while GOx is adsorbed on SWCNTs with multiple orientations. However, this dynamic mechanism still remains unclear at the atomic level due to the coenzyme being embedded in the apo-GOx and the limitations of appropriate experimental methods. In this study, a molecular dynamics (MD simulation was performed to investigate the conformational mobility mechanism of the coenzyme. The trajectory and the interaction energy clearly indicate that the adsorption of GOx onto SWCNTs plays an important role in the conformational mobility of the coenzyme, and its mobility is greatly affected by the distribution of water molecules due to it being hydrophobic.

  17. The complex environment of the bright carbon star TX Psc as probed by spectro-astrometry

    CERN Document Server

    Hron, J; Aringer, B; Klotz, D; Lebzelter, T; Paladini, C; Wiedemann, G

    2015-01-01

    Context: Stars on the asymptotic giant branch (AGB) show broad evidence of inhomogeneous atmospheres and circumstellar envelopes. These have been studied by a variety of methods on various angular scales. In this paper we explore the envelope of the well-studied carbon star TX Psc by the technique of spectro-astrometry. Aims: We explore the potential of this method for detecting asymmetries around AGB stars. Methods:We obtained CRIRES observations of several CO $\\Delta$v=1 lines near 4.6 $\\mu$m and HCN lines near 3 $\\mu$m in 2010 and 2013. These were then searched for spectro-astrometric signatures. For the interpretation of the results, we used simple simulated observations. Results: Several lines show significant photocentre shifts with a clear dependence on position angle. In all cases, tilde-shaped signatures are found where the positive and negative shifts (at PA 0deg) are associated with blue and weaker red components of the lines. The shifts can be modelled with a bright blob 70 mas to 210 mas south of...

  18. Electrocatalytic oxidation of some amino acids on a nickel-curcumin complex modified glassy carbon electrode

    International Nuclear Information System (INIS)

    This study investigated the electrocatalytic oxidation of alanine, L-arginine, L-phenylalanine, L-lysine and glycine on poly-Ni(II)-curcumin film (curcumin: 1,7-bis [4-hydroxy-3-methoxy phenyl]-1,6-heptadiene-3,5-dione) electrodeposited on a glassy carbon electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques. Voltammetric studies indicated that in the presence of amino acids the anodic peak current of low valence nickel species increased, followed by a decrease in the corresponding cathodic current. This indicates that amino acids were oxidized on the redox mediator which was immobilized on the electrode surface via an electrocatalytic mechanism. Using Laviron's equation, the values of α and k s for the immobilized redox species were determined as 0.43 ± 0.03 and 2.47 ± 0.02 x 106 s-1, respectively. The rate constant, the electron transfer coefficient and the diffusion coefficients involved in the electrocatalytic oxidation of amino acids were determined

  19. Suzuki-Miyaura, Mizoroki-Heck carbon-carbon coupling and hydrogenation reactions catalysed by PdII and RhI complexes containing cyclodiphosphazane cis-{tBuNP(OC6H4OMe-)}2

    Indian Academy of Sciences (India)

    Sasmita Mohanty; Maravanji S Balakrishna

    2010-03-01

    The catalytic activity of the palladium complex cis-[PdCl2{(tBuNP(OC6H4OMe-))2- }2] (2) containing cis-{tBuNP(OC6H4OMe-)}2 (1) in Suzuki-Miyaura and Mizoroki-Heck carbon-carbon cross coupling reactions is described. The compound 2 also displays very high activity in Mizoroki-Heck coupling reactions. The rhodium(I) complex [RhCl(COD){(tBuNP(OC6H4OMe-))2- }] (3) acts as an excellent catalyst for the hydrogenation of several terminal olefins.

  20. A study of the catalytic activity of symmetric and unsymmetric macrocyclic [N42−] coordinated nickel complexes for electrochemical reduction of carbon dioxide

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • The electrochemical behavior of two Ni (II) complexes was studied. • Symmetric and unsymmetric Ni (II) complexes were used for electrocatalytic reduction of CO2. • The symmetric complexe is more convenient for electrocatalytic reduction of CO2. • There is no visible loss of activity of the complexes in the presence of CO2. - Abstract: The electrochemical behavior of [NiII(Me4-(NO2Bzo)2[14]tetraeneN4)] (as a symmetric complex) and [NiII(Me4-NO2Bzo[15]tetraeneN4)] (as an unsymmetric complex) was studied at different electrode surfaces using cyclic voltammetry and chronoamperometry methods. The cyclic voltammograms of the complexes showed two one-electron irreversible oxidation processes (ligand-localized) as well as a one-electron quasi-reversible redox couple (metal-localized) at a more negative potential. The electropolymerization was performed by one-electron oxidation of the complexes at Pt and glassy carbon electrodes. The heterogeneous and homogeneous electrocatalytic activities of the complexes for CO2 reduction were also studied. In each case, both complexes exhibited excellent electrocatalytic activities for the reduction of carbon dioxide in an ACN solution. This was with an increase of the cathodic current and a diminution of the over-potential more than 600 mV, as compared to the processes at the absence of the complexes. The diffusion coefficients, D, of the complexes and the homogeneous electron transfer rate constants of the reaction between the electrochemically reduced nickel complex and CO2 were also determined using electrochemical methods. Finally, deactivation of complexes by follow-up reactions with CO2 was tested using cyclic voltammetric and electrolysis experiments

  1. Liposome encapsulation of lipophilic N-alkyl-propanediamine platinum complexes: impact on their cytotoxic activity and influence of the carbon chain length

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Heveline; Fontes, Ana Paula S. [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica; Lopes, Miriam Teresa P. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Farmacologia; Frezard, Frederic, E-mail: frezard@icb.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica

    2010-07-01

    Antitumor platinum(II) complexes derived from N-alkyl-propanediamine differing in the length of their carbon chain (C8, C10, C12 and C14) were incorporated in liposomes and the cytotoxic activity of these formulations was evaluated against tumor (A{sub 549}, MDA-MB-231, B16-F1 and B16-F10) and non-tumor (BHK-21 and CHO) cell lines. Stable and monodisperse liposome suspensions incorporating the platinum complexes were obtained from the lipid composition consisting of distearoyl-sn-glycero-3-phosphocholine, cholesterol and 1,2-distearoyl-sn-glycero- 3-phosphoethanolamine-N-(methoxy(polyethylene glycol)-2000) at 5:3:0.3 molar ratio. The entrapment efficiency (EE%) of the platinum complexes in liposomes increased with the carbon chain length. EE% was higher than 80% in C12- and C14-derivatives. The effect of liposome encapsulation on the cytotoxic activity of the complexes was found to depend on the carbon chain length. These data indicate that the highest drug bioavailability from liposome formulations was achieved with the complex showing intermediate carbon chain length and partition between the liposome membrane and aqueous phase. (author)

  2. Gas-phase noncovalent functionalization of carbon nanotubes with a Ni(II) tetraaza[14]annulene complex

    International Nuclear Information System (INIS)

    The noncovalent functionalization of carbon nanotubes (CNTs) with aromatic polyazamacrocyclic compounds, based on π–π-interactions, keeps the intrinsic electronic structure of CNTs totally intact and allows for combining unique properties of the two interacting components. In addition to porphyrins and phthalocyanines, there are other, simpler compounds exhibiting similar properties, potentially useful for photovoltaic, catalytic and electrochemical applications: for example, tetraaza[14]annulenes. Many of them are highly thermally stable, which makes it possible to employ physical vapor deposition for the preparation of macrocycle–nanotube hybrids. One of such compounds is Ni(II) complex of 5,7,12,14-tetramethyldibenzo-1,4,8,11-tetraazacyclotetradeca-3,5,7,10,12, 14-hexaene (also called Ni(II)-tetramethyldibenzotetraaza[14]annulene, or NiTMTAA for simplicity). In the present work, we attempted the noncovalent functionalization of both single-walled and multi-walled CNTs with NiTMTAA in the gas phase at two selected temperatures of 220 and 270 °C, which does not require the use of organic solvents and therefore can be considered as ecologically friendly. The nanohybrids obtained were characterized by means of scanning and transmission electron microscopy, energy dispersive X-ray, Fourier-transform infrared and Raman spectroscopy, as well as thermogravimetric analysis. An additional insight into the structure of adsorption complexes of NiTMTAA on CNTs was provided from density functional theory and molecular mechanics calculations.

  3. In vitro platelet activation, aggregation and platelet-granulocyte complex formation induced by surface modified single-walled carbon nanotubes.

    Science.gov (United States)

    Fent, János; Bihari, Péter; Vippola, Minnamari; Sarlin, Essi; Lakatos, Susan

    2015-08-01

    Surface modification of single-walled carbon nanotubes (SWCNTs) such as carboxylation, amidation, hydroxylation and pegylation is used to reduce the nanotube toxicity and render them more suitable for biomedical applications than their pristine counterparts. Toxicity can be manifested in platelet activation as it has been shown for SWCNTs. However, the effect of various surface modifications on the platelet activating potential of SWCNTs has not been tested yet. In vitro platelet activation (CD62P) as well as the platelet-granulocyte complex formation (CD15/CD41 double positivity) in human whole blood were measured by flow cytometry in the presence of 0.1mg/ml of pristine or various surface modified SWCNTs. The effect of various SWCNTs was tested by whole blood impedance aggregometry, too. All tested SWCNTs but the hydroxylated ones activate platelets and promote platelet-granulocyte complex formation in vitro. Carboxylated, pegylated and pristine SWCNTs induce whole blood aggregation as well. Although pegylation is preferred from biomedical point of view, among the samples tested by us pegylated SWCNTs induced far the most prominent activation and a well detectable aggregation of platelets in whole blood. PMID:25956790

  4. Electro-oxidation of chlorophenols at glassy carbon electrodes modified with polyNi(II)complexes

    International Nuclear Information System (INIS)

    The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (-NH2 or -SO3-) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic C=O stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH)2 clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH)2 clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH)2 clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs.

  5. Insight into the Iron-Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands.

    Science.gov (United States)

    Čorić, Ilija; Holland, Patrick L

    2016-06-15

    Nitrogenase enzymes are used by microorganisms for converting atmospheric N2 to ammonia, which provides an essential source of N atoms for higher organisms. The active site of the molybdenum-dependent nitrogenase is the unique carbide-containing iron-sulfur cluster called the iron-molybdenum cofactor (FeMoco). On the FeMoco, N2 binding is suggested to occur at one or more iron atoms, but the structures of the catalytic intermediates are not clear. In order to establish the feasibility of different potential mechanistic steps during biological N2 reduction, chemists have prepared iron complexes that mimic various structural aspects of the iron sites in the FeMoco. This reductionist approach gives mechanistic insight, and also uncovers fundamental principles that could be used more broadly for small-molecule activation. Here, we discuss recent results and highlight directions for future research. In one direction, synthetic iron complexes have now been shown to bind N2, break the N-N triple bond, and produce ammonia catalytically. Carbon- and sulfur-based donors have been incorporated into the ligand spheres of Fe-N2 complexes to show how these atoms may influence the structure and reactivity of the FeMoco. Hydrides have been incorporated into synthetic systems, which can bind N2, reduce some nitrogenase substrates, and/or reductively eliminate H2 to generate reduced iron centers. Though some carbide-containing iron clusters are known, none yet have sulfide bridges or high-spin iron atoms like the FeMoco. PMID:27171599

  6. Hydrogen and carbon abundances and isotopic ratios in apatite from alkaline intrusive complexes, with a focus on carbonatites

    Energy Technology Data Exchange (ETDEWEB)

    Nadeau, S.L.; Epstein, S.; Stolper, E. [California Inst. of Tech., Pasadena, CA (United States). Div. of Geological and Planetary Sciences

    1999-06-01

    The authors report H and C contents and {delta}D and {delta}{sup 13}C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating temperatures up to 1,500 C is needed to extract fully H{sub 2}O and CO{sub 2} from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2--1.1 wt% H{sub 2}O and 0.05--0.70 wt% CO{sub 2}; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1--0.2% H{sub 2}O and 0.01--0.11% CO{sub 2}). D/H ratios in apatites from these rocks are bimodally distributed. The authors suggest that the {delta}D values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H{sub 2}O contents and {delta}D values. In contrast to H{sub 2}O contents and {delta}D values, CO{sub 2} contents and {delta}{sup 13}C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other could be associated with hydrocarbons.

  7. Electro-oxidation of chlorophenols at glassy carbon electrodes modified with polyNi(II)complexes

    Energy Technology Data Exchange (ETDEWEB)

    Berrios, Cristhian [Facultad de Quimica y Biologia, Departamento de Ciencias del Ambiente, Universidad de Santiago de Chile (USACh), casilla 40, correo 33, Santiago (Chile); Marco, Jose F.; Gutierrez, Claudio [Instituto de Quimica Fisica ' Rocasolano' , CSIC, C. Serrano, 119, 28006, Madrid (Spain); Ureta-Zanartu, Maria Soledad [Facultad de Quimica y Biologia, Departamento de Ciencias del Ambiente, Universidad de Santiago de Chile (USACh), casilla 40, correo 33, Santiago (Chile)], E-mail: soledad.ureta@usach.cl

    2009-11-01

    The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (-NH{sub 2} or -SO{sub 3}{sup -}) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic C=O stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH){sub 2} clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH){sub 2} clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH){sub 2} clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs.

  8. Amazon Rainforest Exchange of Carbon and Subcanopy Air Flow: Manaus LBA Site—A Complex Terrain Condition

    Directory of Open Access Journals (Sweden)

    Julio Tóta

    2012-01-01

    Full Text Available On the moderately complex terrain covered by dense tropical Amazon Rainforest (Reserva Biologica do Cuieiras—ZF2—02°36′17.1′′ S, 60°12′24.4′′ W, subcanopy horizontal and vertical gradients of the air temperature, CO2 concentration and wind field were measured for the dry and wet periods in 2006. We tested the hypothesis that horizontal drainage flow over this study area is significant and can affect the interpretation of the high carbon uptake rates reported by previous works at this site. A similar experimental design as the one by Tóta et al. (2008 was used with a network of wind, air temperature, and CO2 sensors above and below the forest canopy. A persistent and systematic subcanopy nighttime upslope (positive buoyancy and daytime downslope (negative buoyancy flow pattern on a moderately inclined slope (12% was observed. The microcirculations observed above the canopy (38 m over the sloping area during nighttime presents a downward motion indicating vertical convergence and correspondent horizontal divergence toward the valley area. During the daytime an inverse pattern was observed. The micro-circulations above the canopy were driven mainly by buoyancy balancing the pressure gradient forces. In the subcanopy space the microcirculations were also driven by the same physical mechanisms but probably with the stress forcing contribution. The results also indicated that the horizontal and vertical scalar gradients (e.g., CO2 were modulated by these micro-circulations above and below the canopy, suggesting that estimates of advection using previous experimental approaches are not appropriate due to the tridimensional nature of the vertical and horizontal transport locally. This work also indicates that carbon budget from tower-based measurement is not enough to close the system, and one needs to include horizontal and vertical advection transport of CO2 into those estimates.

  9. Genesis of supported carbon-coated Co nanoparticles with controlled magnetic properties, prepared by decomposition of chelate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tarasov, Konstantin; Beaunier, Patricia; Che, Michel; Marceau, Eric, E-mail: eric.marceau@upmc.fr [Laboratoire de Reactivite de Surface (UMR 7197, CNRS), UPMC (Universite Pierre et Marie Curie) (France); Li Yanling [CNRS (France)

    2011-05-15

    Following procedures formerly developed for the preparation of supported heterogeneous catalysts, carbon-coated cobalt nanoparticles dispersed on porous alumina have been prepared by impregnation of {gamma}-Al{sub 2}O{sub 3} with (NH{sub 4}){sub 2}[Co(EDTA)] and thermal decomposition in inert atmosphere. Below 350 Degree-Sign C, Co(II) ions are complexed in a hexa-coordinated way by the EDTA ligand. The thermal treatment at 400-900 Degree-Sign C leads to the EDTA ligand decomposition and recovering of the support porosity, initially clogged by the impregnated salt. According to X-ray absorption spectroscopy, and due to in situ redox reactions between the organic ligand and Co(II), both oxidic and metallic cobalt phases are formed. Characterisation by transmission electron microscopy, X-ray diffraction and magnetic measurements reveals that an increase in the treatment temperature leads to an increase of the degree of cobalt reduction as well as to a growth of the cobalt metal particles. As a consequence, the samples prepared at 400-700 Degree-Sign C exhibit superparamagnetism and a saturation magnetisation of 1.7-6.5 emu g{sup -1} at room temperature, whilst the sample prepared at 900 Degree-Sign C has a weak coercivity (0.1 kOe) and a saturation magnetisation of 12 emu g{sup -1}. Metal particles are homogeneously dispersed on the support and appear to be protected by carbon; its elimination by a heating in H{sub 2} at 400 Degree-Sign C is demonstrated to cause sintering of the metal particles. The route investigated here can be of interest for obtaining porous magnetic adsorbents or carriers with high magnetic moments and low coercivities, in which the magnetic nanoparticles are protected from chemical aggression and sintering by their coating.

  10. Creep-resistant porous structures based on stereo-complex forming triblock copolymers of 1,3-trimethylene carbonate and lactides

    NARCIS (Netherlands)

    Zhang, Zheng; Grijpma, Dirk W.; Feijen, Jan

    2004-01-01

    Stereo-complexes (poly(ST–TMC–ST)) of enantiomeric triblock copolymers based on 1,3-trimethylene carbonate (TMC) and L- or D-lactide (poly(LLA–TMC–LLA) and poly(DLA–TMC–DLA)) were prepared. Films of poly(ST–TMC–ST) could be prepared by solvent casting mixtures of equal amounts of poly(LLA–TMC–LLA) a

  11. Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Mohebbi, Sajjad, E-mail: smohebbi@uok.ac.ir; Eslami, Saadat

    2015-06-15

    Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT and new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.

  12. Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

    International Nuclear Information System (INIS)

    Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N2O2 Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT and new N2O2 unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO2 and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity

  13. Depletion of the "gamma-type carbonic anhydrase-like" subunits of complex I affects central mitochondrial metabolism in Arabidopsis thaliana.

    Science.gov (United States)

    Fromm, Steffanie; Göing, Jennifer; Lorenz, Christin; Peterhänsel, Christoph; Braun, Hans-Peter

    2016-01-01

    "Gamma-type carbonic anhydrase-like" (CAL) proteins form part of complex I in plants. Together with "gamma carbonic anhydrase" (CA) proteins they form an extra domain which is attached to the membrane arm of complex I on its matrix exposed side. In Arabidopsis two CAL and three CA proteins are present, termed CAL1, CAL2, CA1, CA2 and CA3. It has been proposed that the carbonic anhydrase domain of complex I is involved in a process mediating efficient recycling of mitochondrial CO2 for photosynthetic carbon fixation which is especially important during growth conditions causing increased photorespiration. Depletion of CAL proteins has been shown to significantly affect plant development and photomorphogenesis. To better understand CAL function in plants we here investigated effects of CAL depletion on the mitochondrial compartment. In mutant lines and cell cultures complex I amount was reduced by 90-95% but levels of complexes III and V were unchanged. At the same time, some of the CA transcripts were less abundant. Proteome analysis of CAL depleted cells revealed significant reduction of complex I subunits as well as proteins associated with photorespiration, but increased amounts of proteins participating in amino acid catabolism and stress response reactions. Developmental delay of the mutants was slightly alleviated if plants were cultivated at high CO2. Profiling of selected metabolites revealed defined changes in intermediates of the citric acid cycle and amino acid catabolism. It is concluded that CAL proteins are essential for complex I assembly and that CAL depletion specifically affects central mitochondrial metabolism. PMID:26482706

  14. Reservoir Modeling of Carbonate on Fika Field: The Challenge to Capture the Complexity of Rock and Oil Types

    Directory of Open Access Journals (Sweden)

    Erawati Fitriyani Adji

    2014-09-01

    Full Text Available DOI: 10.17014/ijog.v1i2.181The carbonate on Fika Field has a special character, because it grew above a basement high with the thickness and internal character variation. To develop the field, a proper geological model which can be used in reservoir simulation was needed. This model has to represent the complexity of the rock type and the variety of oil types among the clusters. Creating this model was challenging due to the heterogeneity of the Baturaja Formation (BRF: Early Miocene reef, carbonate platform, and breccia conglomerate grew up above the basement with a variety of thickness and quality distributions. The reservoir thickness varies between 23 - 600 ft and 3D seismic frequency ranges from 1 - 80 Hz with 25 Hz dominant frequency. Structurally, the Fika Field has a high basement slope, which has an impact on the flow unit layering slope. Based on production data, each area shows different characteristics and performance: some areas have high water cut and low cumulative production. Oil properties from several clusters also vary in wax content. The wax content can potentially build up a deposit inside tubing and flow-line, resulted in a possible disturbance to the operation. Five well cores were analyzed, including thin section and XRD. Seven check-shot data and 3D seismic Pre-Stack Time Migration (PSTM were available with limited seismic resolution. A seismic analysis was done after well seismic tie was completed. This analysis included paleogeography, depth structure map, and distribution of reservoir and basement. Core and log data generated facies carbonate distribution and rock typing, defining properties for log analysis and permeability prediction for each zone. An Sw prediction for each well was created by J-function analysis. This elaborates capillary pressure from core data, so it is very similar to the real conditions. Different stages of the initial model were done i.e. scale-up properties, data analysis, variogram modeling

  15. Miocene reefs evolution within the shelf carbonates and fan delta complexes of the Antalya basin, southern Turkey

    Science.gov (United States)

    Karabiyikoglu, M.; Çiner, A.; Tuzcu, S.

    2003-04-01

    Coral reefs provide sensitive records of tectonics, climatic and sea-level changes as well as palaeoecological conditions of the environmental settings that prevailed during their development. Miocene coral reefs and reef-derived sediments are common constituents of the clastic-dominated succession of the late orogenic depositional fill of the Late Cenozoic Antalya Basin (subdivided into Manavgat, Köprüçay and Aksu sub-basins) in the western Taurides Mountains. Two distinct developments of coral reefs have been recognised: 1) Late Burdigalian-Langhian reefs: They occur as massive, small, isolated, mound-like patch reefs formed on clast-supported conglomerate facies of fan delta and algal-foraminiferal wacke-packstone facies of transgressive open shelf carbonates within the Manavgat and the Köprüçay sub-basins. They are characterized by a massive reef core facies, largely made-up of rich and diversified Faviidae (Porites, Stylophora) dominated hermatypic coral colonies comprising occasional single corals (Mussidae, Caryophyllidae) reflecting relative changes in the bathimetry. The hermatypic coral colonies are mainly composed of massive, domal and branching forms without any distinct zonation within the reef framework. Abundant calcareous algae, bryozoans, bivalves, echinoids, gastropods and benthic and planktic foraminifers are also common within the reef bodies. 2) Tortonian-Messinian reefs: They only occur in the Aksu sub-basin as massive, relatively larger, oval bodies developed on clast-supported conglomerate facies of coastal alluvial fan/fan-delta complexes that formed in a paralic-shallow marine setting. The reef framework is characteristically dominated by Porites (branching and nodular forms) with subordinate Tarbellastraea and rare Siderastraea (massive globular forms), Plesiastraea and Favites. The Miocene coral reef growth and development in the western Taurides are closely related to the complex interaction of sporadic influxes of coarse

  16. Complexation of manganese(II) by cyclohexano-15-crown-5 in propylene carbonate: Calorimetric and X-ray crystallographic investigation

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Yanpei; Burns, J.H.; Moyer, B.A. [Oak Ridge National Lab., TN (United States)

    1995-01-04

    Calorimetric titrimetry reveals that cyclohexano-15-crown-5 (C15C5) forms a 1:1 complex with Mn(II) ions (2.5 mM) in propylene carbonate (PC) solution to which was added levels of water up to 134 mM. The reaction proceeds with a strong driving force (log K = 4.7-5.0) and is enthalpically driven overall, but the magnitude of the enthalpy change decreases with increasing water concentration in the case of the Mn(II) nitrate salt. A minor anion effect occurs in which the trifluoromethansulfonate ion gives slightly more negative values of {Delta}H and T{Delta}S than the nitrate ion. Values of log K, however, do not change appreciably with increasing water concentration, nor are they dependent on the anion. The crystal structure of Mn(C15C5)(CF{sub 3}SO{sub 3}){sub 2} was determined, showing that the Mn(II) ion is coordinated by a pentagonal bipyramid of oxygen atoms provided by the equatorial crown {Angstrom}, b=14.145(1) {Angstrom}, c = 13,420(1) {Angstrom} {beta} = 100.31(2){degrees}, V = 5028 {Angstrom}{sup 3}, Z = 8, t = 26 {degrees}C. For 2178 reflections with I > {sigma}(I), and 325 parameters, R(F) = 0.050 and R{sub w}(F) = 0.054.

  17. Cooperative effect by monopodal silica-supported niobium com-plexes pairs enhancing catalytic cyclic carbonate production

    KAUST Repository

    D'Elia, Valerio

    2015-05-07

    Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica supported Nb-species by reacting a molecular niobium precursor [NbCl5•OEt2] with silica dehydroxylated at 700 °C (SiO2-700) or at 200 oC (SiO2-200) to generate diverse surface complexes. The product of the reaction between SiO2-700 and [NbCl5•OEt2] was identified as a monopodal supported surface species [≡SiONbCl4•OEt2] (1a). The reactions of SiO2-200 with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3•OEt2]. 93Nb SSNMR spectra of 1a-3a and 31P SSNMR on their PMe3 derivatives (1b-3b) led to the unambiguous assignment of 1a as a single site, monopodal Nb-species while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4•OEt2] and 3a being mostly bipodal [≡S ONbCl3•OEt2]. Double-quantum/single-quantum 31P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprece-dented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of the NbCl5 catalyzed cycloaddition in the homogeneous phase.

  18. Assignment of hyperfine shifted haem methyl carbon resonances in paramagnetic low-spin met-cyano complex of sperm whale myoglobin

    International Nuclear Information System (INIS)

    The hyperfine shifted resonances arising from all four individual haem carbons of the paramagnetic low-spin met-cyano complex of sperm whale myoglobin have been clearly identified and assigned for the first time with the aid of 1H-13C heteronuclear chemical shift correlated spectroscopy. Alteration of the in-plane symmetry of the electronic structure of haem induced by the ligation of proximal histidyl imidazole spreads the haem carbon resonances to 32 ppm at 220C, indicating the sensitivity of those resonances to the haem electronic/molecular structure. Those resonances are potentially powerful probes in characterizing the nature of haem electronic structure. 25 refs.; 2 figs.; 1 table

  19. Tumor Acidity-Induced Sheddable Polyethylenimine-Poly(trimethylene carbonate)/DNA/Polyethylene Glycol-2,3-Dimethylmaleicanhydride Ternary Complex for Efficient and Safe Gene Delivery.

    Science.gov (United States)

    Zhao, Caiyan; Shao, Leihou; Lu, Jianqing; Deng, Xiongwei; Wu, Yan

    2016-03-16

    Amphiphilic PEI derivatives/DNA complexes are widely used for DNA delivery, but they are unstable in vivo and have cytotoxicity due to the excess cationic charge. PEGylation of cationic complexes can improve sterical stability and biocompatibility. However, PEGylation significantly inhibits cellular uptake and endosomal escape. In this work, sheddable ternary complexes were developed by coating a tumor acidity-sensitive β-carboxylic amide functionalized PEG layer on the binary complexes of amphiphilic cationic polyethylenimine-poly(trimethylene carbonate) nanoparticles/DNA (PEI-PTMC/DNA). Such sheddable ternary complexes markedly reduced their nonspecific interactions with serum protein in the bloodstream and obtained minimal cytotoxicity due to the protection of the PEG shell. At the tumor site, the PEG layer was deshielded by responding to the tumor acidic microenvironment and the positively charged complexes re-exposed that had higher affinity with negatively charged cell membranes. Meanwhile the positively charged complexes facilitated endosomal escape. Accordingly, this delivery system improved the biocompatibility of gene-loaded complexes and enhanced the gene transfection efficiency. Such PEGylated complexes with the ability to deshield the PEG layer at the target tissues hold great promise for efficient and safe gene delivery in vivo. PMID:26904916

  20. Paramagnetic ion binding to amino acids: The structure of the manganese (II)-L-proline complex from carbon-13 relaxation data

    International Nuclear Information System (INIS)

    Carbon-13 longitudinal relaxation times T1 of aqueous solutions of proline at pH = 11 containing 10-4-10-5M manganese(II) perchlorate are measured at 62.86 MHz und 600C. Under these conditions, the Mn2+ cation is bound to three proline molecules in their dibasic form to form the complex [Mn(L-PRO-)3]-. The relaxation of carbons α, β, γ, delta in this complex is shown to be dipolar. The relevant correlation time is rotational tausub(r) = 4.3 x 1011s (at 600C). A method is given to compute the Mn2+-13C distances in the complex from the paramagnetic relaxation rates 1/T1sub(M) of carbons α to delta and an assumed geometry of the proline molecule. The manganes (II) cation may be positioned with respect to each proline ligand, thus determining the structure of the hexacoordinated complex. The sites of coordination are the uncharged nitrogen and one carboxylic oxygen atom of the proline molecules, their distance to the Mn2+ cation are respectively 2.22 and 1.97 A. (orig.)

  1. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Directory of Open Access Journals (Sweden)

    A. Yool

    2013-02-01

    Full Text Available MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically-driven change in the World Ocean (Yool et al., 2011. The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. Since the beginning of the industrial era, the atmospheric concentration of carbon dioxide (CO2 has significantly increased above its natural, inter-glacial background concentration. Simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, therefore requires that both organic and inorganic carbon be afforded a full representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter, as well as a simple benthic formulation and extended parameterisations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal hindcast simulation described (1860–2005, to evaluate the biogeochemical performance of the model.

  2. Inhibition of precipitation of carbonate apatite by trisodium citrate analysed in base of the formation of chemical complexes in growth solution

    Science.gov (United States)

    Prywer, Jolanta; Olszynski, Marcin; Mielniczek-Brzóska, Ewa

    2015-11-01

    Effect of trisodium citrate on the precipitation of carbonate apatite is studied. The experimental series are performed in the solution of artificial urine. The investigations are related to infectious urinary stones formation as carbonate apatite is one of the main components of this kind of stones. To mimic a real infection in urinary tract the aqueous ammonia solution was added to the solution of artificial urine. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to carbonate apatite formation and decreases the efficiency of carbonate apatite precipitation. The inhibitory effect of trisodium citrate on the precipitation of carbonate apatite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is mainly related with the fact that trisodium citrate binds Ca2+ ions and causes the formation of CaCit- and Ca10(PO4)6CO3 complexes. Trisodium citrate binds Ca2+ ions in the range of pH from 6 to 9.5 for which carbonate apatite is favored to be formed.

  3. Les trifluoro(organo)borates de potassium : nouvelles perspectives pour la formation de liaisons carbone-carbone à l'aide de complexes du rhodium

    OpenAIRE

    Pucheault, Mathieu

    2004-01-01

    This manuscript describes the use of potassium trifluoro(organo)borates in rhodiumcatalyzed carbon-carbon bond forming reactions. These easy to purify and very stable reagents turned out to constitute a valuable alternative to other boron reagents commonly used in transition metal catalyzed reactions. Asymmetric rhodium-catalyzed 1,4-additions of trifluoroborates were developed with the use of a chiral diphosphine which allowed a good control of the enantioselectivity. Under neutral condition...

  4. pH coupled co-precipitation of alkaline-earth carbonates and silica - complex materials from simple chemistry

    OpenAIRE

    Eiblmeier, Josef

    2013-01-01

    The present work deals with the mineralization of alkaline-earth carbonates (mainly barium carbonate) from dilute silica solutions at high pH. It has for long been known that the concerted interaction between these purely inorganic components leads to amazing architectures with intricately curved and helical shapes, which were termed silica-carbonate biomorphs. Recently a general concept was proposed by García-Ruiz and co-workers that explains the spontaneous formation of these biomimetic agg...

  5. Synthesis of superparamagnetic carbon nanotubes immobilized Pt and Pd pincer complexes: highly active and selective catalysts towards cyclohexane oxidation with dioxygen.

    Science.gov (United States)

    Machado, Kelly; Mishra, Jaya; Suzuki, Shinzo; Mishra, Gopal S

    2014-12-14

    Single-walled carbon nanotubes (SWNTs) with Ni/Co have been prepared using an arc discharge technique and Ni/Co-carbon composite rods in an inert atmosphere and were surface modified using 3-aminophenyl trimethoxysilane. These NH2-functionalized magnetic carbon nanotubes have been used as a novel support for Pd((II)) and Pt((II)) pincer complexes immobilized as magnetic nano-catalysts. The morphology of the support and the catalysts have been characterized by IR, EPR, SEM, TGA, TEM, XRD, AAS and EDS analysis. These magnetic nano-catalysts have been tested on the industrially important cyclohexane (Cy-hx) oxidation with O2 and significantly high TONs of 1678 to 1946 were achieved under solvent free and relatively mild conditions. The SWNTs/Pd catalyst provided the best conversion, 22.7%, but the SWNTs/Pt system also provided a good conversion of 20.7%. PMID:25340475

  6. A glassy carbon electrode modified with the nickel(II)-bis(1,10-phenanthroline) complex and multi-walled carbon nanotubes, and its use as a sensor for ascorbic acid

    International Nuclear Information System (INIS)

    A glassy carbon electrode (GCE) was modified with the nickel(II)-bis(1,10-phenanthroline) complex and with multi-walled carbon nanotubes (MWCNTs). The nickel complex was electrodeposited on the MWCNTs by cyclic voltammetry. The modified GCE displays excellent electrocatalytic activity to the oxidation of ascorbic acid (AA). The effects of fraction of MWCNTs, film thickness and pH values were optimized. Response to AA is linear in the 10 to 630 μM concentration range, and the detection limit is 4 μM (at a signal-to-noise ratio of 3:1). The modified electrode was applied to determine AA in vitamin C tablets and in spiked fruit juice. (author)

  7. Low temperature in situ synthesis and the formation mechanism of various carbon-encapsulated nanocrystals by the electrophilic oxidation of metallocene complexes

    Science.gov (United States)

    Liu, Boyang; Fan, Chunhua; Chen, Jianwei; Wang, Junhua; Lu, Zepeng; Ren, Jiayuan; Yu, Shuaiqin; Dong, Lihua; Li, Wenge

    2016-02-01

    The core-shell nanostructures have the advantages of combining distinctive properties of varied materials and improved properties over their single-component counterparts. Synthesis approaches for this class of nanostructures have been intensively explored, generally involving multiple steps. Here, a general and convenient strategy is developed for one-step in situ synthesis of various carbon-encapsulated nanocrystals with a core-shell structure via a solid-state reaction of metallocene complexes with (NH4)2S2O8 in an autoclave at 200 °C. A variety of near-spherical and equiaxed nanocrystals with a small median size ranging from 6.5 to 50.6 nm are prepared as inner cores, including Fe7S8, Ni3S4 and NiS, CoS, TiO2, TiO2 and S8, ZrO2, (NH4)3V(SO4)3 and VO2, Fe7S8 and Fe3O4, MoS2 and MoO2. The worm-like carbon shell provides exclusive room for hundreds of nanocrystals separated from each other, preventing nanocrystal aggregation. The synergistic effect of ammonium and a strong oxidizing anion on the electrophilic oxidation of metallocene complexes containing a metal-ligand π bond contributes to the carbon formation at low temperature. It is considered that the cyclopentadienyl ligand in a metallocene complex will decompose into highly reactive straight chain olefinic pieces and the metal-olefin π interaction enables an ordered self-assembly of olefinic pieces on nanocrystals to partially form graphitizable carbon and a core-shell structure. The high capacity, good cycling behavior and rate capability of Fe7S8@C and Ni3S4 and NiS@C electrodes are attributed to the good protection and electrical conductivity of the carbon shell.

  8. Promoting the activity of LiFePO4 (olivine) cathode of Li-ion battery by supramolecular complexes with single walled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Exnar, I.; Graetzel, M.

    Boca Raton : CRC Press, 2009, s. 58-61. ISBN 978-1-4398-1784-1 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : olivine cathode * Li-ion battery * carbon nanotubes * Ru-bipyridine complexes Subject RIV: CG - Electrochemistry

  9. The electrochemical behavior of Co(TPTZ){sub 2} complex on different carbon based electrodes modified with TiO{sub 2} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ortaboy, Sinem, E-mail: ortaboy@istanbul.edu.tr; Atun, Gülten, E-mail: gatun@istanbul.edu.tr

    2015-04-15

    Electrochemical behavior of cobalt (II) complex with the N-donor ligand 2,2′-bipyridyl-1,3,5-tripyridyl-s-triazine (TPTZ) was investigated to elucidate the electron-proton transfer mechanisms. The electrochemical response of the complex was studied using square-wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques. A conventional three-electrode system, consisting of glassy carbon (GCE), TiO{sub 2} modified glassy carbon (T/GCE), carbon paste (CPE) and TiO{sub 2} modified carbon paste (T/CPE) working electrodes were employed. The ligand/metal ratio and stability constant of the complex as well as the mechanisms of the electrode processes were elucidated by examining the effects of pH, ligand concentration and frequency on the voltammograms. The EIS results indicated that the samples modified with TiO{sub 2} had the higher charge transfer resistance than that of the bare electrodes and also suggested that the electroactivity of the electrode surfaces increased in the following order, T/CPE > CPE > T/GCE > GCE. The surface morphology of the working electrodes was also characterized by atomic force microscopy (AFM). The values of surface roughness parameters were found to be consistent with the results obtained by EIS experiments. - Graphical abstract: Schematic illustration of the experimental process. - Highlights: • Electrochemical behavior of Co(TPTZ){sub 2} complex studied by SWV and EIS techniques. • GCE, CPE T/GCE and T/CPE were used as working electrodes for comparative studies. • The surface morphologies of the electrodes were characterized by AFM. • Mechanisms were proposed from the effects of pH, ligand concentration and frequency. • EIS and morphologic relationships of the surfaces were established successfully.

  10. Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

    OpenAIRE

    Fujita, Shin-ichiro; Akihara, Shuji; Arai, Masahiko

    2006-01-01

    The recyclability of water-soluble ruthenium–phosphine complex catalysts was investigated in water–toluene and in water–pressurized carbon dioxide systems for selective hydrogenation of trans-cinnamaldehyde (CAL). For the first hydrogenation run, the selectivity for cinnamyl alcohol (COL) is high for both toluene and dense CO2, because of interfacial catalysis in which the reaction mainly occurs at the interface between the aqueous phase and the other toluene or dense CO2 phase. The total CAL...

  11. Evolution of chemical and isotopic composition of inorganic carbon in a complex semi-arid zone environment: Consequences for groundwater dating using radiocarbon

    Science.gov (United States)

    Meredith, K. T.; Han, L. F.; Hollins, S. E.; Cendón, D. I.; Jacobsen, G. E.; Baker, A.

    2016-09-01

    Estimating groundwater age is important for any groundwater resource assessment and radiocarbon (14C) dating of dissolved inorganic carbon (DIC) can provide this information. In semi-arid zone (i.e. water-limited environments), there are a multitude of reasons why 14C dating of groundwater and traditional correction models may not be directly transferable. Some include; (1) the complex hydrological responses of these systems that lead to a mixture of different ages in the aquifer(s), (2) the varied sources, origins and ages of organic matter in the unsaturated zone and (3) high evaporation rates. These all influence the evolution of DIC and are not easily accounted for in traditional correction models. In this study, we determined carbon isotope data for; DIC in water, carbonate minerals in the sediments, sediment organic matter, soil gas CO2 from the unsaturated zone, and vegetation samples. The samples were collected after an extended drought, and again after a flood event, to capture the evolution of DIC after varying hydrological regimes. A graphical method (Han et al., 2012) was applied for interpretation of the carbon geochemical and isotopic data. Simple forward mass-balance modelling was carried out on key geochemical processes involving carbon and agreed well with observed data. High values of DIC and δ13CDIC, and low 14CDIC could not be explained by a simple carbonate mineral-CO2 gas dissolution process. Instead it is suggested that during extended drought, water-sediment interaction leads to ion exchange processes within the top ∼10-20 m of the aquifer which promotes greater calcite dissolution in saline groundwater. This process was found to contribute more than half of the DIC, which is from a mostly 'dead' carbon source. DIC is also influenced by carbon exchange between DIC in water and carbonate minerals found in the top 2 m of the unsaturated zone. This process occurs because of repeated dissolution/precipitation of carbonate that is dependent on

  12. Molecular dynamics study of human carbonic anhydrase II in complex with Zn(2+) and acetazolamide on the basis of all-atom force field simulations.

    Science.gov (United States)

    Wambo, Thierry O; Chen, Liao Y; McHardy, Stanton F; Tsin, Andrew T

    2016-01-01

    Human carbonic anhydrase II (hCAII) represents an ultimate example of the perfectly efficient metalloenzymes, which is capable of catalyzing the hydration of carbon dioxide with a rate approaching the diffusion controlled limit. Extensive experimental studies of this physiologically important metalloprotein have been done to elucidate the fundamentals of its enzymatic actions: what residues anchor the Zn(2+) (or another divalent cation) at the bottom of the binding pocket; how the relevant residues work concertedly with the divalent cation in the reversible conversions between CO2 and HCO3(-); what are the protonation states of the relevant residues and acetazolamide, an inhibitor complexed with hCAII, etc. In this article, we present a detailed computational study on the basis of the all-atom CHARMM force field where Zn(2+) is represented with a simple model of divalent cation using the transferrable parameters available from the current literature. We compute the hydration free energy of Zn(2+), the characteristics of hCAII-Zn(2+) complexation, and the absolute free energy of binding acetazolamide to the hCAII-Zn(2+) complex. In each of these three problems, our computed results agree with the experimental data within the known margin of error without making any case-by-case adjustments to the parameters. The quantitatively accurate insights we gain in this all-atom molecular dynamics study should be helpful in the search and design of more specific inhibitors of this and other carbonic anhydrases. PMID:27232456

  13. Effectiveness of submersed angiosperm-epiphyte complexes on exchange of nutrients and organic carbon in littoral systems. III. Refractory organic carbon

    Energy Technology Data Exchange (ETDEWEB)

    Mickle, A.M.; Wetzel, R.G.

    1979-01-01

    Refractory dissolved organic compounds, consisting mainly of fulvic acids labelled with /sup 14/C of aquatic plant origin, were added to the inlet stream water of a hardwater lake and passed through two continuously, very slowly flowing (3 1/24 h) littoral systems. System I contained a natural stand of Scripus subterminalis Torr. and System II contained Myriophyllum heterophyllum Michx. Macrophytic epiphytes were left intact. Control systems, containing similar sediments without macrophytes, received identical treatments. Dissolved organic carbon (DOC), both labelled and unlabelled, of inflow and outflow water was fractionated into several molecular weight fractions; uv absorption and fluorescence of dissolved organic matter, particulate organic carbon (POC), and major cationic concentrations were also analyzed in inflowing and outflowing water. The pathways of the labelled refractory organic carbon amendments were followed in the water, the plant foliage and roots, epiphytes, and the sediments.

  14. Highly versatile catalytic hydrogenation of carboxylic and carbonic acid derivatives using a Ru-triphos complex: molecular control over selectivity and substrate scope.

    Science.gov (United States)

    vom Stein, Thorsten; Meuresch, Markus; Limper, Dominik; Schmitz, Marc; Hölscher, Markus; Coetzee, Jacorien; Cole-Hamilton, David J; Klankermayer, Jürgen; Leitner, Walter

    2014-09-24

    The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)(Solvent)H2] or the cationic intermediate [Ru(Triphos)(Solvent)(H)(H2)](+) in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to C═O groups and C-O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H2] and [Ru(Triphos)(μ-H)]2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources. PMID:25208046

  15. The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

    Science.gov (United States)

    Goenawan, Joshua; Trisanti, P. N.; Sumarno

    2015-12-01

    This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

  16. Deposition of new thia-containing Schiff-base iron (III) complexes onto carbon nanotube-modified glassy carbon electrodes as a biosensor for electrooxidation and determination of amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Saghatforoush, Lotfali [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Hasanzadeh, Mohammad, E-mail: mhmmd_hasanzadeh@yahoo.co [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology (KNTU), Tehran (Iran, Islamic Republic of); Shadjou, Nasrin [Department of Chemistry, Faculty of Science, Payame Noor University (PNU), P.O. Box 58168-45164, Khoy (Iran, Islamic Republic of); Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology (KNTU), Tehran (Iran, Islamic Republic of); Khalilzadeh, Balal [Department of Analytical Chemistry, Faculty of Science, Arak University, Arak (Iran, Islamic Republic of)

    2011-01-01

    Multiwall carbon nanotubes (MWCNTs) were used as an immobilization matrix to incorporate an Fe (III)-Schiff base complex as an electron-transfer mediator onto a glassy carbon electrode surface. First, the preheated glassy carbon was subjected to abrasive immobilization of MWCNTs by gently rubbing the electrode surface on filter paper supporting the carbon nanotubes. Second, the electrode surface was modified by casting 100 {mu}L of an Fe (III)-complex solution (0.01 M in ACN). The cyclic voltammograms of the modified electrode in an aqueous solution displayed a pair of well-defined, stable and nearly reversible reductive oxidation redox systems with surface confined characteristics. Combinations of unique electronic and electrocatalytic properties of MWCNTs and Fe (III)-Schiff base complexes resulted in a remarkable synergistic augmentation of the response. The electrochemical behavior and stability of the modified electrode in aqueous solutions at pH 1-9 were characterized by cyclic voltammetry. The apparent electron transfer rate constant (K{sub s}) and transfer coefficient (a) were determined by cyclic voltammetry and were approximately 7 s{sup -1} and 0.55, respectively. The modified electrodes showed excellent catalytic activity towards the oxidation of amino acids at an unusually positive potential in acidic solution. They also displayed inherent stability at a wide pH range, fast response time, high sensitivity, low detection limit and had a remarkably positive potential oxidation of amino acids that decreased the effect of interferences in analysis. The linear concentration range, limits of detection (LOD), limits of quantization (LOQ) and relative standard deviation of the proposed sensor for the amino acid detection were 1-55,000, 1.10-13.70, 2.79-27.14 and 1.30-5.11, respectively.

  17. 13C and 17O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    International Nuclear Information System (INIS)

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U02(CO3)34- and (UO2)3(CO3)66- in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = -log(aH+) versus p[H] = -log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA

  18. Stability constants important to the understanding of plutonium in environmental waters, hydroxy and carbonate complexation of PuO{sub 2}{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, D A [California Univ., Berkeley, CA (USA). Dept. of Chemistry

    1990-04-20

    The formation constants for the reactions PuO{sub 2}{sup +} + H{sub 2}O = PuO{sub 2}(OH) + H{sup +} and PuO{sub 2}{sup +} + CO{sub 3}{sup 2} = PuO{sub 2}(CO{sub 3}){sup {minus}} were determined in aqueous sodium perchlorate solutions by laser-induced photoacoustic spectroscopy. The molar absorptivity of the PuO{sub 2}{sup +} band at 569 nm decreased with increasing hydroxide concentration. Similarly, spectral changes occurred between 540 and 580 nm as the carbonate concentration was increased. The absorption data were analyzed by the non-linear least-squares program SQUAD to yield complexation constants. Using the specific ion interaction theory, both complexation constants were extrapolated to zero ionic strength. These thermodynamic complexation constants were combined with the oxidation-reduction potentials of Pu to obtain Eh versus pH diagrams. 120 refs., 35 figs., 12 tabs.

  19. Free Energy Minimization Calculation of Complex Chemical Equilibria. Reduction of Silicon Dioxide with Carbon at High Temperature.

    Science.gov (United States)

    Wai, C. M.; Hutchinson, S. G.

    1989-01-01

    Discusses the calculation of free energy in reactions between silicon dioxide and carbon. Describes several computer programs for calculating the free energy minimization and their uses in chemistry classrooms. Lists 16 references. (YP)

  20. The effect of pH on the complexation of Cd, Ni and Zn by dissolved organic carbon from leachate-polluted groundwater

    DEFF Research Database (Denmark)

    Christensen, J. B.; Christensen, Thomas Højlund

    2000-01-01

    Complexation of cadmium (Cd), nickel (Ni) and zinc (Zn) by dissolved organic carbon (DOC) in leachate-polluted groundwater was measured using a resin equilibrium method. Metal-DOC complexation was measured at di€erent DOC concentrations over a range of pH values . The results were compared to...... simulations made by two speciation models (WHAM and MINTEQA2). Of these models, WHAM came closest to simulating the experimental observations although it systematically overestimated the pH dependence of metal-DOC complexation. Accepting a variation in the free metal ion activity of a factor of 3±4 the WHAM...... model provided useful predictions of the complexation of Cd and Zn by DOC in the pH range 5±8, and of Ni in the pH range 5±7. At pH 8, however, the model overestimates the extent of Ni-DOC complexation to an unacceptable degree. The MINTEQA2 model predicts virtually no pH dependence for DOC complexation...

  1. Effectiveness of submersed angiosperm--epiphyte complexes on exchange of nutrients and organic carbon in littoral systems. II. Dissolved organic carbon

    Energy Technology Data Exchange (ETDEWEB)

    Mickle, A.M.; Wetzel, R.G.

    1978-01-01

    Dissolved organic carbon concentrations, UV absorption, and fluorescence were measured daily for several weeks in water from an inlet stream of a hardwater lake before and after passing through three continuously, very slowly flowing (31/24 h) littoral systems. System I contained a natural stand of Scirpus subterminalis Torr. and Systems II and III contained Myriophyllum heterophyllum Michx. Macrophytic epiphytes were left intact. Dissolved organic matter of inflow and outflow water from System III was fractionated into several molecular weight fractions. Dissolved organic carbon concentrations and UV absorption increased as inflow water passed through all three littoral systems. This increase consisted only of organic compounds of >1000 molecular weight. Fluorescence increased in outflow waters of Systems I and III, but consistently decreased in System II. During periods of rainfall, but not snowfall, all three parameters in inflow water increased significantly. All three littoral systems were effective in dampening these higher concentrations; only slight increases appeared in the outflows.

  2. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Directory of Open Access Journals (Sweden)

    A. Yool

    2013-10-01

    Full Text Available MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically driven change in the World Ocean (Yool et al., 2011. The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. However, due to anthropogenic activity, the atmospheric concentration of carbon dioxide (CO2 has significantly increased above its natural, inter-glacial background. As such, simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, requires that both organic and inorganic carbon be afforded a more complete representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter, as well as a simple benthic formulation and extended parameterizations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal spin-up simulation (1860–2005 is performed. The biogeochemical performance of the model is evaluated using a diverse range of observational data, and MEDUSA-2.0 is assessed relative to comparable models using output from the Coupled Model Intercomparison Project (CMIP5.

  3. MEDUSA-2.0: an intermediate complexity biogeochemical model of the marine carbon cycle for climate change and ocean acidification studies

    Science.gov (United States)

    Yool, A.; Popova, E. E.; Anderson, T. R.

    2013-10-01

    MEDUSA-1.0 (Model of Ecosystem Dynamics, nutrient Utilisation, Sequestration and Acidification) was developed as an "intermediate complexity" plankton ecosystem model to study the biogeochemical response, and especially that of the so-called "biological pump", to anthropogenically driven change in the World Ocean (Yool et al., 2011). The base currency in this model was nitrogen from which fluxes of organic carbon, including export to the deep ocean, were calculated by invoking fixed C:N ratios in phytoplankton, zooplankton and detritus. However, due to anthropogenic activity, the atmospheric concentration of carbon dioxide (CO2) has significantly increased above its natural, inter-glacial background. As such, simulating and predicting the carbon cycle in the ocean in its entirety, including ventilation of CO2 with the atmosphere and the resulting impact of ocean acidification on marine ecosystems, requires that both organic and inorganic carbon be afforded a more complete representation in the model specification. Here, we introduce MEDUSA-2.0, an expanded successor model which includes additional state variables for dissolved inorganic carbon, alkalinity, dissolved oxygen and detritus carbon (permitting variable C:N in exported organic matter), as well as a simple benthic formulation and extended parameterizations of phytoplankton growth, calcification and detritus remineralisation. A full description of MEDUSA-2.0, including its additional functionality, is provided and a multi-decadal spin-up simulation (1860-2005) is performed. The biogeochemical performance of the model is evaluated using a diverse range of observational data, and MEDUSA-2.0 is assessed relative to comparable models using output from the Coupled Model Intercomparison Project (CMIP5).

  4. Determination of porosity and facies trends in a complex carbonate reservoir, by using 3-D seismic, borehole tools, and outcrop geology

    Energy Technology Data Exchange (ETDEWEB)

    Zacharakis, T.G. Jr.; Comet, J.N.; Murillo, A.A. [Respol Exploracion, S.A., Madrid (Spain)] [and others

    1996-08-01

    Mesozoic carbonate reservoirs are found in the Mediterranean Sea, off the east coast of Spain. A wide variation of porosities are found in the core samples and logs: vuggy, breccia, fractures, and cavern porosity. In addition, complex Tertiary carbonate geometries include olistostromes, breccia bodies, and reef buildups, which are found on top of Mesozoic carbonates. Predicting the porosity trends within these oil productive reservoirs requires an understanding of how primary porosity was further enhanced by secondary processes, including fractures, karstification, and dolomitization in burial conditions. Through an extensive investigation of field histories, outcrop geology, and seismic data, a series of basic reservoir styles have been identified and characterized by well log signature and seismic response. The distribution pattern of the different reservoirs styles is highly heterogeneous, but by integrating subsurface data and outcrop analogs, it is possible to distinguish field-scale and local patterns of both vertical and local variations in reservoir properties. Finally, it is important to quantify these reservoir properties through the study of seismic attributes, such as amplitude variations, and log responses at the reservoir interval. By incorporating 3-D seismic data, through the use of seismic inversion, it is possible to predict porosity trends. Further, the use of geostatistics can lead to the prediction of reservoir development within the carbonate facies.

  5. Carbon supported polyindole-5-carboxylic acid covalently bonded with pyridine-2,4-diamine copper complex as a non-precious oxygen reduction catalyst

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • The carbon supported catalyst was prepared by a novel method. • The composite is a non-precious electrocatalyst with excellent stability and electrocatalytic activity. • The oxygen reduction reaction of the composite is a four electron based mixed mode. - Abstract: Indole-5-carboxylic acid monomer was electropolymerized on carbon modified glass carbon (GC) electrode, followed by the covalent bonding with pyridine-2,4-diamine by using 1-ethyl-(3-(dimethyl-amino-propyl)carbodiimide (EDAC), N-hydroxysulfosuccinimide sodium salt (NHS) catalyst, and then was complexed with copper ions to obtain the composite (CuINPD/C). The morphology and the chemical composition of the CuINPD/C catalyst were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. Electrochemical measurements such as cyclic voltammetry, rotating disk electrode, rotating ring-disk electrode and electrochemical impedance spectroscopy were applied to obtain the mechanisms of the oxygen reduction reaction (ORR). All electrochemical measurements demonstrate that CuINPD/C is a good catalyst with excellent stability due to copper ions doping and carbon modification, which play a key role in increasing the current density and enhancing the charge transfer kinetics. Moreover, the average electron transfer number is about 3.1, indicating the ORR of CuINPD/C may takes a coexisting pathway involving both the two-electron and four-electron transfers

  6. A stability comparison of redox-active layers produced by chemical coupling of an osmium redox complex to pre-functionalized gold and carbon electrodes

    International Nuclear Information System (INIS)

    The production of stable redox active layers on electrode surfaces is a key factor for the development of practical electronic and electrochemical devices. Here, we report on a comparison of the stability of redox layers formed by covalently coupling an osmium redox complex to pre-functionalized gold and graphite electrode surfaces. Pre-treatment of gold and graphite electrodes to provide surface carboxylic acid groups is achieved via classical thiolate self-assembled monolayer formation on gold surfaces and the electro-reduction of an in situ generated aryldiazonium salt from 4-aminobenzoic acid on gold, glassy carbon and graphite surfaces. These surfaces have been characterized by AFM and electrochemical blocking studies. The surface carboxylate is then used to tether an osmium complex, [Os(2,2'-bipyridyl)2(4-aminomethylpyridine)Cl]PF6, to provide a covalently bound redox active layer, E0'' of 0.29 V (vs. Ag/AgCl in phosphate buffer, pH 7.4), on the pre-treated electrodes. The aryldiazonium salt-treated carbon-based surfaces showed the greatest stability, represented by a decrease of <5% in the peak current for the Os(II/III) redox transition of the immobilized complex over a 3-day period, compared to a decrease of 19% and 14% for the aryldiazonium salt treated and thiolate treated gold surfaces, respectively, over the same period

  7. A stability comparison of redox-active layers produced by chemical coupling of an osmium redox complex to pre-functionalized gold and carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Boland, Susan; Foster, Kevin [School of Chemistry, National University of Ireland, Galway (Ireland); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland)], E-mail: donal.leech@nuigalway.ie

    2009-02-28

    The production of stable redox active layers on electrode surfaces is a key factor for the development of practical electronic and electrochemical devices. Here, we report on a comparison of the stability of redox layers formed by covalently coupling an osmium redox complex to pre-functionalized gold and graphite electrode surfaces. Pre-treatment of gold and graphite electrodes to provide surface carboxylic acid groups is achieved via classical thiolate self-assembled monolayer formation on gold surfaces and the electro-reduction of an in situ generated aryldiazonium salt from 4-aminobenzoic acid on gold, glassy carbon and graphite surfaces. These surfaces have been characterized by AFM and electrochemical blocking studies. The surface carboxylate is then used to tether an osmium complex, [Os(2,2'-bipyridyl){sub 2}(4-aminomethylpyridine)Cl]PF{sub 6}, to provide a covalently bound redox active layer, E{sup 0}'' of 0.29 V (vs. Ag/AgCl in phosphate buffer, pH 7.4), on the pre-treated electrodes. The aryldiazonium salt-treated carbon-based surfaces showed the greatest stability, represented by a decrease of <5% in the peak current for the Os(II/III) redox transition of the immobilized complex over a 3-day period, compared to a decrease of 19% and 14% for the aryldiazonium salt treated and thiolate treated gold surfaces, respectively, over the same period.

  8. Covalent functionalization of multi-wall carbon nanotubes (MWNTs) by nickel(II) Schiff-base complex: Synthesis, characterization and liquid phase oxidation of phenol with hydrogen peroxide

    International Nuclear Information System (INIS)

    The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized nickel(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV-vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest that the symmetrical Schiff-base; N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H2[(OH)2-salen]; is a bivalent anion with tetradentate N2O2 donors derived from the phenolic oxygen and azomethine nitrogen. The formula was found to be [Ni((OH)2-salen)] for the 1:1 non-electrolytic complex. Multi-wall carbon nanotubes covalently anchored nickel(II) complex ([Ni((OH)2-salen)]-MWNTs) catalyze the oxidation of phenol with H2O2. Oxidation of phenol catalyzed by this complex gave catechol and hydroquinone as major products. A suitable reaction condition has been optimized for [Ni((OH)2-salen)]MWNTs by considering the effect of various parameters such as reaction time and amount of oxidant, different solvents, concentration of substrate, etc. for the maximum transformation of phenol

  9. Covalent functionalization of multi-wall carbon nanotubes (MWNTs) by nickel(II) Schiff-base complex: Synthesis, characterization and liquid phase oxidation of phenol with hydrogen peroxide

    Science.gov (United States)

    Salavati-Niasari, Masoud; Bazarganipour, Mehdi

    2008-12-01

    The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized nickel(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV-vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest that the symmetrical Schiff-base; N, N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H 2[(OH) 2-salen]; is a bivalent anion with tetradentate N 2O 2 donors derived from the phenolic oxygen and azomethine nitrogen. The formula was found to be [Ni((OH) 2-salen)] for the 1:1 non-electrolytic complex. Multi-wall carbon nanotubes covalently anchored nickel(II) complex ([Ni((OH) 2-salen)]@MWNTs) catalyze the oxidation of phenol with H 2O 2. Oxidation of phenol catalyzed by this complex gave catechol and hydroquinone as major products. A suitable reaction condition has been optimized for [Ni((OH) 2-salen)]@MWNTs by considering the effect of various parameters such as reaction time and amount of oxidant, different solvents, concentration of substrate, etc. for the maximum transformation of phenol.

  10. Separation of flavonoids and phenolic acids in complex natural products by microemulsion electrokinetic chromatography using surfactant-coated and carboxylic single-wall carbon nanotubes as additives.

    Science.gov (United States)

    Cao, Jun; Qu, Haibin; Cheng, Yiyu

    2010-05-01

    In this paper, we investigated the analytical potential of the use of single-walled carbon nanotubes (SWNTs) with different dispersion as additives in MEEKC. The addition of surfactant-coated single-walled carbon nanotubes (SC-SWNTs) in microemulsion provided a more efficient method than carboxylic SWNTs for the separation of three flavonoids and six phenolic acids depending on the interaction between the analytes and SWNTs surface. Additionally, the effect of important factors was examined by changing experimental variables such as the dispersion of SWNTs, surfactants and cosurfactants. Finally, the MEEKC method using SC-SWNTs was successfully applied to complex natural products (drug pair of Radix Astragali and Radix et Rhizoma Salvia Miltiorrhizae), with satisfactory results. PMID:20414881

  11. CALCIUM CARBONATE REDUCES IRON ABSORPTION FROM IRON SULFATE, BUT NOT WHEN IRON IS PRESENTED AS AN ORGANIC COMPLEX

    OpenAIRE

    E. C. CONCEI�O; Machado, A.A.; C. IZUMI; O. Freitas

    2008-01-01

    Experimental and epidemiological evidences have demonstrated that calcium inhibits iron absorption; calcium carbonate being one of the most effective calcium sources to reduce iron absorption from dietary origin or from iron sulfate. In the present work, the short-term effect of calcium from calcium carbonate on iron absorption was studied in rats, using different ir...

  12. Mild formation of cyclic carbonates using Zn(II) complexes based on N2S2-chelating ligands

    NARCIS (Netherlands)

    D. Anselmo; V. Bocokic; A. Decortes; E.C. Escudero-Adan; J. Benet-Buchholz; J.N.H. Reek; A.W. Kleij

    2012-01-01

    We have prepared a series of Zn(II) complexes (1-3) based on a versatile N2S2-chelating ligand abbreviated as btsc [btsc = bis-(thiosemicarbazonato)] derived from simple and accessible building blocks. These complexes comprise a Lewis acidic Zn(II) center useful for substrate activation, and we have

  13. Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s).

    Science.gov (United States)

    Terao, Jun; Kambe, Nobuaki

    2008-11-18

    Transition metal-catalyzed cross-coupling reactions of organic halides and pseudo-halides containing a C-X bond (X = I, Br, Cl, OTf, OTs, etc.) with organometallic reagents are among the most important transformations for carbon-carbon bond formation between a variety of sp, sp(2), and sp(3)-hybridized carbon atoms. In particular, researchers have widely employed Ni- and Pd-catalyzed cross-coupling to synthesize complex organic structures from readily available components. The catalytic cycle of this process comprises oxidative addition, transmetalation, and reductive elimination steps. In these reactions, various organometallic reagents could bear a variety of R groups (alkyl, vinyl, aryl, or allyl), but the coupling partner has been primarily limited to sp and sp(2) carbon compounds: alkynes, alkenes, and arenes. With alkyl coupling partners, these reactions typically run into two problems within the catalytic cycle. First, oxidative addition of alkyl halides to a metal catalyst is generally less efficient than that of aryl or alkenyl compounds. Second, the alkylmetal intermediates formed tend to undergo intramolecular beta-hydrogen elimination. In this Account, we describe our efforts to overcome these problems for Ni and Pd chemistry. We have developed new catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate. For example, we developed a unique cross-coupling reaction of alkyl halides with organomagnesium or organozinc reagents catalyzed by using a 1,3-butadiene as the additive. This reaction follows a new catalytic pathway: the Ni or Pd catalyst reacts first with R-MgX to form an anionic complex, which then reacts with alkyl halides. Bis-dienes were also effective additives for the Ni-catalyzed cross-coupling reaction of organozinc reagents with alkyl halides. This catalytic system tolerates a wide variety of functional groups, including nitriles, ketones, amides, and esters. In addition, we have extended

  14. Single-walled carbon nanotube-induced crystallinity on the electropolymeric film of tetraaminophthalocyaninatonickel(II) complex: Impact on the rate of heterogeneous electron transfer

    Science.gov (United States)

    Pillay, Jeseelan; Ozoemena, Kenneth I.

    2007-06-01

    We present a fundamental investigation on the impact of single-walled carbon nanotube (SWCNT) on the film structure and redox behaviour of tetraaminophthalocyaninatonickel(II) complex (NiTAPc) electropolymer immobilized on a basal plane pyrolytic graphite electrode (BPPGE). SWCNT induces crystallinity on the NiTAPc electropolymeric film structure and increases its apparent electron transfer rate constant ( kapp). We proved that there is potential advantage of using electrode based on the SWCNT- poly-NiTAPc hybrid for catalytic and sensing applications as it enhances the catalytic current for the detection of nitric oxide more than twice compared to bare BPPGE, BPPGE-SWCNT and other electrodes without SWCNTs.

  15. Five phosphonate operon gene products as components of a multi-subunit complex of the carbon-phosphorus lyase pathway

    DEFF Research Database (Denmark)

    Jochimsen, Bjarne; Lolle, Signe; McSorley, Fern R.;

    2011-01-01

    Organophosphonate utilization by Escherichia coli requires the 14 cistrons of the phnCDEFGHIJKLMNOP operon, of which the carbon-phosphorus lyase has been postulated to consist of the seven polypeptides specified by phnG to phnM. A 5,660-bp DNA fragment encompassing phnGHIJKLM is cloned, followed by...

  16. Controlling the Direction of the Molecular Axis of Rod-Shaped Binuclear Ruthenium Complexes on Single-Walled Carbon Nanotubes.

    Science.gov (United States)

    Ozawa, Hiroaki; Kosaka, Kazuma; Kita, Tomomi; Yoshikawa, Kai; Haga, Masa-aki

    2016-05-01

    We report the synthesis of a mixed-valence ruthenium complex, bearing pyrene moieties on one side of the ligands as anchor groups. Composites consisting of mixed-valence ruthenium complexes and SWNTs were prepared by noncovalent π-π interactions between the SWNT surface and the pyrene anchors of the Ru complex. In these composites, the long axis of the Ru complexes was aligned in parallel to the principal direction of the SWNT. The optimized conformation of these complexes on the SWNT surface was calculated by molecular mechanics. The composites were examined by UV/Vis absorption and FT-IR spectroscopy, XPS, and SEM analysis. Furthermore, their electrochemical properties were evaluated. Cyclic voltammograms of the composites showed reversible oxidation waves at peak oxidation potentials (Epox ) = 0.86 and 1.08 V versus Fc(+) /Fc, which were assigned to the Ru(II) -Ru(II) /Ru(II) -Ru(III) and the Ru(II) -Ru(III) /Ru(III) -Ru(III) oxidation events of the dinuclear ruthenium complex, respectively. Based on these observations, we concluded that the electrochemical properties and mixed-valence state of the dinuclear ruthenium complexes were preserved upon attachment to the SWNT surface. PMID:27010865

  17. Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

    International Nuclear Information System (INIS)

    Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH)2-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH)2-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the 'neat' complexes than over the encapsulated complexes.

  18. Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

    Energy Technology Data Exchange (ETDEWEB)

    Salavati-Niasari, Masoud, E-mail: salavati@kashanu.ac.ir [Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167 (Iran, Islamic Republic of); Department of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167 (Iran, Islamic Republic of); Bazarganipour, Mehdi [Department of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167 (Iran, Islamic Republic of)

    2009-06-15

    Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH){sub 2}-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH){sub 2}-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the 'neat' complexes than over the encapsulated complexes.

  19. The integrative segment of the quail Coturnix coturnix japonica. Occurrence and distribution of carbonic anhydrase and complex carbohydrates.

    OpenAIRE

    Gabriella, M G; Menghi, G

    1994-01-01

    As part of a more extensive study into the involvement of carbonic anhydrase in avian excretory function, the occurrence and distribution of this enzyme was investigated in the quail integrative segment. The integrative segment represents, in birds, that part of the intestinal tract where ureteral urine undergoes postrenal modification to form definitive urine. To define the structural peculiarities within the intestinal epithelium, the constituent parts, namely cloaca, rectum and caecum, as ...

  20. Effect of the porous structure of activated carbon on the adsorption kinetics of gold(I) cyanide complex

    Science.gov (United States)

    Ibragimova, P. I.; Grebennikov, S. F.; Gur'yanov, V. V.; Fedyukevich, V. A.; Vorob'ev-Desyatovskii, N. V.

    2014-06-01

    The effect the porous structure of activated carbons obtained from furfural and coconut shells has on the kinetics of [Au(CN)2]- ion adsorption is studied. Effective diffusion coefficients for [Au(CN)2]- anions in transport and adsorbing pores and mass transfer coefficients in a transport system of the pores and in microporous zones are calculated using the statistical moments of the kinetic curve.

  1. Real-time imaging of complex nanoscale mechanical responses of carbon nanotubes in highly compressible porous monoliths

    Energy Technology Data Exchange (ETDEWEB)

    Whitby, Raymond L D; Mikhalovsky, Sergey V [Brighton Nanoscience and Nanotechnology Group, PABS, University of Brighton, Lewes Road, Brighton, BN2 4GJ (United Kingdom); Fukuda, Takahiro; Maekawa, Toru [Bio-Nano Electronics Research Centre, Toyo University, 2100 Kujirai, Kawagoe Saitama 350-8585 (Japan); Cundy, Andrew B, E-mail: r.whitby@brighton.ac.uk [School of Environment and Technology, University of Brighton, Lewes Road, Brighton, BN2 4GJ (United Kingdom)

    2010-02-19

    A facile and rapid assembly of powdered carbon nanotubes (CNTs) into compressible, porous, macroscale monoliths is reported. Despite a Poisson's ratio just above zero, we found that the sample under compression inside a scanning electron microscope (SEM) revealed CNT regions behaving in auxetic and vortex-like rotational modes as well as standard collapse responses. This method is crucial in understanding the macroscale behaviour based on the accumulation of nanoscale responses to an applied force.

  2. Application of solid state silicon-29 and carbon-13 nuclear magnetic resonance spectroscopy to the characterization of inorganic matter-humic complexes in Athabasca oil sands

    International Nuclear Information System (INIS)

    In Athabasca oil sands there is a fraction of non-crystalline solids tightly bound to humic matter. It is believed, that the presence of this fraction, which resists subsequent wetting by water, introduces serious problems in bitumen recovery when using water based processes. In the present work, 29Si and 13C solid state magic angle spinning (MAS) NMR techniques were applied to characterize these solids which were isolated from Athabasca oil sands of estuarine and marine origin. On the basis of 29Si results it is suggested that there is a short-range disorder in these samples. It is also shown that aluminum is present in the nearest-neighbor environment of the silicon atoms, thus demonstrating that these solids are comprised of disordered alumino-silicates (allophanes). 13C CP/MAS NMR spectra of demineralized inorganic matter-humic complexes derived from both estuarine and marine oil sands indicate that the distribution of carbon types in each region of the spectra is similar, with aromatic carbon being the predominant type of carbon

  3. Soil redistribution rate and its relationship with soil organic carbon and total nitrogen using {sup 137}Cs technique in a cultivated complex hillslope in western Iran

    Energy Technology Data Exchange (ETDEWEB)

    Afshar, Farideh Abbaszadeh [Department of Soil Science, College of Agriculture, Isfahan University of Technology, 84156-83111 Isfahan (Iran, Islamic Republic of); Ayoubi, Shamsollah, E-mail: ayoubi@cc.iut.ac.i [Department of Soil Science, College of Agriculture, Isfahan University of Technology, 84156-83111 Isfahan (Iran, Islamic Republic of); Jalalian, Ahmad [Department of Soil Science, College of Agriculture, Isfahan University of Technology, 84156-83111 Isfahan (Iran, Islamic Republic of)

    2010-08-15

    The spatial pattern of soil redistribution rate was investigated using cesium-137 ({sup 137}Cs) within a cultivated complex hillslope in western Iran. The relationship between soil redistribution rate and soil organic carbon and total nitrogen pattern were studied using co-regionalization analysis. Ninety-one soil cores were sampled for {sup 137}Cs, total nitrogen, and soil organic carbon measurements. The simplified mass balance model estimated a gross erosion rate of 29.8 t ha{sup -1} yr{sup -1} and a net soil deposition rate of 21.8 t ha{sup -1} yr{sup -1}; hence, a net soil loss rate of 8 t ha{sup -1} yr{sup -1}. This magnitude of soil erosion rate is higher than the acceptable rate in semiarid regions. Co-regionalization analysis and co-dispersive coefficients among the selected variables showed that only a small fraction of the variability in total nitrogen and soil organic carbon could be explained by soil redistribution and that the remaining might be the result of different management practices by local farmers.

  4. Soil redistribution rate and its relationship with soil organic carbon and total nitrogen using 137Cs technique in a cultivated complex hillslope in western Iran

    International Nuclear Information System (INIS)

    The spatial pattern of soil redistribution rate was investigated using cesium-137 (137Cs) within a cultivated complex hillslope in western Iran. The relationship between soil redistribution rate and soil organic carbon and total nitrogen pattern were studied using co-regionalization analysis. Ninety-one soil cores were sampled for 137Cs, total nitrogen, and soil organic carbon measurements. The simplified mass balance model estimated a gross erosion rate of 29.8 t ha-1 yr-1 and a net soil deposition rate of 21.8 t ha-1 yr-1; hence, a net soil loss rate of 8 t ha-1 yr-1. This magnitude of soil erosion rate is higher than the acceptable rate in semiarid regions. Co-regionalization analysis and co-dispersive coefficients among the selected variables showed that only a small fraction of the variability in total nitrogen and soil organic carbon could be explained by soil redistribution and that the remaining might be the result of different management practices by local farmers.

  5. Determination of formation constants of hydroxo carbonate complexes of Pr3+ in 2M NaCl at 303 K

    International Nuclear Information System (INIS)

    The hydrolysis of Praseodymium III in 2M sodium chloride at 303 K was studied. Two methods were used: pH titration followed by a computational refinement and solvent extraction in the presence of a competitive ligand. The hydrolysis constants obtained by pH titration were: log β1,H = -7.68 ± 0.07, log β1,2H = -15.10 ± 0.03, and β1,3H -23.8 ± 0.04. The stability constants of Praseodymium carbonates were determined by pH titration as well and were: log β1,CO32- = 5.94 ± 0.08 and log β1,2CO32- = 11.15 ± 0.15. Praseodymium carbonate species were taken into consideration for calculating the first hydrolysis constants by the solvent extraction method and the value obtained was: log β1,H = -7.69 ± 0.27. The values for log β1,H attained by both methods are the same. The species-distribution diagram was obtained from the stability constants of Praseodymium carbonates and hydrolysis products in the conditions of the present work. (Author)

  6. Cytotoxicity study of iron oxide nanoparticles, single-wall carbon nanotubes and their complexes applied to MCF7 breast cancer cells

    Science.gov (United States)

    Mege, Karine

    Reactive Oxygen Species (ROS) are radicals of great concern to biologists. Their role in several diseases---such as neurodegenerative disease, diabetes, premature aging and cancer---has been intensively investigated during the last decade. Since a major focus in cancer research is to better understand how it is induced and therefore how it can be cured, the study of the cytotoxic effects of ROS production within cancer cells is vital. Nanotechnology is an emerging field of science that promises great improvements in a number of disciplines. Nano medicine is one of its daughter fields. Various nanomaterials are used for diagnosis and disease detection, therapy and medical imaging, and many are already being used in oncology medicine. The two most frequently used nanomaterials in cancer research are Carbon nanotubes (CNTs) and iron oxide nanoparticles (IONPs). They have been proven to play a significant role in the ROS production of various cancer cells. In this context, this thesis emphasizes the need to study the impact of nanoparticles, such as single-walled carbon nanotubes (SWCNTs), iron oxide nanoparticles (IONPs) and their complexes, on a human breast cancer cell line (MCF-7). To date, there have been very few studies assessing the effect on the oxidative stress activity of this cell line using these nanoparticles and their complexes.

  7. Carbon dioxide is tightly bound in the [Co(Pyridine)(CO{sub 2})]{sup −} anionic complex

    Energy Technology Data Exchange (ETDEWEB)

    Graham, Jacob D.; Buytendyk, Allyson M.; Zhang, Xinxing; Bowen, Kit H., E-mail: kbowen@jhu.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Kim, Seong K. [Department of Chemistry, Seoul National University, Seoul 151-747 (Korea, Republic of)

    2015-11-14

    The [Co(Pyridine)(CO{sub 2})]{sup −} anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO{sub 2} binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO{sub 2})]{sup −} in which a central cobalt atom is bound to pyridine and CO{sub 2} moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO{sub 2} to be bound within the anionic complex by 1.4 eV.

  8. Late Norian δ13Corg record in the Tethyan realm: New clues on the complex Late Triassic carbon cycle from the Lagonegro Basin (southern Italy)

    Science.gov (United States)

    Zaffani, Mariachiara; Agnini, Claudia; Concheri, Giuseppe; Godfrey, Linda; Katz, Miriam; Maron, Matteo; Rigo, Manuel

    2016-04-01

    The Late Triassic (ca. 237-201 Ma) is characterized by complex and extreme environmental, climatic and biotic changes (e.g.: the break-up of the supercontinent Pangaea; the humid event known as the Carnian Pluvial Event; the End-Triassic mass extinction; the emplacement of the CAMP volcanism). A global δ13Corg curve for the Late Triassic would provide new clues on this perturbed time interval and would have the potential for global correlations. In particular, the few available data from North American successions define the late Norian (ca. 220-206 Ma) as a "chaotic carbon interval", with rapid vacillations of the carbon isotope values paired with low faunal diversity. Our goal is to reconstruct a global δ13Corg profile for the late Norian, as a contribution to the construction of a more complete global carbon isotope curve for the Late Triassic. For this purpose, we analyzed three sections from the Lagonegro Basin (southern Italy), originally located in the western Tethys, on the other side of the supercontinent Pangaea respect to the North America. The obtained δ13Corg profiles show four negative shifts correlatable with those of the North American record, suggesting that these carbon cycle perturbations have a widespread occurrence. These perturbations are associated with negative shifts of the 87Sr/86Sr, indicating that these global δ13Corg and 87Sr/86Sr negative excursions were possibly caused by emplacement of a Large Igneous Province (LIP). The input of volcanogenic CO2 to the atmosphere-ocean system is supported also by the 12C enrichment observed, as well as by the increase of atmospheric pCO2 inferred by different models for the Norian- Rhaetian interval. This Norian magmatic activity may be ascribed to the Angayucham province (Alaska, North America), a large oceanic plateau active ca. 214 Ma ±7 Myr, with an estimated volume comparable to other two Late Triassic LIPs: the Wrangellia and the CAMP.

  9. Novel tridentate diamino organomanganese(II) complexes as homogeneous catalysts in manganese(II)/copper(I) catalyzed carbon-carbon bond forming reactions

    OpenAIRE

    van Koten, G; Donkervoort, J.G.; Vicario, J.L.; Jastrzebski, J.T.B.H.; Gossage, R.A.; Cahiez, G.

    1998-01-01

    The new, paramagnetic arylmanganese(II) complex Li[MnCl2(NCN)] (2, NCN [C6H3(CH2NMe2)2-2,6]−) has been obtained in high yield from the reaction of MnCl2 and [Li(NCN)]2 in a 2:1 molar ratio. In THF solution, 2 is likely an ionic species [Li(THF)n] [MnCl2(NCN)] (molecular weight determination and conductivity measurements), while magnetic measurements indicate that a high spin d5 manganese(II) center is present. Subsequent reaction of 2 with RLi afforded [MnR(NCN)] (R=Me (3a), n-Bu (3b)). Compl...

  10. Complex Physiological Response of Norway Spruce to Atmospheric Pollution - Decreased Carbon Isotope Discrimination and Unchanged Tree Biomass Increment.

    Science.gov (United States)

    Čada, Vojtěch; Šantrůčková, Hana; Šantrůček, Jiří; Kubištová, Lenka; Seedre, Meelis; Svoboda, Miroslav

    2016-01-01

    Atmospheric pollution critically affects forest ecosystems around the world by directly impacting the assimilation apparatus of trees and indirectly by altering soil conditions, which subsequently also leads to changes in carbon cycling. To evaluate the extent of the physiological effect of moderate level sulfate and reactive nitrogen acidic deposition, we performed a retrospective dendrochronological analysis of several physiological parameters derived from periodic measurements of carbon stable isotope composition ((13)C discrimination, intercellular CO2 concentration and intrinsic water use efficiency) and annual diameter increments (tree biomass increment, its inter-annual variability and correlation with temperature, cloud cover, precipitation and Palmer drought severity index). The analysis was performed in two mountain Norway spruce (Picea abies) stands of the Bohemian Forest (Czech Republic, central Europe), where moderate levels of pollution peaked in the 1970s and 1980s and no evident impact on tree growth or link to mortality has been reported. The significant influence of pollution on trees was expressed most sensitively by a 1.88‰ reduction of carbon isotope discrimination (Δ(13)C). The effects of atmospheric pollution interacted with increasing atmospheric CO2 concentration and temperature. As a result, we observed no change in intercellular CO2 concentrations (Ci), an abrupt increase in water use efficiency (iWUE) and no change in biomass increment, which could also partly result from changes in carbon partitioning (e.g., from below- to above-ground). The biomass increment was significantly related to Δ(13)C on an individual tree level, but the relationship was lost during the pollution period. We suggest that this was caused by a shift from the dominant influence of the photosynthetic rate to stomatal conductance on Δ(13)C during the pollution period. Using biomass increment-climate correlation analyses, we did not identify any clear pollution

  11. Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates†

    Science.gov (United States)

    Wolf, Stephan E.; Müller, Lars; Barrea, Raul; Kampf, Christopher J.; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten

    2011-01-01

    During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. PMID:21218241

  12. Complex Physiological Response of Norway Spruce to Atmospheric Pollution – Decreased Carbon Isotope Discrimination and Unchanged Tree Biomass Increment

    Science.gov (United States)

    Čada, Vojtěch; Šantrůčková, Hana; Šantrůček, Jiří; Kubištová, Lenka; Seedre, Meelis; Svoboda, Miroslav

    2016-01-01

    Atmospheric pollution critically affects forest ecosystems around the world by directly impacting the assimilation apparatus of trees and indirectly by altering soil conditions, which subsequently also leads to changes in carbon cycling. To evaluate the extent of the physiological effect of moderate level sulfate and reactive nitrogen acidic deposition, we performed a retrospective dendrochronological analysis of several physiological parameters derived from periodic measurements of carbon stable isotope composition (13C discrimination, intercellular CO2 concentration and intrinsic water use efficiency) and annual diameter increments (tree biomass increment, its inter-annual variability and correlation with temperature, cloud cover, precipitation and Palmer drought severity index). The analysis was performed in two mountain Norway spruce (Picea abies) stands of the Bohemian Forest (Czech Republic, central Europe), where moderate levels of pollution peaked in the 1970s and 1980s and no evident impact on tree growth or link to mortality has been reported. The significant influence of pollution on trees was expressed most sensitively by a 1.88‰ reduction of carbon isotope discrimination (Δ13C). The effects of atmospheric pollution interacted with increasing atmospheric CO2 concentration and temperature. As a result, we observed no change in intercellular CO2 concentrations (Ci), an abrupt increase in water use efficiency (iWUE) and no change in biomass increment, which could also partly result from changes in carbon partitioning (e.g., from below- to above-ground). The biomass increment was significantly related to Δ13C on an individual tree level, but the relationship was lost during the pollution period. We suggest that this was caused by a shift from the dominant influence of the photosynthetic rate to stomatal conductance on Δ13C during the pollution period. Using biomass increment-climate correlation analyses, we did not identify any clear pollution

  13. Carbon isotopic evidence for biodegradation of organic contaminants in the shallow vadose zone of the radioactive waste management complex

    International Nuclear Information System (INIS)

    Waste material buried in drums in the shallow subsurface at the Radioactive Waste Management Facility (RWMC) of the Idaho National Engineering and Environmental Laboratory (INEEL) contained significant amounts of organic compounds including lubricating oils and chlorinated solvents. CO2 concentrations in pore gas samples from monitoring wells in the vicinity of the disposal pits are 3 to 5 times higher than the concentrations in nearby background wells. The stable carbon isotope ratios ((delta)13C values) of CO2 from the disposal pits averaged 2.4. less than CO2 from the background wells, indicating that the elevated CO2 concentrations around the pits were derived from source materials with (delta)13C values in the range of -24(perthousand) to -29(perthousand). These (delta)13C values are typical of lubricating oils, but higher than most solvents. The radiocarbon (14C) contents of CO2 across most of the site were significantly elevated above modern concentrations due to reactor blocks buried in a subsurface vault at the site. However, several samples collected from the high-CO2 zone on the far side of the RWMC from the reactor blocks had very low 14C contents (less than 0.13 times modern), confirming production from lubricating oils manufactured from fossil hydrocarbons. The magnitude of the CO2 anomaly observed at the site is consistent with intrinsic biodegradation rates on the order of 0.5 to 3.0 metric tons of carbon per year

  14. Demonstration of carbon-carbon bond cleavage of acetyl coenzyme A by using isotopic exchange catalyzed by the CO dehydrogenase complex from acetate-grown Methanosarcina thermophila

    International Nuclear Information System (INIS)

    The purified nickel-containing CO dehydrogenase complex isolated from methanogenic Methanosarcina thermophila grown on acetate is able to catalyze the exchange of [1-14C] acetyl-coenzyme A (CoA) (carbonyl group) with 12CO as well as the exchange of [3'-32P]CoA with acetyl-CoA. Kinetic parameters for the carbonyl exchange have been determined: Km (acetyl-CoA) = 200 microM, Vmax = 15 min-1. CoA is a potent inhibitor of this exchange (Ki = 25 microM) and is formed under the assay conditions because of a slow but detectable acetyl-CoA hydrolase activity of the enzyme. Kinetic parameters for both exchanges are compared with those previously determined for the acetyl-CoA synthase/CO dehydrogenase from the acetogenic Clostridium thermoaceticum. Collectively, these results provide evidence for the postulated role of CO dehydrogenase as the key enzyme for acetyl-CoA degradation in acetotrophic bacteria

  15. Dissolved organic carbon reduces uranium bioavailability and toxicity. 1. Characterization of an aquatic fulvic acid and its complexation with uranium[VI].

    Science.gov (United States)

    Trenfield, Melanie A; McDonald, Suzanne; Kovacs, Krisztina; Lesher, Emily K; Pringle, Jennifer M; Markich, Scott J; Ng, Jack C; Noller, Barry; Brown, Paul L; van Dam, Rick A

    2011-04-01

    Fulvic acid (FA) from a tropical Australian billabong (lagoon) was isolated with XAD-8 resin and characterized using size exclusion chromatography, solid state cross-polarization magic angle spinning, 13C nuclear magnetic resonance spectroscopy, elemental analysis, and potentiometric acid-base titration. Physicochemical characteristics of the billabong FA were comparable with those of the Suwannee River Fulvic Acid (SRFA) standard. The greater negative charge density of the billabong FA suggested it contained protons that were more weakly bound than those of SRFA, with the potential for billabong water to complex less metal contaminants, such as uranium (U). This may subsequently influence the toxicity of metal contaminants to resident freshwater organisms. The complexation of U with dissolved organic carbon (DOC) (10 mg L(-1)) in billabong water was calculated using the HARPHRQ geochemical speciation model and also measured using flow field-flow fractionation combined with inductively coupled plasma mass-spectroscopy. Agreement between both methods was very good (within 4% as U-DOC). The results suggest that in billabong water at pH 6.0, containing an average DOC of 10 mg L(-1) and a U concentration of 90 μg L(-1), around 10% of U is complexed with DOC. PMID:21351802

  16. Study of copper and purine-copper complexes on modified carbon electrodes by cyclic and elimination voltammetry

    Czech Academy of Sciences Publication Activity Database

    Trnková, L.; Zerzánková, L.; Dyčka, F.; Mikelová, R.; Jelen, František

    2008-01-01

    Roč. 8, č. 1 (2008), s. 429-444. ISSN 1424-8220 R&D Projects: GA AV ČR(CZ) IAA100040602; GA AV ČR(CZ) IAA400040804 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : copper-purine complexes * paraffin-impregnated graphite electrode * mercury-film electrode Subject RIV: BO - Biophysics Impact factor: 1.870, year: 2008

  17. Selective continuous flow catalysis using transition metal complexes in supported ionic liquid phase with supercritical carbon dioxide

    OpenAIRE

    Hintermair, Ulrich

    2011-01-01

    The present thesis deals with the development of a novel, efficient reaction concept which allows selective catalysis mediated by molecularly defined transition metal complexes to be conducted in a continuous manner with fully integrated product separation. Such systems may open up new opportunities in chemical synthesis and catalysis research, and also pave the way for a broader application of organometallic catalysis in the chemical industry. In this context, the general merits and conceptu...

  18. Carbon isotopic evidence for biodegradation of organic contaminants in the shallow vadose zone of the radioactive waste management complex

    Energy Technology Data Exchange (ETDEWEB)

    Conrad, Mark E.; DePaolo, Donald J.

    2003-09-04

    Waste material buried in drums in the shallow subsurface at the Radioactive Waste Management Facility (RWMC) of the Idaho National Engineering and Environmental Laboratory (INEEL) contained significant amounts of organic compounds including lubricating oils and chlorinated solvents. CO{sub 2} concentrations in pore gas samples from monitoring wells in the vicinity of the disposal pits are 3 to 5 times higher than the concentrations in nearby background wells. The stable carbon isotope ratios ({delta}{sup 13}C values) of CO{sub 2} from the disposal pits averaged 2.4. less than CO{sub 2} from the background wells, indicating that the elevated CO{sub 2} concentrations around the pits were derived from source materials with {delta}{sup 13}C values in the range of -24{per_thousand} to -29{per_thousand}. These {delta}{sup 13}C values are typical of lubricating oils, but higher than most solvents. The radiocarbon ({sup 14}C) contents of CO{sub 2} across most of the site were significantly elevated above modern concentrations due to reactor blocks buried in a subsurface vault at the site. However, several samples collected from the high-CO{sub 2} zone on the far side of the RWMC from the reactor blocks had very low {sup 14}C contents (less than 0.13 times modern), confirming production from lubricating oils manufactured from fossil hydrocarbons. The magnitude of the CO{sub 2} anomaly observed at the site is consistent with intrinsic biodegradation rates on the order of 0.5 to 3.0 metric tons of carbon per year.

  19. Fabrication of TiO2 nanoparticles/surfactant polymer complex film on glassy carbon electrode and its application to sensing trace dopamine

    International Nuclear Information System (INIS)

    A novel method for the fabrication of a TiO2/Nafion nano-film on glassy carbon electrode (NTGCE) is described. In the presence of dispersant, TiO2 nanoparticles were dispersed into water to give a homogeneous and stable suspension. After the solvent evaporation, a porous and uniform TiO2 nano-film was obtained on the GCE surface. Further coated with Nafion, the complex film possesses remarkable stability in aqueous solution. This nano-film was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The prepared electrode showed excellent electrocatalytic behavior of dopamine and high concentration of ascorbic acid does not interfere with the dopamine detection. Based on this, an electrochemical method is developed for the determination of dopamine with simplicity and high sensitivity

  20. Improving the Spatial Prediction of Soil Organic Carbon Stocks in a Complex Tropical Mountain Landscape by Methodological Specifications in Machine Learning Approaches.

    Directory of Open Access Journals (Sweden)

    Mareike Ließ

    Full Text Available Tropical forests are significant carbon sinks and their soils' carbon storage potential is immense. However, little is known about the soil organic carbon (SOC stocks of tropical mountain areas whose complex soil-landscape and difficult accessibility pose a challenge to spatial analysis. The choice of methodology for spatial prediction is of high importance to improve the expected poor model results in case of low predictor-response correlations. Four aspects were considered to improve model performance in predicting SOC stocks of the organic layer of a tropical mountain forest landscape: Different spatial predictor settings, predictor selection strategies, various machine learning algorithms and model tuning. Five machine learning algorithms: random forests, artificial neural networks, multivariate adaptive regression splines, boosted regression trees and support vector machines were trained and tuned to predict SOC stocks from predictors derived from a digital elevation model and satellite image. Topographical predictors were calculated with a GIS search radius of 45 to 615 m. Finally, three predictor selection strategies were applied to the total set of 236 predictors. All machine learning algorithms-including the model tuning and predictor selection-were compared via five repetitions of a tenfold cross-validation. The boosted regression tree algorithm resulted in the overall best model. SOC stocks ranged between 0.2 to 17.7 kg m-2, displaying a huge variability with diffuse insolation and curvatures of different scale guiding the spatial pattern. Predictor selection and model tuning improved the models' predictive performance in all five machine learning algorithms. The rather low number of selected predictors favours forward compared to backward selection procedures. Choosing predictors due to their indiviual performance was vanquished by the two procedures which accounted for predictor interaction.

  1. Arene ruthenium oxinato complexes: Synthesis, molecular structure and catalytic activity for the hydrogenation of carbon dioxide in aqueous solution

    OpenAIRE

    Thai, Trieu-Tien; Therrien, Bruno; Süss-Fink, Georg

    2010-01-01

    Two families of arene ruthenium oxinato complexes of the types [(η6-arene)Ru(η2-N,O-L)Cl] and [(η6-arene)Ru(η2-N,O-L)(OH2)]+ have been synthesized from the dinuclear precursors [(η6-arene)RuCl2]2 (arene = para-cymeme or hexamethylbenzene) and the corresponding oxine LH (LH = 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5,7-dichloro-2-methyl-8-hydroxyquinoline). The molecular structures of the neu...

  2. Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N-Heterocyclic Carbene-Copper Complex.

    Science.gov (United States)

    Gholap, Sandeep Suryabhan; Takimoto, Masanori; Hou, Zhaomin

    2016-06-13

    The alkylative carboxylation of allenamide catalyzed by an N-heterocyclic carbene (NHC)-copper(I) complex [(IPr)CuCl] with CO2 and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO2 (1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)-α,β-dehydro-β-amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ-carbon, and the carboxyl group introduced onto the β-carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO2 . A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β-hydrogen atoms, such as Et2 Zn or Bu2 Zn, also gave the corresponding alkylative carboxylation products without β-hydride elimination. The present methodology provides an easy route to alkyl-substituted α,β-dehydro-β-amino acid ester derivatives under mild reaction conditions with high regio- and stereoselectivtiy. PMID:27167688

  3. An infrared study of carbon monoxide complexes of hemocyanins. Evidence for the structure of the CO-binding site from vibrational analysis

    International Nuclear Information System (INIS)

    A vibrational analysis was carried out showing that the infrared experimental data of 13C and 18O carbon monoxide complexes of hemocyanin of Fager and Alben (Biochemistry 11 (1972) 4786) are consistent with a coordination of the carbon atom of CO to one of the two copper ions in the active site. This conclusion contradicts the original interpretation of Fager and Alben in which oxygen-coordination to copper was suggested. This vibrational analysis can also be applied to the study of Alben and Caughey (Biochemistry 7 (1968) 175) with 13C and 18O carbonyl hemoglobin, in which oxygen-coordination to iron was suggested. Carbonyl hemocyanins from several sources have also been studied by infrared spectroscopy. The single stretching vibration of CO bound to arthropodal (Cancer magister) hemocyanin (γsub(CO)) is at 2042.5 cm-1, while γsub(CO) for gastropod (Helix pomatia of the phylum Mollusca) α and β hemocyanin is at 2064.5 cm-1 and 2062.5 cm-1, respectively. The intensities of the CO stretching bands were all around 1.5 X 104 M-1 cm-2. Calculations show that with the present attainable accuracy it is impossible to detect hydrogen bonding of exchangeable protons to small molecules bound to proteins (for example CO), by comparing its stretching frequencies in H2O and D2O buffers. (Auth.)

  4. Nickel-phendione complex covalently attached onto carbon nanotube/cross linked glucose dehydrogenase as bioanode for glucose/oxygen compartment-less biofuel cell

    Science.gov (United States)

    Korani, Aazam; Salimi, Abdollah; Hadadzadeh, Hasan

    2015-05-01

    Here, [Ni(phendion) (phen)]Cl2 complex, (phendion and phen are 1,10-phenanthroline-5,6-dione and 5-amino-1, 10-phenanthrolin) covalently attached onto carboxyl functionalized multi walls carbon nanotube modified glassy carbon electrode (GCE/MWCNTs-COOH) using solid phase interactions and combinatorial approaches.The attached [Ni(phendion) (phen)]Cl2 complex displays a surface controlled electrode process and it acts as an effective redox mediator for electrocatalytic oxidation of dihydronicotinamide adenine dinucleotide (NADH) at reduced overpotentials. With co-immobilization of glucose dehydrogenase enzyme (GDH) by crosslinking an effective biocatalyst for glucose oxidation designed. The onset potential and current density are -0.1 V versus Ag/AgCl electrode and 0.550 mA cm-2, which indicate the applicability of the proposed system as an efficient bioanode for biofuel cell (BFC) design. A GCE/MWCNTs modified with electrodeposited gold nanoparticles (AuNPs) as a platform for immobilization of bilirubin oxidase (BOD) and the prepared GCE/MWCNTs/AuNPs/BOD biocathode exhibits an onset potential of 0.56 V versus Ag/AgCl. The performance of the fabricated bioanode and biocathode in a membraneless enzyme based glucose/O2 biofuel cell is evaluated. The open circuit voltage of the cell and maximum current density are 520 mV and 0.233 mA cm-2, respectively, while maximum power density of 40 μWcm-2 achieves at voltage of 280 mV with stable output power after 24 h continues operation.

  5. Effectiveness of submersed angiosperm-epiphyte complexes on exchange of nutrients and organic carbon in littoral systems. I. Inorganic nutrients

    Energy Technology Data Exchange (ETDEWEB)

    Mickle, A.M.; Wetzel, R.G.

    1978-01-01

    Inorganic chemical parameters were analyzed daily for several weeks in water from an inlet stream of a small hardwater lake before and after passing through two replicated continuously, very slowly flowing (3 1/24 h) littoral systems containing natural stands of submerged Scirpus subterminalis Torr. and of Myriophyllum heterophyllum Michx. Macrophytic epiphytes were left intact. Calcium and alkalinity concentrations of the inflowing water decreased 40 to 45% in passing through the littoral systems. In both systems, pH values increased significantly, but to a greater extent in the more metabolically active Myriophyllum (than the Scirpus) littoral bed. Magnesium concentrations remained constant in passage through both systems. Sodium concentrations were unaffected by the Scirpus system but increased (8%) in the outflow from the Myriophyllum system. In contrast to the Scirpus system where potassium increased slightly, potassium concentrations decreased markedly (> 30%) in passage through the Myriophyllum complex. Nitrate-nitrogen concentrations were reduced significantly and NH/sub 4/-N decreased only slightly in both plant systems. Concentrations of NH/sub 4/-N and potassium increased markedly in inflow water after periods of rainfall. Both littoral systems were extremely effective in dampening these higher concentrations; only slight increases appeared in the outflows after passing slowly through the littoral complexes.

  6. Effectiveness of submersed angiosperm-epiphyte complexes on exchange of nutrients and organic carbon in littoral systems. I. Inorganic nutrients

    Energy Technology Data Exchange (ETDEWEB)

    Mickle, A.M.; Wetzel, R.G.

    1978-01-01

    Inorganic chemical parameters were analyzed daily for several weeks in water from an inlet stream of a small hardwater lake before and after passing through two replicated continuously, very slowly flowing (3 1/24 h) littoral systems containing natural strands of submerged Scripus subterminalis Torr. and of Myriophyllum heterophyllum Michx. Macrophytic epiphytes were left intact. Calcium and alkalinity concentrations of the inflowing water decreased 40 to 45% in passing through the littoral systems. In both systems, pH values increased significantly, but to a greater extent in the more metabolically active Myriophyllum (than the Scirpus) littoral bed. Magnesium concentrations remained constant in passage through both systems. Sodium concentrations were unaffected by the Scirpus system but increased (8%) in the outflow from the Myriophyllum system. In contrast to the Scirpus system where potassium increased slightly, potassium concentrations decreased markedly (> 30%) in passage through the Myriophyllum complex. Nitrate-nitrogen concentrations were reduced significantly and NH/sub 4/-N decreased only slightly in both plant systems. Concentrations of NH/sub 4/-N and potassium increased markedly in inflow water after periods of rainfall. Both littoral systems were extremely effective in dampening these higher concentrations; only slight increases appeared in the outflows after passing slowly through the littoral complexes.

  7. Olivine Carbonation and Multiple Episodes of Carbonate Veining during Basement Rock Denudation in an Oceanic Core Complex, ODP Site 1275, Mid-Atlantic Ridge: A Natural Analog for Engineered Carbon Sequestration

    Science.gov (United States)

    Schroeder, T. J.; Bach, W.; Joens, N.; Rausch, S.; Monien, P.; Kluegel, A.

    2014-12-01

    Carbonate precipitation in oceanic olivine-bearing rocks provides a natural case to study engineered CO2-sequestration via olivine carbonation. ODP Site 1275 recovered tectonically denuded gabbro and troctolite on the west flank of the Mid-Atlantic Ridge (15°45'N). Carbonate veins comprise ~0.15 vol.% of the recovered core, corresponding to CO2 uptake of only 0.075 wt.%. However, troctolite cores are comprised of 0.8 vol.% calcite veins, and individual troctolite samples contain up to 15 vol.% calcite that directly replaced olivine in association with talc. Carbonate precipitated from multiple types of fluids during and following denudation. Calcite replaced olivine concurrently with the formation of high-temperature (δ18OSMOW = 11 to 20‰, corresponding to 75-180°C for fluid δ18OSMOW of 0‰) calcite veins in active shear zones. These veins are enriched in LREEs (2-10x chondrite) with strong positive Eu anomalies (Eu/Eu* = 5 to 500), and have 87/86Sr ratios of ~0.704 and δ13CVPDB ranging from -2 to -5‰. Later veins (70% calcite and 30% aragonite) cut high-T veins. These veins precipitated near seawater temperatures (δ18OSMOW ~ 35.1), and have seawater C and Sr isotopic signatures. Both late calcite and aragonite veins have lower REE contents than high-T veins and have little or no Eu anomalies; aragonite veins have negative Ce anomalies. These low-T veins precipitated in both gabbro and troctolite from seawater with varying degrees of rock interaction. High-T veins and replacive calcite precipitated from a mixture of seawater and high-T hydrothermal fluids, and are common in troctolite but rare in gabbro. Geochemical reaction path modeling suggests that the replacive calcite-talc assemblage in troctolite forms only at high fluid-to-rock ratios. The calcite's low 87/86Sr ratios, however, indicate that the seawater-derived fluids had exchanged Sr with large volumes of rock. The olivine carbonation may hence result from upflow of deeply rooted fluids during

  8. Extraction of uranium from simulated ore by the supercritical carbon dioxide fluid extraction method with nitric acid-TBP complex

    International Nuclear Information System (INIS)

    The supercritical fluid extraction (SFE) method using CO2 as a medium with an extractant of HNO3-tri-n-butyl phosphate (TBP) complex was applied to extract uranium from several uranyl phosphate compounds and simulated uranium ores. An extraction method consisting of a static extraction process and a dynamic one was established, and the effects of the experimental conditions, such as pressure, temperature, and extraction time, on the extraction of uranium were ascertained. It was found that uranium could be efficiently extracted from both the uranyl phosphates and simulated ores by the SFE method using CO2. It was thus demonstrated that the SFE method using CO2 is useful as a pretreatment method for the analysis of uranium in ores. (author)

  9. C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis,Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions%C-H Bond Activation of Bisimines by Palladium (Ⅱ) and Platinum (Ⅱ).Synthesis, Characterization of Bis (imino) aryl-palladium (Ⅱ) Pincer Complexes and Their Application in Carbon-Carbon Cross Coupling Reactions

    Institute of Scientific and Technical Information of China (English)

    CHEN Rong; CHEN Ying; LIU Fang; LI Ping; HU Zhao-xia; WANG Hong-xing

    2013-01-01

    Abstract:The reactions of a variety of 4,6-dimethyl-1,3-bis (imino) benzenes 2a-g derived from 4,6-dimethylisophthalaldehyde and anilines or benzylamine with palladium (Ⅱ) acetate in anhydrous acetic acid under nitrogen were investigated.Experiment results demonstrate that cyclopalladations in such condition are applicable not only to the present system under study but also to the 5-substituted bis(imino)benzenes 6,7.The molecular structure of 3 b was further confirmed by X-Ray single-crystal diffraction.3b Crystallizes in orthorhombic,space groupP2 (1) 2 (1) 2 (1) with a =0.734 53 (8),b =1.683 8 (3),c =1.691 7(2) nm,α =β =γ =90°.Treatment of 2b with K2PtCl4 in anhydrous acetic acid affords the corresponding NCN-platinum pincer.Carbon-carbon cross coupling reactions catalyzed with 3b were investigated.These palladium complexes have been proved to be high effective catalysts for Suzuki coupling reaction.

  10. Influence of domestic pets on soil concentrations of dissolved organic carbon, nitrogen, and phosphorus under turfgrass in apartment complexes of Central Texas, USA

    Science.gov (United States)

    Steele, M.; Aitkenhead-Peterson, J. A.

    2009-12-01

    High nitrogen (N) and phosphorus (P) watershed loading rates increases the concentration and loads present in urban streams and rivers, resulting in eutrophication and degradation of surface water quality. Domestic pet animal feed may represent a significant proportion of nitrogen loading in urban watersheds, and because it is deposited directly on the watershed surface may have a large effect on N loads in urban surface waters (Baker et al. 2001). Animal manure has long been used to increase soil N and phosphorus concentrations for the purpose of growing agricultural crops; however, little is known about unintentional urban manuring resulting from a high density of domesticated pets. The purpose of this study is to determine if the presence of domesticated animals in high density urban developments results in increased concentrations of soil dissolved organic carbon (DOC), N, and P and the potential to contribute to loading of urban streams. Composite soil samples from the 0 to 5 cm and 5 to 10 cm soil depth were collected from apartment complexes in Bryan/College Station (BCS) and San Antonio, Texas during August, 2009. Apartment complexes were randomly located around the city and were chosen based on their rules regarding pet ownership. Four apartment complexes that allowed all domestic pets were compared to four that did not allow any domestic pets on the property. A 10:1 water extraction of field moist soil was conducted immediately after sampling. Soil water extracts were analyzed for DOC, total dissolved nitrogen (TDN), nitrate-N, ammonium-N, dissolved organic N, and orthophosphate-P. Results indicated significantly increased concentrations of DOC and N species at both depths in BCS apartments that allowed pets compared to those that did not; however, opposite trends were found in San Antonio. There is a trend for increased concentrations of orthophosphate-P at both locations. Baker, L.A., D. Hope, Y. Xu, et al. 2001. Nitrogen balance for the central Arizona

  11. Accumulation and δ 13C Composition of Soil Carbon Across a Chronosequence of Dune Complexes at Mono Lake, CA

    Science.gov (United States)

    Aanderud, Z. T.; Shuldman, M. I.; Richards, J. H.

    2004-12-01

    The amount of C sequestered and its permanence in some deserts could be higher than normally appreciated. Limited soil water availability and slow decomposition rates in desert soils may induce the long-term accumulation of soil organic C and coarse woody litter. We inventoried C in soils along a chronosequence of Sarcobatus vermiculatus shrub islands and interspaces at the Mono Basin Ecosystem Research Site, CA. Such shrub-island/interspace dune systems are widespread in basin habitats across the Great Basin Desert. We hypothesized that organic C stores would increase across the chronosequence (48, 84, ˜300, and 1800-3000 years since exposure by lake recession) and that δ 13C values of soil organic C (SOC) would become enriched over time due to isotopic fractionation associated with C mineralization of leaf and root litter. C stores quantified in 0-50 cm soils included: SOC, soil inorganic C (SIC; i.e. carbonates removed by 12 M HCl fumigation), and C in partially decomposed woody and fine litter. The youngest dune system contains at least 13.6 Mg C ha-1 and the oldest contains at least 37.9 Mg C ha-1. Our data suggest slow turnover rates of SOC (C:N ratios ˜10) and substantial accumulation of organic C (coarse litter, fine litter, and SOC) in shrub islands across the chronosequence (islands at the youngest site = 8.0 g kg-1 and islands at the oldest site = 24.0 g kg-1. Large pools of SOC and C in woody debris are potentially protected in this shrub-dominated desert, especially in shrub islands of "old-growth" dune systems. Most of the C in the soil is SIC (94% in youngest dunes to 83% at the oldest dunes). The decrease in SIC proportion as the dune systems age is correlated with a decrease in pH across the chronosequence (10.6 at the youngest site and 9.7 at the oldest site). As dunes age, total soil C isotopic composition shifts from positive δ 13C values (2.8 to 3.6 ‰ ), indicative inorganic processes, to slightly negative values (-1.2 to -3.7 ‰ ) as a

  12. Planting increases the abundance and structure complexity of soil core functional genes relevant to carbon and nitrogen cycling

    Science.gov (United States)

    Wang, Feng; Liang, Yuting; Jiang, Yuji; Yang, Yunfeng; Xue, Kai; Xiong, Jinbo; Zhou, Jizhong; Sun, Bo

    2015-09-01

    Plants have an important impact on soil microbial communities and their functions. However, how plants determine the microbial composition and network interactions is still poorly understood. During a four-year field experiment, we investigated the functional gene composition of three types of soils (Phaeozem, Cambisols and Acrisol) under maize planting and bare fallow regimes located in cold temperate, warm temperate and subtropical regions, respectively. The core genes were identified using high-throughput functional gene microarray (GeoChip 3.0), and functional molecular ecological networks (fMENs) were subsequently developed with the random matrix theory (RMT)-based conceptual framework. Our results demonstrated that planting significantly (P soils and 83.5% of microbial alpha-diversity can be explained by the plant factor. Moreover, planting had significant impacts on the microbial community structure and the network interactions of the microbial communities. The calculated network complexity was higher under maize planting than under bare fallow regimes. The increase of the functional genes led to an increase in both soil respiration and nitrification potential with maize planting, indicating that changes in the soil microbial communities and network interactions influenced ecological functioning.

  13. An enigmatic source of hematitic carbonate beds containing vast amounts of iron oxidizers in a paleozoic metamorphic complex, South Hungary, Geresd-Hills, Ófalu.

    Science.gov (United States)

    Jáger, Viktor; Dabi, Gergely; Menyhárt, Adrienn

    2013-04-01

    Near the village of Ófalu, in the Geresd Hills, South Hungary, within the "Mecsekalja tectonic belt", low and intermediate grade paleozoic metamorphic complex (phyllite, gneiss) contains vein-like hematitic carbonate beds, up to 30 cm in thickness. The carbonate mineral is calcite. These hematitic carbonate beds cross-cut the foliation of the phyllite, and show no signs of any metamorphic alteration. In the studied section the red carbonate beds are associated with a vein system filled with multiple generations of vein carbonates(Dabi et al., 2011). The red carbonate beds contain a vaste number of twisted stalks of the iron oxidizing taxon of Gallionella. Rarely in some siliceous parts, Leptothrix-like microbial fossils can be found and these beds also contain numerous unidentifiable, hematitic foraminifers. According to ICP-AES measurements, the hematitic carbonate beds contains 8 % Fe, 0.86 % Mn and 0.12 % Ba. XRD and Raman measurements proved that the iron phase is hematite. The SEM observations revealed that the bacterial microfossils and foraminifers are built up of micron-submicron sized pseudohexagonal platy hematite. The bacterial microfossils of the Gallionella iron oxidizer are very well preserved and reaches about 80 µm length and about 2-3 µm width. The above observations raise the following issues: 1. how did these non metamorphic hematitic-carbonatic beds get inside into the metamorphic complex?, 2. what is the age of the formation of these beds?, and 3. what was the source of the iron? If we consider that the hematitic beds contain foraminifers and iron oxidizing bacteria, and no signs of metamorphic alteration nor foliations can be observed in these beds, the only answer for the first question is that the formations are fractures filled with lime-mud, i.e. neptunian dykes, which penetrated into the cracks of the phyllite. The presence of foraminifers and the geotectonic situation of the unit imply marine origin. Considering that these beds are

  14. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Frantisek Jelen

    2008-01-01

    Full Text Available Using a paraffin impregnated graphite electrode (PIGE and mercury-modifiedpyrolytic graphite electrode with basal orientation (Hg-PGEb copper(II and Cu(II-DNApurine base solutions have been studied by cyclic (CV and linear sweep voltammetry(LSV in connection with elimination voltammetry with linear scan (EVLS. In chlorideand bromide solutions (pH 6, the redox process of Cu(II proceeded on PIGE with twocathodic and two anodic potentially separated signals. According to the eliminationfunction E4, the first cathodic peak corresponds to the reduction Cu(II e- → Cu(I withthe possibility of fast disproportionation 2Cu(I → Cu(II Cu(0. The E4 of the secondcathodic peak signalized an electrode process controlled by a surface reaction. Theelectrode system of Cu(II on Hg-PGEb in borate buffer (pH 9.2 was characterized by onecathodic and one anodic peak. Anodic stripping voltammetry (ASV on PIGE and cathodicstripping voltammetry (CSV on Hg-PGEb were carried out at potentials where thereduction of copper ions took place and Cu(I-purine complexes were formed. By usingASV and CSV in combination with EVLS, the sensitivity of Cu(I-purine complexdetection was enhanced relative to either ASV or CSV alone, resulting in higher peakcurrents of more than one order of magnitude. The statistical treatment of CE data wasused to determine the reproducibility of measurements. Our results show that EVLS inconnection with the stripping procedure is useful for both qualitative and quantitativemicroanalysis of purine derivatives and can also reveal details of studied electrodeprocesses.

  15. 碳纳米管-苯胺电荷转移复合物中的胺荧光淬灭效应%Quenching Effects of Amine on Fluorescence of Carbon Nanotube-Aniline Charge Transfer Complex

    Institute of Scientific and Technical Information of China (English)

    SUN Xu-feng; WANG Yu; JIN Wei-jun

    2005-01-01

    Under refluxing, carbon nanotube (CNT) and aniline (An) can form the charge transfer complex (CTC) of CNT-An.The corresponding fluorescence emission peaks lied at 564nm and 606nm, respectively, with the excitation wavelength of 516nm in the acetone solution. The quenching effects of various amines on CNT- An CTC fluorescence were investigated in detail.

  16. Toxicity of cobalt-complexed cyanide to Oncorhynchus mykiss, Daphnia magna, and Ceriodaphnia dubia: Potentiation by ultraviolet radiation and attenuation by dissolved organic carbon and adaptive UV tolerance

    Science.gov (United States)

    Little, E.E.; Calfee, R.D.; Theodorakos, P.; Brown, Z.A.; Johnson, C.A.

    2007-01-01

    Background. Cobalt cyanide complexes often result when ore is treated with cyanide solutions to extract gold and other metals. These have recently been discovered in low but significant concentrations in effluents from gold leach operations. This study was conducted to determine the potential toxicity of cobalt-cyanide complexes to freshwater organisms and the extent to which ultraviolet radiation (UV) potentiates this toxicity. Tests were also conducted to determine if humic acids or if adaptation to UV influenced sensitivity to the cyanide complexes. Methods. Rainbow trout (Oncorhynchus mykiss), Daphnia magna, and Ceriodaphnia dubia were exposed to potassium hexacyanocobaltate in the presence and absence of UV radiation, in the presence and absence of humic acids. Cyano-cobalt exposures were also conducted with C. dubia from cultures adapted to elevated UV. Results. With an LC50 concentration of 0.38 mg/L, cyanocobalt was over a 1000 times more toxic to rainbow trout in the presence of UV at a low, environmentally relevant irradiance level (4 ??W/cm2 as UVB) than exposure to this compound in the absence of UV with an LC50 of 112.9 mg/L. Toxicity was immediately apparent, with mortality occurring within an hour of the onset of exposure at the highest concentration. Fish were unaffected by exposure to UV alone. Weak-acid dissociable cyanide concentrations were observed in irradiated aqueous solutions of cyanocobaltate within hours of UV exposure and persisted in the presence of UV for at least 96 hours, whereas negligible concentrations were observed in the absence of UV. The presence of humic acids significantly diminished cyanocobalt toxicity to D. magna and reduced mortality from UV exposure. Humic acids did not significantly influence survival among C. dubia. C. dubia from UV-adapted populations were less sensitive to metallocyanide compounds than organisms from unadapted populations. Conclusions. The results indicate that metallocyanide complexes may pose a

  17. Preparation and binding study of a complex made of DNA-treated single-walled carbon nanotubes and antibody for specific delivery of a “molecular heater” platform

    Directory of Open Access Journals (Sweden)

    Kawaguchi M

    2012-08-01

    Full Text Available Minoru Kawaguchi,1,2 Jun Yamazaki,2,3 Jun Ohno,2,4 Tadao Fukushima2,51Department of Dental Engineering, Biomaterials Section, Fukuoka Dental College, Sawara-ku, Fukuoka; 2Japan Science and Technology Agency, Core Research of Evolutional Science and Technology, Chiyoda-ku, Tokyo; 3Department of Physiological Science and Molecular Biology, Section of Cellular and Molecular Regulation, 4Department of Morphological Biology, Pathology Section, 5Center for Regenerative Medicine, Fukuoka Dental College, Sawara-ku, Fukuoka, JapanAbstract: Carbon nanotubes have been explored as heat-delivery vehicles for thermal ablation of tumors. To use single-walled carbon nanotubes (SWNT as a “molecular heater” for hyperthermia therapy in cancer, stable dispersibility and smart-delivery potential will be needed, as well as lack of toxicity. This paper reports the preparation of a model complex comprising DNA-treated SWNT and anti-human IgG antibody and the specific binding ability of this model complex with the targeted protein, ie, human IgG. Treatment with double-stranded DNA enabled stable dispersibility of a complex composed of SWNT and the antibody under physiological conditions. Quartz crystal microbalance results suggest that there was one immobilized IgG molecule to every 21,700 carbon atoms in the complex containing DNA-treated SWNT and the antibody. The DNA-SWNT antibody complex showed good selectivity for binding to the targeted protein. Binding analysis revealed that treatment with DNA did not interfere with binding affinity or capacity between the immobilized antibody and the targeted protein. The results of this study demonstrate that the DNA-SWNT antibody complex is a useful tool for use as a smart “molecular heater” platform applicable to various types of antibodies targeting a specific antigen.Keywords: carbon nanotubes, DNA functionalization, complex, antibody, binding ability

  18. Complex terrain in the Critical Zone: How topography drives ecohydrological patterns of soil and plant carbon exchange in a semiarid mountainous system

    Science.gov (United States)

    Barron-Gafford, G.; Minor, R. L.; Heard, M. M.; Sutter, L. F.; Yang, J.; Potts, D. L.

    2015-12-01

    The southwestern U.S. is predicted to experience increasing temperatures and longer periods of inter-storm drought. High temperature and water deficit restrict plant productivity and ecosystem functioning, but the influence of future climate is predicted to be highly heterogeneous because of the complex terrain characteristic of much of the Critical Zone (CZ). Within our Critical Zone Observatory (CZO) in the Southwestern US, we monitor ecosystem-scale carbon and water fluxes using eddy covariance. This whole-ecosystem metric is a powerful integrating measure of ecosystem function over time, but details on spatial heterogeneity resulting from topographic features of the landscape are not captured, nor are interactions among below- and aboveground processes. We supplement eddy covariance monitoring with distributed measures of carbon flux from soil and vegetation across different aspects to quantify the causes and consequences of spatial heterogeneity through time. Given that (i) aspect influences how incoming energy drives evaporative water loss and (ii) seasonality drives temporal patterns of soil moisture recharge, we were able to examine the influence of these processes on CO2 efflux by investigating variation across aspect. We found that aspect was a significant source of spatial heterogeneity in soil CO2 efflux, but the influence varied across seasonal periods. Snow on South-facing aspects melted earlier and yielded higher efflux rates in the spring. However, during summer, North- and South-facing aspects had similar amounts of soil moisture, but soil temperatures were warmer on the North-facing aspect, yielding greater rates of CO2 efflux. Interestingly, aspect did not influence photosynthetic rates. Taken together, we found that physical features of the landscape yielded predictable patterns of levels and phenologies of soil moisture and temperature, but these drivers differentially influenced below- and aboveground sources of carbon exchange. Conducting

  19. Spectroscopy, dynamics and molecular theory of carbon plasmas and vapors advances in the understanding of the most complex high-temperature elemental system

    CERN Document Server

    Nemes, Laszlo

    2011-01-01

    This book is a stop-gap contribution to the science and technology of carbon plasmas and carbon vapors. It strives to cover two strongly related fields: the molecular quantum theory of carbon plasmas and carbon nanostructures; and the molecular and atomic spectroscopy of such plasmas and vapors. These two fields of research are strongly intertwined and thus reinforce one another. Even though the use of carbon nanostructures is increasing by the day and their practical uses are emerging, there is no modern review on carbon plasmas, especially from molecular theoretical and spectroscopic viewpoi

  20. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    Science.gov (United States)

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-01

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed. PMID:26331776

  1. Novel carbon-supported Fe-N electrocatalysts synthesized through heat treatment of iron tripyridyl triazine complexes for the PEM fuel cell oxygen reduction reaction

    International Nuclear Information System (INIS)

    2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPTZ) was used as a ligand to prepare iron-TPTZ (Fe-TPTZ) complexes for the development of a new oxygen reduction reaction (ORR) catalyst. The prepared Fe-TPTZ complexes were then heat-treated at temperatures ranging from 400 deg. C to 1100 deg. C to obtain carbon-supported Fe-N catalysts (Fe-N/C). These catalysts were characterized in terms of catalyst composition, structure, and morphology by several instrumental methods such as energy dispersive X-ray, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. With respect to the ORR activity, the Fe-N/C catalysts were also evaluated by cyclic voltammetry, as well as rotating disk and ring-disk electrodes. The results showed that among the heat-treated catalysts, that obtained at a heat-treatment temperature of 800 deg. C is the most active ORR catalyst. The overall electron transfer number for the catalyzed ORR was determined to be between 3.5 and 3.8, with 10-30% H2O2 production. The ORR catalytic activity of this catalyst was also tested in a hydrogen-air proton exchange membrane (PEM) fuel cell. At a cell voltage of 0.30 V, this fuel cell can give a current density of 0.23 A cm-2 with a maximum MEA power density of 0.070 W cm-2 indicating that this catalyst has potential to be used as a non-noble catalyst in PEM fuel cells

  2. Immobilized organoruthenium(II) complexes onto polyethyleneimine-wrapped carbon nanotubes/in situ formed gold nanoparticles as a novel electrochemical sensing platform

    Energy Technology Data Exchange (ETDEWEB)

    Azadbakht, Azadeh, E-mail: Azadbakht.a@gmail.com; Abbasi, Amir Reza; Derikvand, Zohreh; Amraei, Shiba

    2015-03-01

    The polyethyleneimine (PEI) wrapped multi-walled carbon nanotubes functionalized with a carboxylic acid group (CNTs–COOH) gold nanoparticle (AuNP)-modified gold (Au) electrode has been utilized as a platform to immobilize organoruthenium(II) complexes (ORC). The surface structure and composition of the sensor were characterized by scanning electron microscopy (SEM). Electrocatalytic reduction of iodate and nitrite on the surface of modified electrode was investigated with cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and hydrodynamic voltammetry methods. The cyclic voltammetric results indicated the ability of AuNPs/PEI/CNT–COOH/ORC modified Au electrode to catalyze the reduction of this compound. AuNPs/PEI/CNTs–COOH nanocomposite combined the advantages of PEI-well dispersed CNTs–COOH and in situ formed AuNPs. - Highlights: • We prepared composite containing polyethyleneimine (PEI), CNTs and AuNPs. • AuNPs were in situ formed on the surface of CNTs–PEI. • When the AuNPs were in situ formed the stability would be improved. • Nanocomposite combined the advantages of PEI–CNTs and in situ formed AuNPs. • Modified nanocomposite Au electrode catalyzes the reduction of iodate and nitrite.

  3. Immobilized organoruthenium(II) complexes onto polyethyleneimine-wrapped carbon nanotubes/in situ formed gold nanoparticles as a novel electrochemical sensing platform

    International Nuclear Information System (INIS)

    The polyethyleneimine (PEI) wrapped multi-walled carbon nanotubes functionalized with a carboxylic acid group (CNTs–COOH) gold nanoparticle (AuNP)-modified gold (Au) electrode has been utilized as a platform to immobilize organoruthenium(II) complexes (ORC). The surface structure and composition of the sensor were characterized by scanning electron microscopy (SEM). Electrocatalytic reduction of iodate and nitrite on the surface of modified electrode was investigated with cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and hydrodynamic voltammetry methods. The cyclic voltammetric results indicated the ability of AuNPs/PEI/CNT–COOH/ORC modified Au electrode to catalyze the reduction of this compound. AuNPs/PEI/CNTs–COOH nanocomposite combined the advantages of PEI-well dispersed CNTs–COOH and in situ formed AuNPs. - Highlights: • We prepared composite containing polyethyleneimine (PEI), CNTs and AuNPs. • AuNPs were in situ formed on the surface of CNTs–PEI. • When the AuNPs were in situ formed the stability would be improved. • Nanocomposite combined the advantages of PEI–CNTs and in situ formed AuNPs. • Modified nanocomposite Au electrode catalyzes the reduction of iodate and nitrite

  4. Mineralogical and field aspects of magma fragmentation deposits in a carbonate phosphate magma chamber: evidence from the Catalão I complex, Brazil

    Science.gov (United States)

    Ribeiro, Carlos Cordeiro; Brod, José Affonso; Junqueira-Brod, Tereza Cristina; Gaspar, José Carlos; Petrinovic, Ivan Alejandro

    2005-03-01

    The Catalão I carbonatite complex, central Brazil consists of ultramafic silicate rocks with subordinate carbonatite and associated phoscorite, nelsonite, and monazitite. In the Lagoa Seca area, lacustrine sediments discordantly overlie a 15-m thick unit of horizontally layered alkaline rocks that consist of a basal apatitite/nelsonite overlain by monazitite. The unit contains cylindrical to conic pipes filled with breccia, limited at the top by a discordance and at the bottom by phoscorites and carbonatites. X-ray diffraction and microprobe studies show that the pipes are filled dominantly by gorceixite and ilmenite, with subordinate apatite, calcite, pyrochlore, baryte, anatase, vivianite, and quartz and rare perovskite. This assemblage has possible primary phases and common alteration products of late-stage phoscorite-series rocks, such as carbonate nelsonites. The lower and intermediate portions of some pipes are fine grained, with cross- and coarsening-upward bedding. These structures are typical of diluted particulate flows (e.g. surges), which suggests that magma fragmentation occurred inside the chamber. The rocks and structures described here seem to represent an extreme case in which surge-like deposits formed within a conduit or even inside the magma chamber, implying that surge processes may develop at higher-than-atmospheric pressures.

  5. Synthesis, structure, and reactivity of iridium perfluorocarbene complexes: regio- and stereo-specific addition of HCl across a metal carbon double bond.

    Science.gov (United States)

    Yuan, Jian; Bourgeois, Cheryl J; Rheingold, Arnold L; Hughes, Russell P

    2015-12-01

    Reductive activation of an α-fluorine in the perfluoroalkyl complexes Cp*(L)(i)Ir-CF2RF using Mg/graphite leads to perfluorocarbene complexes Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3; RF = CF3, C2F5, C6F5). New complexes E-Cp*(PMe3)Ir[double bond, length as m-dash]CFC2F5 and E-Cp*(CO)Ir[double bond, length as m-dash]CFC6F5 have been characterized by single crystal X-ray diffraction studies, and a comparison of metric parameters with previously reported analogues is reported. Experimental NMR and computational DFT (B3LYP/LACV3P**++) studies agree that for Ir[double bond, length as m-dash]CFRF complexes (RF = CF3, CF2CF3) the thermodynamic preference for the E or Z isomer depends on the steric requirements of ligand L; when L = CO the Z-isomer (F cis to Cp*) is preferred and for L = PMe3 the E-isomer is preferred. When reduction of the precursors is carried out in the dark the reaction is completely selective to produce E- or Z-isomers. Exposure of solutions of these compounds to ambient light results in slow conversion to a photostationary non-equilibrium mixture of E and Z isomers. In the dark, these E/Z mixtures convert thermally to their preferred E or Z equilibrium geometries in an even slower reaction. A study of the temperature dependent kinetics of this dark transformation allows ΔG(‡)298 for rotation about the Ir[double bond, length as m-dash]CFCF3 double bond to be experimentally determined as 25 kcal mol(-1); a DFT/B3LYP/LACV3P**++ calculation of this rotation barrier is in excellent agreement (27 kcal mol(-1)) with the experimental value. Reaction of HCl with toluene solutions of Cp*(L)Ir[double bond, length as m-dash]CFRF (L = CO, PMe3) or Cp*(CO)Ir[double bond, length as m-dash]C(CF3)2 at low temperature resulted in regiospecific addition of HCl across the metal carbon double bond, ultimately yielding Cp*(L)Ir(CHFRF)Cl and Cp*(CO)Ir[CH(CF3)2]Cl. Reaction of HCl with single E or Z diastereomers of Cp*(L)Ir[double bond, length as m

  6. Warm ISM in the Sagittarius A Complex. I. Mid-J CO, atomic carbon, ionized atomic carbon, and ionized nitrogen sub-mm/FIR line observations with the Herschel-HIFI and NANTEN2/SMART telescopes

    Science.gov (United States)

    García, P.; Simon, R.; Stutzki, J.; Güsten, R.; Requena-Torres, M. A.; Higgins, R.

    2016-04-01

    Aims: We investigate the spatial and spectral distribution of the local standard of rest (LSR) velocity resolved submillimetre emission from the warm (25-90 K) gas in the Sgr A Complex, located in the Galactic centre. Methods: We present large-scale submillimetre heterodyne observations towards the Sgr A Complex covering ~300 arcmin2. These data were obtained in the frame of the Herschel EXtraGALactic guaranteed time key program (HEXGAL) with the Herschel-HIFI satellite and are complemented with submillimetre observations obtained with the NANTEN2/SMART telescope as part of the NANTEN2/SMART Central Nuclear Zone Survey. The observed species are CO(J = 4-3) at 461.0 GHz observed with the NANTEN2/SMART telescope, and [CI] 3P1-3P0 at 492.2 GHz, [CI] 3P2-3P1 at 809.3 GHz, [NII] 3P1-3P0 at 1461.1 GHz, and [CII] 2P3/2-2P1/2 at 1900.5 GHz observed with the Herschel-HIFI satellite. The observations are presented in a 1 km s-1 spectral resolution and a spatial resolution ranging from 46 arcsec to 28 arcsec. The spectral coverage of the three lower frequency lines is ±200 km s-1, while in the two high frequency lines, the upper LSR velocity limit is +94 km s-1 and +145 km s-1 for the [NII] and [CII] lines, respectively. Results: The spatial distribution of the emission in all lines is very widespread. The bulk of the carbon monoxide emission is found towards Galactic latitudes below the Galactic plane, and all the known molecular clouds are identified. Both neutral atomic carbon lines have their brightest emission associated with the +50 km s-1 cloud. Their spatial distribution at this LSR velocity describes a crescent-shape structure, which is probably the result of interaction with the energetic event (one or several supernovae explosions) that gave origin to the non-thermal Sgr A-East source. The [CII] and [NII] emissions have most of their flux associated with the thermal arched-filaments and the H region and bright spots in [CII] emission towards the central nuclear

  7. σ-Aromatic cyclic M3(+) (M = Cu, Ag, Au) clusters and their complexation with dimethyl imidazol-2-ylidene, pyridine, isoxazole, furan, noble gases and carbon monoxide.

    Science.gov (United States)

    Pan, Sudip; Saha, Ranajit; Mandal, Subhajit; Chattaraj, Pratim K

    2016-04-28

    The σ-aromaticity of M3(+) (M = Cu, Ag, Au) is analyzed and compared with that of Li3(+) and a prototype σ-aromatic system, H3(+). Ligands (L) like dimethyl imidazol-2-ylidene, pyridine, isoxazole and furan are employed to stabilize these monocationic M3(+) clusters. They all bind M3(+) with favorable interaction energy. Dimethyl imidazol-2-ylidene forms the strongest bond with M3(+) followed by pyridine, isoxazole and furan. Electrostatic contribution is considerably more than that of orbital contribution in these M-L bonds. The orbital interaction arises from both L → M σ donation and L ← M back donation. M3(+) clusters also bind noble gas atoms and carbon monoxide effectively. In general, among the studied systems Au3(+) binds a given L most strongly followed by Cu3(+) and Ag3(+). Computation of the nucleus-independent chemical shift (NICS) and its different extensions like the NICS-rate and NICS in-plane component vs. NICS out-of-plane component shows that the σ-aromaticity in L bound M3(+) increases compared to that of bare clusters. The aromaticity in pyridine, isoxazole and furan bound Au3(+) complexes is quite comparable with that in the recently synthesized Zn3(C5(CH3)5)3(+). The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital also increases upon binding with L. The blue-shift and red-shift in the C-O stretching frequency of M3(CO)3(+) and M3(OC)3(+), respectively, are analyzed through reverse polarization of the σ- and π-orbitals of CO as well as the relative amount of OC → M σ donation and M → CO π back donation. The electron density analysis is also performed to gain further insight into the nature of interaction. PMID:26624276

  8. Neutron structure of human carbonic anhydrase II in complex with methazolamide: mapping the solvent and hydrogen-bonding patterns of an effective clinical drug

    Directory of Open Access Journals (Sweden)

    Mayank Aggarwal

    2016-09-01

    Full Text Available Carbonic anhydrases (CAs; EC 4.2.1.1 catalyze the interconversion of CO2 and HCO3−, and their inhibitors have long been used as diuretics and as a therapeutic treatment for many disorders such as glaucoma and epilepsy. Acetazolamide (AZM and methazolamide (MZM, a methyl derivative of AZM are two of the classical CA inhibitory drugs that have been used clinically for decades. The jointly refined X-ray/neutron structure of MZM in complex with human CA isoform II (hCA II has been determined to a resolution of 2.2 Å with an Rcryst of ∼16.0%. Presented in this article, along with only the second neutron structure of a clinical drug-bound hCA, is an in-depth structural comparison and analyses of differences in hydrogen-bonding network, water-molecule orientation and solvent displacement that take place upon the binding of AZM and MZM in the active site of hCA II. Even though MZM is slightly more hydrophobic and displaces more waters than AZM, the overall binding affinity (Ki for both of the drugs against hCA II is similar (∼10 nM. The plausible reasons behind this finding have also been discussed using molecular dynamics and X-ray crystal structures of hCA II–MZM determined at cryotemperature and room temperature. This study not only allows a direct comparison of the hydrogen bonding, protonation states and solvent orientation/displacement of AZM and MZM, but also shows the significant effect that the methyl derivative has on the solvent organization in the hCA II active site.

  9. Studies on the sorption of thoron - metal complexes on activated carbon - extension of work for determination of chromium in water and effluents at PPB levels by flame AAS

    International Nuclear Information System (INIS)

    The determination of indicator trace elements like Cr, Ni, Cu, Pb, Co, Cd, Mn in hydrogeochemical samples assumes significance from the point of view of application in geochemical exploration of uranium. The direct determination of these trace elements in water and effluents is beyond the scope of Flame AAS and ICP-OES as their concentration in these samples are at ppb and sub ppb levels. Hence an enrichment factor of 200 is very essential to have quantifiable data for meaningful interpretation in uranium exploration studies and elsewhere. Hence systematic pre concentration studies have been carried out based on sorption of Metal-Thoron (2- (2-hydroxy-3,6-disulfo-1-naphthylazo) benzenearsonic acid)) complexes on powdered activated carbon (PAC) in the pH range of 1 to 9. It was found experimentally that >90% sorption obtained for Cr, Cu, Pb, and Ni in the pH range of 3-7; 4-9; 4-9 and 5-9 respectively whereas for Co, Cd and Mn sorption increases gradually from pH-4 onwards and reaches up to 90% at pH-9. An interesting experimental factor was observed wherein at pH∼3.5±0.5 only chromium was sorbed on PAC quantitatively (∼95%) and sorption of Cd, Co, Mn is negligible (<5%). Based on experimental studies the optimal conditions for Cr are fixed with respect to sample volume (2000 ml),Thoron concentration (20 ml of 0.1%), pH (3.5±0.5), amount of AC (0.2 g), contact time (4 h) and desorption (1 M HNO3). The Cr is desorbed from activated carbon simply by treating AC with 1 M nitric acid, thus avoiding tedious and time consuming operation of ashing of AC. An enrichment factor 200 is easily achievable based on preconcentration of Cr present in one litre water (effluent) sample to 5 ml. The % RSD of the method is 10 at the practical determination limit of 5 ppb for Cr with an enrichment factor of 200. Thus based on said studies a simple, rapid and field oriented pre-concentrated method is described for the determination of chromium in ground water and effluent samples

  10. Nanoparticle complex fluids

    OpenAIRE

    2008-01-01

    The work presented in this thesis concerns the study of complex nanofluids. The interaction of particles in dispersions under the influence of electric and magnetic fields has been studied. The main focus has been the investigation of the behavior of carbon particle dispersions. A novel type of carbon material, namely carbon cone (CC) material, has been characterized using atomic force microscope, scanning tunnelling microscope and scanning electron microscope. The CC material is a mixed powd...

  11. Preparation and electrochemical properties of core-shell carbon coated Mn–Sn complex metal oxide as anode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    In this study, we synthesized a carbon coated Mn–Sn metal oxide composite with core-shell structure (MTO@C) via a simple glucose hydrothermal reaction and subsequent carbonization approach. When the MTO@C composite was applied as an anode material for lithium-ion batteries, it maintained a reversible capacity of 409 mA h g−1 after 200 cycles at a current density of 100 mA g−1. The uniformed and continuous carbon layer formed on the MTO nanoparticles, effectively buffered the volumetric change of the active material and increased electronic conductivity, which thus prolonged the cycling performance of the MTO@C electrode.

  12. Occurrence of faecal pellet-filled simple and composite burrows in cold seep carbonates: A glimpse of a complex benthic ecosystem

    Digital Repository Service at National Institute of Oceanography (India)

    Mazumdar, A.; Joshi, R.K.; Peketi, A.; Kocherla, M.

    ) tubular burrow casts are also present. Filled tubes with speites are occasionally observed. (Fig. 2 j and k). Polished, transverse cross sections (Fig. 2 l) of the burrow casts show uniform pellets filling without any discernible inner burrow wall. 4...) Carbonate tubes showing spreites like structures (arrows), (l) Polished cross section of burrow cast showing homogenous pellet filling and absence of any inner burrow wall. Figure 3. Morphology and texture of the carbonate faecal pellets. (a) Faecal...

  13. Simultaneous determination of hydrazine and phenyl hydrazine using 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine diacetonitrile triphenylphosphine ruthenium(II) tetrafluoroborate complex functionalized multiwalled carbon nanotubes modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Ida, E-mail: idatiwari_2001@rediffmail.com [Department of Chemistry (Center of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi (India); Gupta, Mandakini; Sinha, Preeti [Department of Chemistry (Center of Advanced Study), Faculty of Science, Banaras Hindu University, Varanasi (India); Banks, Craig E. [Faculty of Science and Engineering, School of Science and the Environment, Division of Chemistry and Environmental Science, Manchester Metropolitan University, Chester Street, Manchester M1 5GD (United Kingdom)

    2014-12-15

    Highlights: • A nanocomposite of ruthenium(II) terpyridine, triphenylphosphine based complex and multiwalled carbon nanotubes have been used first time for simultaneous detection of hydrazine and phenyl hydrazine. • The detection limit reported is lower as compared to other reported works. • The paper also focuses towards effect of ligand variation attached to ruthenium(II) terpyridine based complexes complex for the hydrazine and phenyl hydrazine detection. • Nanocomposite does not involve any biological entity hence high stability. - Abstract: A nanocomposite based on the incorporation of the complex 4′-(4-carboxyphenyl)-2,2′:6′,2″ terpyridine triphenylphosphine diacetonitrile ruthenium(II) tetrafluoroborate with multiwalled carbon nanotubes and ionomer supported upon a glassy carbon electrode substrate is reported and characterized with scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The electrochemical behavior and stability of the composite electrode was investigated via cyclic voltammetry. The modified electrode exhibits an electro-catalytic activity towards the oxidation of both hydrazine and phenyl hydrazine in 0.1 M phosphate buffer solution (PBS, pH 7.4). The oxidation of hydrazine and phenyl hydrazine occurs at 0.81 V and 0.32 V with limit of detection found to be 3.7 × 10{sup −7} M and 1.15 × 10{sup −7} M and having a linear range from 5 × 10{sup −6} M to 6.5 × 10{sup −3} M, and 5 × 10{sup −6} M to 0.2 × 10{sup −3} M, respectively.

  14. 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.

  15. Preparation and electrochemical properties of core-shell carbon coated Mn–Sn complex metal oxide as anode materials for lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ruixue [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Fang, Guoqing; Liu, Weiwei [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Changzhou Institute of Energy Storage Materials and Devices, Changzhou 213000 (China); Xia, Bingbo; Sun, Hongdan; Zheng, Junwei [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China); Li, Decheng, E-mail: lidecheng@suda.edu.cn [Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of chemical power sources, Soochow University, Suzhou 215006 (China)

    2014-02-15

    In this study, we synthesized a carbon coated Mn–Sn metal oxide composite with core-shell structure (MTO@C) via a simple glucose hydrothermal reaction and subsequent carbonization approach. When the MTO@C composite was applied as an anode material for lithium-ion batteries, it maintained a reversible capacity of 409 mA h g{sup −1} after 200 cycles at a current density of 100 mA g{sup −1}. The uniformed and continuous carbon layer formed on the MTO nanoparticles, effectively buffered the volumetric change of the active material and increased electronic conductivity, which thus prolonged the cycling performance of the MTO@C electrode.

  16. Small-angle scattering, contrast variation and the study of complex composite materials: A study of the structure of carbon black

    International Nuclear Information System (INIS)

    Detailed studies are presented on the structure and aggregation of an experimental high surface area carbon black (HSA) using small-angle neutron scattering and the method of contrast variation. We find that the approximately 27 mn HSA particle form small, linear aggregates of average aggregation number 5 when suspended in cyclohexane. There is considerable density fluctuation in the interior of these particles, with the denser regions being toward the outer part of the spherically-averaged structure. This information would not have been obtained from studies of carbon black without solvent. The results will be applied to similar scattering studies on solvent-swollen bound rubber gels made from HSA-polyisoprene. These result show, however, that the strong internal fluctuations of the carbon black will limit the information that can be obtained on the structure and conformation of the elastomer in the gel. There are additional limitation from compositional heterogeneity of the sample

  17. Fluid circulation and carbonate vein precipitation in the footwall of an oceanic core complex, Ocean Drilling Program Site 175, Mid-Atlantic Ridge

    Science.gov (United States)

    Schroeder, Tim; Bach, Wolfgang; Jöns, Niels; Jöns, Svenja; Monien, Patrick; Klügel, Andreas

    2015-10-01

    Carbonate veins recovered from the mafic/ultramafic footwall of an oceanic detachment fault on the Mid-Atlantic Ridge record multiple episodes of fluid movement through the detachment and secondary faults. High-temperature (˜75-175°C) calcite veins with elevated REE contents and strong positive Eu-anomalies record the mixing of up-welling hydrothermal fluids with infiltrating seawater. Carbonate precipitation is most prominent in olivine-rich troctolite, which also display a much higher degree of greenschist and sub-greenschist alteration relative to gabbro and diabase. Low-temperature calcite and aragonite veins likely precipitated from oxidizing seawater that infiltrated the detachment fault and/or within secondary faults late or post footwall denudation. Oxygen and carbon isotopes lie on a mixing line between seawater and Logatchev-like hydrothermal fluids, but precipitation temperatures are cooler than would be expected for isenthalpic mixing, suggesting conductive cooling during upward flow. There is no depth dependence of vein precipitation temperature, indicating effective cooling of the footwall via seawater infiltration through fault zones. One sample contains textural evidence of low-temperature, seawater-signature veins being cut by high-temperature, hydrothermal-signature veins. This indicates temporal variability in the fluid mixing, possibly caused by deformation-induced porosity changes or dike intrusion. The strong correlation between carbonate precipitation and olivine-rich troctolites suggests that the presence of unaltered olivine is a key requirement for carbonate precipitation from seawater and hydrothermal fluids. Our results also suggest that calcite-talc alteration of troctolites may be a more efficient CO2 trap than serpentinized peridotite.

  18. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    Science.gov (United States)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  19. Promoting the activity of LiFePO4 (olivine) cathode of Li-ion battery by supramolecular complexes with single walled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Exnar, I.; Graetzel, M.

    Boca Raton: CRC PRESS-TAYLOR & FRANCIS GROUP, 2009, s. 58-61. ISBN 978-1-4398-1784-1. [NANOTECH CONFERENCE & EXPO 2009. Houston (US), 03.05.2009-07.05.2009] R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : olivine cathode * carbon electrode * Li-ion battery Subject RIV: CG - Electrochemistry

  20. Holocene growth history of a reef complex on a cool-water carbonate margin: Easter Group of the Houtman Abrolhos, Eastern Indian Ocean

    OpenAIRE

    Collins, L. B.; Zhu, Z. R.; Wyrwoll, K.-H.; Hatcher, B. G.; Playford, P. E.; A. Eisenhauer; Chen, J. H.; Wasserburg, G. J.; Bonani, G.

    1993-01-01

    The Houtman Abrolhos reefs, situated on the western continental margin of Australia, occupy a transitional position between cool-water shelf carbonate sediments to the south and more tropical environments to the north. Their existence at the outer limits of the geographical range for coral reef growth is a result of the warm, poleward-flowing Leeuwin Current. Though the modern reefs differ ecologically from tropical reefs, their geological characteristics have been little known until recently...

  1. Molecular wiring of olivine LiFePO4 by ruthenium(II)-bipyridine complexes and by their assemblies with single-walled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Exnar, I.; Zakeeruddin, S. M.; Graetzel, M.

    2008-01-01

    Roč. 112, č. 23 (2008), s. 8708-8714. ISSN 1932-7447 R&D Projects: GA MŠk LC510; GA MŠk 1P05OC069; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : molecular wiring * LiFePO4 * carbon nanotube Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.396, year: 2008

  2. Textural analyses of carbon fiber materials by 2D-FFT of complex images obtained by high frequency eddy current imaging (HF-ECI)

    Science.gov (United States)

    Schulze, Martin H.; Heuer, Henning

    2012-04-01

    Carbon fiber based materials are used in many lightweight applications in aeronautical, automotive, machine and civil engineering application. By the increasing automation in the production process of CFRP laminates a manual optical inspection of each resin transfer molding (RTM) layer is not practicable. Due to the limitation to surface inspection, the quality parameters of multilayer 3 dimensional materials cannot be observed by optical systems. The Imaging Eddy- Current (EC) NDT is the only suitable inspection method for non-resin materials in the textile state that allows an inspection of surface and hidden layers in parallel. The HF-ECI method has the capability to measure layer displacements (misaligned angle orientations) and gap sizes in a multilayer carbon fiber structure. EC technique uses the variation of the electrical conductivity of carbon based materials to obtain material properties. Beside the determination of textural parameters like layer orientation and gap sizes between rovings, the detection of foreign polymer particles, fuzzy balls or visualization of undulations can be done by the method. For all of these typical parameters an imaging classification process chain based on a high resolving directional ECimaging device named EddyCus® MPECS and a 2D-FFT with adapted preprocessing algorithms are developed.

  3. Structural Characterisation of Complex Layered Double Hydroxides and TGA-GC-MS Study on Thermal Response and Carbonate Contamination in Nitrate- and Organic-Exchanged Hydrotalcites.

    Science.gov (United States)

    Conterosito, Eleonora; Palin, Luca; Antonioli, Diego; Viterbo, Davide; Mugnaioli, Enrico; Kolb, Ute; Perioli, Luana; Milanesio, Marco; Gianotti, Valentina

    2015-10-12

    Layered double hydroxides (LDHs) are versatile materials used for intercalating bioactive molecules in the fields of pharmaceuticals, nutraceuticals and cosmetics, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability and improving their pharmacokinetic properties and formulation stability. Moreover, LDHs are used in various technological applications to improve stability and processability. The crystal chemistry of hydrotalcite-like compounds was investigated by X-ray powder diffraction (XRPD), automated electron diffraction tomography (ADT) and thermogravimetric analysis (TGA)-GC-MS to shed light on the mechanisms involved in ion exchange and absorption of contaminants, mainly carbonate anions. For the first time, ADT allowed a structural model of LDH_NO3 to be obtained from experiment, shedding light on the conformation of nitrate inside LDH and on the loss of crystallinity due to the layer morphology. The ADT analysis of a hybrid LDH sample (LDH_EUS) clearly revealed an increase in defectivity in this material. XRPD demonstrated that the presence of carbonate can influence the intercalation of organic molecules into LDH, since CO3 -contaminated samples tend to adopt d spacings that are approximate multiples of the d spacing of LDH_CO3 . TGA-GC-MS allowed intercalated and surface- adsorbed organic molecules to be distinguished and quantified, the presence and amount of carbonate to be confirmed, especially at low concentrations (<2 wt %), and the different types and strengths of adsorption to be classified with respect to the temperature of elimination. PMID:26269963

  4. Renewable-surface sol-gel derived carbon ceramic-modified electrode fabricated by a newly synthesized polypyridil and phosphine Ru (II) complex and its application as an amperometric sensor for hydrazine

    International Nuclear Information System (INIS)

    A chemically modified carbon ceramic composite electrode (CCE) containing Dichloro{(8, 9-dimethyl-dipyridio [2,3-a;2',3'-c] phenazine-κ2-N,N') bis(triphenylphosphine-κ-P)}ruthenium (II) complex which synthesized newly was constructed by the sol-gel technique. Electrochemical behavior and stability of modified CCE were investigated by cyclic voltammetry. The electrocatalytic activity of CCE was investigated and showed a good effect for oxidation of hydrazine in phosphate buffer solution (PBS). A linear concentration range of 6 μM to 1.2 mM of hydrazine with an experimental detection limit of 1 μM of hydrazine was obtained. The diffusion coefficient of hydrazine and its catalytic rate constant for electrocatalytic reaction along with the apparent electron transfer rate constant (ks) and transfer coefficient (α) were also determined. The modified carbon ceramic electrode doped with this new Ru-complex showed good reproducibility, short response time (t 3 month) and especially good surface renewability by simple mechanical polishing. The results showed that this electrode could be used as an electrochemical sensor for determination of hydrazine in real water samples used in Fars Power Plant Station, including its heat recovery steam generator (HRSG) water (at different operational condition), cooling system and clean waste water

  5. Renewable-surface sol-gel derived carbon ceramic-modified electrode fabricated by a newly synthesized polypyridil and phosphine Ru (II) complex and its application as an amperometric sensor for hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Abbaspour, Abdolkarim [Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Fars 7145685464 (Iran, Islamic Republic of)], E-mail: abbaspour@chem.susc.ac.ir; Shamsipur, Mojtaba [Department of Chemistry, College of Sciences, Razi University, Kermanshah (Iran, Islamic Republic of); Siroueinejad, Arash [Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Fars 7145685464 (Iran, Islamic Republic of); Kia, Reza; Raithby, Paul R. [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom)

    2009-04-01

    A chemically modified carbon ceramic composite electrode (CCE) containing Dichloro{l_brace}(8, 9-dimethyl-dipyridio [2,3-a;2',3'-c] phenazine-{kappa}{sup 2}-N,N') bis(triphenylphosphine-{kappa}-P){r_brace}ruthenium (II) complex which synthesized newly was constructed by the sol-gel technique. Electrochemical behavior and stability of modified CCE were investigated by cyclic voltammetry. The electrocatalytic activity of CCE was investigated and showed a good effect for oxidation of hydrazine in phosphate buffer solution (PBS). A linear concentration range of 6 {mu}M to 1.2 mM of hydrazine with an experimental detection limit of 1 {mu}M of hydrazine was obtained. The diffusion coefficient of hydrazine and its catalytic rate constant for electrocatalytic reaction along with the apparent electron transfer rate constant (k{sub s}) and transfer coefficient ({alpha}) were also determined. The modified carbon ceramic electrode doped with this new Ru-complex showed good reproducibility, short response time (t < 2 s), remarkable long-term stability (>3 month) and especially good surface renewability by simple mechanical polishing. The results showed that this electrode could be used as an electrochemical sensor for determination of hydrazine in real water samples used in Fars Power Plant Station, including its heat recovery steam generator (HRSG) water (at different operational condition), cooling system and clean waste water.

  6. Electrochemical quantification of the thermodynamic equilibrium constant of the tenoxicam-β-cyclodextrin inclusion complex formed on the surface of a poly-β cyclodextrin-modified carbon paste electrode

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • A carbon paste electrode (CPE) was modified with a β-CD polymer. • Tenoxicam oxidation on the CPE/poly-β-CD was adsorption controlled. • Influence of pH, scan rate, angular velocity and concentration was evaluated. • Fittings of i-E plots were done considering an irreversible surface reaction. • Electrochemical evaluation of the surface inclusion constant is presented. - Abstract: In this work it is shown that when a carbon paste electrode, CPE, is modified with a β-cyclodextrin polymer, the tenoxicam oxidation becomes an adsorption controlled process due to formation of a surface inclusion complex with the β-CD molecules comprising the surface of the polymer. It was found that such surface inclusion complex can be formed independently of the tenoxicam predominant species, Tenox’, in the aqueous solution namely: H2Tenox+, HTenox or Tenox−, depending on the solution pH. The electrochemical quantification of the thermodynamic constant of the equilibrium Tenox’ + β-CD (polymer) = Tenox’-β-CD (polymer) was estimated as log Kincl. = 4.26 ± 0.01. Furthermore, from the analyses of the experimental voltammograms according with Laviron's equation for an irreversible surface reaction [E. Laviron, J. Electroanal. Chem. 52 (1974) 355-393] it is shown that the surface concentration, ΓR, of tenoxicam increases as its concentration in solution does, reaching a maximum value of 1.51 × 10−10 mol cm−2 at 64 μM

  7. Single-walled Carbon Nanotube/DNAzyme Complex-based Elctrochemical Biosensors%基于单壁碳纳米管-DNA酶复合结构的电化学生物传感器

    Institute of Scientific and Technical Information of China (English)

    封科军; 姚艳玲; 沈国励; 俞汝勤

    2012-01-01

    Taking advantage of the excellent catalytic redox activity andthe electrochemical property of DNAzyme and carbon nanotubes, a novel nano-complex of single-walled carbon nanotubes ( SWNTs)/ DNAzyme was prepared, and the obtained nano-complex was finally immobilized on the surface of glass carbon electrode (GCE) with the assistance of chitosan to fabricate electrochemical biosensing interface. The catalytic property of the SWNTs/DNAzyme complex was explored, and a glucose oxidase biosensor was then prepared based on the fabricated electrochemical biosensing platform. The SWNTs/DNAzyme complex-based biosensing platform can direct response to hydrogen peroxide at low potential of -0. 24 V with high sensitivity (the detection limit is 1×10-6 mol/L) and wide linear range(5×10-6 —1×10-2 mol/L) , and the prepared glucose oxidase biosensor was used to fast and sensitive detection of glucose.%结合DNA酶优异的氧化还原催化特性和碳纳米管的电化学特性,制备了单壁碳纳米管-DNA酶复合材料,并通过壳聚糖将其固定到玻碳电极表面构建了电化学生物传感界面.研究了单壁碳纳米管-DNA酶复合结构的氧化还原反应催化特性,并以此为传感平台构建了葡萄糖氧化酶电化学生物传感器.结果表明,单壁碳纳米管-DNA酶复合材料修饰的电极对过氧化氢的响应具有较宽的线性范围(5×10-6~1×10-2 mol/L)和良好的检测灵敏度(检出限为1×10-6mol/L).采用制备的葡萄糖氧化酶传感器实现了对葡萄糖的快速灵敏检测.

  8. Two-dimensional NMR studies of staphylococcal nuclease. 2. Sequence-specific assignments of carbon-13 and nitrogen-15 signals from the nuclease H124L-thymidine 3',5'-bisphosphate-Ca2+ ternary complex

    International Nuclear Information System (INIS)

    Samples of staphylococcal nuclease H124L (cloned protein overproduced in Escherichia coli whose sequence is identical with that of the nuclease isolated from the V8 strain of Staphylococcus aureus) were labeled uniformly with carbon-13 (26% ul 13C), uniformly with nitrogen-15 (95% ul 15N), and specifically by incorporating nitrogen-15-labeled leucine ([98% 15N]Leu) or carbon-13-labeled lysine ([26% ul 13C]Lys), arginine ([26% ul 13C]Arg), or methionine ([26% ul 13C]Met). Solutions of the ternary complexes of these analogues (nuclease H124L-pdTp-Ca2+) at pH 5.1 (H2O) or pH 5.5 (2H2O) at 45 degree C were analyzed as appropriate to the labeling pattern by multinuclear two-dimensional (2D) NMR experiments spectrometer fields of 14.09 and 11.74 T. The results have assisted in spin system assignments and in identification of secondary structural elements. Nuclear Overhauser enhancements (NOE's) characteristic of antiparellel β-sheet (dαα NOE's) were observed in the 1H(13C)-SBC-NOE spectrum of the nuclease ternary complex labeled uniformly with 13C. NOE's characteristic of α-helix were observed in the 1H(15N)SBC-NOE spectrum of the complex prepared from protein labeled uniformly with 15N. The assignments obtained from these multinuclear NMR studies have confirmed and extended assignments based on 1H(1H) 2D NMR experiments

  9. Complexation of uranyl ions. III. Investigation of the sorption of uranium of the VP-1Ap anion exchanger from carbonate media by x-ray spectrometric microanalysis

    International Nuclear Information System (INIS)

    The spatial distribution of uranium in granules of the VP-1Ap anion exchanger during heightened sorption from carbonate media has been investigated by x-ray spectroscopic microanalysis. Variation of the form of the concentration profile as a function of the extent of sorption from a uniform profile across the diameter, then to a meniscus-shaped profile, and finally to a smoothed profile with an increase in the coefficient of nonuniformity of the distribution of uranium in the granules from 0.026 to 0.045 has been established

  10. Quantification of the abundance and mean residence time of carbon associated with metal-humus complexes, short-range-order Al and Fe hydroxides, and crystalline Fe oxyhydroxides across a suite of ecosystems

    Science.gov (United States)

    Heckman, K. A.; Lawrence, C. R.

    2013-12-01

    Stabilization of SOM (soil organic matter) is regulated in part by sorption and desorption reactions happening at mineral surfaces, as well as precipitation and dissolution of metal-humus complexes. Fe and Al hydroxides play a particularly significant role in SOM stabilization in soils due to their ubiquitous distribution and their highly reactive surface properties. Fe and Al hydroxides exist in soils across a wide spectrum of crystallinity, ranging from dissolved Fe and Al cations which combine with organics to form metal-humus precipitates to the more crystalline end members, goethite and gibbsite, which sorb SOM through a variety of molecular interactions. Though the importance of these sorption and precipitation reactions has long been recognized, the distribution of SOM among Fe and Al hydroxides of differing crystallinity has not been well quantified, nor has the timescales over which these stabilization mechanisms operate. In an attempt to measure the distribution of organic C among i) Al- and Fe-humus complexes ii) short-range-order Al and Fe hydroxide surfaces and iii) crystalline Fe oxyhydroxide surfaces, a suite of selective dissolutions were applied to soils of four different geneses (a tropical forest Andisol, a temperate forest basaltic Mollisol, a mediterranean coastal prairie Mollisol, and a northern mixed hardwood forest Spodosol. The traditional reactants used in selective dissolutions were replaced with carbon-free analogues so that the carbon released along with the Fe and Al at each stage of the selective dissolution process could be examined. Selective dissolutions were performed sequentially: Na-pyrophosphate (Al- and Fe-humus complexes) followed by hydroxylamine (short-range-order Al and Fe hydroxides) followed by dithionite/HCl (crystalline Fe hydroxides). C, Al, and Fe concentrations, as well as Δ14C were measured for the solutions yielded by each stage of the selective dissolution process. Δ14C data were used to estimate a MRT (mean

  11. Carbon Carbon Composites: An Overview .

    OpenAIRE

    G. Rohini Devi; K. Rama Rao

    1993-01-01

    Carbon carbon composites are a new class of engineering materials that are ceramic in nature but exhibit brittle to pseudoplastic behaviour. Carbon-carbon is a unique all-carbon composite with carbon fibre embeded in carbon matrix and is known as an inverse composite. Due to their excellent thermo-structural properties, carbon-carbon composites are used in specialised application like re-entry nose-tips, leading edges, rocket nozzles, and aircraft brake discs apart from several indust...

  12. Influence of the nature of the oxidizing agents on the mechanism of the oxidation of carbon monoxide in the presence of an aqua complex of palladium (II)

    International Nuclear Information System (INIS)

    The kinetics of the oxidation of CO in the presence of an aqua complex of Pd(II) by VO+2 and Fe(III) ions and by heteropolyacids (HPA) viz., H3PMo12O40,H4PMo11 VO40, and H4PW11VO40, was studied. A comparison of the data obtained with the results of the oxidation of CO by strong oxidizing agents - Cr2O72- and Ce(IV) ions - made it possible to conclude that rapid occurrence of the reaction requires an optimum potential of the oxidizing agent 0.7 < E < 1 V. This confirms the assumption that the intermediate carbonyl complexes of partially reduced palladium are the most active in this reaction

  13. Trace enrichment with activated carbon and determination of Ni, Hg, Sn and Cd using diethyldithiocarbamate as complexant by atomic emission spectrography (AES)

    International Nuclear Information System (INIS)

    A methods has been developed for the preconcentration and determination of trace amounts of Hg, Ni, Sn and Cd in aqueous solutions. The complexes of these elements with sodium diethyl dithiocarbamate were adsorbed on activated charcoal and determined by atomic emission spectrography d-c arc technique. Factors which affect the quantitative recovery of the microamounts of the elements were optimised. Pd was used as an internal standard. The detection limits ranged from 0.01 to 0.05 ppm. (author)

  14. Cobalt(III) complexes of [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane. Report of an inert, chelate hydrogen carbonate ion

    DEFF Research Database (Denmark)

    Broge, Louise; Søtofte, Inger; Olsen, Carl Erik;

    2001-01-01

    Three cobalt(III) complexes of themacrocyclic tetraamine [3(5)]adamanzane (1,5,9,13-tetraazabicyclo[7.7.3]-nonadecane) were isolated as salts. The X-ray crystal structures were solved for the compounds [Co([3(5)]adz)-(CO3)AsF6 (1b), [Co([3(5)]adz)(HCO3)]znBr(4).H2O (2a), and [Co([35]adz)(SO4)]AsF...

  15. Carbon Nanomembranes.

    Science.gov (United States)

    Turchanin, Andrey; Gölzhäuser, Armin

    2016-08-01

    Carbon nanomembranes (CNMs) are synthetic 2D carbon sheets with tailored physical or chemical properties. These depend on the structure, molecular composition, and surroundings on either side. Due to their molecular thickness, they can be regarded as "interfaces without bulk" separating regions of different gaseous, liquid, or solid components and controlling the materials exchange between them. Here, a universal scheme for the fabrication of 1 nm-thick, mechanically stable, functional CNMs is presented. CNMs can be further modified, for example perforated by ion bombardment or chemically functionalized by the binding of other molecules onto the surfaces. The underlying physical and chemical mechanisms are described, and examples are presented for the engineering of complex surface architectures, e.g., nanopatterns of proteins, fluorescent dyes, or polymer brushes. A simple transfer procedure allows CNMs to be placed on various support structures, which makes them available for diverse applications: supports for electron and X-ray microscopy, nanolithography, nanosieves, Janus nanomembranes, polymer carpets, complex layered structures, functionalization of graphene, novel nanoelectronic and nanomechanical devices. To close, the potential of CNMs in filtration and sensorics is discussed. Based on tests for the separation of gas molecules, it is argued that ballistic membranes may play a prominent role in future efforts of materials separation. PMID:27281234

  16. Scientific Opinion on the efficacy of Lenziaren (iron, aqua carbonate hydroxyl oxo starch sucrose complex) as a feed additive for cats

    OpenAIRE

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP)

    2014-01-01

    Lenziaren is a polynuclear Fe(III) starch–saccharose complex intended to be used in food for adult cats to reduce phosphate absorption in the gastrointestinal tract in order to prevent chronic kidney disease. The recommended minimum and maximum levels are 0.25 and 1.0 g/cat per day, equivalent to 5 000 and 20 000 mg/kg complete feed, respectively. In a previous opinion, the Panel concluded that the minimum effective dose was 1 g/cat per day based on three studies which showed either a signifi...

  17. Scientific Opinion on the safety and efficacy of Lenziaren (iron, aqua carbonate hydroxyl oxo starch sucrose complex) as a feed additive for cats

    OpenAIRE

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP)

    2013-01-01

    The additive Lenziaren is a polynuclear Fe(III) starch/saccharose complex intended to be used in food for adult cats to reduce phosphate absorption in the gastrointestinal tract in order to prevent chronic kidney disease. The recommended minimum and maximum levels are 0.25 g and 1.0 g per cat per day, equivalent to 5 000 and 20 000 mg/kg feed, respectively. The FEEDAP Panel considers that Lenziaren is safe for adult cats at the maximum recommended dose. However, the consequences of chronic ex...

  18. A Holocene record of endogenic iron and manganese precipitation, isotopic composition of endogenic carbonate, and vegetation history in a lake-fen complex in northwestern Minnesota

    Science.gov (United States)

    Dean, Walter E.; Doner, Lisa A.

    2011-01-01

    percent in the LSL-B core and 15.5 percent in the LSF-10 core. Values of delta18O in mollusk (Pisidium) and ostracode shells increase by only about 20 per mil from the bottom to the top of the LSL-B core (about 12600-2200 calendar years). The remarkably constant oxygen-isotope composition throughout the Holocene suggests that environmental conditions affecting values of delta18O (temperature, salinity, composition of the water, composition of precipitation) did not change greatly. Values of delta13C in carbonate shells generally decreased by about 2 per mil from 9000 calendar years to 6000 calendar years, but they did not increase in organic carbon. This mid-Holocene increase in delta13C in shells but not in organic carbon is likely due to an increase in residence time. A late Pleistocene forest dominated by spruce was replaced in the early Holocene by a pine forest. The pine forest migrated east during the middle Holocene and was replaced by an open sagebrush-oak savanna. The western migration of forests into northwestern Minnesota is marked first by a hardwood forest and finally a pine forest.

  19. Carbon dioxide gasification of carbon black: isotope study of carbonate catalysis

    International Nuclear Information System (INIS)

    Temperature-programmed reaction was used with labeled isotopes (13C and 18O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO2/90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 and 950 K, and in the presence of gaseous CO2, the complexes participated in C and O exchange with the gas phase while oxygen atoms within the complexes also exchanged with those on the carbon surface. As the temperature rose, the complexes decomposed, with CO2 the initial product. Decomposition started around 500 K in pure He, and around 950 K in CO2/He. Catalytic gasification began only after decomposition of significant portions of the complexes. Elemental potassium formed, and the active catalyst appears to alternate between being potassium metal and a potassium-oxygen-carbon complex. Potassium carbonate is not part of the catalytic cycle. 20 references, 10 figures

  20. Including Complexity, Heterogeneity and Vegetation Response Characteristics into Carbon Balance Assessments at Continental Scale: Stepwise Development of a Simulation Framework with the Bottom-Up Core Model PIXGRO

    Science.gov (United States)

    Tenhunen, J.; Geyer, R.; Owen, K.; Falge, E.; Reichstein, M.

    2005-12-01

    The cultural landscapes of the European continent are characterized by highly fragmented land cover, distributed along the gradient from extremely sparse, dry Mediterranean shrublands to sub-arctic wetlands and forests. In addition, several mountain systems, in particular the Alps, modify vegetation and land surface exchange characteristics. In the recently begun CARBOEUROPE project, energy, water and CO2 exchanges of selected ecosystem types are monitored via eddy covariance methods. The model PIXGRO is being developed to help relate measurements at flux tower sites to measurements carried out at larger scale and to CO2 exchange estimates obtained with atmospheric inversion techniques. The main question addressed in this modelling effort is how to efficiently include a spectrum of vegetation characteristics into carbon balance assessments at large scale and in such a way that the influence of local response on regional fluxes may be visualized and analyzed. Furthermore, the modelling attempts to demonstrate both strengths and weaknesses in existing ecosystem process information required to understand carbon balances. The model PIXGRO attempts to define continental distribution and controls on net ecosystem CO2 exchange for ca. 12 ecosystem types, including coniferous forest, deciduous forest, grassland, cropland (assumed dominated by grain crops), northern boreal mixed forest, tundra, wetlands, alpine forest, evergreen forest, evergreen shrubland, and Mediterranean oak woodland. The model uses a single layer canopy with two leaf classes (sun and shade) and a three layered rooting zone to estimate GPP, ecosystem respiration and overall ecosystem gas exchange. Maximum LAI is determined during each year from the MODIS LAI-product. In the case of grassland, crops, tundra and wetlands, classical growth routines estimate dynamic changes in the vegetation canopy. Soil/canopy coupling in response to drought reflects a root system hormonal signalling and is calibrated with

  1. Can the financialized atmosphere be effectively regulated? A critical analysis of the proposed Australian carbon pollution reduction scheme as a complex market solution to global warming

    Energy Technology Data Exchange (ETDEWEB)

    Windsor, C. [Bond Univ. (Australia); McNicholas, P. [Monash Univ. (Australia)

    2009-07-01

    A large body of scientific evidence indicates that global warming from human induced greenhouse gases (GHG) emissions is producing harmful climate change that will lead to global environmental and economic catastrophe within 10 years. The threat of human induced global warming has been on the international and public policy agenda for several years; for example on 11 December 1998, government representatives of 108 countries signed the United Nations Framework Convention on Climate Change (UNFCCC) an international agreement to reduce global warming or the Kyoto Protocol, with the then exception of the Australian and the United States (U.S.) governments. International action on GHG emissions reduction was thwarted by U.S. and Australian goverments. The then Australian government (1996-2007) surreptitiously funding by vested interests such as the coal industry, had no intention to act even though scientific evidence reported that Australia had begun to experience the detrimental effects of global warming. To fulfil an electoral promise, the center left Labor government signed the Kyoto Protocol on 3 December 2007. To deal with the global warming crisis, the Australian government has proposed an emissions trading scheme now officially called the 'Carbon Pollution Reduction Scheme' or CPRS. The proposed scheme is a cap and trade market mechanism that purportedly encourages businesses to operate more efficiently, thus reducing GHG emissions through price signalling in a government instigated market. Hence credible, transparent and efficient information underpins such a market in a post-Keynes deregulated world. The purpose of this paper is to critically examine the integrity of using current financial and reporting regulation that will oversee and monitor the veracity of newly commoditized carbon financial products, particularly since the global financial crisis has exposed significant financial regulatory weaknesses. Further we contend that current corporate

  2. Method for the preparation of carbon fiber from polyolefin fiber precursor, and carbon fibers made thereby

    Science.gov (United States)

    Naskar, Amit Kumar; Hunt, Marcus Andrew; Saito, Tomonori

    2015-08-04

    Methods for the preparation of carbon fiber from polyolefin fiber precursor, wherein the polyolefin fiber precursor is partially sulfonated and then carbonized to produce carbon fiber. Methods for producing hollow carbon fibers, wherein the hollow core is circular- or complex-shaped, are also described. Methods for producing carbon fibers possessing a circular- or complex-shaped outer surface, which may be solid or hollow, are also described.

  3. Differential Pulse Anodic Stripping Voltammetry Determination Of Copper (II) At Glassy Carbon Electrode In The Presence Of Bis(Benzylidene)Ethylenediamine As A Novel Complexing Agent

    International Nuclear Information System (INIS)

    This paper reports on the application of synthesized Schiff base bis(benzylidene)ethylenediamine (BBE) to increase the detection sensitivity of copper (II) at 0.01 V vs Ag/ AgCl using glassy carbon electrode. Aliquot of 2.0x10-3 M of BBE in DMF solution containing BR buffer pH 6 was introduced into the voltammetric cell followed by the addition of Cu(II) ions and then further proceeded to differential pulse anodic-stripping scan from -1.4 V to +0.3 V vs Ag/ AgCl. The optimum parameters obtained were; scan rate; 25 mV/ s, accumulation time; 200 sec and accumulation potential; -0.6 V. Under the optimal conditions, the detection limit of 0.4 μgL-1 and a linear response in the range of 1-10 μgL-1 were obtained. The effects of interfering ions such as Cd(II), Cr(III), Fe(II), Pb(II) and Zn(II) were also investigated. The practical applicability of this technique was illustrated by the determination of Cu(II) ions at 3 μgL-1 concentration level in tap water with 94.43 % of recovery. (author)

  4. N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions

    Science.gov (United States)

    Gök, Yetkin; İlhan, İlhan Özer

    2016-01-01

    Summary A series of novel benzimidazolium salts (1–4) and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI) themed palladium N-heterocyclic carbene complexes [PdCl2(NHC)(Py)] (5–8), where NHC = 1-(N-methylphthalimide)-3-alkylbenzimidazolin-2-ylidene and Py = 3-chloropyridine, were synthesized and characterized by means of 1H and 13C{1H} NMR, UV–vis (for 5–8), ESI-FTICR-MS (for 2, 4, 6–8) and FTIR spectroscopic methods and elemental analysis. The synthesized compounds were tested in Suzuki–Miyaura cross-coupling (for 1–8) and arylation (for 5–8) reactions. As catalysts, they demonstrated a highly efficient route for the formation of asymmetric biaryl compounds even though they were used in very low loading. For example, all compounds displayed good catalytic activity for the C–C bond formation of 4-tert-butylphenylboronic acid with 4-chlorotoluene. PMID:26877810

  5. Occupational exposure to complex mixtures of volatile organic compounds in ambient air: desorption from activated charcoal using accelerated solvent extraction can replace carbon disulfide?

    Science.gov (United States)

    Fabrizi, Giovanni; Fioretti, Marzia; Rocca, Lucia Mainero

    2013-01-01

    A desorption study of 57 volatile organic compounds (VOCs) has been conducted by use of accelerated solvent extraction (ASE) and gas chromatography-mass spectrometry. Different solvents were tested to extract activated charcoal tubes with the objective of replacing carbon disulfide, used in official methods, because of its highly toxic health and environmental effects. Extraction conditions, for example temperature and number of cycles, were investigated and optimized. The definitive extraction procedure selected was use of acetone at 150 °C and two consecutive extraction cycles at a pressure of 1,500 psi. Considering a sample volume of 0.005 Nm(3), corresponding to a sampling time of 8 h at a flow rate of 0.01 L min(-1), the method was validated over the concentration range 65-26,300 μg Nm(-3). The lowest limit of quantification was 6 μg Nm(-3), and recovery for the 93 % of analytes ranged from 65 to 102 %. For most of the compounds, relative standard deviations were less than 15 % for inter and intra-day precision. Uncertainty of measurement was also determined: the relative expanded uncertainty was always below 29.6 %, except for dichlorodifluoromethane. This work shows that use of friendlier solvent, for example acetone, coupled with use of ASE, can replace use of CS(2) for chemical removal of VOCs from activated charcoal. ASE has several advantages over traditional solvent-extraction methods, including shorter extraction time, minimum sample manipulation, high reproducibility, and less extraction discrimination. No loss of sensitivity occurs and there is also a salutary effect on bench workers' health and on the smell of laboratory air. PMID:22968683

  6. Anodic Oxidation and Amperometric Sensing of Hydrazine at a Glassy Carbon Electrode Modified with Cobalt (II Phthalocyanine–cobalt (II Tetraphenylporphyrin (CoPc- (CoTPP4 Supramolecular Complex

    Directory of Open Access Journals (Sweden)

    Kenneth I. Ozoemena

    2006-08-01

    Full Text Available This paper describes the electrocatalytic behaviour of a glassy carbon electrode (GCEmodified with cobalt(IIphthalocyanine (CoPc complex peripherally tetrasubstituted withcobalt(IItetraphenylporphyrin (CoTPP complexes via ether linkages (i.e., CoPc-(CoTPP4. Thefeatures of the immobilised pentamer were interrogated with cyclic voltammetry andelectrochemical impedance spectroscopy (EIS using [Fe(CN6]3-/4- as redox probe revealedenhanced electron transfer properties with kapp ≈ 18 x 10-6 cms-1 compared to that of the bareGCE (4.7 x 10-6 cms-1. The viability of this supramolecular complex as a redox mediator for theanodic oxidation and sensitive amperometric determination of hydrazine in alkaline conditions isdescribed. The electrocatalytic oxidation of hydrazine by GCE-CoPc-(CoTPP4 was characterisedwith satisfactory catalytic current response with low non-Faradaic current (ca. 30 times lowerthan the bare GCE and at much lower oxidation potential (ca. 300 mV lower than the bareGCE. A mechanism for the studied electrocatalytic reaction was proposed based on thespectrophotometric evidence that revealed the major involvement of the Co(III/Co(II redox coupleof the central CoPc species rather than the CoTPP component of the pentamer. Rate constant forthe anodic oxidation of hydrazine was estimated from chronoamperometry as ~ 3x103 M-1s-1. Theproposed amperometric sensor displayed excellent charateristics towards the determination ofhydrazine in 0.2 M NaOH ; such as low overpotentials ( 100 mV vs Ag|AgCl, very fastamperometric response time (1 s, linear concentration range of up to 230 μM, with micromolardetection limit, high sensitivity and stability.

  7. Warm ISM in the Sgr A Complex. I: Mid-J CO, atomic carbon, ionized atomic carbon,and ionized nitrogen sub-mm/FIR line observations with the Herschel-HIFI and NANTEN2/SMART telescopes

    CERN Document Server

    García, P; Stutzki, J; Güsten, R; Requena-Torres, M A; Higgins, R

    2016-01-01

    We present large-scale submm observations towards the Sgr A Complex covering ~300 arcmin2. These data were obtained in the frame of the HEXGAL Program with the Herschel-HIFI satellite and are complemented with submm observations obtained with the NANTEN2/SMART telescope as part of the NANTEN2/SMART Central Nuclear Zone Survey. The observed species are CO(4-3) observed with the NANTEN2/SMART telescope, and [CI](1-0), [CI](2-1), [NII](1-0), and [CII](3/2-1/2) observed with the Herschel-HIFI satellite. The observations are presented in a 1 km/s spectral resolution and a spatial resolution ranging from 46" to 28". The spectral coverage of the three lower frequency lines is +-200 km/s, while in the two high frequency lines, the upper LSR velocity limit is +94 km/s and +145 km/s for the [NII] and [CII] lines, respectively. The spatial distribution of the emission in all lines is very widespread. The bulk of the CO emission is found towards Galactic latitudes below the Galactic plane, and all the known molecular clo...

  8. Complex Beauty

    OpenAIRE

    Franceschet, Massimo

    2014-01-01

    Complex systems and their underlying convoluted networks are ubiquitous, all we need is an eye for them. They pose problems of organized complexity which cannot be approached with a reductionist method. Complexity science and its emergent sister network science both come to grips with the inherent complexity of complex systems with an holistic strategy. The relevance of complexity, however, transcends the sciences. Complex systems and networks are the focal point of a philosophical, cultural ...

  9. Scientific Opinion on the efficacy of Lenziaren (iron, aqua carbonate hydroxyl oxo starch sucrose complex as a feed additive for cats

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP

    2014-07-01

    Full Text Available Lenziaren is a polynuclear Fe(III starch–saccharose complex intended to be used in food for adult cats to reduce phosphate absorption in the gastrointestinal tract in order to prevent chronic kidney disease. The recommended minimum and maximum levels are 0.25 and 1.0 g/cat per day, equivalent to 5 000 and 20 000 mg/kg complete feed, respectively. In a previous opinion, the Panel concluded that the minimum effective dose was 1 g/cat per day based on three studies which showed either a significant reduction in serum phosphorus or a reduction in urinary phosphate. Two of these studies showed an effect at 0.25 g/cat per day, while the third one only showed an effect at a level of 1 g/cat per day. The results of a new study submitted in this application showed that overall urine inorganic phosphorus concentrations significantly decreased in cats receiving Lenziaren at 0.25 g/day compared with the control group. Therefore, considering the two previous studies, which showed an effect at 0.25 g/cat per day, and the results of the new study, the FEEDAP Panel considers that Lenziaren has the potential to be efficacious in binding intestinal phosphorus at the minimum recommended dose of 0.25 g/cat per day (equivalent to 5 g/kg complete feed. On balance, the Panel considers that the sex difference seen in the new study is an anomaly, possibly owing, as the applicant suggests, to selective feed intake. However, the Panel notes that sex differences were not explored in the remaining efficacy studies. The Panel still has the reservations expressed in the previous opinion regarding the value of the long-term use of the additive in healthy cats.

  10. Scientific Opinion on the safety and efficacy of Lenziaren (iron, aqua carbonate hydroxyl oxo starch sucrose complex as a feed additive for cats

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP

    2013-05-01

    Full Text Available The additive Lenziaren is a polynuclear Fe(III starch/saccharose complex intended to be used in food for adult cats to reduce phosphate absorption in the gastrointestinal tract in order to prevent chronic kidney disease. The recommended minimum and maximum levels are 0.25 g and 1.0 g per cat per day, equivalent to 5 000 and 20 000 mg/kg feed, respectively. The FEEDAP Panel considers that Lenziaren is safe for adult cats at the maximum recommended dose. However, the consequences of chronic exposure have not been investigated. The additive is not genotoxic. No adverse effects were seen in a repeat-dose toxicity study in mice. Lenziaren had no adverse effects on reproduction and development at dose levels that were not toxic to the mother. A no observed adverse effect level (NOAEL of 500 mg/kg body weight (bw per day was identified for Lenziaren on the basis of maternal toxicity (diarrhoea and reduced body weight gain, which was seen in rabbits at an oral dose of 1 000 mg/kg bw per day or greater. Similar effects were seen in rats, dogs and monkeys at higher doses in repeat-dose toxicity studies. No NOAELs were identified in these studies. Lenziaren is not regarded as an irritant to skin or eyes or as a skin sensitiser. Although some inhalation exposure is possible, it is not expected to be harmful to those exposed as a result of handling the additive. Based on the results of three in vivo efficacy studies, the FEEDAP Panel concludes that Lenziaren has the potential to be efficacious in cats at the highest recommended dose of 1 g/cat per day (equivalent to 20 000 mg/kg feed. However, the FEEDAP Panel has some reservations regarding the value of its long-term use in healthy cats. The Panel concludes that there is a need for a post-market monitoring plan.

  11. Direct Electrochemistry of Glucose Oxidase on A Nano Complex Modified Glassy Carbon Electrode%葡萄糖氧化酶在修饰玻碳电极上的直接电化学

    Institute of Scientific and Technical Information of China (English)

    耿方勇; 李迪; 张钰帅; 杨晓璐; 肖宝林; 洪军

    2016-01-01

    Direct electrochemistry of glucose oxidase was realized when it was immobilized on a nano-complex modified glassy carbon electrode, and the nano-complex was composed of graphene and multi-walled carbon nanotubes. The outermost layer covered with chitosan. Using cyclic voltammetry ( CV ) to measure electrochemical and electro-catalyzed reaction of glucose oxidase that modified electrode, the electron transfer rate constant (ks) was evaluated to be 0. 87 s-1, and electroactive surface density was 1. 54í10-10 mol/cm-2. The apparent Michaelis-Menten constant (Kappm ) was 1. 32í103 μmol/L, linear detection range was 40 ~1000 μmol/L, and the modified electrode had better stability, and modified electrode had good anti-interference ability when detected the substrate. Therefore, the modified electrode can be used to detect glucose, as the third generation biosensors.%将葡萄糖氧化酶( Glucose oxidase, GOD)固定在由多壁碳纳米管( MWCNTS)和石墨烯( Graphene)构成的纳米复合材料修饰的玻碳电极上,最外层用壳聚糖( Chitosan)进行覆盖,利用循环伏安法( Cyclic Voltammetry, CV)来测量葡萄糖氧化酶在修饰电极上的电化学和电催化反应,测得电子传递速率常数ks 为0.87 s-1,电活性物质表面密度Г为1.54×10-10 mol/cm-2,动力学表观米氏常数Km 为1.32×103μmol/L,线性检测范围为:40~1000μmol/L,修饰电极有较好的稳定性,而且修饰电极在检测底物时有较好的抗干扰能力,因此,该体系修饰的电极有希望构建第三代葡萄糖生物传感器。

  12. Complex chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-15

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  13. Complex chemistry

    International Nuclear Information System (INIS)

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  14. Carbon isotopes in mollusk shell carbonates

    Science.gov (United States)

    McConnaughey, Ted A.; Gillikin, David Paul

    2008-10-01

    Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

  15. Bucolic Complexes

    CERN Document Server

    Brešar, Bostjan; Chepoi, Victor; Gologranc, Tanja; Osajda, Damian

    2012-01-01

    In this article, we introduce and investigate bucolic complexes, a common generalization of systolic complexes and of CAT(0) cubical complexes. This class of complexes is closed under Cartesian products and amalgamations over some convex subcomplexes. We study various approaches to bucolic complexes: from graph-theoretic and topological viewpoints, as well as from the point of view of geometric group theory. Bucolic complexes can be defined as locally-finite simply connected prism complexes satisfying some local combinatorial conditions. We show that bucolic complexes are contractible, and satisfy some nonpositive-curvature-like properties. In particular, we prove a version of the Cartan-Hadamard theorem, the fixed point theorem for finite group actions, and establish some results on groups acting geometrically on such complexes. We also characterize the 1-skeletons (which we call bucolic graphs) and the 2-skeletons of bucolic complexes. In particular, we prove that bucolic graphs are precisely retracts of Ca...

  16. Complex Sleep Apnea Syndrome

    OpenAIRE

    Muhammad Talha Khan; Rose Amy Franco

    2014-01-01

    Complex sleep apnea is the term used to describe a form of sleep disordered breathing in which repeated central apneas (>5/hour) persist or emerge when obstructive events are extinguished with positive airway pressure (PAP) and for which there is not a clear cause for the central apneas such as narcotics or systolic heart failure. The driving forces in the pathophysiology are felt to be ventilator instability associated oscillation in PaCO2 arterial partial pressure of Carbon Dioxide, continu...

  17. Organic Mineral Complex Component and Distribution Character of Organic Carbon for High Yield Soil of the Corn Belt of the Songliao Plain%松辽平原玉米带高产土壤有机无机复合体组成及有机碳分布的研究

    Institute of Scientific and Technical Information of China (English)

    周雅娟; 赵兰坡; 张志丹; 姜亦梅

    2012-01-01

    The paper studied the organic mineral complex component and distribution character of organic carbon of black soil under various cultivation pattern by means of ultrasonic dispersion and particle assortment method, in order to discuss the different fertilizer and farming methods of soil organic inorganic compound composition and distribution of organic carbon impact. The high yield soil of Songliao Plain was used as the object of study. The results showed that, organic mineral complex in black soil the finesand size complex was protagonist, about 40%-70% of the total quality. The clay size complex and the silty size complex were marginalia. The result after comparing with the control group soil showed that, the storage of clay size complex is lower than control group soil, the mean difference was 5.05% and 7.60%. The comparing with particle size distribution showed that the silty size complex decreased about 0.1%-3.7%, the finesand size complex and the clay size complex creased about 0.1%-5%. The organic carbon primarily consisted in the small granule diameter of organic mineral complex. There was a accumulation tendency for organic carbon to the small granule diameter of organic mineral complex (A1>A2>A3). The result after comparing with the control group soil showed that, the content of organic carbon in organic mineral complexes was higher than control group soil (No.l>No.6, No.l0>No.l4), and the reserves of organic carbon of clay size complex was lower than control group soil (No.lNo.6, No.l0>No.l4).%为了探讨不同施肥和耕作方式对土壤有机无机复合体组成及有机碳分布的影响,采用超声波分散、颗粒大小分组法对松辽平原玉米高产土壤进行研究.结果表明,土壤中有机无机复合体以细砂复合体为主,约占40%~70%,粘粒、粉粒复合体次之;与对照相比,高产土壤粘粒复合体含量较小,平均差值为5.05%和7.60%;结合无机颗粒对比,粉粒、细砂复

  18. Dispersions of Carbon nanotubes in Polymer Matrices

    Science.gov (United States)

    Wise, Kristopher Eric (Inventor); Park, Cheol (Inventor); Siochi, Emilie J. (Inventor); Harrison, Joycelyn S. (Inventor); Lillehei, Peter T. (Inventor); Lowther, Sharon E. (Inventor)

    2010-01-01

    Dispersions of carbon nanotubes exhibiting long term stability are based on a polymer matrix having moieties therein which are capable of a donor-acceptor complexation with carbon nanotubes. The carbon nanotubes are introduced into the polymer matrix and separated therein by standard means. Nanocomposites produced from these dispersions are useful in the fabrication of structures, e.g., lightweight aerospace structures.

  19. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry; Complexes aqueux de lanthanides (3) et actinides (3) avec les ions carbonate et sulfate. Etude thermodynamique par spectrofluorimetrie laser resolue en temps et spectrometrie de masse a ionisation electrospray

    Energy Technology Data Exchange (ETDEWEB)

    Vercouter, Th

    2005-03-15

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO{sub 3}){sub 3}{sup 3-}, is identified by solubility measurements in Na{sub 2}CO{sub 3} solutions. Then the formation constants of the complexes Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) and Eu(SO{sub 4}){sub i}{sup 3-2i} (i=1-2) are measured by TRLFS. The formation of aqueous LaSO{sub 4}{sup +} is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO{sub 3}){sub 2}{sup -} + CO{sub 3}{sup 2-} {r_reversible} Cm(CO{sub 3}){sub 3}{sup 3-} are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  20. Carbon isotope anomalies in carbonates of the Karelian series

    Science.gov (United States)

    Iudovich, Ia. E.; Makarikhin, V. V.; Medvedev, P. V.; Sukhanov, N. V.

    1990-07-01

    Results are presented on carbon isotope distributions in carbonates of the Karelian complex. A highly anomalous isotopic composition was found in carbonate rocks aged from 2.6 to 1.9 b.y. In the stromatolitic carbonates of the Onega water table, delta-(C-13) reaches a value of +18 percent, while the shungite layer of the Zaonega horizon is characterized by a wide dispersion (from +7.9 to -11.8 percent). These data are in good agreement with the known geochemical boundary (about 2.2 b.y. ago) in the history of the earth.

  1. 城市复合生态系统碳氧平衡分析——以沿海城市厦门为例%Analysis of the carbon and oxygen balance of a complex urban ecosystem:A case study in the coastal city of Xiamen

    Institute of Scientific and Technical Information of China (English)

    马巾英; 尹锴; 吝涛

    2011-01-01

    通过综合城市复合生态系统内社会经济活动的主要排碳、耗氧行为,以及城市区域内湿地、淡水、海洋、森林和农田5种遗留自然生态系统的固碳释氧功能,构建了城市碳氧平衡分析模型(UCOB),并估算了城市社会经济活动和城市中自然生态系统的碳氧收支,对城市生态系统平衡状况进行定量化指征.最后,以中国东南沿海城市厦门为例进行研究.结果显示:厦门市2007年碳平衡系数为9.03,即二氧化碳释放量是其所能吸收能力的9.03倍;氧平衡系数为5.78,即社会经济活动消耗的氧气是当地自然生态系统所能提供氧气量的5.78倍.如果不考虑%Through combining the major oxygen consumption and carbon emission of socioeconomic activities and the carbon sequestration and oxygen emission of five remnant natural ecosystems in a complex urban ecosystem,we built an urban carbon and oxygen balance model(UCOB) to estimate the input and output of carbon and oxygen and to quantitatively indicate the ecological balance of an urban ecosystem.The results from a case study of Xiamen,a coastal city in southeastern China,showed:In 2007,the carbon balance index and oxygen balance index of the city were 9.03 and 5.78 respectively,which means the total amount of oxygen consumption and carbon emission from urban socioeconomic activities were 9.03 and 5.78 times greater than the amount of natural oxygen emission and carbon sequestration in Xiamen,respectively.Without considering the indirect oxygen consumption and carbon emission from electricity consumption,the balance indices of carbon and oxygen of Xiamen City were 5.26 and 1.47 respectively.Carbon and oxygen balance indices showed a significant variation among the six administrative districts of Xiamen,because of differences in their socioeconomic functions and distribution of natural ecosystems.As an old industrial zone,Huli district suffered the highest imbalance of carbon and

  2. Tropical complexes

    OpenAIRE

    Cartwright, Dustin

    2013-01-01

    We introduce tropical complexes, which are Delta-complexes together with additional numerical data. On a tropical complex, we define divisors and linear equivalence between divisors, analogous to the notions for algebraic varieties, and generalizing previous work for graphs. We prove a comparison theorem showing that divisor-curve intersection numbers agree under certain conditions.

  3. Medical Complex

    OpenAIRE

    Kumaraswamy, Mohan

    2002-01-01

    One element of the CIVCAL project Web-based resources containing images, tables, texts and associated data on the construction of the Medical Complex. This project covers the construction of a new Hong Kong University Medical Complex on Sassoon Road, Pokfulam. The complex will comprise two buildings, one will house laboratories and a car park, while the other will contain lecture halls

  4. Communication complexity and information complexity

    Science.gov (United States)

    Pankratov, Denis

    Information complexity enables the use of information-theoretic tools in communication complexity theory. Prior to the results presented in this thesis, information complexity was mainly used for proving lower bounds and direct-sum theorems in the setting of communication complexity. We present three results that demonstrate new connections between information complexity and communication complexity. In the first contribution we thoroughly study the information complexity of the smallest nontrivial two-party function: the AND function. While computing the communication complexity of AND is trivial, computing its exact information complexity presents a major technical challenge. In overcoming this challenge, we reveal that information complexity gives rise to rich geometrical structures. Our analysis of information complexity relies on new analytic techniques and new characterizations of communication protocols. We also uncover a connection of information complexity to the theory of elliptic partial differential equations. Once we compute the exact information complexity of AND, we can compute exact communication complexity of several related functions on n-bit inputs with some additional technical work. Previous combinatorial and algebraic techniques could only prove bounds of the form theta( n). Interestingly, this level of precision is typical in the area of information theory, so our result demonstrates that this meta-property of precise bounds carries over to information complexity and in certain cases even to communication complexity. Our result does not only strengthen the lower bound on communication complexity of disjointness by making it more exact, but it also shows that information complexity provides the exact upper bound on communication complexity. In fact, this result is more general and applies to a whole class of communication problems. In the second contribution, we use self-reduction methods to prove strong lower bounds on the information

  5. The changing carbon cycle of the coastal ocean

    OpenAIRE

    Bauer, James E; Cai, Wei-Jun; Raymond, Peter A.; Bianchi, Thomas S.; Hopkinson, Charles S.; Regnier, Pierre A. G.

    2013-01-01

    The carbon cycle of the coastal ocean is a dynamic component of the global carbon budget. But the diverse sources and sinks of carbon and their complex interactions in these waters remain poorly understood. Here we discuss the sources, exchanges and fates of carbon in the coastal ocean and how anthropogenic activities have altered the carbon cycle. Recent evidence suggests that the coastal ocean may have become a net sink for atmospheric carbon dioxide during post-industrial times. Continued ...

  6. Complexity Plots

    KAUST Repository

    Thiyagalingam, Jeyarajan

    2013-06-01

    In this paper, we present a novel visualization technique for assisting the observation and analysis of algorithmic complexity. In comparison with conventional line graphs, this new technique is not sensitive to the units of measurement, allowing multivariate data series of different physical qualities (e.g., time, space and energy) to be juxtaposed together conveniently and consistently. It supports multivariate visualization as well as uncertainty visualization. It enables users to focus on algorithm categorization by complexity classes, while reducing visual impact caused by constants and algorithmic components that are insignificant to complexity analysis. It provides an effective means for observing the algorithmic complexity of programs with a mixture of algorithms and black-box software through visualization. Through two case studies, we demonstrate the effectiveness of complexity plots in complexity analysis in research, education and application. © 2013 The Author(s) Computer Graphics Forum © 2013 The Eurographics Association and Blackwell Publishing Ltd.

  7. Formation of complex organic molecules in methanol and methanol-carbon monoxide ices exposed to ionizing radiation--a combined FTIR and reflectron time-of-flight mass spectrometry study.

    Science.gov (United States)

    Maity, Surajit; Kaiser, Ralf I; Jones, Brant M

    2015-02-01

    The radiation induced chemical processing of methanol and methanol-carbon monoxide ices at 5.5 K exposed to ionizing radiation in the form of energetic electrons and subsequent temperature programmed desorption is reported in this study. The endogenous formation of complex organic molecules was monitored online and in situ via infrared spectroscopy in the solid state and post irradiation with temperature programmed desorption (TPD) using highly sensitive reflectron time-of-flight (ReTOF) mass spectrometry coupled with single photoionization at 10.49 eV. Infrared spectroscopic analysis of the processed ice systems resulted in the identification of simple molecules including the hydroxymethyl radical (CH2OH), formyl radical (HCO), methane (CH4), formaldehyde (H2CO), carbon dioxide (CO2), ethylene glycol (HOCH2CH2OH), glycolaldehyde (HOCH2CHO), methyl formate (HCOOCH3), and ketene (H2CCO). In addition, ReTOF mass spectrometry of subliming molecules following temperature programmed desorption definitely identified several closed shell C/H/O bearing organics including ketene (H2CCO), acetaldehyde (CH3COH), ethanol (C2H5OH), dimethyl ether (CH3OCH3), glyoxal (HCOCOH), glycolaldehyde (HOCH2CHO), ethene-1,2-diol (HOCHCHOH), ethylene glycol (HOCH2CH2OH), methoxy methanol (CH3OCH2OH) and glycerol (CH2OHCHOHCH2OH) in the processed ice systems. Additionally, an abundant amount of molecules yet to be specifically identified were observed sublimating from the irradiated ices including isomers with the formula C3H(x=4,6,8)O, C4H(x=8,10)O, C3H(x=4,6,8)O2, C4H(x=6,8)O2, C3H(x=4,6)O3, C4H8O3, C4H(x=4,6,8)O4, C5H(x=6,8)O4 and C5H(x=6,8)O5. The last group of molecules containing four to five oxygen atoms observed sublimating from the processed ice samples include an astrobiologically important class of sugars relevant to RNA, phospholipids and energy storage. Experiments are currently being designed to elucidate their chemical structure. In addition, several reaction pathways were

  8. Engaging complexity

    Directory of Open Access Journals (Sweden)

    Gys M. Loubser

    2014-01-01

    Full Text Available In this article, I discuss studies in complexity and its epistemological implications for systematic and practical theology. I argue that engagement with complexity does not necessarily assurea non-reductionist approach. However, if complexity is engaged transversally, it becomes possible to transcend reductionist approaches. Moreover, systematic and practical the ologians can draw on complexity in developing new ways of understanding and, therefore, new ways of describing the focus, epistemic scope and heuristic structures of systematic and practical theology. Firstly, Edgar Morin draws a distinction between restricted and general complexity based on the epistemology drawn upon in studies in complexity. Moving away from foundationalist approaches to epistemology, Morin argues for a paradigm of systems. Secondly,I discuss Kees van Kooten Niekerk�s distinction between epistemology, methodology andontology in studies in complexity and offer an example of a theological argument that drawson complexity. Thirdly, I argue for the importance of transversality in engaging complexity by drawing on the work of Wentzel van Huyssteen and Paul Cilliers. In conclusion, I argue that theologians have to be conscious of the epistemic foundations of each study in complexity, and these studies illuminate the heart of Reformed theology.Intradisciplinary and/or interdisciplinary implications: Therefore, this article has both intradisciplinary and interdisciplinary implications. When theologians engage studies incomplexity, the epistemological roots of these studies need to be considered seeing thatresearchers in complexity draw on different epistemologies. Drawing on transversality wouldenhance such considerations. Furthermore, Edgar Morin�s and Paul Cilliers� approach tocomplexity will inform practical and theoretical considerations in church polity and unity.

  9. Two-point versus multiple-point geostatistics: the ability of geostatistical methods to capture complex geobodies and their facies associations—an application to a channelized carbonate reservoir, southwest Iran

    Science.gov (United States)

    Hashemi, Seyyedhossein; Javaherian, Abdolrahim; Ataee-pour, Majid; Khoshdel, Hossein

    2014-12-01

    Facies models try to explain facies architectures which have a primary control on the subsurface heterogeneities and the fluid flow characteristics of a given reservoir. In the process of facies modeling, geostatistical methods are implemented to integrate different sources of data into a consistent model. The facies models should describe facies interactions; the shape and geometry of the geobodies as they occur in reality. Two distinct categories of geostatistical techniques are two-point and multiple-point (geo) statistics (MPS). In this study, both of the aforementioned categories were applied to generate facies models. A sequential indicator simulation (SIS) and a truncated Gaussian simulation (TGS) represented two-point geostatistical methods, and a single normal equation simulation (SNESIM) selected as an MPS simulation representative. The dataset from an extremely channelized carbonate reservoir located in southwest Iran was applied to these algorithms to analyze their performance in reproducing complex curvilinear geobodies. The SNESIM algorithm needs consistent training images (TI) in which all possible facies architectures that are present in the area are included. The TI model was founded on the data acquired from modern occurrences. These analogies delivered vital information about the possible channel geometries and facies classes that are typically present in those similar environments. The MPS results were conditioned to both soft and hard data. Soft facies probabilities were acquired from a neural network workflow. In this workflow, seismic-derived attributes were implemented as the input data. Furthermore, MPS realizations were conditioned to hard data to guarantee the exact positioning and continuity of the channel bodies. A geobody extraction workflow was implemented to extract the most certain parts of the channel bodies from the seismic data. These extracted parts of the channel bodies were applied to the simulation workflow as hard data. This

  10. Two-point versus multiple-point geostatistics: the ability of geostatistical methods to capture complex geobodies and their facies associations—an application to a channelized carbonate reservoir, southwest Iran

    International Nuclear Information System (INIS)

    Facies models try to explain facies architectures which have a primary control on the subsurface heterogeneities and the fluid flow characteristics of a given reservoir. In the process of facies modeling, geostatistical methods are implemented to integrate different sources of data into a consistent model. The facies models should describe facies interactions; the shape and geometry of the geobodies as they occur in reality. Two distinct categories of geostatistical techniques are two-point and multiple-point (geo) statistics (MPS). In this study, both of the aforementioned categories were applied to generate facies models. A sequential indicator simulation (SIS) and a truncated Gaussian simulation (TGS) represented two-point geostatistical methods, and a single normal equation simulation (SNESIM) selected as an MPS simulation representative. The dataset from an extremely channelized carbonate reservoir located in southwest Iran was applied to these algorithms to analyze their performance in reproducing complex curvilinear geobodies. The SNESIM algorithm needs consistent training images (TI) in which all possible facies architectures that are present in the area are included. The TI model was founded on the data acquired from modern occurrences. These analogies delivered vital information about the possible channel geometries and facies classes that are typically present in those similar environments. The MPS results were conditioned to both soft and hard data. Soft facies probabilities were acquired from a neural network workflow. In this workflow, seismic-derived attributes were implemented as the input data. Furthermore, MPS realizations were conditioned to hard data to guarantee the exact positioning and continuity of the channel bodies. A geobody extraction workflow was implemented to extract the most certain parts of the channel bodies from the seismic data. These extracted parts of the channel bodies were applied to the simulation workflow as hard data

  11. Carney Complex

    Science.gov (United States)

    ... of Carney complex are Cushing’s syndrome and multiple thyroid nodules (tumors). Cushing’s syndrome features a combination of weight gain, ... with Carney complex include adrenocortical carcinoma , pituitary gland tumors , thyroid , colorectal , liver and pancreatic cancers . Ovarian cancer in ...

  12. Simplifying complexity

    NARCIS (Netherlands)

    Leemput, van de I.A.

    2016-01-01

    In this thesis I use mathematical models to explore the properties of complex systems ranging from microbial nitrogen pathways and coral reefs to the human state of mind. All are examples of complex systems, defined as systems composed of a number of interconnected parts, where the systemic behavior

  13. Hamiltonian complexity

    International Nuclear Information System (INIS)

    In recent years we have seen the birth of a new field known as Hamiltonian complexity lying at the crossroads between computer science and theoretical physics. Hamiltonian complexity is directly concerned with the question: how hard is it to simulate a physical system? Here I review the foundational results, guiding problems, and future directions of this emergent field.

  14. Managing Complexity

    DEFF Research Database (Denmark)

    Maylath, Bruce; Vandepitte, Sonia; Minacori, Patricia;

    2013-01-01

    and into French. The complexity of the undertaking proved to be a central element in the students' learning, as the collaboration closely resembles the complexity of international documentation workplaces of language service providers. © Association of Teachers of Technical Writing.......This article discusses the largest and most complex international learning-by-doing project to date- a project involving translation from Danish and Dutch into English and editing into American English alongside a project involving writing, usability testing, and translation from English into Dutch...

  15. Complex variables

    CERN Document Server

    Fisher, Stephen D

    1999-01-01

    The most important topics in the theory and application of complex variables receive a thorough, coherent treatment in this introductory text. Intended for undergraduates or graduate students in science, mathematics, and engineering, this volume features hundreds of solved examples, exercises, and applications designed to foster a complete understanding of complex variables as well as an appreciation of their mathematical beauty and elegance. Prerequisites are minimal; a three-semester course in calculus will suffice to prepare students for discussions of these topics: the complex plane, basic

  16. Complex Covariance

    Directory of Open Access Journals (Sweden)

    Frieder Kleefeld

    2013-01-01

    Full Text Available According to some generalized correspondence principle the classical limit of a non-Hermitian quantum theory describing quantum degrees of freedom is expected to be the well known classical mechanics of classical degrees of freedom in the complex phase space, i.e., some phase space spanned by complex-valued space and momentum coordinates. As special relativity was developed by Einstein merely for real-valued space-time and four-momentum, we will try to understand how special relativity and covariance can be extended to complex-valued space-time and four-momentum. Our considerations will lead us not only to some unconventional derivation of Lorentz transformations for complex-valued velocities, but also to the non-Hermitian Klein-Gordon and Dirac equations, which are to lay the foundations of a non-Hermitian quantum theory.

  17. Simplifying complexity

    OpenAIRE

    Leemput, van de, J.C.H.

    2016-01-01

    In this thesis I use mathematical models to explore the properties of complex systems ranging from microbial nitrogen pathways and coral reefs to the human state of mind. All are examples of complex systems, defined as systems composed of a number of interconnected parts, where the systemic behavior leads to the emergence of properties that would not be expected from behavior or properties of the individual parts of the system. Although the full behavior of the systems I address will probably...

  18. Porous carbons

    Indian Academy of Sciences (India)

    Satish M Manocha

    2003-02-01

    Carbon in dense as well as porous solid form is used in a variety of applications. Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. Pyrolysed woods replicate the structure of original wood but as such possess very low surface areas and poor adsorption capacities. On activation, these exhibit increased adsorption volumes of 0.5–0.8 cm3 /gm and surface areas of 700–1800 m2 /gm depending on activation conditions, whether physical or chemical. Former carbons possess mixed pore size distribution while chemically activated carbons predominantly possess micropores. Thus, these carbons can be used for adsorption of wide distributions of molecules from gas to liquid. The molecular adsorption within the pores is due to single layer or multilayer molecule deposition at the pore walls and hence results in different types of adsorption isotherm. On the other hand, activated carbon fibres with controlled microporous structure and surface area in the range of 2500 m2 /gm can be developed by controlled pyrolysis and physical activation of amorphous carbon fibres. Active carbon fibres with unmatchable pore structure and surface characteristics are present and futuristic porous materials for a number of applications from pollution control to energy storage.

  19. 基于碳纳米管复合物的电化学生物传感器研究进展%Research progress of electrochemical biosensor based on carbon nanotubes complex

    Institute of Scientific and Technical Information of China (English)

    韩莉; 陶菡; 张义明; 张学俊

    2009-01-01

    In recent years, development of novel carbon nanotubes composite and their applications in electrochem-istry biosensor are the research focuses in materials and analytical chemistry field, the research process of electrochemical biosensor based on carbon nanotubes composite was previewed. Sensor based on carbon nanotubes-nanoparticles, carbon nanotubes-polymer and carbon nanotubes-ionic liquid composite were focused on.%新型碳纳米管复合物的开发及其在电化学生物传感器中的应用是近年来材料学和分析领域的研究热点.介绍了碳纳米管复合物在电化学生物传感领域的研究发展,重点对碳纳米管与纳米颗粒、聚合物及离子液体复合材料在电化学生物传感中的应用进行了论述.

  20. Carbon price volatility: Evidence from EU ETS

    International Nuclear Information System (INIS)

    This paper examines carbon price volatility using data from the European Union Emission Trading Scheme from a nonlinear dynamics point of view. First, we use a random walk model, including serial correlation and variance ratio tests, to determine whether carbon price history information is fully reflected in current carbon price. The empirical research results show that carbon price is not a random walk: the price history information is not fully reflected in current carbon price. Second, use R/S, modified R/S and ARFIMA to analyse the memory of carbon price history. For the period April 2005-December 2008, the modified Hurst index of the carbon price is 0.4859 and the d value of ARFIMA is -0.1191, indicating short-term memory of the carbon price. Third, we use chaos theory to analyse the influence of the carbon market internal mechanism on carbon price, i.e., the market's positive and negative feedback mechanism and the heterogeneous environment. Chaos theory proves that the correlation dimension of carbon price increases. The maximal Lyapunov exponent is positive and large. There is no obvious complex endogenous phenomenon of nonlinear dynamics the carbon price fluctuation. The carbon market is mildly chaotic, showing both market and fractal market characteristics. Price fluctuation is not only influenced by the internal market mechanism, but is also impacted by the heterogeneous environment. Finally, we provide suggestions for regulation and development of carbon market.

  1. Complex networks: Patterns of complexity

    Science.gov (United States)

    Pastor-Satorras, Romualdo; Vespignani, Alessandro

    2010-07-01

    The Turing mechanism provides a paradigm for the spontaneous generation of patterns in reaction-diffusion systems. A framework that describes Turing-pattern formation in the context of complex networks should provide a new basis for studying the phenomenon.

  2. The Bio-accessibility of Synthetic Fe-Organo Complexes in Subsurface Soil with Elevated Temperature: a Proxy for the Vulnerability of Mineral Associated Carbon to Warming Rachel C. Porras, Peter S. Nico, and Margaret Torn Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Science.gov (United States)

    Porras, R. C.; Hicks Pries, C.

    2015-12-01

    Globally, subsurface soils (>30 cm) represent an important reservoir of soil organic carbon (SOC). However, the vulnerability of this deep SOC and, in particular mineral-associated SOC, to warming, and its potential to amplify the effects of climate change is highly uncertain. To gain insight into the bio-accessibility and temperature sensitivity of mineral-associated organic C, we conducted a series of incubations using soils collected from three depths (0-10, 50-60, and 80-90 cm) under coniferous forest. The soils are moderately acidic (mean pH=6.5) sandy, mixed, mesic Ultic Haploxeralfs. To understand how mechanisms controlling SOC bio-accessibilty or temperature sensitivity differ with depth and with the properties of Fe-organo complexes (i.e.,degree of crystallinity, amount of reactive surface area, or surface saturation), we used a 13C labeled glucose substrate to prepare synthetic Fe-organo complexes spanning a range of crystallinity and mineral surface saturation. The synthetic Fe-organo complexes were then added to soil from three depths. The soils containing the 13C labeled Fe-organo adduct were incubated at two temperatures (ambient and +4°C) and respired 13CO2 was measured and used to estimate flux rates. Differences in measured 13CO2 fluxes as a function of depth, surface loading, and mineral properties are discussed in terms of their implications for the temperature sensitivity of mineral protected organic carbon in subsurface soils.

  3. Organometallic Complexes of Graphene

    CERN Document Server

    Sarkar, Santanu; Bekyarova, Elena; Haddon, Robert C

    2013-01-01

    We demonstrate the organometallic hexahapto complexation of chromium with graphene, graphite and carbon nanotubes. All of these extended periodic pi-electron systems exhibit some degree of reactivity toward the reagents CrCO)6 and (eta6-benzene)Cr(CO)3, and we are able to demonstrate the formation of (eta6-rene)Cr(CO)3 or (eta6-arene)2Cr, where arene = single-walled carbon nanotubes (SWNT), exfoliated graphene (XG), epitaxial graphene (EG) and highly-oriented pyrolytic graphite (HOPG). We find that the SWNTs are the least reactive presumably as a result of the effect of curvature on the formation of the hexahapto bond; in the case of HOPG, (eta6-HOPG)Cr(CO)3 was isolated while the exfoliated graphene samples were found to give both (eta6-graphene)2Cr, and (eta6-graphene)Cr(CO)3 structures. We report simple and efficient routes for the mild decomplexation of the graphene-chromium complexes which appears to restore the original pristine graphene state. This study represents the first example of the use of graph...

  4. Complex analysis

    CERN Document Server

    Freitag, Eberhard

    2005-01-01

    The guiding principle of this presentation of ``Classical Complex Analysis'' is to proceed as quickly as possible to the central results while using a small number of notions and concepts from other fields. Thus the prerequisites for understanding this book are minimal; only elementary facts of calculus and algebra are required. The first four chapters cover the essential core of complex analysis: - differentiation in C (including elementary facts about conformal mappings) - integration in C (including complex line integrals, Cauchy's Integral Theorem, and the Integral Formulas) - sequences and series of analytic functions, (isolated) singularities, Laurent series, calculus of residues - construction of analytic functions: the gamma function, Weierstrass' Factorization Theorem, Mittag-Leffler Partial Fraction Decomposition, and -as a particular highlight- the Riemann Mapping Theorem, which characterizes the simply connected domains in C. Further topics included are: - the theory of elliptic functions based on...

  5. Carbon Management Response curves: estimates of temporal soil carbon dynamics.

    Science.gov (United States)

    West, Tristram O; Marland, Gregg; King, Anthony W; Post, Wilfred M; Jain, Atul K; Andrasko, Kenneth

    2004-04-01

    Measurement of the change in soil carbon that accompanies a change in land use (e.g., forest to agriculture) or management (e.g., conventional tillage to no-till) can be complex and expensive, may require reference plots, and is subject to the variability of statistical sampling and short-term variability in weather. In this paper, we develop Carbon Management Response (CMR) curves that could be used as an alternative to in situ measurements. The CMR curves developed here are based on quantitative reviews of existing global analyses and field observations of changes in soil carbon. The curves show mean annual rates of soil carbon change, estimated time to maximum rates of change, and estimated time to a new soil carbon steady state following the initial change in management. We illustrate how CMR curves could be used in a carbon accounting framework while effectively addressing a number of potential policy issues commonly associated with carbon accounting. We find that CMR curves provide a transparent means to account for changes in soil carbon accumulation and loss rates over time, and also provide empirical relationships that might be used in the development or validation of ecological or Earth systems models. PMID:15453404

  6. Binding of calcium and carbonate to polyacrylates.

    Science.gov (United States)

    Tribello, Gareth A; Liew, CheeChin; Parrinello, Michele

    2009-05-21

    Polyacrylate molecules can be used to slow the growth of calcium carbonate. However, little is known about the mechanism by which the molecules impede the growth rate. A recent computational study (Bulo et al. Macromolecules 2007, 40, 3437) used metadynamics to investigate the binding of calcium to polyacrylate chains and has thrown some light on the coiling and precipitation of these polymers. We extend these simulations to examine the binding of calcium and carbonate to polyacrylate chains. We show that calcium complexed with both carbonate and polyacrylate is a very stable species. The free energies of calcium-carbonate-polyacrylate complexes, with different polymer configurations, are calculated, and differences in the free energy of the binding of carbonate are shown to be due to differences in the amount of steric hindrance about the calcium, which prevents the approach of the carbonate ion. PMID:19400592

  7. Isotherm And Kinetic Studies On The Electrosorption Of Uranyl Tricarbonate Complex [UO{sub 2}(CO{sub 3}){sub 3}]{sup 4-} From Aqueous Solutions By Activated Carbon Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Aznan Fazli; Yim, Man Sung [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2015-05-15

    Many types of adsorbent materials have been developed over the past 50 years, and the most recognizable is amidoxime based materials which is known to have high affinity in in chelating uranyl ions from seawater. However, the fabrication cost of amidoxime based materials was high which lead to high uranium extraction cost. In recent studies, use of porous carbon materials combined with the electrosorption technique was shown to have high selectivity for uranium separation from seawater. It is clear that the electrosorption capacity increase with the increasing of electrolyte concentration. The investigated activated carbon electrode still not reach the maximum adsorption capacity in the test condition. The morphology analysis confirmed that the fabricated activated carbon electrode has a porous structure, where BET analysis has revealed that the size of the pores can be categorized in mesopores region which is the optimum condition for electrosorption purposes. Other than that, the FT-IR analysis has enough evident that the molecular interaction of the activated carbon electrode involves the intermolecular interaction (physical crosslink/bonding) and stable for electrosorption application.

  8. Complex Networks

    CERN Document Server

    Evsukoff, Alexandre; González, Marta

    2013-01-01

    In the last decade we have seen the emergence of a new inter-disciplinary field focusing on the understanding of networks which are dynamic, large, open, and have a structure sometimes called random-biased. The field of Complex Networks is helping us better understand many complex phenomena such as the spread of  deseases, protein interactions, social relationships, to name but a few. Studies in Complex Networks are gaining attention due to some major scientific breakthroughs proposed by network scientists helping us understand and model interactions contained in large datasets. In fact, if we could point to one event leading to the widespread use of complex network analysis is the availability of online databases. Theories of Random Graphs from Erdös and Rényi from the late 1950s led us to believe that most networks had random characteristics. The work on large online datasets told us otherwise. Starting with the work of Barabási and Albert as well as Watts and Strogatz in the late 1990s, we now know th...

  9. Calcium Carbonate

    Science.gov (United States)

    ... before being swallowed; do not swallow them whole. Drink a full glass of water after taking either the regular or chewable tablets or capsules. Some liquid forms of calcium carbonate must be shaken well before use.Do not ...

  10. Carbon Stars

    Indian Academy of Sciences (India)

    T. Lloyd Evans

    2010-12-01

    In this paper, the present state of knowledge of the carbon stars is discussed. Particular attention is given to issues of classification, evolution, variability, populations in our own and other galaxies, and circumstellar material.

  11. Carbon dioxide and methane emissions from estuaries

    OpenAIRE

    Abril, G.; Borges, Alberto

    2005-01-01

    Carbon dioxide and methane emissions from estuaries are reviewed in relationwith biogeochemical processes and carbon cycling. In estuaries, carbondioxide and methane emissions show a large spatial and temporalvariability, which results from a complex interaction of river carbon inputs,sedimentation and resuspension processes, microbial processes in watersand sediments, tidal exchanges with marshes and flats and gas exchangewith the atmosphere. The net mineralization of land-derived organic ca...

  12. Exoelectron Emission of a Carbon Nanomaterial

    Science.gov (United States)

    Kortov, V. S.; Slesarev, A. I.; Tkachev, A. G.

    2008-03-01

    The exoemission properties of a Taunite carbon nanomaterial consisting of nanosized multiwalled nanotubes and nanofibers were investigated by thermally stimulated exoelectron emission (TSEE). The TSEE spectra of the carbon nanomaterial differed from the spectra of pressed graphite. It was assumed that defect—adsorbate complexes were emission-active centers on the surface of the nanomaterial

  13. Simulating Carbon cycle and phenology in complex forests using a multi-layer process based ecosystem model; evaluation and use of 3D-CMCC-Forest Ecosystem Model in a deciduous and an evergreen neighboring forests, within the area of Brasschaat (Be)

    Science.gov (United States)

    Marconi, S.; Collalti, A.; Santini, M.; Valentini, R.

    2013-12-01

    3D-CMCC-Forest Ecosystem Model is a process based model formerly developed for complex forest ecosystems to estimate growth, water and carbon cycles, phenology and competition processes on a daily/monthly time scale. The Model integrates some characteristics of the functional-structural tree models with the robustness of the light use efficiency approach. It treats different heights, ages and species as discrete classes, in competition for light (vertical structure) and space (horizontal structure). The present work evaluates the results of the recently developed daily version of 3D-CMCC-FEM for two neighboring different even aged and mono specific study cases. The former is a heterogeneous Pedunculate oak forest (Quercus robur L. ), the latter a more homogeneous Scot pine forest (Pinus sylvestris L.). The multi-layer approach has been evaluated against a series of simplified versions to determine whether the improved model complexity in canopy structure definition increases its predictive ability. Results show that a more complex structure (three height layers) should be preferable to simulate heterogeneous scenarios (Pedunculate oak stand), where heights distribution within the canopy justify the distinction in dominant, dominated and sub-dominated layers. On the contrary, it seems that using a multi-layer approach for more homogeneous stands (Scot pine stand) may be disadvantageous. Forcing the structure of an homogeneous stand to a multi-layer approach may in fact increase sources of uncertainty. On the other hand forcing complex forests to a mono layer simplified model, may cause an increase in mortality and a reduction in average DBH and Height. Compared with measured CO2 flux data, model results show good ability in estimating carbon sequestration trends, on both a monthly/seasonal and daily time scales. Moreover the model simulates quite well leaf phenology and the combined effects of the two different forest stands on CO2 fluxes.

  14. Managing Complexity

    Energy Technology Data Exchange (ETDEWEB)

    Chassin, David P.; Posse, Christian; Malard, Joel M.

    2004-08-01

    Physical analogs have shown considerable promise for understanding the behavior of complex adaptive systems, including macroeconomics, biological systems, social networks, and electric power markets. Many of today’s most challenging technical and policy questions can be reduced to a distributed economic control problem. Indeed, economically-based control of large-scale systems is founded on the conjecture that the price-based regulation (e.g., auctions, markets) results in an optimal allocation of resources and emergent optimal system control. This paper explores the state of the art in the use physical analogs for understanding the behavior of some econophysical systems and to deriving stable and robust control strategies for them. In particular we review and discussion applications of some analytic methods based on the thermodynamic metaphor according to which the interplay between system entropy and conservation laws gives rise to intuitive and governing global properties of complex systems that cannot be otherwise understood.

  15. Cocatalyzed oxidation of carbon monoxide and triphenylphosphine using complexes derived from hexarhodium hexadecacarbonyl as homogeneous catalyst. Characterization of rhodium carbonyl intermediates, oxygen-18 labeling to identify oxygen atom sources, and observation of catalyzed oxygen atom exchange between carbon dioxide and water

    International Nuclear Information System (INIS)

    Hexarhodium hexadecacarbonyl, Rh6(CO)16, will cocatalyze a reaction with molecular oxygen involving the conversion both of carbon monoxide to carbon dioxide and of triphenylphosphine (PPh3) to triphenylphosphine oxide (OPPh3). Solution infrared spectroscopy in the carbonyl region in benzene solvent shows that the catalytic cycle passes through the red Rh2(CO)2-(PPh3)4(C6H6)2, the yellow Rh2(CO)6(PPh3)2, and the red Rh4(CO)10(PPh3)2. Final return to Rh6(CO)16 does not occur under the ambient temperature and pressure conditions used but can be achieved by elevating these conditions. Addition of carbon dioxide to a mixture of Rh6(CO)16, CO, and PPh3 in the presence of added 18OH2 shows that the rhodium compounds will catalyze oxygen exchange between carbon dioxide and the oxygen atom of water. A pathway for equilibration of oxygen isotope in the catalyzed conversion of coordinated carbonyl to carbon dioxide via metallocarboxylate intermediates is proposed. The equilibration of oxygen isotope from water into carbon dioxide catalyzed by rhodium carbonyl clusters is suggested to proceed via hydroxyrhodium intermediates. 3 figures, 3 tables

  16. Solubility of ThO2 . xH2O(am) and the formation of ternary Th(IV) hydroxide-carbonate complexes in NaHCO3-Na2CO3 solutions containing 0-4 M NaCl

    International Nuclear Information System (INIS)

    The solubility of ThO2 . xH2O(am) is studied at I = 0.1-4.0 M (NaHCO3-Na2CO3-NaCl) and 22 C. Several sets of closed system experiments are performed at total carbonate concentrations of Ctot = [HCO3-] + [CO32-] = 0.02 and 0.1 M in the range pHc = 8-11. In our recent study at I = 0.5 M, the simultaneous evaluation of solubility data at widely varied pHc and carbonate concentrations has shown that Th(OH)(CO3)45-, Th(OH)2(CO3)22- and Th(OH)4(CO3)2- are the most important ternary complexes. The present results at I = 0.1-4.0 M are used to describe the ionic strength dependence of the equilibrium constants log Ks,1yz (for the reactions Th(OH)4(am) + zCO32- Th(OH)y(CO3)z4-y-2z + (4 - y)OH-) with the SIT. EXAFS measurements in 0.1 and 1.0 M carbonate solutions support the calculated speciation. They show clearly different spectra for the predominant species Th(OH)(CO3)45- and Th(CO3)56-, respectively. (orig.)

  17. Nanoparticle complex fluids

    Energy Technology Data Exchange (ETDEWEB)

    Svaasand, Eldrid

    2008-04-15

    The work presented in this thesis concerns the study of complex nano fluids. The interaction of particles in dispersions under the influence of electric and magnetic fields has been studied. The main focus has been the investigation of the behavior of carbon particle dispersions. A novel type of carbon material, namely carbon cone (CC) material, has been characterized using atomic force microscope, scanning tunneling microscope and scanning electron microscope. The CC material is a mixed powder consisting of carbon particles with the shape of disks and cones and a small amount of amorphous carbon particles. The length or diameter of the particles vary between 0.5-5 mum with thickness varying between 10-50 nm. The results confirm the cone angles as predicted by theory. The various microscopy images show that the surfaces of the particles seem corrugated. It should be noted that it is the mixed particle powder which it is referred to when it is written 'carbon cone particles' or 'CC particles'. The dispersion of CC particles in silicon oil was studied under the influence of an electric field. The particles were found to align in an ac electric field and structure formation was observed at very low electric fields. The growth rate was found to vary exponentially with the electric field. The structure formations were permanent (under zero shear rate), not dissolving when the electric field was turned off. This was attributed to the strong Van der Waals forces associated with carbon particles. Electrorheological measurements were carried out for dispersions with varying CC particle concentrations. All samples showed a Bingham fluid behavior with a finite yield stress. The yield stress was found to depend only weakly on the electric field. The results showed that the ER efficiency as measured by the relative increase in viscosity compared to the zero field viscosity, increases with decreasing concentration with a maximum factor of approx10 for the

  18. Carbon particles

    Science.gov (United States)

    Hunt, Arlon J.

    1984-01-01

    A method and apparatus whereby small carbon particles are made by pyrolysis of a mixture of acetylene carried in argon. The mixture is injected through a nozzle into a heated tube. A small amount of air is added to the mixture. In order to prevent carbon build-up at the nozzle, the nozzle tip is externally cooled. The tube is also elongated sufficiently to assure efficient pyrolysis at the desired flow rates. A key feature of the method is that the acetylene and argon, for example, are premixed in a dilute ratio, and such mixture is injected while cool to minimize the agglomeration of the particles, which produces carbon particles with desired optical properties for use as a solar radiant heat absorber.

  19. Carbon classified?

    DEFF Research Database (Denmark)

    Lippert, Ingmar

    2012-01-01

    . Using an actor- network theory (ANT) framework, the aim is to investigate the actors who bring together the elements needed to classify their carbon emission sources and unpack the heterogeneous relations drawn on. Based on an ethnographic study of corporate agents of ecological modernisation over a...... corporations construing themselves as able and suitable to manage their emissions, and, additionally, given that the construction of carbon emissions has performative consequences, the underlying practices need to be declassified, i.e. opened for public scrutiny. Hence the paper concludes by arguing for a...

  20. Complex dynamics

    CERN Document Server

    Carleson, Lennart

    1993-01-01

    Complex dynamics is today very much a focus of interest. Though several fine expository articles were available, by P. Blanchard and by M. Yu. Lyubich in particular, until recently there was no single source where students could find the material with proofs. For anyone in our position, gathering and organizing the material required a great deal of work going through preprints and papers and in some cases even finding a proof. We hope that the results of our efforts will be of help to others who plan to learn about complex dynamics and perhaps even lecture. Meanwhile books in the field a. re beginning to appear. The Stony Brook course notes of J. Milnor were particularly welcome and useful. Still we hope that our special emphasis on the analytic side will satisfy a need. This book is a revised and expanded version of notes based on lectures of the first author at UCLA over several \\Vinter Quarters, particularly 1986 and 1990. We owe Chris Bishop a great deal of gratitude for supervising the production of cour...

  1. Complex Systems

    Directory of Open Access Journals (Sweden)

    Yi Zhao

    2012-01-01

    Full Text Available Quantum instanton (QI approximation is recently proposed for the evaluations of the chemical reaction rate constants with use of full dimensional potential energy surfaces. Its strategy is to use the instanton mechanism and to approximate time-dependent quantum dynamics to the imaginary time propagation of the quantities of partition function. It thus incorporates the properties of the instanton idea and the quantum effect of partition function and can be applied to chemical reactions of complex systems. In this paper, we present the QI approach and its applications to several complex systems mainly done by us. The concrete systems include, (1 the reaction of H+CH4→H2+CH3, (2 the reaction of H+SiH4→H2+SiH3, (3 H diffusion on Ni(100 surface; and (4 surface-subsurface transport and interior migration for H/Ni. Available experimental and other theoretical data are also presented for the purpose of comparison.

  2. Huella del Carbono. Parte 1: Conceptos, Métodos de Estimación y Complejidades Metodológicas Carbon Footprint. Part 1: Concepts, Estimation Methods and Methodological Complexities

    Directory of Open Access Journals (Sweden)

    César Espíndola

    2012-01-01

    Full Text Available Se presenta y analiza el concepto de huella del carbono, su origen, su relación con los gases efecto invernadero, y sobre los procedimientos para cuantificarla. El efecto invernadero provoca que la energía que llega a la Tierra sea devuelta más lentamente, por lo que es mantenida más tiempo junto a la superficie elevando la temperatura. Es aceptado hoy en día que este efecto es producido por algunos gases liberados en forma natural o por las acciones humanas. La Huella de Carbono es considerada una de las más importantes herramientas para cuantificar las emisiones de gases efecto invernadero y en forma muy general, representa la cantidad de gases efecto invernadero emitidos a la atmósfera derivados de las actividades de producción o consumo de bienes y servicios. Al no existir consenso en cuanto a la definición y menos en la cuantificación de la huella del carbono, la primera parte de este trabajo analiza las principales corrientes y enfoques actuales.The concept of Carbon Footprint, its origin, its relation with greenhouse gases and the methods to quantify it are presented and analyzed. The so-called greenhouse effect causes that the energy that reaches the earth at a certain rate is returned to a slower rate, increasing the temperature of the earth surface. Additionally, it is nowadays accepted that this effect is produced by some gases that are naturally emitted or produced by human actions. The Carbon Footprint is considered to be one of the most important tools for quantifying greenhouse emissions and in a general form it represents the quantity of gases emitted to the atmosphere and that is produced by human activities, and by goods and service consumption. Since there is no consensus about the definition of Carbon Footprint or the forms of quantifying it, this first part of the paper series analyzes the main concept and the main present views on the Carbon Footprint.

  3. Cosmic Complexity

    Science.gov (United States)

    Mather, John C.

    2012-01-01

    What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and

  4. Complex silumins

    Directory of Open Access Journals (Sweden)

    S. Pietrowski

    2007-09-01

    Full Text Available Purpose: The study presents the results of investigations carried out on silumins with additions of Mg, Ni, Cu, Cr, Mo and W. The silumins containing Mg, Cu and Ni are well-known and commonly used in construction of machines and equipment.Design/methodology/approach: Additions of Cr, Mo and W have not been thoroughly investigated yet. They are considered a new family of innovative cast aluminium alloys.Findings: In Al-Si systems they form silicides, like Cr3Si, Mo3Si, W3Si and intermetallic phases of Al13Cr4Si4, Al12Mo, Al12W and AlWSi. The silicides crystallise in cubic lattice of parameters similar to aluminium and silicon.Research limitations/implications: Therefore they can act as crystallisation substrates and occur as separate phases. The examinations under the microscope and X-ray microanalysis of the linear and point distribution of elements confirmed the presence of the above mentioned phases. A combination of two elements, e.g. Cr and Mo, or Cr and W, was observed to cause the formation of complex silicide layers of Mo3Si and (Cr, Mo3Si, or Cr3Si as well as (W, Cr3Si.Originality/value: The presence of the silicides has been indicated as a possible source of the refinement of α(Al and β(Si phases. The precipitations of these phases and of the intermetallic phases favour a high degree of the silumins hardening. A characteristic feature is the fact that nucleation and crystallisation of the successive phases takes place at the phase boundaries formed between the previously precipitated phase and solid solution α. The studies carried out so far have indicated that in complex silumins at high temperatures crystallise the silicides and peritectic phases of Al12W, AlWSi, Al12Mo and Al13Cr4Si4. Phases α or β are the next ones to crystallise, followed by complex eutectic α + β +Al(Si, Cr, Mo, W, Fe. Further crystallise the phases of Mg2Si, Al3Ni and Al2Cu. The silumins presented here are characterised by high mechanical properties: Rp0

  5. An Organocobalt–Carbon Nanotube Chemiresistive Carbon Monoxide Detector

    OpenAIRE

    Liu, Sophie F.; Lin, Sibo; Swager, Timothy M.

    2016-01-01

    A chemiresistive detector for carbon monoxide was created from single-walled carbon nanotubes (SWCNTs) by noncovalent modification with diiodo(η5: η1-1-[2-(N,N-dimethylamino)ethyl]-2,3,4,5-tetramethylcyclopentadienyl)-cobalt(III) ([Cp^CoI2]), an organocobalt complex with an intramolecular amino ligand coordinated to the metal center that is displaced upon CO binding. The unbound amino group can subsequently be transduced chemiresistively by the SWCNT network. The resulting device was shown to...

  6. Zirconium sulfate interaction with sodium carbonate in solution

    International Nuclear Information System (INIS)

    Zirconium sulfate interaction with sodium carbonate is studied in aqueous solution. By pH-metry and infrared spectroscopy it is stated that depending on the carbonate concentration Zr(OH)2x(CO3)22-, ZrOH(CO3)33- and Zr(CO3)44- compounds can be formed in sulfatocarbonate solutions. pH range in which soluble carbonate complexes exist also depends on the concentration of sodium carbonate. Calculated is the fourth stability constant

  7. Solid-state Synthesis of Carbon-nanostructures

    Institute of Scientific and Technical Information of China (English)

    R.Wilhelm; A.Winkel; D.Jain

    2007-01-01

    1 Results In addition to single wall and multiwall carbon nanotubes[1], several structures,which are more or less related to fullerenes,including carbon nanohorns[2a], carbon nanospheres[2b] and onion like carbon structures[2c] have been reported.A new simple straight forward method to access some of these structures is the solid-state pyrolysis of different organometallic complexes in a sealed vessel,which led so far to carbon nanotubes[3a,b], carbon nanocables[3c] and onions[3d].

  8. Digital carbonate rock physics

    Science.gov (United States)

    Saenger, Erik H.; Vialle, Stephanie; Lebedev, Maxim; Uribe, David; Osorno, Maria; Duda, Mandy; Steeb, Holger

    2016-08-01

    Modern estimation of rock properties combines imaging with advanced numerical simulations, an approach known as digital rock physics (DRP). In this paper we suggest a specific segmentation procedure of X-ray micro-computed tomography data with two different resolutions in the µm range for two sets of carbonate rock samples. These carbonates were already characterized in detail in a previous laboratory study which we complement with nanoindentation experiments (for local elastic properties). In a first step a non-local mean filter is applied to the raw image data. We then apply different thresholds to identify pores and solid phases. Because of a non-neglectable amount of unresolved microporosity (micritic phase) we also define intermediate threshold values for distinct phases. Based on this segmentation we determine porosity-dependent values for effective P- and S-wave velocities as well as for the intrinsic permeability. For effective velocities we confirm an observed two-phase trend reported in another study using a different carbonate data set. As an upscaling approach we use this two-phase trend as an effective medium approach to estimate the porosity-dependent elastic properties of the micritic phase for the low-resolution images. The porosity measured in the laboratory is then used to predict the effective rock properties from the observed trends for a comparison with experimental data. The two-phase trend can be regarded as an upper bound for elastic properties; the use of the two-phase trend for low-resolution images led to a good estimate for a lower bound of effective elastic properties. Anisotropy is observed for some of the considered subvolumes, but seems to be insignificant for the analysed rocks at the DRP scale. Because of the complexity of carbonates we suggest using DRP as a complementary tool for rock characterization in addition to classical experimental methods.

  9. Developing a Carbon Observing System

    Science.gov (United States)

    Moore, B., III

    2015-12-01

    There is a clear need to better understand and predict future climate change, so that science can more confidently inform climate policy, including adaptation planning and future mitigation strategies. Understanding carbon cycle feedbacks, and the relationship between emissions (fossil and land use) and the resulting atmospheric carbon dioxide (CO2) and methane (CH4) concentrations in a changing climate has been recognized as an important goal by the IPCC. The existing surface greenhouse gas observing networks provide accurate and precise measurements of background values, but they are not configured to target the extended, complex and dynamic regions of the carbon budget. Space Agencies around the globe are committed to CO2 and CH4 observations: GOSAT-1/2, OCO-2/3, MERLin, TanSat, and CarbonSat. In addition to these Low Earth Orbit (LEO) missions, a new mission in Geostationary Orbit (GEO), geoCARB, which would provide mapping-like measurements of carbon dioxide, methane, and carbon monoxide concentrations over major land areas, has been recently proposed to the NASA Venture Program. These pioneering missions do not provide the spatial/temporal coverage to answer the key carbon-climate questions at process relevant scales nor do they address the distribution and quantification of anthropogenic sources at urban scales. They do demonstrate, however, that a well-planned future system of system integrating space-based LEO and GEO missions with extensive in situ observations could provide the accuracy, spatial resolution, and coverage needed to address critical open issues in the carbon-climate system. Dr. Diana Wickland devoted enormous energy in developing a comprehensive apprioach to understand the global carbon cycle; she understood well that an integrated, coordinated, international approach is needed. This shines through in her recent contribution in co-chairing the team that produced the "CEOS Strategy for Carbon Observations from Space." A NASA-funded community

  10. Belowground carbon trade among tall forest trees

    Science.gov (United States)

    Klein, Tamir; Siegwolf, Rolf; Koerner, Christian

    2016-04-01

    Just imagine one tree could hand over large quantities of carbon to another tree. How would that change our thinking about carbon relations of forests, the single biggest biological C reservoir on earth? If such a tree-to-tree C shuttle would exist, it required a demand-supply gradient and a pipeline. Here we show that exactly this unthinkable does occur in overlapping root spheres of tall trees in a mixed temperate forest. Using canopy scale stable carbon isotope labelling applied from a construction crane, we demonstrate that carbon assimilated by spruce is traded over to neighbouring beech, larch, and pine in amounts so large that fine roots almost equilibrate the carbon source signature. The isotope mixing ratio indicated that the interspecific transfer accounted for 40% of the fine root carbon, which is ca. 280 kg ha-1 a-1. This is the first forest scale evidence of a large flux of carbon among mature trees from evolutionary distant taxa. Carbon transfer most likely occurred through common ectomycorrhiza networks, which also exhibited the labelled carbon signal. These observations indicate that while competition for resources (e.g. light, water, nutrients) is often considered the dominant tree-tree interaction in a forest, trees actually interact in more complex pathways including a massive carbon exchange.

  11. Preparation of hollow spherical carbon nanocages

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, C.-K.; Kang, H. Y.; Hong, C.-I; Huang, C.-H.; Chang, F.-C.; Wang, H. Paul, E-mail: wanghp@mail.ncku.edu.tw [National Cheng Kung University, Department of Environmental Engineering, Taiwan (China)

    2012-12-15

    This study presents a new and simple method for the synthesis of hollow carbon spheres possessing nanocage sizes of 7.1, 14, and 20 nm in diameter. The core-shell (i.e., Cu-C) nanoparticles prepared by carbonization of the Cu{sup 2+}-cyclodextrin (CD) complexes at 573 K for 2 h was etched with HCl (6N) to yield the hollow carbon spheres. The carbon-shell of the hollow carbon nanospheres, which consisted of mainly diamond-like and graphite carbons, is not perturbed during etching. In addition to the nanocages, the hollow carbon nanospheres also possess micropores with an opening of 0.45 nm, allowing small molecules to diffuse in and out through the carbon-shell. Many elements (such as Zn{sup 2+} or Cu{sup 2+}) can therefore be filled into the nanocages of the hollow carbon nanospheres. With these unique properties, for instance, designable active species such as Cu and ZnO encapsulated in the carbon-shell can act as Cu-ZnO-C yolk-shell nanoreactors which are found very effective in the catalytic decomposition of methanol.

  12. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry

    International Nuclear Information System (INIS)

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO3)33-, is identified by solubility measurements in Na2CO3 solutions. Then the formation constants of the complexes Eu(CO3)i3-2i (i=1-3) and Eu(SO4)i3-2i (i=1-2) are measured by TRLFS. The formation of aqueous LaSO4+ is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO3)2- + CO32- ↔ Cm(CO3)33- are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  13. The foil equilibration method for carbon in sodium

    International Nuclear Information System (INIS)

    Among the non-metallic impurities in sodium, carbon plays an important role since at high temperatures the structural materials exposed to sodium are subject to carburization and decarburization depending on the carbon activity of the sodium. Carburization of austenitic stainless steels leads to reduction in ductility and fatigue properties whereas decarburization results in a decrease in the high temperature creep strength. A knowledge of the carbon activities in sodium will help understanding of the carbon transfer phenomena in operating sodium systems of the fast reactors, and also carbon diffusion, microstructural stability and mechanical behaviour of materials under different service conditions. An understanding of the carbon behaviour in sodium becomes difficult in view of the complexities of the different species present as elemental carbon, carbide, acetylide, carbonate, and cyanide. Carbon estimation techniques for sodium presently in use are: chemical analytical methods, on-line carbon monitors, and oil equilibration method. Various chemical methods have been developed for the estimation of different species like acetylide, cyanide, carbonate, elemental carbon, and total carbon in sodium. All these methods are time consuming and subject to various errors. The on-line monitors developed for carbon in sodium are able to give continuous indication of carbon activities and have higher sensitivity than the chemical methods. A still more simple method for the determination of carbon activities is by the foil equilibration first published by Natesan et al. Because of its simplicity like the vanadium wire equilibration for oxygen it is being used widely for the estimation of carbon activities in sodium systems. Carbon concentrations in operating sodium systems estimated by this procedure by applying solubility relation to carbon activities have yielded very low values of carbon, lower than the sensitivity limits of the chemical estimation methods. Foil

  14. Carbon Footprints

    OpenAIRE

    Rahel Aichele; Gabriel Felbermayr

    2011-01-01

    Lässt sich der Beitrag eines Landes zum weltweiten Klimaschutz an der Veränderung seines CO2-Ausstoßes messen, wie es im Kyoto-Abkommen implizit unterstellt wird? Oder ist aufgrund der Bedeutung des internationalen Güterhandels der Carbon Footprint – der alle CO2-Emissionen erfasst, die durch die Absorption (d.h. Konsum und Investitionen) eines Landes entstehen – das bessere Maß? Die Autoren erstellen eine Datenbank mit den Footprints von 40 Ländern für den Zeitraum 1995–2007. Die deskriptive...

  15. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth

    OpenAIRE

    Horita, Juske; Polyakov, Veniamin B.

    2014-01-01

    Due to its bonding environments, carbon can make up numerous compounds with many other elements. However, the abundance and dynamics of carbon in the deep Earth remains uncertain due to its complex behavior during the primary accretion and differentiation of the Earth in its early history. The naturally occurring stable isotopes of carbon serve as a useful tracer to study the carbon cycle, both on the surface and in the deep Earth. Here, a new model is presented for understanding a first-orde...

  16. Periodate and tellurate complexes of terbium(IV)

    International Nuclear Information System (INIS)

    Solutions and solid complexes of Tb(IV) tellurate and periodate were prepared on the basis of synthesis methods developed. Data provided by X-ray diffraction of powder and electron spectroscopy suggest individuality of Tb(IV) derivatives. Data on transition energies with charge transfer in absorption spectra of the complexes and literature data permit defining the following stability series of Tb(IV) complexes: heteropolytungstates feature the highest stability, then stability decreases to periodate and subsequently to tellurite and carbonate complexes

  17. Production of precipitated calcium carbonate from calcium silicates and carbon dioxide

    International Nuclear Information System (INIS)

    The possibilities for reducing carbon dioxide emissions from the pulp and paper industry by calcium carbonation are presented. The current precipitated calcium carbonate (PCC) production uses mined, crushed calcium carbonate as raw materials. If calcium silicates were used instead, carbon dioxide emissions from the calcination of carbonates would be eliminated. In Finland, there could, thus, be a potential for eliminating 200 kt of carbon dioxide emissions per year, considering only the PCC used in the pulp and paper industry. A preliminary investigation of the feasibility to produce PCC from calcium silicates and the potential to replace calcium carbonate as the raw material was made. Calcium carbonate can be manufactured from calcium silicates by various methods, but only a few have been experimentally verified. The possibility and feasibility of these methods as a replacement for the current PCC production process was studied by thermodynamic equilibrium calculations using HSC software and process modelling using Aspen Plus[reg]. The results from the process modelling showed that a process that uses acetic acid for extraction of the calcium ions is a high potential option for sequestering carbon dioxide by mineral carbonation. The main obstacle seems to be the limited availability and relatively high price of wollastonite, which is a mineral with high calcium silicate content. An alternative is to use the more common, but also more complex, basalt rock instead

  18. Trading forest carbon

    Science.gov (United States)

    The nature of carbon in forests is discussed from the perspective of carbon trading. Carbon inventories, specifically in the area of land use and forestry are reviewed for the Pacific Northwest. Carbon turnover in forests is discussed as it relates to carbon sequestration. Scient...

  19. Lanthanide Ternary Complexes Relevent to the Nuclear Fuel Cycle

    OpenAIRE

    Roughley, Georgina

    2012-01-01

    This project has been focused on modelling actinide behaviour using lanthanide analogues. Ternary complexes of Lanthanides-EDTA-Carbonate have been studied with techniques such as potentiometry and ultraviolet-visible absorption spectroscopy.It was found that ternary complexes of Ln-EDTA-Carbonate and Ln-EDTA-OH do exist for La, Eu and Lu. Log K values were calculated from potentiometry titrations which involve the formation of these ternary species. For lanthanum, the log K values for the co...

  20. Optimal Carbon Capture and Storage Policies

    OpenAIRE

    Ayong Le Kama, Alain; Mouez FODHA; Lafforgue, Gilles

    2011-01-01

    Following the IPCC's report (2005), which recommended the development and the use of carbon capture and sequestration (CCS) technologies in order to achieve the environmental goals, defined by the Kyoto Protocol, the issue addressed in this paper concerns the optimal strategy regarding the long-term use of CCS technologies. The aim of this paper is to study the optimal carbon capture and sequestration policy. The CCS technologies has motivated a number of empirical studies, via complex int...

  1. Supercritical fluid extraction of actinide element complexes. II. SCF of actinide complexes with β-diketones

    International Nuclear Information System (INIS)

    Data on solubility of β-diketones complexes with uranium (VI), plutonium, neptunium, and americium in supercritical carbon dioxide (SC-CO2) are presented. It is established that content of actinide complexes with β-diketones in SC-CO2 can achieve 10-100 g/l. Complexes with dipivaloylmethane, trifluoroacetylacetone and hexafluoroacetylacetone and adducts with tributylphosphate and water in particular are the most highly soluble in it. Residues of complexes after dissolution in SC-CO2 are investigated spectroscopically

  2. Synthesis and Characterization of Carbon Metal Nano Tubes

    Science.gov (United States)

    Tiwari, B.; Tripathi, I. P.; Saxena, Sanjay; Singh, Sudhanshu; Haribhushan

    2010-11-01

    Nano technology is emerging as the latest technology these days. It is proving its importance in every sphere of life. Metal carbon nano tube due to their vast applications is being used very frequently. So to prepare CNTs a new method is developed. In this methods Complexes of transition metal Ni(II) with amino acids present in egg albumin have been synthesized. The complex is analyzed on the basis of spectroscopic methods of UV, IR, and NMR Spectroscopy. The amino acid metal Complex is decomposed at higher temperature to obtain metal carbon nano tubes. These metal carbon nano tubes are characterized using scanning probe instruments like DLS.

  3. Carbon-14 measurements in aquifers with methane

    International Nuclear Information System (INIS)

    A survey of various groundwater systems indicates that methane is a common trace constituent and occasionally a major carbon species in groundwaters. Thermocatalytic methane had delta13Csub(CH4)>-45 per mille and microbially produced or biogenic methane had delta13Csub(CH4)13C values for the inorganic carbon. Thermocatalytic methane had no apparent effect on the inorganic carbon. Because methanogenesis seriously affects the carbon isotope geochemistry of groundwaters, the correction of raw 14C ages of affected groundwaters must consider these effects. Conceptual models are developed which adjust the 14C activity of the groundwater for the effects of methanogenesis and for the dilution of carbon present during infiltration by simple dissolution of rock carbonate. These preliminary models are applied to groundwaters from the Alliston sand aquifer where methanogenesis has affected most samples. In this system, methanogenic bacteria using organic matter present in the aquifer matrix as substrate have added inorganic carbon to the groundwater which has initiated further carbonate rock dissolution. These processes have diluted the inorganic carbon 14C activity. The adjusted groundwater ages can be explained in terms of the complex hydrogeology of this aquifer, but also indicate that these conceptual models must be more rigorously tested to evaluate their appropriateness. (author)

  4. Carbon Farming as a Carbon Negative Technology

    Science.gov (United States)

    Anderson, C.; Laird, D.; Hayes, D. J.

    2015-12-01

    Carbon farms have a pivotal role in national and international efforts to mitigate and adapt to climate change. A carbon farm in its broadest sense is one that reduces greenhouse gas (GHG) emissions or captures and holds carbon in vegetation and soils. Their capacity to remove carbon from the air and store it safely and permanently, while providing additional human and ecosystem benefits, means they could contribute significantly to national efforts to stabilize or reduce GHGs. We examine carbon farms in the context of corn and soybean production agriculture. We illustrate, using Iowa data but with relevance across United States corn and soybean production, the potential for carbon farms to reduce human GHG emissions and sequester carbon permanently at a rate that has meaningful impact on global greenhouse gas concentration. Carbon has been viewed as a next generation cash crop in Iowa for over a decade. The carbon farm perspective, however, goes beyond carbon as cash crop to make carbon the center of an entire farm enterprise. The transformation is possible through slight adjustment crop practices mixed with advances in technology to sequester carbon through biochar. We examine carbon balance of Iowa agriculture given only the combination of slight reduction in fertilizer and sequestration by biochar. We find the following. Iowa carbon farms could turn Iowa agriculture into a carbon sink. The estimated range of GHG reduction by statewide implementation of carbon farms is 19.46 to 90.27 MMt CO2-equivalent (CO2-e), while the current agricultural CO2-e emission estimate is 35.38 MMt CO2-e. Iowa carbon farm GHG reduction would exceed Iowa GHG reduction by wind energy (8.7 MMt CO2-e) and could exceed combined reductions from wind energy and corn grain ethanol (10.7 MMt CO2-e; 19.4 MMt CO2-e combined). In fact, Iowa carbon farms alone could exceed GHG reduction from national corn grain ethanol production (39.6 MMt CO2-e). A carbon price accessible to agricultural

  5. Studies on an aluminium-carbon cell

    Science.gov (United States)

    Verma, L. K.

    The current-voltage behaviour of an electrochemical cell that consists of an aluminium anode and a carbon cathode in a medium containing aqueous NH 4SCN has been studied, both in the presence and in the absence of a coating on the carbon electrode. It is found that activation polarization is the main factor that limits the current output when using an untreated carbon electrode. This problem is eliminated by coating the carbon electrode with an in situ deposition of HgI 2. In this condition, the current output is reduced mainly by ohmic polarization. Further studies with a coated HgI 2-carbon cathode and an aluminium anode, in a medium containing SCN - and Cl - ions together with a complexing agent (EDTA, sodium salt), revealed that a cell performance close to ideal, (i.e, showing no appreciable polarization) can be obtained at currents up to 0.6 mA/cm 2 and above.

  6. Nonequilibrium Thermodynamic Model of Manganese Carbonate Oxidation

    Institute of Scientific and Technical Information of China (English)

    郝瑞霞; 彭省临

    1999-01-01

    Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.

  7. Carbon ion radiotherapy for pancreatic cancer

    International Nuclear Information System (INIS)

    The Heavy Ion Medical Accelerator in Chiba (HIMAC) is the world's first heavy ion accelerator complex dedicated to medical use in a hospital environment. Carbon ion therapy offers the potential advantages of improved dose localization and enhanced biological effects. It has been suggested that carbon ion therapy is effective against radioresistant pancreatic cancer. In April 2000, clinical studies examining the treatment of pancreatic cancer with carbon ions were begun at the HIMAC. As of February 2010, 48 patients treated with preoperative carbon ion radiotherapy and 89 patients treated for locally advanced pancreatic cancer were enrolled into the clinical trials. Both protocols are still ongoing. The interim results of these clinical trials suggest that carbon ion radiotherapy provides good local control and offers a survival advantage for patients with otherwise hard to cure pancreatic cancer, without unacceptable morbidity. (author)

  8. Nanostructured Deep Carbon: A Wealth of Possibilities

    Science.gov (United States)

    Navrotsky, A.

    2012-12-01

    The materials science community has been investigating novel forms of carbon including C60 buckyballs, nanodiamond, graphene, carbon "onion" structures with a mixture of sp2 and sp3 bonding , and multicomponent nanostructured Si-O-C-N polymer derived ceramics. Though such materials are generally viewed as metastable, recently measured energetics of several materials suggest that this may not always be the case in multicomponent systems. Finely disseminated carbon phases, including nanodiamonds, have been found in rocks from a variety of deep earth settings. The question then is whether some of the more exotic forms of carbon can also exist in the deep earth or other planetary interiors. This presentation discusses thermodynamic constraints related to surface and interface energies, nanodomain structures, and compositional effects on the possible existence of complex carbon, carbide and oxycarbide nanomaterials at high pressure.

  9. Carbon Monoxide Poisoning

    Science.gov (United States)

    ... Recommend on Facebook Tweet Share Compartir What is Carbon Monoxide? Carbon monoxide, or “CO,” is an odorless, colorless gas that can kill you. Carbon monoxide detector Where is CO found? CO is ...

  10. Net Ecosystem Carbon Flux

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Net Ecosystem Carbon Flux is defined as the year-over-year change in Total Ecosystem Carbon Stock, or the net rate of carbon exchange between an ecosystem and the...

  11. Carbon Monoxide (CO)

    Science.gov (United States)

    ... IAQ) » Carbon Monoxide's Impact on Indoor Air Quality Carbon Monoxide's Impact on Indoor Air Quality On this ... length of exposure. Top of Page Sources of Carbon Monoxide Sources of CO include: unvented kerosene and ...

  12. Carbon nanofillers for machining insulating ceramics

    Directory of Open Access Journals (Sweden)

    Olivier Malek

    2011-10-01

    Full Text Available The implementation of ceramics in emerging applications is principally limited by the final machining process necessary for producing microcomponents with complex geometries. The addition of carbon nanotubes greatly enhances the electrical properties of insulating ceramics allowing electrical discharge machining to be used to manufacture intricate parts. Meanwhile other properties of the ceramic may be either preserved or even improved. For the first time, a silicon nitride/carbon nanotubes microgear is electrically discharge machined with a remarkably high material removal rate, low surface roughness, and low tool wear. This offers unprecedented opportunities for the manufacture of complicated ceramic parts by adding carbon nanotubes for new engineering and biomedical applications.

  13. Research on Welding Test of Grey Cast Iron and Low-Carbon Steel

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Grey cast iron's welding itself is a complex proble m.So proper welding materials must be selected,complex welding techniques such as preheating before weldingslow cooling after welding etc,should be taken. However the carbon component in low-carbon steel is comparatively low,the carbo n of welded joint will diffuse to the low-carbon steel when it is welded with gr ey cast iron,which will cause the component of carbon greatly increased at the low-carbon steel side in HAZ,high carbon martensite and cracks ...

  14. Carbon dioxide stripping in aquaculture. part 1: terminology and reporting

    Science.gov (United States)

    Colt, John; Watten, Barnaby; Pfeiffer, Tim

    2012-01-01

    The removal of carbon dioxide gas in aquacultural systems is much more complex than for oxygen or nitrogen gas because of liquid reactions of carbon dioxide and their kinetics. Almost all published carbon dioxide removal information for aquaculture is based on the apparent removal value after the CO2(aq) + HOH ⇔ H2CO3 reaction has reached equilibrium. The true carbon dioxide removal is larger than the apparent value, especially for high alkalinities and seawater. For low alkalinity freshwaters (carbon dioxide removal.

  15. Measuring Tax Complexity

    OpenAIRE

    David Ulph

    2014-01-01

    This paper critically examines a number of issues relating to the measurement of tax complexity. It starts with an analysis of the concept of tax complexity, distinguishing tax design complexity and operational complexity. It considers the consequences/costs of complexity, and then examines the rationale for measuring complexity. Finally it applies the analysis to an examination of an index of complexity developed by the UK Office of Tax Simplification (OTS). Postprint

  16. Integral Ring Carbon-Carbon Piston

    Science.gov (United States)

    Northam, G. Burton (Inventor)

    1999-01-01

    An improved structure for a reciprocating internal combustion engine or compressor piston fabricate from carbon-carbon composite materials is disclosed. An integral ring carbon-carbon composite piston, disclosed herein, reduces the need for piston rings and for small clearances by providing a small flexible, integral component around the piston that allows for variation in clearance due to manufacturing tolerances, distortion due to pressure and thermal loads, and variations in thermal expansion differences between the piston and cylinder liner.

  17. Carbon dioxide sequestration by mineral carbonation

    OpenAIRE

    Huijgen, W.J.J.

    2007-01-01

    The increasing atmospheric carbon dioxide (CO2) concentration, mainly caused by fossil fuel combustion, has lead to concerns about global warming. A possible technology that can contribute to the reduction of carbon dioxide emissions is CO2 sequestration by mineral carbonation. The basic concept behind mineral CO2 sequestration is the mimicking of natural weathering processes in which calcium or magnesium containing minerals react with gaseous CO2 and form solid calcium or magnesium carbonate...

  18. Uranium nucleophilic carbene complexes

    International Nuclear Information System (INIS)

    The only stable f-metal carbene complexes (excluding NHC) metals f present R2C2- groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the di-anion C{Ph2P(=S)}22- (SCS2-) to extend the organometallic chemistry of this element in its various oxidation states (+3-+6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U. We first isolated the reactants M(SCHS) (M = Li and K) and demonstrated the role of the cation M+ on the evolution of the di-anion M2SCS (M = Li, K, Tl) which is transformed into LiSCHS in THF or into product of intramolecular cyclization K2[C(PhPS)2(C6H4)]. We have developed the necessary conditions mono-, bis- and tris-carbene directly from the di-anion SCS2- and UCl4, as the precursor used in uranium chemistry. The protonolysis reactions of amides compounds (U-NEt2) by the neutral ligand SCH2S were also studied. The compounds [Li(THF)]2[U(SCS)Cl3] and [U(SCS)Cl2(THF)2] were then used to prepare a variety of cyclopentadienyl and mono-cyclo-octa-tetra-enyliques uranium(IV) carbene compounds of the DFT analysis of compounds [M(SCS)Cl2(py)2] and [M(Cp)2(SCS)] (M = U, Zr) reveals the strong polarization of the M=C double bond, provides information on the nature of the σ and π interactions in this binding, and shows the important role of f orbitals. The influence of ancillary ligands on the M=C bond is revealed by examining the effects of replacing Cl- ligands and pyridine by C5H5- groups. Mulliken and NBO analyzes show that U=C bond, unlike the Zr=C bond, is not affected by the change in environment of the metal center. While the oxidation tests of carbene complexes of U(IV) were disappointing, the first carbene complex of uranium (VI), [UO2(SCS)(THF)2], was isolated with the uranyl ion UO22+. The reactions of compounds UO2X2 (X = I, OTf) with anions SCS2- and SCHS- provide the

  19. Carbon dioxide sequestration by mineral carbonation

    NARCIS (Netherlands)

    Huijgen, W.J.J.

    2007-01-01

    The increasing atmospheric carbon dioxide (CO2) concentration, mainly caused by fossil fuel combustion, has lead to concerns about global warming. A possible technology that can contribute to the reduction of carbon dioxide emissions is CO2 sequestration by mineral carbonation. The basic concept beh

  20. A Theoretical Simulation of Deformed Carbon Nanotubes with Adsorbed Metal Atoms: Enhanced Reactivity by Deformation

    OpenAIRE

    Hosoya, Naoki; Kusakabe, Koichi; Maheswari, S. Uma

    2010-01-01

    First-principles simulations were performed to investigate reaction of carbon nanotubes with adsorbed metal atoms. Mechanical modification of their structures enhances chemical reactivity of carbon nanotubes. Adsorption of a tungsten, tantalum, or niobium atom on a (5, 0) nanotube with a Stone-Wales defect was shown to have characteristically strong chemisorption. Bond-breaking in the carbon-carbon network and formation of a local metal-carbon complex were observed during the simulation. Adso...

  1. On State Complexes and Special Cube Complexes

    Science.gov (United States)

    Peterson, Valerie J.

    2009-01-01

    This thesis presents the first steps toward a classification of non-positively curved cube complexes called state complexes. A "state complex" is a configuration space for a "reconfigurable system," i.e., an abstract system in which local movements occur in some discrete manner. Reconfigurable systems can be used to describe, for example,…

  2. Composite carbon foam electrode

    Science.gov (United States)

    Mayer, S.T.; Pekala, R.W.; Kaschmitter, J.L.

    1997-05-06

    Carbon aerogels used as a binder for granulated materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivity and power to system energy. 1 fig.

  3. Pricing complexity options

    OpenAIRE

    Malihe Alikhani; Bj{\\o}rn Kjos-Hanssen; Amirarsalan Pakravan; Babak Saadat

    2015-01-01

    We consider options that pay the complexity deficiency of a sequence of up and down ticks of a stock upon exercise. We study the price of European and American versions of this option numerically for automatic complexity, and theoretically for Kolmogorov complexity. We also consider run complexity, which is a restricted form of automatic complexity.

  4. Prospects in using carbon-carbon composite materials based on viscose carbon fibers for the space technology needs

    International Nuclear Information System (INIS)

    Due to the unique combination of low density, high mechanical strength under elevated temperatures, high resistance to thermal shock loads and ablation resistance, carbon-carbon composite materials (CCCM) are widely used for manufacturing of highly thermally loaded structural components. The important scientific and technical difficulty is to increase and stabilize CCCM properties, reduce cost and leads to searching for new raw materials and engineering solutions. The article describes the prospects of replacing carbon fiber fills based on PAN-precursors which are traditionally used for producing CCCM by carbon fillers on the basis of viscose raw material; shows the advantages of using viscose-based carbon fibers when forming products of complex shape as well as the possibility of obtaining products with high functional characteristics. The creation of CCCM of layered reinforcement structure, in which carbon fabric layers interleave with layers of discontinuous carbon fibers, enabled to increase the overall density of carbon composites, to ensure sufficiently high level of mechanical characteristics and resistance to ablation

  5. 维生素C-稀土配合物在天然橡胶/炭黑复合材料中的防老化作用%Antiaging Effect of Vitamin C-Rare Earth Complex on Natural Rubber/Carbon Black Composites

    Institute of Scientific and Technical Information of China (English)

    罗远芳; 杨超; 贾志欣; 贾德民; 陈俊; 郑德

    2012-01-01

    A novel rare earth complex was prepared from lanthanum ( La) and vitamin C and was used as a new type of antioxidant in natural rubber/carbon black ( NR/CB) composites. Then, the effects of the vitamin C-rare earth complex on the curing characteristics of NR/CB compounds and the mechanical properties of NR/CB vulcani-zates were investigated. Moreover, by means of FT-IR and according to the retention of mechanical properties and the variation of surface morphology, the effects of the rare earth complex on the antiaging properties of the NR/CB vulcanizates were also analyzed in detail and were compared with those of the commonly-used rubber antioxidants 4010NA, RD and MB. The results show that (1) the rare earth complex can accelerate the vulcanization of the NR/ CB compounds to a certain degree and improve the mechanical properties of the NR/CB vulcanizates; (2) the rare earth complex has a good antiaging effect on the NR/CB vulcanizates; (3) the thermo-oxidative aging resistance and UV aging resistance of the rare earth complex are close to those of 4010NA and RD and are superior to those of MB; and (4) the ozone aging resistance of the rare earth complex is particularly strong for the NR/CB vulcanizates, which is superior to those of RD and MB as well as to those of 4010NA with an excellent ozone aging resistance.%以镧和维生素C为原料制备了一种新型稀土配合物,将该新型稀土配合物作为一种新型防老剂应用于天然橡胶/炭黑(NR/CB)复合材料中,研究了该稀土配合物对NR/CB混炼胶硫化特性和硫化胶力学性能的影响,通过红外光谱、力学性能保持率及表面形貌变化详细分析了该稀土配合物对NR/CB硫化胶耐老化性能的影响,并与常用橡胶防老剂4010NA、RD和MB进行了比较.结果表明:维生素C-稀土配合物对NR/CB混炼胶具有一定的硫化促进作用,并能提高NR/CB硫化胶的力学性能;维生素C-稀土配合物在NR/CB复合材料中有优良的抗老化

  6. Measurement of carbon for carbon sequestration and site monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Madhavi Z [ORNL; Wullschleger, Stan D [ORNL; Garten Jr, Charles T [ORNL; Palumbo, Anthony Vito [ORNL

    2007-01-01

    A 2 to 6 degree C increase in global temperature by 2050 has been predicted due to the production of greenhouse gases that is directly linked to human activities. This has encouraged an increase in the international efforts on ways to reduce anthropogenic emissions of greenhouse gases particularly carbon dioxide (CO{sub 2}) as evidence for the link between atmospheric greenhouse gases and climate change has been established. Suggestion that soils and vegetation could be managed to increase their uptake and storage of CO{sub 2}, and thus become 'land carbon sinks' is an incentive for scientists to undertake the ability to measure and quantify the carbon in soils and vegetation to establish base-line quantities present at this time. The verification of the permanence of these carbon sinks has raised some concern regarding the accuracy of their long-term existence. Out of the total percentage of carbon that is potentially sequestered in the terrestrial land mass, only 25% of that is sequestered above ground and almost 75% is hypothesized to be sequestered underground. Soil is composed of solids, liquids, and gases which is similar to a three-phase system. The gross chemical composition of soil organic carbon (SOC) consists of 65% humic substances that are amorphous, dark-colored, complex, polyelectrolyte-like materials that range in molecular weight from a few hundred to several thousand Daltons. The very complex structure of humic and fulvic acid makes it difficult to obtain a spectral signature for all soils in general. The humic acids of different soils have been observed to have polymeric structure, appearing as rings, chains and clusters as seen in electron microscope observations. The humification processes of the soils will decide the sizes of their macromolecules that range from 60-500 angstroms. The percentage of the humus that occurs in the light brown soils is much lower than the humus present in dark brown soils. The humus of forest soils is

  7. Carbon doped ZnO: Synthesis, characterization and interpretation

    International Nuclear Information System (INIS)

    A novel thermal plasma in-flight technique has been adopted to synthesize nanocrystalline ZnO and carbon doped nanocrystalline ZnO matrix. Transmission electron microscopy (TEM) studies on these samples show the average particle sizes to be around 32 nm for ZnO and for carbon doped ZnO. An enhancement of saturation magnetization in nanosized carbon doped ZnO matrix by a factor of 3.8 has been found in comparison to ZnO nanoparticles at room temperature. Raman measurement clearly indicates the presence of Zn–C complexes surrounded by ZnO matrix in carbon doped ZnO. This indicates that the ferromagnetic signature in carbon doped ZnO arises from the creation of defects or the development of oxy-carbon clusters, in the carbon doped ZnO system. Theoretical studies based on density functional theory also support the experimental analyses. - Highlights: ► Synthesis of nanocrystalline ZnO and carbon doped ZnO matrix by inflight thermal plasma reactor. ► Enhancement of ferromagnetism in nanosized carbon doped ZnO in comparison to ZnO nanoparticles. ► Raman measurement indicates the presence of Zn–C complexes surrounded by ZnO matrix. ► Ferromagnetic signature in carbon doped ZnO arises from the development of oxy-carbon clusters. ► DFT supports experimental evidence of ferromagnetism in C doped ZnO nanoparticles.

  8. Benchmarking carbon emissions performance in supply chains

    OpenAIRE

    Acquaye, Adolf; Genovese, Andrea; Barrett, John W.; Koh, Lenny

    2014-01-01

    Purpose – The paper aims to develop a benchmarking framework to address issues such as supply chain complexity and visibility, geographical differences and non-standardized data, ensuring that the entire supply chain environmental impact (in terms of carbon) and resource use for all tiers, including domestic and import flows, are evaluated. Benchmarking has become an important issue in supply chain management practice. However, challenges such as supply chain complexity and visibility, geogra...

  9. Conformal Carbon Nanotubes for Stray Light Suppression Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Our objective is to apply CVD and non-CVD carbon nanotubes to complex shapes that numerous scientists have requested for stray light control.  Currently, CVD...

  10. CATALYTIC ACTIVITIES OF RARE-EARTH CALIXARENE COMPLEXES IN POLYMER SYNTHESES

    Institute of Scientific and Technical Information of China (English)

    Zhi-quan Shen

    2005-01-01

    The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene,styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

  11. Potential for carbon adsorption on concrete: surface XPS analyses.

    Science.gov (United States)

    Haselbach, Liv M; Ma, Shuguo

    2008-07-15

    The concrete industry is a contributor to the global carbon cycle particularly with respect to the contribution of carbon dioxide in the manufacturing of cement (calcination). The reverse reaction of carbonation is known to occur in concrete, but is usually limited to exterior surfaces exposed to carbon dioxide and humidity in the air. As alternate concrete uses expand which have more surface area, such as crushed concrete for recycling, it is important to understand surface adsorption of carbon dioxide and the positive impacts it might have on the carbon cycle. X-ray photoelectron spectroscopy (XPS) is used in this study to evaluate carbon species on hydrated cement mortar surfaces. Initial estimates for carbon absorption in concrete using othertechniques predictthe potential for carbonate species to be a fraction of the calcination stoichiometric equivalent The XPS results indicate that there is a rapid and substantial uptake of carbon dioxide on the surfaces of these mortars, sometimes exceeding the calcination stoichiometric equivalents, indicative of carbon dioxide surface complexation species. On pure calcite, the excess is on the order of 30%. This accelerated carbon dioxide surface adsorption phenomenon may be importantfor determining novel and effective carbon sequestration processes using recycled concrete. PMID:18754389

  12. Mutagenicity of carbon nanomaterials

    DEFF Research Database (Denmark)

    Wallin, Håkan; Jacobsen, Nicklas Raun; White, Paul A;

    2011-01-01

    Carbon nanomaterials such carbon nanotubes, graphene and fullerenes are some the most promising nanomaterials. Although carbon nanomaterials have been reported to possess genotoxic potential, it is imperitive to analyse the data on the genotoxicity of carbon nanomaterials in vivo and in vitro and...

  13. Ab initio simulation of helium inside carbon nanotubes

    International Nuclear Information System (INIS)

    In present work we consider the complex behaviour of quantum liquids like liquid He-4 inside carbon nanotubes. Interactions between helium atoms and carbon atoms of the short-length atomistic model and model with periodical boundary conditions of carbon nanotube were studied via ab initio quantum simulations. Effects of geometrical confinement of the tube on the He behaviour inside CNT (13,0) have been explored. Nanotubes with typical average diameter of 10 angstroms are under consideration.

  14. Factors effecting carbonate equilibria in natural waters

    International Nuclear Information System (INIS)

    This study is related to preliminary stie evaluations to be carried out in 1987-1992 for spent nuclear fuel disposal in Finland. Near surface and shallow groundwaters are characterized by high concentration of calcium and bicarbonate due to dissolution of calcite. The input of carbon dioxide in the upper zone of the bedrock has a strong influence on the pH giving a pH around neutral. In deep groundwaters when the system is no longer open to the input of carbon dioxide the pH rises as the carbonate system is displaced towards the bicarbonate-carbonate site. In still deeper parts of the rock weathering of other minerals such as feldspars affects the chemistry raising the pH and resulting in saturation and precipitation of calcite. The more advanced these reactions become the higher is the pH and the lower is the carbonate content. The equilibrium concentrations of carbonate species are affected both by temperature and ionic strength of the waters, at high ionic strength especially the distribution between bicarbonate and carbonate ions is affected. The total concentration of carbonates in groundwaters is determined through complex interaction between calcite and carbonates in the water. In deep groundwaters which are closed for input of CO2 the concentration is stated to be regulated by dissolution of calcium carbonate. In deep granitic groundwaters pH is stated to be buffered to 6.5 to 10, where a high pH would correspond to a low total carbonate concentration and often also a low calcium concentration and a low pH would correspond to high carbonae and calcium concentrations

  15. Electroanalysis with carbon paste electrodes

    CERN Document Server

    Svancara, Ivan; Walcarius, Alain; Vytras, Karel

    2011-01-01

    Introduction to Electrochemistry and Electroanalysis with Carbon Paste-Based ElectrodesHistorical Survey and GlossaryField in Publication Activities and LiteratureCarbon Pastes and Carbon Paste ElectrodesCarbon Paste as the Binary MixtureClassification of Carbon Pastes and Carbon Paste ElectrodesConstruction of Carbon Paste HoldersCarbon Paste as the Electrode MaterialPhysicochemical Properties of Carbon PastesElectrochemical Characteristics of Carbon PastesTesting of Unmodified CPEsIntera

  16. Structurally simple complexes of CO2

    OpenAIRE

    Murphy, Luke J.; Katherine N. Robertson; Kemp, Richard A.; Tuononen, Heikki; Clyburne, Jason A. C.

    2015-01-01

    The ability to bind CO2 through the formation of low-energy, easily-broken, bonds could prove invaluable in a variety of chemical contexts. For example, weak bonds to CO2 would greatly decrease the cost of the energy-intensive sorbent-regeneration step common to most carbon capture technologies. Furthermore, exploration of this field could lead to the discovery of novel CO2 chemistry. Reduction of complexed carbon dioxide might generate chemical feedstocks for the preparation of value-added p...

  17. Investigation of the action of irradiation with electrons on the structure and properties of VMN-4 carbon fibers

    International Nuclear Information System (INIS)

    Electron irradiation of VMN-4 carbon fibers in various environments results in structural modification with increased surface roughening, elasticity, strength, and shrinkage. Chemical evolution of water, carbon dioxide, carbon monoxide was found to correlate with complex chemical alteration at the fiber surface. Here, the authors report on the effects of electron irradiation of carbon fibers. Relaxation of the surface after irradiation was also discussed

  18. Pyrolyzed thin film carbon

    Science.gov (United States)

    Tai, Yu-Chong (Inventor); Liger, Matthieu (Inventor); Harder, Theodore (Inventor); Konishi, Satoshi (Inventor); Miserendino, Scott (Inventor)

    2010-01-01

    A method of making carbon thin films comprises depositing a catalyst on a substrate, depositing a hydrocarbon in contact with the catalyst and pyrolyzing the hydrocarbon. A method of controlling a carbon thin film density comprises etching a cavity into a substrate, depositing a hydrocarbon into the cavity, and pyrolyzing the hydrocarbon while in the cavity to form a carbon thin film. Controlling a carbon thin film density is achieved by changing the volume of the cavity. Methods of making carbon containing patterned structures are also provided. Carbon thin films and carbon containing patterned structures can be used in NEMS, MEMS, liquid chromatography, and sensor devices.

  19. RESPONSE OF LEAD SOLUBILITY TO DISSOLVED CARBONATE IN DRINKING WATER

    Science.gov (United States)

    A model is presented showing the detailed response of the theoretical solubility curves for lead to changes in dissolved inorganic carbonate concentration (TIC) and pH at 25 C. Aqueous Pb(II) ion, lead carbonate complexes, lead hydroxide monomers and polymers, and the solids lead...

  20. Explorations of soil microbial processes driven by dissolved organic carbon

    NARCIS (Netherlands)

    Straathof, A.L.

    2015-01-01

    Explorations of soil microbial processes driven by dissolved organic carbon Angela L. Straathof June 17, 2015, Wageningen UR ISBN 978-94-6257-327-7 Abstract Dissolved organic carbon (DOC) is a complex, heterogeneous mixture of C compounds which, as

  1. Using Carbon Emissions Data to "Heat Up" Descriptive Statistics

    Science.gov (United States)

    Brooks, Robert

    2012-01-01

    This article illustrates using carbon emissions data in an introductory statistics assignment. The carbon emissions data has desirable characteristics including: choice of measure; skewness; and outliers. These complexities allow research and public policy debate to be introduced. (Contains 4 figures and 2 tables.)

  2. CARBON NANOTUBES AND PHARMACEUTICAL APPLICATIONS

    Directory of Open Access Journals (Sweden)

    Ram Pavani

    2011-07-01

    Full Text Available Carbon nanotubes (CNTs are often described as a graphene sheet rolled up into the shape of a cylinder. These have fascinated scientists with their extraordinary properties. These compounds have become increasingly popular in various fields simply because of their small size and amazing optical, electric and magnetic properties when used alone or with additions of metals. Carbon nanotubes have potential therapeutic applications in the field of drug delivery, diagnostics, and biosensing. Functionalized carbon nanotubes can also act as vaccine delivery systems.Carbon nanotubes (CNTs are considered to be one of the innovative resources in nanotechnology with possible use in wide range of biomedical applications viz. cancer treatment, bioengineering, cardiac autonomic regulation, platelet activation and tissue regeneration. The effect of CNTs on cells and tissues are extremely important for their use in various complex biological systems. With the increasing interest shown by the nanotechnology research community in this field, it is expected that plenty of applications of CNTs will be explored in future.

  3. Complexity, Metastability and Nonextensivity

    Science.gov (United States)

    Beck, C.; Benedek, G.; Rapisarda, A.; Tsallis, C.

    Work and heat fluctuations in systems with deterministic and stochastic forces / E. G. D. Cohen and R. Van Zon -- Is the entropy S[symbol] extensive or nonextensive? / C. Tsallis -- Superstatistics: recent developments and applications / C. Beck -- Two stories outside Boltzmann-Gibbs statistics: Mori's Q-phase transitions and glassy dynamics at the onset of chaos / A. Robledo, F. Baldovin and E. Mayoral -- Time-averages and the heat theorem / A. Carati -- Fundamental formulae and numerical evidences for the central limit theorem in Tsallis statistics / H. Suyari -- Generalizing the Planck distribution / A. M. C. Soma and C. Tsallis -- The physical roots of complexity: renewal or modulation? / P. Grigolini -- Nonequivalent ensembles and metastability / H. Touchette and R. S. Ellis -- Statistical physics for cosmic structures / L. Pietronero and F. Sylos Labini -- Metastability and anomalous behavior in the HMF model: connections to nonextensive thermodynamics and glassy dynamics / A. Pluchino, A. Rapisarda and V. Latora -- Vlasov analysis of relaxation and meta-equilibrium / C. Anteneodo and R. O. Vallejos -- Weak chaos in large conservative systems - infinite-range coupled standard maps / L. G. Moyano, A. P. Majtey and C. Tsallis -- Deterministc aging / E. Barkai -- Edge of chaos of the classical kicked top map: sensitivity to initial conditions / S. M. Duarte Queirós and C. Tsallis -- What entropy at the edge of chaos? / M. Lissia, M. Coraddu and R. Tonelli -- Fractal growth of carbon schwarzites / G. Benedek ... [et al.] -- Clustering and interface propagation in interacting particle dynamics / A. Provata and V. K. Noussiou -- Resonant activation and noise enhanced stability in Josephson junctions / A. L. Pankratov and B. Spagnolo -- Symmetry breaking induced directed motions / C.-H. Chang and T. Y. Tsong -- General theory of Galilean-invariant entropic lattic Boltzmann models / B. M. Boghosian -- Unifying approach to the jamming transition in granular media and

  4. Wood - a carbon depot

    OpenAIRE

    Lipušček, Igor; Tišler, Vesna

    2003-01-01

    The article examines the global movement of carbon dioxide, the most important greenhouse gas due to its large quantities. We studied the carbon cycle with possibilities of its extension, and analysed the mechanisms that remove carbon dioxide from the atmosphere and bind it into solid substances for a longer period of time. The focus was on carbon dioxide sink into biomass and carbon deposit in wood. On the basis of wood component data and chemical analysis of the components, we calculated th...

  5. Synthesis, spectroscopic characterization and electronic structure of some new Cu(I) carbene complexes

    Indian Academy of Sciences (India)

    Chinnappan Sivasankar; Christina Baskaran; Ashoka G Samuelson

    2006-05-01

    Reaction of oligomeric Cu(I) complexes [Cu{-S-C(=NR)(O-Ar-CH3)}] with Lewis acids gave Cu(I) carbene complexes, which were characterized by 1H and 13C NMR spectroscopy. Cu(I) carbene complexes could be directly generated from RNCS, Cu(I)-OAr and Lewis acids; this method can be used to prepare Cu(I) carbene complexes with different substitutents on the carbene carbon. The complexes were unreactive towards olefins and do not undergo cyclopropanation. Electronic structure calculations (DFT) show that the charge on the carbene carbon plays an important role in controlling the reactivity of the carbene complex.

  6. Immobilized Ruthenium Catalyst for Carbon Dioxide Hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Ying Min YU; Jin Hua FEI; Yi Ping ZHANG; Xiao Ming ZHENG

    2006-01-01

    Three kinds of cross linked polystyrene resin (PS) supported ruthenium complexes were developed as catalysts for the synthesis of formic acid from carbon dioxide hydrogenation. Many factors, such as the functionalized supports, solvents and ligands, could influence their activities and reuse performances greatly. These immobilized catalysts also offer the industrial advantages such as easy separation.

  7. Hydrothermal carbonization of municipal waste streams

    Science.gov (United States)

    Hydrothermal carbonization (HTC) is a novel thermal conversion process that can be used to convert municipal waste streams into sterilized, value-added hydrochar. HTC has been mostly applied and studied on a limited number of feedstocks, ranging from pure substances to slightly more complex biomass ...

  8. High frequency conductivity in carbon nanotubes

    Directory of Open Access Journals (Sweden)

    S. S. Abukari

    2012-12-01

    Full Text Available We report on theoretical analysis of high frequency conductivity in carbon nanotubes. Using the kinetic equation with constant relaxation time, an analytical expression for the complex conductivity is obtained. The real part of the complex conductivity is initially negative at zero frequency and become more negative with increasing frequency, until it reaches a resonance minimum at ω ∼ ωB for metallic zigzag CNs and ω < ωB for armchair CNs. This resonance enhancement is indicative for terahertz gain without the formation of current instabilities induced by negative dc conductivity. We noted that due to the high density of states of conduction electrons in metallic zigzag carbon nanotubes and the specific dispersion law inherent in hexagonal crystalline structure result in a uniquely high frequency conductivity than the corresponding values for metallic armchair carbon nanotubes. We suggest that this phenomenon can be used to suppress current instabilities that are normally associated with a negative dc differential conductivity.

  9. ELECTROCHEMICAL PROPERTIES OF NANOPOROUS CARBON ELECTRODES

    Directory of Open Access Journals (Sweden)

    P.Nigu

    2002-01-01

    Full Text Available Electrical double layer and electrochemical characteristics at the nanoporous carbon | (C2H54NBF4 + acetonitrile interface have been studied by the cyclic voltammetry and impedance spectroscopy methods. The value of zero charge potential (0.23 V vs. SCE in H2O, the region of ideal polarizability and other characteristics have been established. Analysis of complex plane plots shows that the nanoporous carbon | x M (C2H54NBF4 + acetonitrile interface can be simulated by the equivalent circuit, in which the two parallel conduction parts in the solid and liquid phases are interconnected by the double layer capacitance in parallel with the complex admittance of hindered reaction of the charge transfer process. The values of the characteristic frequency depend on the electrolyte concentration and on the electrode potential, i.e. on the nature of ions adsorbed at the surface of nanoporous carbon electrode.

  10. Escaping carbon lock-in

    Energy Technology Data Exchange (ETDEWEB)

    Unruh, G.C. [Instituto de Empresa, Madrid (Spain)

    2002-03-01

    This article explores the climate policy implications of the arguments made in ''Understanding carbon lock-in'' (Unruh, 2000), which posited that industrial countries have become locked-into fossil fuel-based energy systems through path dependent processes driven by increasing returns to scale. Carbon lock-in arises through technological, organizational, social and institutional co-evolution, ''culminating'' in what was termed as techno-institutional complex (TIC). In order to resolve the climate problem, an escape from the lock-in condition is required. However, due to the self-referential nature of TIC, escape conditions are unlikely to be generated internally and it is argued here that erogenous forces are probably required. (author)

  11. Catalytic Coupling of Carbon Dioxide with Terpene Scaffolds: Access to Challenging Bio-Based Organic Carbonates.

    Science.gov (United States)

    Fiorani, Giulia; Stuck, Moritz; Martín, Carmen; Belmonte, Marta Martínez; Martin, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

    2016-06-01

    The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway. PMID:27159151

  12. Probing carbon coatings on nanoparticle decorated carbon nanotubes by scanning transmission X-ray microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ming; Gao, Jing; Bai, Lili; Pu, Aiwu; Liu, Jinyin; Zhao, Guanqi; Sun, Xuhui; Zhong, Jun, E-mail: jzhong@suda.edu.cn

    2013-11-15

    Two kinds of carbon coating on carbon nanotubes (CNTs) after decoration with nanoparticles were observed by scanning transmission X-ray microscopy with a concurrent characterization of the electronic structure, revealing the complex compositions in CNTs after chemical modification. Moreover, a sandwich structure shown as CNT-nanoparticle-coating can be created with the exposure to X-ray for CNTs decorated with nanoparticle outside the wall. The coating shows an effective way for site-selective modification of CNTs with various carbon structures.

  13. Atomic resolution studies of carbonic anhydrase II

    International Nuclear Information System (INIS)

    The structure of human carbonic anhydrase II has been solved with a sulfonamide inhibitor at 0.9 Å resolution. Structural variation and flexibility is seen on the surface of the protein and is consistent with the anisotropic ADPs obtained from refinement. Comparison with 13 other atomic resolution carbonic anhydrase structures shows that surface variation exists even in these highly ordered isomorphous crystals. Carbonic anhydrase has been well studied structurally and functionally owing to its importance in respiration. A large number of X-ray crystallographic structures of carbonic anhydrase and its inhibitor complexes have been determined, some at atomic resolution. Structure determination of a sulfonamide-containing inhibitor complex has been carried out and the structure was refined at 0.9 Å resolution with anisotropic atomic displacement parameters to an R value of 0.141. The structure is similar to those of other carbonic anhydrase complexes, with the inhibitor providing a fourth nonprotein ligand to the active-site zinc. Comparison of this structure with 13 other atomic resolution (higher than 1.25 Å) isomorphous carbonic anhydrase structures provides a view of the structural similarity and variability in a series of crystal structures. At the center of the protein the structures superpose very well. The metal complexes superpose (with only two exceptions) with standard deviations of 0.01 Å in some zinc–protein and zinc–ligand bond lengths. In contrast, regions of structural variability are found on the protein surface, possibly owing to flexibility and disorder in the individual structures, differences in the chemical and crystalline environments or the different approaches used by different investigators to model weak or complicated electron-density maps. These findings suggest that care must be taken in interpreting structural details on protein surfaces on the basis of individual X-ray structures, even if atomic resolution data are available

  14. Accelerating Mineral Carbonation Using Carbonic Anhydrase.

    Science.gov (United States)

    Power, Ian M; Harrison, Anna L; Dipple, Gregory M

    2016-03-01

    Carbonic anhydrase (CA) enzymes have gained considerable attention for their potential use in carbon dioxide (CO2) capture technologies because they are able to catalyze rapidly the interconversion of aqueous CO2 and bicarbonate. However, there are challenges for widespread implementation including the need to develop mineralization process routes for permanent carbon storage. Mineral carbonation of highly reactive feedstocks may be limited by the supply rate of CO2. This rate limitation can be directly addressed by incorporating enzyme-catalyzed CO2 hydration. This study examined the effects of bovine carbonic anhydrase (BCA) and CO2-rich gas streams on the carbonation rate of brucite [Mg(OH)2], a highly reactive mineral. Alkaline brucite slurries were amended with BCA and supplied with 10% CO2 gas while aqueous chemistry and solids were monitored throughout the experiments (hours to days). In comparison to controls, brucite carbonation using BCA was accelerated by up to 240%. Nesquehonite [MgCO3·3H2O] precipitation limited the accumulation of hydrated CO2 species, apparently preventing BCA from catalyzing the dehydration reaction. Geochemical models reproduce observed reaction progress in all experiments, revealing a linear correlation between CO2 uptake and carbonation rate. Data demonstrates that carbonation in BCA-amended reactors remained limited by CO2 supply, implying further acceleration is possible. PMID:26829491

  15. Carbon fuel cells with carbon corrosion suppression

    Science.gov (United States)

    Cooper, John F.

    2012-04-10

    An electrochemical cell apparatus that can operate as either a fuel cell or a battery includes a cathode compartment, an anode compartment operatively connected to the cathode compartment, and a carbon fuel cell section connected to the anode compartment and the cathode compartment. An effusion plate is operatively positioned adjacent the anode compartment or the cathode compartment. The effusion plate allows passage of carbon dioxide. Carbon dioxide exhaust channels are operatively positioned in the electrochemical cell to direct the carbon dioxide from the electrochemical cell.

  16. Second Quantized Kolmogorov Complexity

    OpenAIRE

    Rogers, Caroline; Vedral, Vlatko; Nagarajan, Rajagopal

    2008-01-01

    The Kolmogorov complexity of a string is the length of its shortest description. We define a second quantised Kolmogorov complexity where the length of a description is defined to be the average length of its superposition. We discuss this complexity's basic properties. We define the corresponding prefix complexity and show that the inequalities obeyed by this prefix complexity are also obeyed by von Neumann entropy.

  17. Complex Multiplicative Calculus

    OpenAIRE

    Bashirov, Agamirza; Riza, Mustafa

    2011-01-01

    In the present paper we extend the concepts of multiplicative de- rivative and integral to complex-valued functions of complex variable. Some drawbacks, arising with these concepts in the real case, are explained satis- factorily. Properties of complex multiplicative derivatives and integrals are studied. In particular, the fundamental theorem of complex multiplicative calculus, relating these concepts, is proved. It is shown that complex multi- plicative calculus is not just another realizat...

  18. Modelling carbon overconsumption and the formation of extracellular particulate organic carbon

    Directory of Open Access Journals (Sweden)

    M. Schartau

    2007-01-01

    Full Text Available During phytoplankton growth a fraction of dissolved inorganic carbon (DIC assimilated by phytoplankton is exuded in the form of dissolved organic carbon (DOC, which can be transformed into extracellular particulate organic carbon (POC. A major fraction of extracellular POC is associated with carbon of transparent exopolymer particles (TEP; carbon content = TEPC that form from dissolved polysaccharides (PCHO. The exudation of PCHO is linked to an excessive uptake of DIC that is not directly quantifiable from utilisation of dissolved inorganic nitrogen (DIN, called carbon overconsumption. Given these conditions, the concept of assuming a constant stoichiometric carbon-to-nitrogen (C:N ratio for estimating new production of POC from DIN uptake becomes inappropriate. Here, a model of carbon overconsumption is analysed, combining phytoplankton growth with TEPC formation. The model describes two modes of carbon overconsumption. The first mode is associated with DOC exudation during phytoplankton biomass accumulation. The second mode is decoupled from algal growth, but leads to a continuous rise in POC while particulate organic nitrogen (PON remains constant. While including PCHO coagulation, the model goes beyond a purely physiological explanation of building up carbon rich particulate organic matter (POM. The model is validated against observations from a mesocosm study. Maximum likelihood estimates of model parameters, such as nitrogen- and carbon loss rates of phytoplankton, are determined. The optimisation yields results with higher rates for carbon exudation than for the loss of organic nitrogen. It also suggests that the PCHO fraction of exuded DOC was 63±20% during the mesocosm experiment. Optimal estimates are obtained for coagulation kernels for PCHO transformation into TEPC. Model state estimates are consistent with observations, where 30% of the POC increase was attributed to TEPC formation. The proposed model is of low complexity and is

  19. Modelling carbon overconsumption and the formation of extracellular particulate organic carbon

    Directory of Open Access Journals (Sweden)

    C. Völker

    2007-07-01

    Full Text Available During phytoplankton growth a fraction of dissolved inorganic carbon (DIC assimilated by phytoplankton is exuded in the form of dissolved organic carbon (DOC, which can be transformed into extracellular particulate organic carbon (POC. A major fraction of extracellular POC is associated with carbon of transparent exopolymer particles (TEP; carbon content = TEPC that form from dissolved polysaccharides (PCHO. The exudation of PCHO is linked to an excessive uptake of DIC that is not directly quantifiable from utilisation of dissolved inorganic nitrogen (DIN, called carbon overconsumption. Given these conditions, the concept of assuming a constant stoichiometric carbon-to-nitrogen (C:N ratio for estimating new production of POC from DIN uptake becomes inappropriate. Here, a model of carbon overconsumption is analysed, combining phytoplankton growth with TEPC formation. The model describes two modes of carbon overconsumption. The first mode is associated with DOC exudation during phytoplankton biomass accumulation. The second mode is decoupled from algal growth, but leads to a continuous rise in POC while particulate organic nitrogen (PON remains constant. While including PCHO coagulation, the model goes beyond a purely physiological explanation of building up carbon rich particulate organic matter (POM. The model is validated against observations from a mesocosm study. Maximum likelihood estimates of model parameters, such as nitrogen- and carbon loss rates of phytoplankton, are determined. The optimisation yields results with higher rates for carbon exudation than for the loss of organic nitrogen. It also suggests that the PCHO fraction of exuded DOC was 63±20% during the mesocosm experiment. Optimal estimates are obtained for coagulation kernels for PCHO transformation into TEPC. Model state estimates are consistent with observations, where 30% of the POC increase was attributed to TEPC formation. The proposed model is of low complexity and is

  20. Complex networks analysis of language complexity

    CERN Document Server

    Amancio, Diego R; Oliveira, Osvaldo N; Costa, Luciano da F; 10.1209/0295-5075/100/58002

    2013-01-01

    Methods from statistical physics, such as those involving complex networks, have been increasingly used in quantitative analysis of linguistic phenomena. In this paper, we represented pieces of text with different levels of simplification in co-occurrence networks and found that topological regularity correlated negatively with textual complexity. Furthermore, in less complex texts the distance between concepts, represented as nodes, tended to decrease. The complex networks metrics were treated with multivariate pattern recognition techniques, which allowed us to distinguish between original texts and their simplified versions. For each original text, two simplified versions were generated manually with increasing number of simplification operations. As expected, distinction was easier for the strongly simplified versions, where the most relevant metrics were node strength, shortest paths and diversity. Also, the discrimination of complex texts was improved with higher hierarchical network metrics, thus point...

  1. Preliminary research on movement regularity of fine carbon fiber powder injected into intracrania of mice

    Institute of Scientific and Technical Information of China (English)

    FEI Ke-xiang; LI Guo-wei; GONG Ti; WANG Hong; PENG Xian-gao; GAO Lin; Zhang Yan-xiang; LIU Lian-tao

    2001-01-01

    @@ The carbon fiber and carbon fiber for complex materials implanted have been applied to the clinic medicine, in which they are served as the materials for repairing tissues and organs as well as the materials of artificial tissuesand organs. The carbon fiber also acts as the surrogate of extracellular matrix in the study of tissue engineering tendon,and so on.

  2. Multiscale Modeling with Carbon Nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Maiti, A

    2006-02-21

    Technologically important nanomaterials come in all shapes and sizes. They can range from small molecules to complex composites and mixtures. Depending upon the spatial dimensions of the system and properties under investigation computer modeling of such materials can range from equilibrium and nonequilibrium Quantum Mechanics, to force-field-based Molecular Mechanics and kinetic Monte Carlo, to Mesoscale simulation of evolving morphology, to Finite-Element computation of physical properties. This brief review illustrates some of the above modeling techniques through a number of recent applications with carbon nanotubes: nano electromechanical sensors (NEMS), chemical sensors, metal-nanotube contacts, and polymer-nanotube composites.

  3. Air/Water-Stable Tridentate NHC-PdII Complex; Catalytic C-H Activation of Hydrocarbons via H/D Exchange Process in D2O

    OpenAIRE

    Lee, Joo Ho; Yoo, Kyung Soo; Park, Chan Pil; Olsen, Janet M.; Sakaguchi, Satoshi; Surya Prakash, G. K.; Mathew, Thomas; Jung, Kyung Woon

    2009-01-01

    While developing novel catalysts for carbon-carbon or carbon-heteroatom coupling (N, O, or F), we were able to introduce tridentate NHC-amidate-alkoxide palladium(II) complexes. In aqueous solution, these NHC-Pd(II) complexes showed high ability for C-H activation of various hydrocarbons (cyclohexane, cyclopentane, dimethyl ether, THF, acetone, and toluene) under mild conditions.

  4. Carbon Nanomaterials for Road Construction

    Directory of Open Access Journals (Sweden)

    Zaporotskova Irina Vladimirovna

    2015-05-01

    Full Text Available The requirement of developing and modernizing the roads in Russia and in the Volgograd region in particular, is based on need of expanding the directions of scientific research on road and transport complexes. They have to be aimed at the development of the theory of transport streams, traffic safety increase, and, first of all, at the application of original methods of road development and modernization, introduction of modern technologies and road-building materials.On the basis of the analysis of the plans for transportation sphere development in the Volgograd region assuming the need to apply the new technologies allowing to create qualitative paving, the authors propose the technology of creating a heavy-duty paving with the use of carbon nanomaterial. The knowledge on strengthening the characteristics of carbon nanotubes is a unique material for nanotechnology development which allowed to assume the analysis of general information about asphalt concrete. The analysis showed that carbon nanotubes can be used for improvement of operational characteristics of asphalt concrete, and it is possible to carry out additives of nanotubes in hot as well as in cold bitumen. The article contains the basic principles of creation of the new road material received by means of bitumen reinforcing by carbon nanotubes. The structures received by the offered technique binding on the basis of the bitumens modified by carbon nanomaterial can be used for coverings and bases on highways of all categories in all road and climatic zones of Russia. The technical result consists in increasing the durability and elasticity of the received asphalt covering, and also the increase of water resistance, heat resistance and frost resistance, the expansion of temperature range of its laying in the field of negative temperatures.

  5. Exploring the uranyl organometallic chemistry: from single to double uranium carbon bonds

    International Nuclear Information System (INIS)

    Uranyl organometallic complexes featuring uranium(VI) carbon single and double bonds have been obtained from uranyl UO2X2 precursors by avoiding reduction of the metal center. X-ray diffraction and density functional theory analyses of these complexes showed that the UC and UdC bonds are polarized toward the nucleophilic carbon. (authors)

  6. Thorium oxide dissolution kinetics for hydroxide and carbonate complexation

    International Nuclear Information System (INIS)

    The purpose of this project was to determine the kinetics and thermodynamics of thorium oxide dissolution in the environment. Solubility is important because it establishes an upper concentration limit on the concentration of a dissolved radionuclide in solution L1. While understanding the behavior of thorium fuels in the proposed repository at Yucca Mountain is most applicable, a more rigorous study of thorium solubility over a wide pH range was performed so that the data could also be used to model the behavior of thorium fuels in any environmental system. To achieve this, the kinetics and thermodynamics of thorium oxide dissolution under both pure argon and argon with PCO2 of 0. 1 were studied under the full pH range available in each atmosphere. In addition, thorium oxide powder remnants were studied after each experiment to examine structural changes that may affect kinetics

  7. Solvent extraction of carbonate complexes of rare earths

    International Nuclear Information System (INIS)

    Extraction of rare earth elements of yttrium subgroup from KHCO3 solutions with solutions of primary alkylamines (C10-C14) in CCl4 with the addition of propanole is investigated using holmium and ytterbium as an example. Using the methods of IR, PRM spectroscopy and chemical analysis of the saturated organic phase associates composition is studied. The simplest extarcted compounds can be presented with the formulas: n-C3H7OH x (C12H25NH3)7 [OH(CO3)5] and n-C3H7OH x bH2O(C12H25NH3)5 [Yb(CO3)4 x (Csub(3)Hsub(7)OH)sub(x)]. In holmium associate carbonatogroup is coordinated mainly according to bidentate type and in ytterbium associate - according to monodentate type. Moleculas of propyl alcohol are included in the coordination sphere of ytterbium associate

  8. Carbon nanotube cathode with capping carbon nanosheet

    Science.gov (United States)

    Li, Xin; Zhao, Dengchao; Pang, Kaige; Pang, Junchao; Liu, Weihua; Liu, Hongzhong; Wang, Xiaoli

    2013-10-01

    Here, we report a vertically aligned carbon nanotube (VACNT) film capped with a few layer of carbon nanosheet (FLCN) synthesized by chemical vapor deposition using a carbon source from iron phthalocyanine pyrolysis. The square resistance of the VACNT film is significantly reduced from 1500 Ω/□ to 300 Ω/□ when it is capped with carbon nanosheet. The VACNT capped with carbon nanosheet was transferred to an ITO glass substrate in an inverted configuration so that the carbon nanosheet served as a flexible transparent electrode at the bottom and the VACNT roots served as emission tips. Because all of the VACNTs start growing from a flat silicon substrate, the VACNT roots are very neat and uniform in height. A field emission test of the carbon nanosheet-capped VACNT film proved that the CNT roots show better uniformity in field emission and the carbon nanosheet cap could also potentially serve as a flexible transparent electrode, which is highly desired in photo-assisted field emission.

  9. Catalytic hydrogenation of carbon monoxide

    International Nuclear Information System (INIS)

    Focus of this project is on developing new approaches for hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. The strategies to accomplish CO reduction are based on favorable thermodynamics manifested by rhodium macrocycles for producing a series of intermediates implicated in the catalytic hydrogenation of CO. Metalloformyl complexes from reactions of H2 and CO, and CO reductive coupling to form metallo α-diketone species provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics are promising candidates for future development

  10. Trading forest carbon - OSU

    Science.gov (United States)

    Issues associate with trading carbon sequestered in forests are discussed. Scientific uncertainties associated with carbon measurement are discussed with respect to proposed accounting procedures. Major issues include: (1) Establishing baselines. (2) Determining additivity from f...

  11. Potassium carbonate poisoning

    Science.gov (United States)

    Potassium carbonate is a white powder used to make soap, glass, and other items. This article discusses poisoning from swallowing or breathing in potassium carbonate. This article is for information only. Do ...

  12. Sodium carbonate poisoning

    Science.gov (United States)

    Sodium carbonate (known as washing soda or soda ash) is a chemical found in many household and ... products. This article focuses on poisoning due to sodium carbonate. This article is for information only. Do ...

  13. Biomass Carbon Stock

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Biomass carbon includes carbon stored in above- and below-ground live plant components (such as leaf, branch, stem and root) as well as in standing and down dead...

  14. Carbon Monoxide Information Center

    Medline Plus

    Full Text Available ... Home / Safety Education / Safety Education Centers En Español Carbon Monoxide Information Center The Invisible Killer Carbon monoxide, also known as CO, is called the "Invisible ...

  15. Carbon Monoxide Safety

    Science.gov (United States)

    ... with the Media Fire Protection Technology Carbon monoxide safety outreach materials Help inform residents in your community ... KB | Spanish PDF 645 KB Handout: carbon monoxide safety Download this handout and add your organization's logo ...

  16. Soil Organic Carbon Stock

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Soil organic carbon (SOC) is the carbon held within soil organic constituents (i.e., products produced as dead plants and animals decompose and the soil microbial...

  17. Carbon Monoxide Information Center

    Medline Plus

    Full Text Available ... Education / Safety Education Centers En Español Carbon Monoxide Information Center The Invisible Killer Carbon monoxide, also known ... Install one and check its batteries regularly. View Information About CO Alarms Other CO Topics Safety Tips ...

  18. Calcium carbonate overdose

    Science.gov (United States)

    Tums overdose; Calcium overdose ... Calcium carbonate can be dangerous in large amounts. ... Some products that contain calcium carbonate are certain: ... and mineral supplements Other products may also contain calcium ...

  19. Carbon nanotube nanoelectrode arrays

    Science.gov (United States)

    Ren, Zhifeng; Lin, Yuehe; Yantasee, Wassana; Liu, Guodong; Lu, Fang; Tu, Yi

    2008-11-18

    The present invention relates to microelectode arrays (MEAs), and more particularly to carbon nanotube nanoelectrode arrays (CNT-NEAs) for chemical and biological sensing, and methods of use. A nanoelectrode array includes a carbon nanotube material comprising an array of substantially linear carbon nanotubes each having a proximal end and a distal end, the proximal end of the carbon nanotubes are attached to a catalyst substrate material so as to form the array with a pre-determined site density, wherein the carbon nanotubes are aligned with respect to one another within the array; an electrically insulating layer on the surface of the carbon nanotube material, whereby the distal end of the carbon nanotubes extend beyond the electrically insulating layer; a second adhesive electrically insulating layer on the surface of the electrically insulating layer, whereby the distal end of the carbon nanotubes extend beyond the second adhesive electrically insulating layer; and a metal wire attached to the catalyst substrate material.

  20. Adaptive evolution of complex innovations through stepwise metabolic niche expansion.

    Science.gov (United States)

    Szappanos, Balázs; Fritzemeier, Jonathan; Csörgő, Bálint; Lázár, Viktória; Lu, Xiaowen; Fekete, Gergely; Bálint, Balázs; Herczeg, Róbert; Nagy, István; Notebaart, Richard A; Lercher, Martin J; Pál, Csaba; Papp, Balázs

    2016-01-01

    A central challenge in evolutionary biology concerns the mechanisms by which complex metabolic innovations requiring multiple mutations arise. Here, we propose that metabolic innovations accessible through the addition of a single reaction serve as stepping stones towards the later establishment of complex metabolic features in another environment. We demonstrate the feasibility of this hypothesis through three complementary analyses. First, using genome-scale metabolic modelling, we show that complex metabolic innovations in Escherichia coli can arise via changing nutrient conditions. Second, using phylogenetic approaches, we demonstrate that the acquisition patterns of complex metabolic pathways during the evolutionary history of bacterial genomes support the hypothesis. Third, we show how adaptation of laboratory populations of E. coli to one carbon source facilitates the later adaptation to another carbon source. Our work demonstrates how complex innovations can evolve through series of adaptive steps without the need to invoke non-adaptive processes. PMID:27197754

  1. Metal filled porous carbon

    Science.gov (United States)

    Gross, Adam F.; Vajo, John J.; Cumberland, Robert W.; Liu, Ping; Salguero, Tina T.

    2011-03-22

    A porous carbon scaffold with a surface and pores, the porous carbon scaffold containing a primary metal and a secondary metal, where the primary metal is a metal that does not wet the surface of the pores of the carbon scaffold but wets the surface of the secondary metal, and the secondary metal is interspersed between the surface of the pores of the carbon scaffold and the primary metal.

  2. Quantitative analysis of complexes in electron irradiated CZ silicon

    International Nuclear Information System (INIS)

    Complexes in helium or electron irradiated silicon are quantitatively analyzed by highly sensitive and accurate infrared (IR) absorption spectroscopy. Carbon concentration (1x1015-1x1017 cm-3) and helium dose (5x1012-5x1013 cm-2) or electron dose (1x1015-1x1017 cm-2) are changed by two orders of magnitude in relatively low regime compared to the previous works. It is demonstrated that the carbon-related complex in low carbon concentration silicon of commercial grade with low electron dose can be detected clearly. Concentration of these complexes is estimated. It is clarified that the complex configuration and thermal behavior in low carbon and low dose samples is simple and almost confined within the individual complex family compared to those in high concentration and high dose samples. Well-established complex behavior in electron-irradiated sample is compared to that in He-irradiated samples, obtained by deep level transient spectroscopy (DLTS) or cathodoluminescence (CL), which had close relation to the Si power device performance

  3. Science Letters: Nitrogen doping of activated carbon loading Fe2O3 and activity in carbon-nitric oxide reaction

    Institute of Scientific and Technical Information of China (English)

    WAN Xian-kai; ZOU Xue-quan; SHI Hui-xiang; WANG Da-hui

    2007-01-01

    Nitrogen doping of activated carbon loading Fe2O3 was performed by annealing in ammonia, and the activity of the modified carbon for NO reduction was studied in the presence of oxygen. Results show that Fe2O3 enhances the amount of surface oxygen complexes and facilitates nitrogen incorporation in the carbon, especially in the form of pyridinic nitrogen. The modified carbon shows excellent activity for NO reduction in the low temperature regime (<500 ℃) because of the cooperative effect of Fe2O3 and the surface nitrogen species.

  4. CARBONATE METHOD OF SEPARATION OF TETRAVALENT PLUTONIUM FROM FISSION PRODUCT VALUES

    Science.gov (United States)

    Duffield, R.B.; Stoughton, R.W.

    1959-02-01

    It has been found that plutonium forms an insoluble precipitate with carbonate ion when the carbonate ion is present in stoichiometric proportions, while an excess of the carbonate ion complexes plutonium and renders it soluble. A method for separating tetravalent plutonium from lanthanum-group rare earths has been based on this discovery, since these rare earths form insoluble carbonates in approximately neutral solutions. According to the process the pH is adjusted to between 5 and 7, and approximately stoichiometric amounts of carbonate ion are added to the solution causing the formation of a precipitate of plutonium carbonate and the lanthanum-group rare earth carbonates. The precipitate is then separated from the solution and contacted with a carbonate solution of a concentration between 1 M and 3 M to complex and redissolve the plutonium precipitate, and thus separate it from the insoluble rare earth precipitate.

  5. Protolytic carbon film technology

    Energy Technology Data Exchange (ETDEWEB)

    Renschler, C.L.; White, C.A.

    1996-04-01

    This paper presents a technique for the deposition of polyacrylonitrile (PAN) on virtually any surface allowing carbon film formation with only the caveat that the substrate must withstand carbonization temperatures of at least 600 degrees centigrade. The influence of processing conditions upon the structure and properties of the carbonized film is discussed. Electrical conductivity, microstructure, and morphology control are also described.

  6. Carbon Goes To…

    Science.gov (United States)

    Savasci, Funda

    2014-01-01

    The purposes of this activity are to help middle school students understand the carbon cycle and realize how human activities affect the carbon cycle. This activity consists of two parts. The first part of the activity focuses on the carbon cycle, especially before the Industrial Revolution, while the second part of the activity focuses on how…

  7. Carbon/Carbon Pistons for Internal Combustion Engines

    Science.gov (United States)

    Taylor, A. H.

    1986-01-01

    Carbon/carbon piston performs same function as aluminum pistons in reciprocating internal combustion engines while reducing weight and increasing mechanical and thermal efficiencies of engine. Carbon/carbon piston concept features low piston-to-cylinder wall clearance - so low piston rings and skirts unnecessary. Advantages possible by negligible coefficient of thermal expansion of carbon/carbon.

  8. Vincristine Lipid Complex Injection

    Science.gov (United States)

    Vincristine lipid complex is used to treat a certain type of acute lymphoblastic leukemia (ALL; a type ... at least two different treatments with other medications. Vincristine lipid complex is in a class of medications ...

  9. Curve complexes are rigid

    OpenAIRE

    Rafi, Kasra; Schleimer, Saul

    2007-01-01

    Any quasi-isometry of the complex of curves is bounded distance from a simplicial automorphism. As a consequence, the quasi-isometry type of the curve complex determines the homeomorphism type of the surface.

  10. Complexity An Introduction

    CERN Document Server

    Parwani, R R

    2002-01-01

    This article summarises a Web-book on "Complexity" that was developed to introduce undergraduate students to interesting complex systems in the biological, physical and social sciences, and the common tools, principles and concepts used for their study.

  11. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  12. Quantum Communication Complexity

    OpenAIRE

    Klauck, Hartmut

    2000-01-01

    This paper surveys the field of quantum communication complexity. Some interesting recent results are collected concerning relations to classical communication, lower bound methods, one-way communication, and applications of quantum communication complexity.

  13. Irinotecan Lipid Complex Injection

    Science.gov (United States)

    Irinotecan lipid complex is used in combination with other medications to treat pancreatic cancer that has spread to other parts of ... after treatment with other chemotherapy medications. Irinotecan lipid complex is in a class of antineoplastic medications called ...

  14. Vincristine Lipid Complex Injection

    Science.gov (United States)

    Vincristine lipid complex is used to treat a certain type of acute lymphoblastic leukemia (ALL; a type of cancer of the ... two different treatments with other medications. Vincristine lipid complex is in a class of medications called vinca ...

  15. Doxorubicin Lipid Complex Injection

    Science.gov (United States)

    Doxorubicin lipid complex is used to treat ovarian cancer that has not improved or that has worsened after treatment with other medications. Doxorubicin lipid complex is also used to treat Kaposi's sarcoma (a ...

  16. Mycobacterium Avium Complex (MAC)

    Science.gov (United States)

    ... Select a Language: Fact Sheet 514 Mycobacterium Avium Complex (MAC) WHAT IS MAC? HOW DO I KNOW ... THE BOTTOM LINE WHAT IS MAC? Mycobacterium Avium Complex (MAC) is a serious illness caused by common ...

  17. Cytarabine Lipid Complex Injection

    Science.gov (United States)

    Cytarabine lipid complex is used to treat lymphomatous meningitis (a type of cancer in the covering of the spinal cord and brain). Cytarabine lipid complex is in a class of medications called antimetabolites. ...

  18. Evolution of biological complexity

    OpenAIRE

    Adami, Christoph; Ofria, Charles; Collier, Travis C.

    2000-01-01

    In order to make a case for or against a trend in the evolution of complexity in biological evolution, complexity needs to be both rigorously defined and measurable. A recent information-theoretic (but intuitively evident) definition identifies genomic complexity with the amount of information a sequence stores about its environment. We investigate the evolution of genomic complexity in populations of digital organisms and monitor in detail the evolutionary transitions that increase complexit...

  19. ACTIVATED CARBON FROM LIGNITE FOR WATER TREATMENT

    Energy Technology Data Exchange (ETDEWEB)

    Edwin S. Olson; Daniel J. Stepan

    2000-07-01

    High concentrations of humate in surface water result in the formation of excess amounts of chlorinated byproducts during disinfection treatment. These precursors can be removed in water treatment prior to disinfection using powdered activated carbon. In the interest of developing a more cost-effective method for removal of humates in surface water, a comparison of the activities of carbons prepared from North Dakota lignites with those of commercial carbons was conducted. Previous studies indicated that a commercial carbon prepared from Texas lignite (Darco HDB) was superior to those prepared from bituminous coals for water treatment. That the high alkali content of North Dakota lignites would result in favorable adsorptive properties for the very large humate molecules was hypothesized, owing to the formation of larger pores during activation. Since no standard humate test has been previously developed, initial adsorption testing was performed using smaller dye molecules with various types of ionic character. With the cationic dye, methylene blue, a carbon prepared from a high-sodium lignite (HSKRC) adsorbed more dye than the Darco HDB. The carbon from the low-sodium lignite was much inferior. With another cationic dye, malachite green, the Darco HDB was slightly better. With anionic dyes, methyl red and azocarmine-B, the results for the HSKRC and Darco HDB were comparable. A humate test was developed using Aldrich humic acid. The HSKRC and the Darco HDB gave equally high adsorption capacities for the humate (138 mg/g), consistent with the similarities observed in earlier tests. A carbon prepared from a high-sodium lignite from a different mine showed an outstanding improvement (201 mg/g). The carbons prepared from the low-sodium lignites from both mines showed poor adsorption capacities for humate. Adsorption isotherms were performed for the set of activated carbons in the humate system. These exhibited a complex behavior interpreted as resulting from two types

  20. Complexity Near Horizons

    CERN Document Server

    Halyo, Edi

    2015-01-01

    We generalize the concept of complexity near horizons to all nondegenerate black holes. For Schwarzschild black holes, we show that Rindler observers see a complexity change of $S$ during proper time $1/\\kappa$ which corresponds to the creation of a causal patch with proper length $1/\\kappa$ inside the horizon. We attempt to describe complexity in the horizon CFT and the Euclidean picture.