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Sample records for equatorial carbonyl ligand

  1. Carbonyl complexes of rhodium with N-donor ligands: factors determining the formation of terminal versus bridging carbonyls

    NARCIS (Netherlands)

    Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.

    2010-01-01

    Cationic rhodium carbonyl complexes supported by a series of different N-3- and N-4-donor ligands were prepared, and their ability to form carbonyl-bridged species was evaluated. Complex [Rh(K3-bpa)(cod)r (1(+)) (bpa = bis(2-picolyBamine, cod = cis,cis-1,5-cyclooctadiene) reacts with I bar of CO to

  2. Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand.

    Science.gov (United States)

    Tatikonda, Rajendhraprasad; Haukka, Matti

    2017-04-01

    Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

  3. Selective transformation of carbonyl ligands to organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A.R.

    1992-05-12

    Studies on the carbonylation of ({eta}{sup 5}-indenyl)(L)(CO)Ru-R complexes (L = CO, PPh{sub 3}; R = CH{sub 2}OMe, CH{sub 3}) have been completed. Particularly noteworthy is that the methoxymethyl complexes readily transform to their acyl derivatives under mild conditions that leave their iron congeners inert towards CO. Surprisingly, even ({eta}{sup 5}-indenyl)(PPh{sub 3}){sub 2}Ru-CH{sub 3} carbonylates and gives ({eta}{sup 5}-indenyl)(PPh{sub 3})(CO)Ru-C(O)CH{sub 3}. Mechanistic studies on the non catalyzed'' hydrosilation of the manganese acyls (CO){sub 5}Mn-C(O)CH{sub 2}R (R = H, OCH{sub 3}, CH{sub 3}) with Et{sub 3}SiH and of cobalt acetyls (CO){sub 3}(PR{sub 3})CoC(O)CH{sub 3} with several monohydrosilanes have been completed. The cobalt acetyls cleanly give ethoxysilanes (not acetaldehyde), and the manganese acyls provide {alpha}-siloxyvinyl complexes Z-(CO){sub 5}Mn-C(OSiEt{sub 3})=CHR (R = H, CH{sub 3}, OCH{sub 3}). Carbonylation and protolytic cleavage of the latter generate pyruvoyl complexes (CO){sub 5}Mn-COCOR (R = CH{sub 3}, CH{sub 2}CH{sub 3}), formally the products of net double carbonylation'' sequences. Studies in progress are concerned with how manganese complexes as diverse as (CO){sub 5}Mn-Y (Y = C(O)R, R, BR - but not SiMe{sub 3} or Mn(CO){sub 5}) and ({eta}{sup 3}-C{sub 3}H{sub 5})Mn(CO){sub 2}L (but not CpMn(CO){sub 3} or CpMn(CO){sub 2}({eta}{sup 2}HSiR{sub 3})) function as efficient hydrosilation catalysts towards Cp(CO){sub 2}FeC(O)CH{sub 3}, for example. These reactions cleanly afford fully characterized {alpha}-siloxyethyl complexes Fp-CH(OSiR{sub 3})CH{sub 3} under conditions where typically Rh(1) hydrosilation catalysts are inactive. Several of these manganese complexes also catalytically hydrosilate organic esters, including lactones, to their ethers R-CH{sub 2}OR; these novel ester reductions occur quantitatively at room temperature and appear to be general in scope.

  4. Electrochemical synthesis of transition element complexes with carboxyl- and carbonyl-containing ligands

    International Nuclear Information System (INIS)

    Frolov, V.Yu.; Bolotin, S.N.; Panyushkin, V.T.

    2005-01-01

    Complexes of d- and f-elements (E = Cu, Ni, Zn, Nd, Tb, Pr, Gd, Er) with carboxyl- and carbonyl-containing ligands were synthesized by the electrochemical method. The products were characterized by elemental analysis, thermal gravimetric analysis and IR spectra. The influence exerted by a number of factors on the process course was studied. The dependence of the electro synthesis parameters on the composition of the forming compounds was established. A new method for anodic synthesis of these compounds was developed [ru

  5. Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

    Science.gov (United States)

    2015-01-01

    Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids. PMID:24666182

  6. Mutual control of axial and equatorial ligands: model studies with [Ni]-bacteriochlorophyll-a.

    Science.gov (United States)

    Yerushalmi, Roie; Noy, Dror; Baldridge, Kim K; Scherz, Avigdor

    2002-07-17

    Modification of the metal's electronic environment by ligand association and dissociation in metalloenzymes is considered cardinal to their catalytic activity. We have recently presented a novel system that utilizes the bacteriochlorophyll (BChl) macrocycle as a ligand and reporter. This system allows for charge mobilization in the equatorial plane and experimental estimate of changes in the electronic charge density around the metal with no modification of the metal's chemical environment. The unique spectroscopy, electrochemistry and coordination chemistry of [Ni]-bacteriochlorophyll ([Ni]-BChl) enable us to follow directly fine details and steps involved in the function of the metal redox center. This approach is utilized here whereby electro-chemical reduction of [Ni]-BChl to the monoanion [Ni]-BChl(-) results in reversible dissociation of biologically relevant axial ligands. Similar ligand dissociation was previously detected upon photoexcitation of [Ni]-BChl (Musewald, C.; Hartwich, G.; Lossau, H.; Gilch, P.; Pollinger-Dammer, F.; Scheer, H.; Michel-Beyerle, M. E. J. Phys. Chem. B 1999, 103, 7055-7060 and Noy, D.; Yerushalmi, R.; Brumfeld, V.; Ashur, I.; Baldridge, K. K.; Scheer, H.; Scherz, A. J. Am. Chem. Soc. 2000, 122, 3937-3944). The electrochemical measurements and quantum mechanical (QM) calculations performed here for the neutral, singly reduced, monoligated, and singly reduced, monoligated [Ni]-BChl suggest the following: (a) Electroreduction, although resulting in a pi anion [Ni]-BChl(-) radical, causes electron density migration to the [Ni]-BChl core. (b) Reduction of nonligated [Ni]-BChl does not change the macrocycle conformation, whereas axial ligation results in a dramatic expansion of the metal core and a flattening of the highly ruffled macrocycle conformation. (c) In both the monoanion and singly excited [Ni]-BChl ([Ni]-BChl*), the frontier singly occupied molecular orbital (SOMO) has a small but nonnegligible metal character. Finally, (d

  7. Interaction between alkaline earth cations and oxo-ligands. DFT study of the affinity of the Ca2+ cation for carbonyl ligands.

    Science.gov (United States)

    da Costa, Leonardo Moreira; Carneiro, José Walkimar de Mesquita; Romeiro, Gilberto Alves; Paes, Lilian Weitzel Coelho

    2011-02-01

    The affinity of the Ca(2+) ion for a set of substituted carbonyl ligands was analyzed with both the DFT (B3LYP/6-31+G(d)) and semi-empirical (PM6) methods. Two types of ligands were studied: a set of monosubstituted [O=CH(R)] and a set of disubstituted ligands [O=C(R)(2)] (R=H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either directly bound to the carbonyl carbon atom or to the para position of a phenyl ring. The interaction energy was calculated to quantify the affinity of the Ca(2+) cation for the ligands. Geometric and electronic parameters were correlated with the intensity of the metal-ligand interaction. The electronic nature of the substituent is the main parameter that determines the interaction energy. Donor groups make the interaction energy more negative (stabilizing the complex formed), while acceptor groups make the interaction energy less negative (destabilizing the complex formed).

  8. Selective transformation of carbonyl ligands to organic molecules. Progress report, September 1, 1989--November 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A.R.

    1992-05-12

    Studies on the carbonylation of ({eta}{sup 5}-indenyl)(L)(CO)Ru-R complexes (L = CO, PPh{sub 3}; R = CH{sub 2}OMe, CH{sub 3}) have been completed. Particularly noteworthy is that the methoxymethyl complexes readily transform to their acyl derivatives under mild conditions that leave their iron congeners inert towards CO. Surprisingly, even ({eta}{sup 5}-indenyl)(PPh{sub 3}){sub 2}Ru-CH{sub 3} carbonylates and gives ({eta}{sup 5}-indenyl)(PPh{sub 3})(CO)Ru-C(O)CH{sub 3}. Mechanistic studies on the ``non catalyzed`` hydrosilation of the manganese acyls (CO){sub 5}Mn-C(O)CH{sub 2}R (R = H, OCH{sub 3}, CH{sub 3}) with Et{sub 3}SiH and of cobalt acetyls (CO){sub 3}(PR{sub 3})CoC(O)CH{sub 3} with several monohydrosilanes have been completed. The cobalt acetyls cleanly give ethoxysilanes (not acetaldehyde), and the manganese acyls provide {alpha}-siloxyvinyl complexes Z-(CO){sub 5}Mn-C(OSiEt{sub 3})=CHR (R = H, CH{sub 3}, OCH{sub 3}). Carbonylation and protolytic cleavage of the latter generate pyruvoyl complexes (CO){sub 5}Mn-COCOR (R = CH{sub 3}, CH{sub 2}CH{sub 3}), formally the products of net ``double carbonylation`` sequences. Studies in progress are concerned with how manganese complexes as diverse as (CO){sub 5}Mn-Y [Y = C(O)R, R, BR - but not SiMe{sub 3} or Mn(CO){sub 5}] and ({eta}{sup 3}-C{sub 3}H{sub 5})Mn(CO){sub 2}L [but not CpMn(CO){sub 3} or CpMn(CO){sub 2}({eta}{sup 2}HSiR{sub 3})] function as efficient hydrosilation catalysts towards Cp(CO){sub 2}FeC(O)CH{sub 3}, for example. These reactions cleanly afford fully characterized {alpha}-siloxyethyl complexes Fp-CH(OSiR{sub 3})CH{sub 3} under conditions where typically Rh(1) hydrosilation catalysts are inactive. Several of these manganese complexes also catalytically hydrosilate organic esters, including lactones, to their ethers R-CH{sub 2}OR; these novel ester reductions occur quantitatively at room temperature and appear to be general in scope.

  9. Mono- and Dinuclear Manganese Carbonyls Supported by 1,8-Disubstituted (L = Py, SMe, SH) Anthracene Ligand Scaffolds.

    Science.gov (United States)

    Manes, Taylor A; Rose, Michael J

    2016-06-06

    Presented herein is a synthetic scheme to generate symmetric and asymmetric ligands based on a 1,8-disubstituted anthracene scaffold. The metal-binding scaffolds were prepared by aryl chloride activation of 1,8-dichloroanthracene using Suzuki-type couplings facilitated by [Pd(dba)2] as a Pd source; the choice of cocatalyst (XPhos or SPhos) yielded symmetrically or asymmetrically substituted scaffolds (respectively): namely, Anth-SMe2 (3), Anth-N2 (4), and Anth-NSMe (6). The ligands exhibit a nonplanar geometry in the solid state (X-ray), owing to steric hindrance between the anthracene scaffold and the coupled aryl units. To determine the flexibility and binding characteristics of the anthracene-based ligands, the symmetric scaffolds were complexed with [Mn(CO)5Br] to afford the mononuclear species [(Anth-SMe2)Mn(CO)3Br] (8) and [(Anth-N2)Mn(CO)3Br] (9), in which the donor moieties chelate the Mn center in a cis fashion. The asymmetric ligand Anth-NSMe (6) binds preferentially through the py moieties, affording the bis-ligated complex [(Anth-NSMe)2Mn(CO)3Br] (10), wherein the thioether-S donors remain unbound. Alternatively, deprotection of the thioether in 6 affords the free thiol ligand Anth-NSH (7), which more readily binds the Mn center. Complexation of 7 ultimately affords the mixed-valence Mn(I)/Mn(II) dimer of formula [(Anth-NS)3Mn2(CO)3] (11), which exhibits a fac-{Mn(CO)3} unit supported by a triad of bridging thiolates, which are in turn ligated to a supporting Mn(II) center (EPR: |D| = 0.053 cm(-1), E/|D| = 0.3, Aiso = -150 MHz). All of the metal complexes have been characterized by single-crystal X-ray diffraction, IR spectroscopy and NMR/EPR measurements-all of which demonstrate that the meta-linked, anthracene-based ligand scaffold is a viable approach for the coordination of metal carbonyls.

  10. Solid-state thermolysis of a fac-rhenium(I) carbonyl complex with a redox non-innocent pincer ligand.

    Science.gov (United States)

    Jurca, Titel; Chen, Wen-Ching; Michel, Sheila; Korobkov, Ilia; Ong, Tiow-Gan; Richeson, Darrin S

    2013-03-25

    The development of rhenium(I) chemistry has been restricted by the limited structural and electronic variability of the common pseudo-octahedral products fac-[ReX(CO)3L2] (L2 = α-diimine). We address this constraint by first preparing the bidentate bis(imino)pyridine complexes [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)3X] (X = Cl 2, Br 3), which were characterized by spectroscopic and X-ray crystallographic means, and then converting these species into tridentate pincer ligand compounds, [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2X] (X = Cl 4, Br 5). This transformation was performed in the solid-state by controlled heating of 2 or 3 above 200 °C in a tube furnace under a flow of nitrogen gas, giving excellent yields (≥95 %). Compounds 4 and 5 define a new coordination environment for rhenium(I) carbonyl chemistry where the metal center is supported by a planar, tridentate pincer-coordinated bis(imino)pyridine ligand. The basic photophysical features of these compounds show significant elaboration in both number and intensity of the d-π* transitions observed in the UV/Vis spec tra relative to the bidentate starting materials, and these spectra were analyzed using time-dependent DFT computations. The redox nature of the bis(imino)pyridine ligand in compounds 2 and 4 was examined by electrochemical analysis, which showed two ligand reduction events and demonstrated that the ligand reduction shifts to a more positive potential when going from bidentate 2 to tridentate 4 (+160 mV for the first reduction step and +90 mV for the second). These observations indicate an increase in electrostatic stabilization of the reduced ligand in the tridentate conformation. Elaboration on this synthetic methodology documented its generality through the preparation of the pseudo-octahedral rhenium(I) triflate complex [(2,6-{2,6-Me2C6H3N=CPh}2C5H3N)Re(CO)2OTf] (7, 93 % yield). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Short Intramolecular N–H⋯C(carbonyl Interactions in Mixed-Ligand Molybdenum Hexacarbonyl Derivatives

    Directory of Open Access Journals (Sweden)

    Matthew G. Budge

    2011-06-01

    Full Text Available The syntheses and single-crystal structures of Mo(CO3(phen(dipy (1, Mo(CO3(biquin(dipy (2 and Mo(CO3(dpme(dipy (3, (phen = 1,10-phenanthroline, C12H8N2; dipy = 2,2'-dipyridylamine, C10H9N3; biquin = 2,2'-biquinoline, C18H12N2; dpme = 2,2'-dipyridylmethane, C11H10N2 are described. In each case, distorted fac-MoC3N3 octahedral coordination geometries arise for the metal atoms. Short intramolecular N–H…C interactions from the dipy N–H group to a carbonyl carbon atom occur in each structure. Crystal data: 1 (C25H17MoN5O3, Mr = 531.38, monoclinic, P21/n (No. 14, Z = 4, a = 11.0965 (5 Å, b = 13.0586 (6 Å, c = 16.6138 (8 Å, b = 108.324 (1°, V = 2285.31 (18 Å3, R(F = 0.035, wR(F2 = 0.070. 2 (C31H21MoN5O3, Mr = 607.47, monoclinic, P21/n (No. 14, Z = 4, a = 11.4788 (6 Å, b = 19.073 (1 Å, c = 11.9881 (6 Å, b = 95.179 (1°, V = 2613.9 (2 Å3, R(F = 0.030, wR(F2 = 0.076. 3 (C24H19MoN5O3, Mr = 521.38, monoclinic, P21/n (No. 14, Z = 4, a = 8.4222 (3 Å, b = 21.5966 (9 Å, c = 12.5011 (5 Å, b = 94.065 (1°, V = 2268.12 (15 Å3, R(F = 0.025, wR(F2 = 0.065.

  12. Ruthenium(II carbonyl compounds with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand

    Directory of Open Access Journals (Sweden)

    Rajendhraprasad Tatikonda

    2017-04-01

    Full Text Available Two ruthenium carbonyl complexes with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand (tpy-Cl, C15H10ClN3, i.e. [RuCl(tpy-Cl(CO2][RuCl3(CO3] (I [systematic name: cis-dicarbonylchlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ3Nruthenium(II fac-tricarbonyltrichloridoruthenate(II], and [RuCl2(tpy-Cl(CO2] (II [cis-dicarbonyl-trans-dichlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ2N1,N1′ruthenium(II], were synthesized and characterized by single-crystal X-ray diffraction. The RuII atoms in both centrosymmetric structures (I and (II display similar, slightly distorted octahedral coordination spheres. The coordination sphere in the complex cation in compound (I is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octahedral [Ru(CO3Cl3]− counter-anion. In the neutral compound (II, the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the RuII atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I and (II, weak C—H...Cl interactions are observed.

  13. Elementary steps of the catalytic oxidation of CO in a gas phase in the presence of rhenium cations with carbonyl and oxygen ligands: a comparison with heterogeneous catalysis

    International Nuclear Information System (INIS)

    Goncharov, V.B.; Fialko, E.F.; Shejnin, D.Eh.; Kikhtenko, A.V.

    1997-01-01

    Reactivity in a gaseous phase o rhenium (Re + ) and rhenium monocarbonyl (ReCO + ) in the reaction of CO oxidation in oxygen-containing reagents (NO, O 2 , H 2 O) is studied through the method of the ionic cyclotron resonance. It is shown that presence of carbonyl ligand essentially influences the ion reactivity. The effective channel of the metal monocarbonyl ions oxidation through molecular oxygen is found. Accounting for this stage makes of possible to explain the low-temperature activity of a number of oxide catalyzer Mo, W in the reaction of CO oxidation by molecular oxygen

  14. Selective transformation of carbonyl ligands to organic molecules: Progress report, 1 September 1986--31 August 1989

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A.R.

    1989-04-18

    Studies on anionic phosphido alkyl and acetyl complexes Cp(CO)(PPh/sub 2/)Fe /minus/ R/sup /minus// (1) and In(CO)(PPh/sub 2/)Fe /minus/ R/sup /minus// (2) (R = CH/sub 3/ (a), COCH/sub 3/ (b); In = /eta//sup 5/-indenyl) and their neutral phosphine derivatives Cp(CO)(PPh/sub 2/H)Fe /minus/ R (3) and In(CO)(PPh/sub 2/H)Fe /minus/ R (4) are complete. Attempts to carbonylate 1a and 2a to 1b and 2b failed; also, 3a and 4a resist carbonylation. Reacting 1b with MeI affords a neutral PPh/sub 2/Me acetyl compound 5, whereas MeOSO/sub 2/CF/sub 3/ gives the Fischer carbene complex Cp(PPh/sub 2/)(CO) Fe = C(OMe)CH/sub 3/ (6). Carbene 6 isomerizes to 5 at room temperature. Reaction conditions have been optimized for tenerating vinylidene compounds In/sub 2/(CO)/sub 3/Fe/sub 2/ ..mu..-(C = CHR) from InFe(CO)/sub 2//sup /minus// and In(CO)/sub 2/Fe /minus/ CH/sub 2/R (R = H, Me, OMe). The bimetallic carbonylation procedure for converting Fp/sup /minus//(Li/sup +/, Na/sup +/, PPN/sup +/) and In(CO)/sub 2/Fe /minus/ CH/sub 3/ to InCp(CO)/sub 3/Fe/sub 2/(COCH/sub 3//sup /minus//) and then regioselectively to FpCOCH/sub 3/ (1 atm CO) has been optimized. Studies are finished on the diastereofacial selectivity observed during reduction of the alkoxycarbenes Cp(P(OR)/sub 3/)(CO)Fe = C(OCH/sub 3/)CH/sub 3//sup +/ (R = Me, Ph) with borohydride reagents R/sub 3/BH/sup /minus// (Li/sup +/, Na/sup +/, K/sup +/) and with (PPh/sub 3/CuH)/sub 6/. A survey of the Rh(I)-catalyzed hydrosilation of a variety of iron acyl complexes has been concluded.

  15. Synthesis and characterization of rhodium(I) complexes with P-N donor ligands and their catalytic application in transfer hydrogenation of carbonyl group

    Energy Technology Data Exchange (ETDEWEB)

    Barah, Geetika; Sarmah, Podma Poliov; Boruah, Devajani [Dept. of Chemistry, Dibrugarh University, Dibrugarh (India)

    2015-04-15

    Three rhodium(I) complexes of the types [Rh(COE)Cl(η{sup 2}-L)] (1a,1b) and [RhCl(η{sup 2}-L) (η{sup 1}-L)] (1c), where L = P⁓N donor ligands 2-[2-(diphenylphosphino) ethyl]pyridine, (PPh{sub 2}Etpy) (a), 2-(diphenylphosphino)pyridine (PPh{sub 2}py) (b), and 3-(diphenylphosphino)-1-propylamine (PPh{sub 2}(CH{sub 2}){sub 3}NH{sub 2}) (c), have been synthesized by reacting [Rh(coe){sub 2}Cl]{sub 2} with the respective ligands in 1:2 molar ratio for 1a, 1b and 1:4 molar ratio for 1c in DCM under refluxing condition. The complexes were characterized using different analytical techniques such as FT-IR, ESI(+) mass spectrometry, {sup 1}H and {sup 31}P{"1H} NMR spectrometry, conductivity measurements, and melting point determination. The synthesized complexes were found to exhibit good catalytic activity for the transfer hydrogenation of carbonyl compounds to corresponding alcohols with high conversion rate.

  16. Synthesis, spectroscopic, DFT calculations and biological activity studies of ruthenium carbonyl complexes with 2-picolinic acid and a secondary ligand

    Science.gov (United States)

    Shohayeb, Shahera M.; Mohamed, Rania G.; Moustafa, H.; El-Medani, Samir M.

    2016-09-01

    Thermal reaction of [Ru3(CO)12] with 2-picolinic acid (Hpic) in the absence and presence of a secondary ligand (pyridine, Py, bipyridine, Bipy, or thiourea, Tu) was investigated. Four complexes with molecular formulae: [Ru(CO)3(Hpic)], 1, [Ru2(CO)5(Hpic)(Py)], 2, [Ru2(CO)5(Hpic)(Tu)], 3 and [Ru2(CO)4(Hpic)(Bipy)], 4, were isolated. All complexes were characterized based on elemental analyses, IR, 1H NMR, magnetic studies, mass spectrometry and thermal analysis. The ligand and its complexes have been screened for antibacterial activities. Density Functional Theory (DFT) calculations at the B3LYP/6-311G (d,p)_ level of theory have been carried out to investigate the equilibrium geometry of the ligands. The optimized geometry parameters of the complexes were evaluated using B3LYP method and LANL2DZ basis set. The extent of natural charge population (core, valence and rydberg), exact electronic configuration, total Lewis and total non-Lewis are estimated and discussed in terms of natural bond orbitals (NBO) analysis.

  17. Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

    Science.gov (United States)

    Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

    2017-07-01

    Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

  18. New ruthenium(II) carbonyl complexes bearing disulfide Schiff base ligands and their applications as catalyst for some organic transformations

    Science.gov (United States)

    Prakash, Govindan; Viswanathamurthi, Periasamy

    2014-08-01

    Schiff base disulfide ligands (H2L1-6) were synthesized from the condensation of cystamine with salicylaldehyde(H2L1), 5-chlorosalicylaldehyde(H2L2), o-vanillin(H2L3), 2-hydroxyacetophenone(H2L4), 3-methyl-2-hydroxyacetophenone(H2L5), and 2-hydroxy-1-naphthaldehyde(H2L6). H2L1-6 reacts with the ruthenium precursor complex [RuHCl(CO)(PPh3)3] in benzene giving rise to six new ruthenium(II) complexes of general formula [Ru(CO)L1-6]. Characterization of the new complexes was carried out by using elemental and spectral (IR, UV-Vis, NMR (1H and 13C) and Mass) techniques. An octahedral geometry was assigned for all the complexes based on the spectral data obtained. The catalytic efficiency of the new complexes in aldehyde to amide conversion in the presence of NaHCO3, N-alkylation of aniline in the presence of t-BuOK, and transfer hydrogenation of ketones in the presence of iPrOH/KOH reactions were studied. Furthermore, the effect of solvents and catalyst/substrate ratio on the catalytic aldehyde to amide conversion were also discussed.

  19. Binding cooperativity between a ligand carbonyl group and a hydrophobic side chain can be enhanced by additional H-bonds in a distance dependent manner: A case study with thrombin inhibitors.

    Science.gov (United States)

    Said, Ahmed M; Hangauer, David G

    2015-01-01

    One of the underappreciated non-covalent binding factors, which can significantly affect ligand-protein binding affinity, is the cooperativity between ligand functional groups. Using four different series of thrombin inhibitors, we reveal a strong positive cooperativity between an H-bond accepting carbonyl functionality and the adjacent P3 hydrophobic side chain. Adding an H-bond donating amine adjacent to the P3 hydrophobic side chain further increases this positive cooperativity thereby improving the Ki by as much as 546-fold. In contrast, adding an amidine multiple H-bond/salt bridge group in the distal S1 pocket does not affect this cooperativity. An analysis of the crystallographic B-factors of the ligand groups inside the binding site indicates that the strong cooperativity is mainly due to a significant mutual reduction in the residual mobility of the hydrophobic side chain and the H-bonding functionalities that is absent when the separation distance is large. This type of cooperativity is important to encode in binding affinity prediction software, and to consider in SAR studies. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  20. Equatorial Guinea.

    Science.gov (United States)

    1989-03-01

    Equatorial Guinea is situated on the Gulf of Guinea along the west African coast between Cameroon and Gabon. The people are predominantly of Bantu origin. The country's ties with Spain are significant; in 1959, it became the Spanish Equatorial region ruled by Spain's commissioner general. Recent political developments in Equatorial Guinea include the formation of the Democratic Party for Equatorial Guinea in July of 1987 and the formation of a 60-member unicameral Chamber of Representatives of the People in 1983. Concerning the population, 83% of the people are Catholic and the official language is Spanish. Poverty and serious health, education and sanitary problems exist. There is no adequate hospital and few trained physicians, no dentists, and no opticians. Malaria is endemic and immunization for yellow fever is required for entrance into the country. The water is not potable and many visitors to the country bring bottled water. The tropical climate of Equatorial Guinea provides the climate for the country's largest exports and source of economy; cacao, wood and coffee. Although the country, as a whole, has progressed towards developing a participatory political system, there are still problems of governmental corruption in the face of grave health and welfare conditions. In recent years, the country has received assistance from the World Bank and the United States to aid in its development.

  1. Protein carbonylation in plants

    DEFF Research Database (Denmark)

    Møller, Ian Max; Havelund, Jesper; Rogowska-Wrzesinska, Adelina

    2017-01-01

    This chapter provides an overview of the current knowledge on protein carbonylation in plants and its role in plant physiology. It starts with a brief outline of the turnover and production sites of reactive oxygen species (ROS) in plants and the causes of protein carbonylation. This is followed...... by a description of the methods used to study protein carbonylation in plants, which is also very brief as the methods are similar to those used in studies on animals. The chapter also focuses on protein carbonylation in plants in general and in mitochondria and in seeds in particular, as case stories where...... specific carbonylated proteins have been identified. Protein carbonylation appears to accumulate at all stages of seed development and germination investigated to date. In some cases, such as seed aging, it is probably simply an accumulation of oxidative damage. However, in other cases protein...

  2. Reactions of ruthenium and osmium cluster carbonyls with heteroatom-substituted and functionalized alkynes

    International Nuclear Information System (INIS)

    Koridze, A.A.

    2000-01-01

    The results of studies of the reactions of ruthenium and osmium cluster carbonyls with metal (M = Re, Mn, Fe) alkynes, silylalkynes, propargyl alcohols and their derivatives, diynes, enynes, and ferrocenylacetylene are summarized. Intramolecular rearrangements in the cluster complexes including migrations of carbonyl, hydride, and hydrocarbon ligands and the metal core reorganization are considered [ru

  3. Reciprocal carbonyl-carbonyl interactions in small molecules and proteins.

    Science.gov (United States)

    Rahim, Abdur; Saha, Pinaki; Jha, Kunal Kumar; Sukumar, Nagamani; Sarma, Bani Kanta

    2017-07-19

    Carbonyl-carbonyl n→π* interactions where a lone pair (n) of the oxygen atom of a carbonyl group is delocalized over the π* orbital of a nearby carbonyl group have attracted a lot of attention in recent years due to their ability to affect the 3D structure of small molecules, polyesters, peptides, and proteins. In this paper, we report the discovery of a "reciprocal" carbonyl-carbonyl interaction with substantial back and forth n→π* and π→π* electron delocalization between neighboring carbonyl groups. We have carried out experimental studies, analyses of crystallographic databases and theoretical calculations to show the presence of this interaction in both small molecules and proteins. In proteins, these interactions are primarily found in polyproline II (PPII) helices. As PPII are the most abundant secondary structures in unfolded proteins, we propose that these local interactions may have implications in protein folding.Carbonyl-carbonyl π* non covalent interactions affect the structure and stability of small molecules and proteins. Here, the authors carry out experimental studies, analyses of crystallographic databases and theoretical calculations to describe an additional type of carbonyl-carbonyl interaction.

  4. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...... protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...... irradiation. Three of the four ELISA carbonyl results fell within 95% confidence intervals. Likely errors in calculating absolute carbonyl values may be attributed to differences in standardisation. Out of up to 88 proteins identified as containing carbonyl groups after tryptic cleavage of irradiated...

  5. THE METAL CARBONYLS.

    Science.gov (United States)

    Blanchard, A A

    1941-10-03

    When the metal carbonyls were first discovered, their properties were startling because they seemed to violate nearly all the previously recognized generalizations of chemistry. Even to-day the existence of the carbonyls is not particularly emphasized in elementary courses of chemistry because it is rather hard to reconcile them with the first presentations of the generalizations of chemistry. Nevertheless, as the student progresses deeper into the knowledge of chemistry it becomes desirable to include the knowledge of the carbonyls both because they become more comprehensible when viewed in the light of Werner's system of coordination and because they themselves contribute to the comprehension of the Werner theory. As long ago as 1931, Reiff in his discussion of cobalt nitrosyl carbonyl recognized the correlation between the effective atomic number and the volatility of carbonyls. A more recent study of charged Werner coordination complexes, that is, of complex ions, has shown a similar role of the effective atomic number. We are standing on fairly firm ground when we point out the correlation between E.A.N. and the volatility of the carbonyl complexes and the existence of complex ions. Be it noted that we have made no postulates as to the arrangement of the electrons in quantum levels. In the inert gases the outer principal quantum group is supposed always to contain eight electrons. In the carbonyls and other Werner complexes there is no compelling reason to suppose that the electrons in the coordinating layer, be this layer of eight, ten, twelve or sixteen electrons, are not all at the same energy level. Although we have confined our discussion almost exclusively to the property of volatility, the carbonyls are very interesting from the standpoint of several other properties, for example, magnetic susceptibility and dielectric constant. Enthusiasts in the interpretation of such properties try to draw conclusions as to the condition of the electrons, sometimes

  6. Intermonsoonal equatorial jets

    Digital Repository Service at National Institute of Oceanography (India)

    Muraleedharan, P.M.

    , respectively. Hydrographic features and transport computations favour a well developed equatorial jet during both seasons. The net surface eastward and subsurface westward flows are well balanced during the premonsoon transition period and appear...

  7. Metal-ligand interactions

    Science.gov (United States)

    Ervin, Kent M.

    Experimental studies of the interactions of small transition-metal cluster anions with carbonyl ligands are reviewed and compared with neutral and cationic clusters. Under thermal conditions, the reaction rates of transition-metal clusters with carbon monoxide are measured as a function of cluster size. Saturation limits for carbon monoxide addition can be related to the geometric structures of the clusters. Both energy-resolved threshold collision-induced dissociation experiments and time-resolved photodissociation experiments are used to measure metal-carbonyl binding energies. For platinum and palladium trimer anions, the carbonyl binding energies are assigned to different geometric binding sites. Platinum and palladium cluster anions catalyse the oxidation of carbon monoxide to carbon dioxide in a full catalytic cycle at thermal energies.

  8. [1,3-Bis(diphenyl-phosphino)pentane-κP,P']tetra-carbonyl-chromium(0).

    Science.gov (United States)

    Shawkataly, Omar Bin; Thangadurai, Daniel T; Pankhi, Mohd Aslam A; Shahinoor Dulal Islam, S M; Fun, Hoong-Kun

    2009-02-04

    In the title compound, [Cr(C(29)H(30)P(2))(CO)(4)], the Cr atom is octa-hedrally coordinated by four carbonyl ligands and one bidentate phosphine ligand, which is bounded as a chelate in a cis position. The average Cr-P and Cr-C bond lengths are 2.377 and 1.865 Å, respectively.

  9. Chapter 19. Design and evaluation of potential 99mTc radiopharmaceuticals based on the Tc-Carbonyl, 4 + 1 mixed ligand chelate system and Tc-nitrido approaches

    International Nuclear Information System (INIS)

    Giglio, J.; Muslera, A.; Leon, E.; Paolino, A.; Leon, A.; Rey, A.; Incerti, M.; Fernandez, R.; Manta, E.; Brugnini, A.; Chabalgoity, A.

    2007-01-01

    The aim of the work was to explore the possibilities of the novel labelling strategies in the development of 99m Tc labelled small biomolecules. Different steps required to fulfil this objective were undertaken: organic synthesis of glucose derivatives, optimization of labelling and in vitro and in vivo evaluation of Rd peptides and anne xin 13 derivatives using either the Hyonic bifunctional ligand, the Tc-tricarbonyl, the 4 + 1 mixed ligand or the Tc(V)-nitri do approaches. Glucose-O-hexyl bromide, glucose- O-butylbromide and glucose-O-butylamine were successfully synthesized, opening the possibility of introducing different chelators according to the desired labelling procedure. c(RGDyK) derivatives bearing different chelators were labelled with 99m Tc using novel approaches and evaluated both in vitro and in vivo in order to compare the effect of the chelator and labelling method on the physicochemical and biological behaviour. Annexin 13 peptides were also labelled using the HYNIC and Tc(I)-tricarbonyl approaches. A primary evaluation in normal animals and in a model of cardiac apoptosis is also presented. Cooperation with other participants was crucial to develop this work. (author)

  10. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.

    2007-01-01

    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  11. Pacific Equatorial Transect

    OpenAIRE

    Pälike, Heiko; Nishi, Hiroshi; Lyle, Mitch; Raffi, Isabella; Klaus, Adam; Gamage, Kusali

    2009-01-01

    Integrated Ocean Drilling Program Expedition 320/321, "Pacific Equatorial Age Transect" (Sites U1331–U1338), was designed to recover a continuous Cenozoic record of the paleoequatorial Pacific by coring above the paleoposition of the Equator at successive crustal ages on the Pacific plate. These sediments record the evolution of the paleoequatorial climate system throughout the Cenozoic. As we gained more information about the past movement of plates and when in Earth's history "critical" cli...

  12. Reductive coupling of carbon monoxide in a rhenium carbonyl complex with pendant Lewis acids.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2008-09-10

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C-C bond has been formed between two reduced CO ligands. This product of C-C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.

  13. Carbonyl{3,3′-di-tert-butyl-5,5′-dimethoxy-2,2′-bis[(4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yloxy]biphenyl-κ2P,P′}hydrido(triphenylphosphane-κPrhodium(I diethyl ether trisolvate

    Directory of Open Access Journals (Sweden)

    Detlef Selent

    2013-01-01

    Full Text Available In the title compound, [RhH(C74H68O8P2(C18H15P(CO]·3C4H10O, the CHP3 coordination set at the RhI ion is arranged in a distorted trigonal–bipyramidal geometry with the P atoms adopting equatorial coordination sites and the C atom of the carbonyl ligand as well as the H atom adopting the axial sites. The asymmetric unit contains two very similar molecules of the rhodium complex, two half-occupied diethyl ether molecules and further diethyl ether solvent molecules which could not be modelled successfully. Therefore contributions of the latter were removed from the diffraction data using the SQUEEZE procedure in PLATON [Spek (2009. Acta Cryst. D65, 148–155].

  14. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  15. Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids

    OpenAIRE

    Miller, Alexander J. M.; Labinger, Jay A.; Bercaw, John E.

    2008-01-01

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C−C bond has been formed between two reduced CO ligands. This prod...

  16. The interaction of metal carbonyl compounds with organic polymers and monomers

    OpenAIRE

    Lyons, Michael P.

    1993-01-01

    The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used ...

  17. Equatorial electrojet in east Brazil longitudes

    Indian Academy of Sciences (India)

    dip latitude as the electrons/ions can move vertically along the inclined magnetic field lines. Equatorial electrojet has been extensively studied from ground, rocket ... Keywords. Equatorial electrojet; Brazilian anomaly in equatorial electrojet; asymmetries in equatorial electrojet. J. Earth Syst. Sci. 119, No. 4, August 2010, pp.

  18. Macrocyclic ligands for uranium complexation. Final report, August 1, 1986--March 31, 1993

    International Nuclear Information System (INIS)

    Potts, K.T.

    1993-01-01

    Macrocycles, designed for complexation of the uranyl ion by computer modeling studies and utilizing six ligating atoms in the equatorial plane of the uranyl ions, have been prepared and their complexation of the uranyl ions evaluated. The ligating atoms, either oxygen or sulfur, were part of acylurea, biuret or thiobiuret subunits with alkane chains or pyridine units completing the macrocyclic periphery. These macrocycles with only partial preorganization formed uranyl complexes in solution but no crystalline complexes were isolated. Refinement of the cavity diameter by variation of the peripheral functional groups is currently studied to achieve an optimized cavity diameter of 4.7--5.2 angstrom. Acyclic ligands containing the same ligating atoms in equivalent functional entities were found to form a crystalline 1:1 uranyl-ligand complex (stability constant log K = 10.7) whose structure was established by X-ray data. This complex underwent a facile, DMSO-induced rearrangement to a 2:1 uranyl-ligand complex whose structure was also established by X-ray data. The intermediates to the macrocycles all behaved as excellent ligands for the complexation of transition metals. Acylthiourea complexes of copper and nickel as well as intermolecular, binuclear copper and nickel complexes of bidentate carbonyl thioureas formed readily and their structures were established in several representative instances by X-ray structural determinations. Tetradentate bis(carbonylthioureas) were found to be very efficient selective reagents for the complexation of copper in the presence of nickel ions. Several preorganized macrocycles were also prepared but in most instances these macrocycles underwent ring-opening under complexation conditions

  19. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias

    2014-01-01

    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  20. [1,3-Bis(diphenyl­phosphino)pentane-κ2 P,P′]tetra­carbonyl­chromium(0)

    Science.gov (United States)

    Shawkataly, Omar bin; Thangadurai, Daniel T.; Pankhi, Mohd. Aslam A.; Shahinoor Dulal Islam, S. M.; Fun, Hoong-Kun

    2009-01-01

    In the title compound, [Cr(C29H30P2)(CO)4], the Cr atom is octa­hedrally coordinated by four carbonyl ligands and one bidentate phosphine ligand, which is bounded as a chelate in a cis position. The average Cr—P and Cr—C bond lengths are 2.377 and 1.865 Å, respectively. PMID:21582044

  1. Kinetics of carbonyl reductase from human brain.

    OpenAIRE

    Bohren, K M; von Wartburg, J P; Wermuth, B

    1987-01-01

    Initial-rate analysis of the carbonyl reductase-catalysed reduction of menadione by NADPH gave families of straight lines in double-reciprocal plots consistent with a sequential mechanism being obeyed. The fluorescence of NADPH was increased up to 7-fold with a concomitant shift of the emission maximum towards lower wavelength in the presence of carbonyl reductase, and both NADPH and NADP+ caused quenching of the enzyme fluorescence, indicating formation of a binary enzyme-coenzyme complex. D...

  2. Protein Carbonylation and Adipocyte Mitochondrial Function*

    Science.gov (United States)

    Curtis, Jessica M.; Hahn, Wendy S.; Stone, Matthew D.; Inda, Jacob J.; Droullard, David J.; Kuzmicic, Jovan P.; Donoghue, Margaret A.; Long, Eric K.; Armien, Anibal G.; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J.; Bernlohr, David A.

    2012-01-01

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte. PMID:22822087

  3. Protein carbonylation and adipocyte mitochondrial function.

    Science.gov (United States)

    Curtis, Jessica M; Hahn, Wendy S; Stone, Matthew D; Inda, Jacob J; Droullard, David J; Kuzmicic, Jovan P; Donoghue, Margaret A; Long, Eric K; Armien, Anibal G; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J; Bernlohr, David A

    2012-09-21

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte.

  4. Reactions of rhodium(I) carbonyl chloride with olefins

    International Nuclear Information System (INIS)

    Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.

    1987-01-01

    The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

  5. Carbonyl[4-(2,3-dimethylphenylaminopent-3-en-2-onato-κ2N,O](triphenylphosphine-κPrhodium(I

    Directory of Open Access Journals (Sweden)

    Gertruida J. S. Venter

    2009-11-01

    Full Text Available In the title compound, [Rh(C13H16NO(C18H15P(CO], the coordination geometry of the RhI atom is square-planar, formed by the coordinating N and O atoms of the bidentate enaminoketonate ligand, one C atom from the carbonyl group and a P atom from triphenylphosphine. The complex displays a 0.591 (3:0.409 (3 ratio disorder of the phenyl unit of the monoanionic N,O-bidentate ligand. Intramolecular hydrogen bonding is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonate ligand.

  6. Aerosol Transport Over Equatorial Africa

    Science.gov (United States)

    Gatebe, C. K.; Tyson, P. D.; Annegarn, H. J.; Kinyua, A. M.; Piketh, S.; King, M.; Helas, G.

    1999-01-01

    Long-range and inter-hemispheric transport of atmospheric aerosols over equatorial Africa has received little attention so far. Most aerosol studies in the region have focussed on emissions from rain forest and savanna (both natural and biomass burning) and were carried out in the framework of programs such as DECAFE (Dynamique et Chimie Atmospherique en Foret Equatoriale) and FOS (Fires of Savanna). Considering the importance of this topic, aerosols samples were measured in different seasons at 4420 meters on Mt Kenya and on the equator. The study is based on continuous aerosol sampling on a two stage (fine and coarse) streaker sampler and elemental analysis by Particle Induced X-ray Emission. Continuous samples were collected for two seasons coinciding with late austral winter and early austral spring of 1997 and austral summer of 1998. Source area identification is by trajectory analysis and sources types by statistical techniques. Major meridional transports of material are observed with fine-fraction silicon (31 to 68 %) in aeolian dust and anthropogenic sulfur (9 to 18 %) being the major constituents of the total aerosol loading for the two seasons. Marine aerosol chlorine (4 to 6 %), potassium (3 to 5 %) and iron (1 to 2 %) make up the important components of the total material transport over Kenya. Minimum sulfur fluxes are associated with recirculation of sulfur-free air over equatorial Africa, while maximum sulfur concentrations are observed following passage over the industrial heartland of South Africa or transport over the Zambian/Congo Copperbelt. Chlorine is advected from the ocean and is accompanied by aeolian dust recirculating back to land from mid-oceanic regions. Biomass burning products are transported from the horn of Africa. Mineral dust from the Sahara is transported towards the Far East and then transported back within equatorial easterlies to Mt Kenya. This was observed during austral summer and coincided with the dying phase of 1997/98 El

  7. Glucosinolates and isothiocyanates from broccoliseed extractsuppressproteinglycationand carbonylation

    Directory of Open Access Journals (Sweden)

    Marina Hirano,

    2018-01-01

    Full Text Available Background: Glucosinolates from brassica plants are hydrolyzed by internal or salivary myrosinase to produce isothiocyanates. Glucoraphanin, a major glucosinolate in broccoli, is hydrolyzed to sulforaphane (SFN, which exhibits antitumor and detoxification activities. Regarding the influence of broccoli and its constituents on the skin, a few studies have reported anti-inflammatory and antioxidant effects. Recently, advanced glycation end products (AGEs and carbonyl proteins have been reported to accelerate skin aging. Objective: We evaluated the effects of broccoli seed extract (BSE and glucosinolates on protein glycation and carbonylation in vitro. Methods: To evaluate the effects of BSE and its constituents, protein glycation and carbonylation were induced by mixing fructose with bovine serum albumin (BSA and then measuring production of AGEs, fructosamine, and carbonyl proteins (CP. Production of CP after mixing fatty acids with BSA was also assessed. Furthermore, the effect of BSE and its constituents on CP production by human fibroblasts (TIG103 was examined. Results: BSE suppressed the production of AGEs, fructosamine, and CP after mixing fructose and BSA. BSE also suppressed production of CP when oxidized linoleic acid was mixed with BSA. Isothiocyanates, including SFN and iberin, suppressed fructose-based CP production, but SFN had no effect on CP production stimulated by oxidized linoleic acid. In contrast, glucosinolates from BSE did not suppress fructose-based CP production, but suppressed CP production due to oxidized linoleic acid. Among the glucosinolates in BSE, glucoberteroin showed the strongest suppression of CP production. CP production in fibroblasts was also suppressed by glucosinolates, including glucoiberin and glucoberteroin. Conclusions: BSE demonstrated anti-glycation and anti-carbonylation effects on protein reactions with fructose and oxidized fatty acids. Isothiocyanates suppressed protein carbonylation induced by

  8. Central Equatorial Pacific Experiment (CEPEX)

    Energy Technology Data Exchange (ETDEWEB)

    1993-01-01

    The Earth's climate has varied significantly in the past, yet climate records reveal that in the tropics, sea surface temperatures seem to have been remarkably stable, varying by less than a few degrees Celsius over geologic time. Today, the large warm pool of the western Pacific shows similar characteristics. Its surface temperature always exceeds 27[degree]C, but never 31[degree]C. Heightened interest in this observation has been stimulated by questions of global climate change and the exploration of stabilizing climate feedback processes. Efforts to understand the observed weak sensitivity of tropical sea surface temperatures to climate forcing has led to a number of competing ideas about the nature of this apparent thermostat. Although there remains disagreement on the processes that regulate tropical sea surface temperature, most agree that further progress in resolving these differences requires comprehensive field observations of three-dimensional water vapor concentrations, solar and infrared radiative fluxes, surface fluxes of heat and water vapor, and cloud microphysical properties. This document describes the Central Equatorial Pacific Experiment (CEPEX) plan to collect such observations over the central equatorial Pacific Ocean during March of 1993.

  9. Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structures of (μ-H)(H)Os3(CO)10(CN-t-C4H9) and (μ-H)2Os3(CO)9(CN-t-C4H9)

    International Nuclear Information System (INIS)

    Adams, R.D.; Golembski, N.M.

    1979-01-01

    The structures of the compounds (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ) and (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ) have been revealed by x-ray crystallographic techniques. For (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ): a = 9.064 (3), b = 12.225 (3), c = 20.364 (4) A; β = 98.73 (3) 0 ; space group P2 1 /c[C/sub 2h/ 5 ], No. 14; Z = 4; d/sub calcd/ = 2.79 g cm -3 . This compound contains a triangular cluster of three osmium atoms; Os(1)--Os(2) = 2.930 (1) A, Os(1)--Os(3) = 2.876 (1) A, and Os(2)--Os(3) = 3.000 (1) A. There are ten linear terminal carbonyl groups and one linear terminal isocyanide ligand which occupies an axial coordination site. The hydrogen atoms were not observed crystallographically, but their positions are strongly inferred from considerations of molecular geometry. For (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ): a = 15.220 (8), b = 12.093 (6), c = 23.454 (5) A; space group Pbcn [D/sub 2h/ 14 ], No. 60; Z = 8; d/sub calcd/ = 2.79 g cm -3 . The compound is analogous to the parent carbonyl (μ-H) 2 Os 3 (CO) 10 and has two normal and one short osmium--osmium bonds: Os(1)--Os(2) = 2.827 (1) A, Os(1)--Os(3) = 2.828 (1) A, Os(2)--Os(3) = 2.691 (1) A. The isocyanide ligand resides in an equatorial coordination site on osmium Os(2). The hydrogen atoms were not observed but are believed to occupy bridging positions as in the parent carbonyl complex. 2 figures, 7 tables

  10. Spatiotemporal distribution of carbonyl compounds in China

    International Nuclear Information System (INIS)

    Ho, K.F.; Ho, Steven Sai Hang; Huang, R.-J.; Dai, W.T.; Cao, J.J.; Tian, Linwei; Deng, W.J.

    2015-01-01

    A sampling campaign was carried out at nine Chinese cities in 2010/2011. Fifteen monocarbonyls (C#= 1–9) were quantified. Temperature is the rate-determining factor of the summertime carbonyl levels. The carbonyl emissions in winter are mainly driven by the primary anthropogenic sources like automobile. A molar ratio of propionaldehyde to nonaldehyde is a barometer of the impact of atmospheric vegetation emission which suggesting that strong vegetation emissions exist in summer and high propionaldehyde abundance is caused by fossil fuel combustion in winter. Potential health risk assessment of formaldehyde and acetaldehyde was conducted and the highest cumulative risks were observed at Chengdu in summer and Wuhan in winter. Because of the strong photochemical reaction and large amount of anthropogenic emissions, high concentrations of carbonyl compounds were observed in Chengdu. The use of ethanol-blended gasoline in Wuhan is the key reason of acetaldehyde emission and action should be taken to avoid potential health risks. - Highlights: • A national wide survey of ambient carbonyl compounds were conducted in China. • Using ethanol-blended gasoline can lead to higher cancer risks. • High concentrations of HMW carbonyls (C6, C7, C8 and C9) were observed in all cities. • HMW carbonyls (C6–C9) species show a very consistent seasonal variation. • C 3 /C 9 acts as an indicator for the impact of vegetation emission in the atmosphere. - Capsule abstract: Strong vegetation emission occurs in summer atmosphere and high acetaldehyde emission due to ethanol-blended gasoline consumption in 9 Chinese cities is discouraged

  11. Quantum cloning machines for equatorial qubits

    International Nuclear Information System (INIS)

    Fan Heng; Matsumoto, Keiji; Wang Xiangbin; Wadati, Miki

    2002-01-01

    Quantum cloning machines for equatorial qubits are studied. For the case of a one to two phase-covariant quantum cloning machine, we present the networks consisting of quantum gates to realize the quantum cloning transformations. The copied equatorial qubits are shown to be separable by using Peres-Horodecki criterion. The optimal one to M phase-covariant quantum cloning transformations are given

  12. Molecular and electronic structure of chromium(V) nitrido complexes with azide and isothiocyanate ligands

    DEFF Research Database (Denmark)

    Bendix, Jesper; Birk, Torben; Weyhermüller, Thomas

    2005-01-01

    . This absorption provides the spectrochemical series for the equatorial ligands, which is found to be numerically almost identical to that determined for chromium(III). DFT calculations reproduce the observed structures and corroborate the ligand field picture of the electronic structure of these complexes....

  13. Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

    Science.gov (United States)

    Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

    2014-02-06

    We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

  14. Convenient Reduction of Carbonyl Compounds to their ...

    African Journals Online (AJOL)

    NICO

    Alcohols and their derivatives occupy an important position in organic synthesis. ... review also reveals that the reduction of carbonyl compounds ..... 1 H.B. Ji and Y.B. She, Green Oxidation and Reduction, China Petrochemi- cal Press, Beijing ...

  15. Protein Carbonylation in Patients with Myelodysplastic Syndromes

    Czech Academy of Sciences Publication Activity Database

    Hlaváčková, A.; Štikarová, J.; Kotlín, R.; Chrastinová, L.; Šácha, Pavel; Májek, P.; Čermák, J.; Suttnar, J.; Dyr, J. E.

    2015-01-01

    Roč. 126, č. 23 (2015), s. 5232 ISSN 0006-4971. [Annual Meeting and Exposition of the American Society of Hematology /55./. 07.12.2013-10.12.2013, New Orleans] Institutional support: RVO:61388963 Keywords : protein carbonylation * myelodysplastic syndromes Subject RIV: CE - Biochemistry

  16. Millimeter wave spectra of carbonyl cyanide ⋆

    Science.gov (United States)

    Bteich, S.B.; Tercero, B.; Cernicharo, J.; Motiyenko, R.A.; Margulès, L.; Guillemin, J.-C.

    2016-01-01

    Context More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods The rotational spectrum of carbonyl cyanide was measured in the frequency range 152 - 308 GHz and analyzed using Watson’s A- and S-reduction Hamiltonians. Results The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. PMID:27738349

  17. Method for conversion of .beta.-hydroxy carbonyl compounds

    Science.gov (United States)

    Lilga, Michael A.; White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Muzatko, Danielle S.; Orth, Rick J.

    2010-03-30

    A process is disclosed for conversion of salts of .beta.-hydroxy carbonyl compounds forming useful conversion products including, e.g., .alpha.,.beta.-unsaturated carbonyl compounds and/or salts of .alpha.,.beta.-unsaturated carbonyl compounds. Conversion products find use, e.g., as feedstock and/or end-use chemicals.

  18. EQUATORIAL SUPERROTATION ON TIDALLY LOCKED EXOPLANETS

    International Nuclear Information System (INIS)

    Showman, Adam P.; Polvani, Lorenzo M.

    2011-01-01

    The increasing richness of exoplanet observations has motivated a variety of three-dimensional (3D) atmospheric circulation models of these planets. Under strongly irradiated conditions, models of tidally locked, short-period planets (both hot Jupiters and terrestrial planets) tend to exhibit a circulation dominated by a fast eastward, or 'superrotating', jet stream at the equator. When the radiative and advection timescales are comparable, this phenomenon can cause the hottest regions to be displaced eastward from the substellar point by tens of degrees longitude. Such an offset has been subsequently observed on HD 189733b, supporting the possibility of equatorial jets on short-period exoplanets. Despite its relevance, however, the dynamical mechanisms responsible for generating the equatorial superrotation in such models have not been identified. Here, we show that the equatorial jet results from the interaction of the mean flow with standing Rossby waves induced by the day-night thermal forcing. The strong longitudinal variations in radiative heating-namely intense dayside heating and nightside cooling-trigger the formation of standing, planetary-scale equatorial Rossby and Kelvin waves. The Rossby waves develop phase tilts that pump eastward momentum from high latitudes to the equator, thereby inducing equatorial superrotation. We present an analytic theory demonstrating this mechanism and explore its properties in a hierarchy of one-layer (shallow-water) calculations and fully 3D models. The wave-mean-flow interaction produces an equatorial jet whose latitudinal width is comparable to that of the Rossby waves, namely the equatorial Rossby deformation radius modified by radiative and frictional effects. For conditions typical of synchronously rotating hot Jupiters, this length is comparable to a planetary radius, explaining the broad scale of the equatorial jet obtained in most hot-Jupiter models. Our theory illuminates the dependence of the equatorial jet

  19. Palladium-catalyzed Reppe carbonylation.

    Science.gov (United States)

    Kiss, G

    2001-11-01

    PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter

  20. Reduction of titanocene dichloride with dysprosium: access to a stable titanocene(ii) equivalent for phosphite-free Takeda carbonyl olefination.

    Science.gov (United States)

    Bousrez, G; Déchamps, I; Vasse, J-L; Jaroschik, F

    2015-05-28

    The reduction of titanocene dichloride with dysprosium yields a new titanocene(ii) equivalent without the need for further stabilising ligands. This reagent can be employed in combination with dithioacetals for the olefination of different carbonyl groups and allows for a simplified all-in-one procedure.

  1. The Effect of the Equatorial Environment on Oxo-Group Silylation of the Uranyl Dication: A Computational Study

    International Nuclear Information System (INIS)

    Yahia, A.; Maron, L.; Yahia, A.; Arnold, P.L.; Love, J.B.

    2010-01-01

    A theoretical investigation of the reductive oxo-group silylation reaction of the uranyl dication held in a Pacman macrocyclic environment has been carried out. The effect of the modeling of the Pacman ligand on the reaction profiles is found to be important, with the dipotassiation of a single oxo group identified as a key component in promoting the reaction between the Si-X and uranium-oxo bonds. This reductive silylation reaction is also proposed to occur in an aqueous environment but was found not to operate on bare ions; in this latter case, substitution of a ligand in the equatorial plane was the most likely reaction. These results demonstrate the importance of the presence but not the identity of the equatorial ligands upon the silylation of the uranyl U-O bond. (authors)

  2. Photoelectric panel with equatorial mounting of drive

    Science.gov (United States)

    Kukhta, M. S.; Krauinsh, P. Y.; Krauinsh, D. P.; Sokolov, A. P.; Mainy, S. B.

    2018-03-01

    The relevance of the work is determined by the need to create effective models for sunny energy. The article considers a photoelectric panel equipped with a system for tracking the sun. Efficiency of the system is provided by equatorial mounting, which compensates for the rotation of the Earth by rotating the sunny panel in the plane of the celestial equator. The specificity of climatic and geographical conditions of Tomsk is estimated. The dynamics of power variations of photoelectric panels with equatorial mounting during seasonal fluctuations in Tomsk is calculated. A mobile photovoltaic panel with equatorial mounting of the drive has been developed. The methods of design strategy for placing photovoltaic panels in the architectural environment of the city are presented. Key words: sunny energy, photovoltaics, equatorial mounting, mechatronic model, wave reducer, electric drive.

  3. Organocatalytic Hydrophosphonylation Reaction of Carbonyl Groups.

    Science.gov (United States)

    Herrera, Raquel P

    2017-09-01

    This revision is covering the limited examples reported for a pivotal strategy in the formation of C-P bonds such as the asymmetric organocatalytic hydrophosphonylation of carbonyl groups (Pudovik reaction). The scope and limitations, and the proposed mechanisms for the scarce different possibilities of asymmetric induction are also shown. The recent evolution and future trends of this undeveloped approach are commented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Spatiotemporal distribution of carbonyl compounds in China.

    Science.gov (United States)

    Ho, K F; Ho, Steven Sai Hang; Huang, R-J; Dai, W T; Cao, J J; Tian, Linwei; Deng, W J

    2015-02-01

    A sampling campaign was carried out at nine Chinese cities in 2010/2011. Fifteen monocarbonyls (C# = 1-9) were quantified. Temperature is the rate-determining factor of the summertime carbonyl levels. The carbonyl emissions in winter are mainly driven by the primary anthropogenic sources like automobile. A molar ratio of propionaldehyde to nonaldehyde is a barometer of the impact of atmospheric vegetation emission which suggesting that strong vegetation emissions exist in summer and high propionaldehyde abundance is caused by fossil fuel combustion in winter. Potential health risk assessment of formaldehyde and acetaldehyde was conducted and the highest cumulative risks were observed at Chengdu in summer and Wuhan in winter. Because of the strong photochemical reaction and large amount of anthropogenic emissions, high concentrations of carbonyl compounds were observed in Chengdu. The use of ethanol-blended gasoline in Wuhan is the key reason of acetaldehyde emission and action should be taken to avoid potential health risks. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki

    2014-10-01

    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  6. Carbonyl(N-nitroso-N-oxido-1-naphtylamine-κ2O,O′(triphenylphosphine-κPrhodium(I acetone solvate

    Directory of Open Access Journals (Sweden)

    T. J. Muller

    2009-12-01

    Full Text Available The title compound, [Rh(C10H7N2O2(C18H15P(CO]·(CH32CO, is the second structural report of a metal complex formed with the O,O′-C10H7N2O2 (neocupferrate ligand. In the crystal structure, the metal centre is surrounded by one carbonyl ligand, one triphenylphosphine ligand and the bidentate neocupferrate ligand, forming a distorted square-planar RhCO2P coordination set which is best illustrated by the small O—Rh—O bite angle of 77.74 (10°. There are no classical hydrogen-bond interactions observed for this complex.

  7. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Daria L. [Department of Chemistry, Yale University, 225; Beltrán-Suito, Rodrigo [Department of Chemistry, Yale University, 225; Thomsen, Julianne M. [Department of Chemistry, Yale University, 225; Hashmi, Sara M. [Department of Chemical and Environmental; Materna, Kelly L. [Department of Chemistry, Yale University, 225; Sheehan, Stafford W. [Catalytic Innovations LLC, 70 Crandall; Mercado, Brandon Q. [Department of Chemistry, Yale University, 225; Brudvig, Gary W. [Department of Chemistry, Yale University, 225; Crabtree, Robert H. [Department of Chemistry, Yale University, 225

    2016-02-05

    This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

  8. Millimeter wave spectra of carbonyl cyanide

    Science.gov (United States)

    Bteich, S. B.; Tercero, B.; Cernicharo, J.; Motiyenko, R. A.; Margulès, L.; Guillemin, J.-C.

    2016-07-01

    Context. More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims: The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods: The rotational spectrum of carbonyl cyanide was measured in the frequency range 152-308 GHz and analyzed using Watson's A- and S-reduction Hamiltonians. Results: The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of

  9. Validation of protein carbonyl measurement: A multi-centre study

    Directory of Open Access Journals (Sweden)

    Edyta Augustyniak

    2015-04-01

    Full Text Available Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial kits. We have further explored the potential causes of variance in carbonyl analysis in a ring study. A soluble protein fraction was prepared from rat liver and exposed to 0, 5 and 15 min of UV irradiation. Lyophilised preparations were distributed to six different laboratories that routinely undertook protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5 min of UV irradiation irrespective of method used. After irradiation for 15 min, less oxidation was detected by half of the laboratories than after 5 min irradiation. Three of the four ELISA carbonyl results fell within 95% confidence intervals. Likely errors in calculating absolute carbonyl values may be attributed to differences in standardisation. Out of up to 88 proteins identified as containing carbonyl groups after tryptic cleavage of irradiated and control liver proteins, only seven were common in all three liver preparations. Lysine and arginine residues modified by carbonyls are likely to be resistant to tryptic proteolysis. Use of a cocktail of proteases may increase the recovery of oxidised peptides. In conclusion, standardisation is critical for carbonyl analysis and heavily oxidised proteins may not be effectively analysed by any existing technique.

  10. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.

    2007-12-01

    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde forcarbonyls and 6-fluoro-4-chromanone for>_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  11. Synthesis, structure and electrochemistry of cationic diruthenium complexes of the type [(N-N)2Ru2(CO)2(.mu.-OOCFc)]+ containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands

    Czech Academy of Sciences Publication Activity Database

    Auzias, M.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 4 (2007), s. 755-760 ISSN 0022-328X Institutional research plan: CEZ:AV0Z40400503 Keywords : carbonyl ligands * carboxylato ligands * ferrocenyl substituents * diimine ligands Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  12. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  13. Pattern of occurrence and occupancy of carbonylation sites in proteins

    DEFF Research Database (Denmark)

    Rao, R Shyama Prasad; Møller, Ian Max

    2011-01-01

    sites. Comparison of metal-catalyzed oxidation of two closely related proteins indicates that this type of carbonylation might not be very specific in proteins. Interestingly, carbonylated sites show a very strong tendency to cluster together in the protein primary sequence hinting at some sort......Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta...

  14. The oil boom in Equatorial Guinea

    International Nuclear Information System (INIS)

    Frynas, J.G.

    2004-01-01

    In less than a decade, Equatorial Guinea has transformed itself from an African backwater into one of the world's fastest growing economies and a sought-after political partner in the Gulf of Guinea. The sole reason for this transformation has been the discovery of oil and gas. This article outlines the rise of Equatorial Guinea as one of Africa's leading oil-producing countries and investigates the political, economic and social effects of becoming a petro-state. The article is based on the author's field research in Equatorial Guinea in the autumn of 2003 and interviews with senior oil company staff, government officials and staff of international organizations as well as secondary sources. This research demonstrates how reliance on oil and gas exports can lead to profound changes in a country's political economy. (author)

  15. Equatorial waves in the stratosphere of Uranus

    Science.gov (United States)

    Hinson, David P.; Magalhaes, Julio A.

    1991-01-01

    Analyses of radio occultation data from Voyager 2 have led to the discovery and characterization of an equatorial wave in the Uranus stratosphere. The observed quasi-periodic vertical atmospheric density variations are in close agreement with theoretical predictions for a wave that propagates vertically through the observed background structure of the stratosphere. Quantitative comparisons between measurements obtained at immersion and at emersion yielded constraints on the meridional and zonal structure of the wave; the fact that the two sets of measurements are correlated suggests a wave of planetary scale. Two equatorial wave models are proposed for the wave.

  16. Narcissistic self-sorting in self-assembled cages of rare Earth metals and rigid ligands.

    Science.gov (United States)

    Johnson, Amber M; Wiley, Calvin A; Young, Michael C; Zhang, Xing; Lyon, Yana; Julian, Ryan R; Hooley, Richard J

    2015-05-04

    Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination. Supramolecular effects allow discrimination between pendant functions as similar as carbonyl or methylene groups in a complex assembly process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. The Emergence of Manganese-Based Carbonyl Hydrosilylation Catalysts.

    Science.gov (United States)

    Trovitch, Ryan J

    2017-11-21

    In recent years, interest in homogeneous manganese catalyst development has intensified because of the earth-abundant and nontoxic nature of this metal. Although compounds of Mn have largely been utilized for epoxidation reactions, recent efforts have revealed that Mn catalysts can mediate a broad range of reductive transformations. Low-valent Mn compounds have proven to be particularly effective for the hydrosilylation of carbonyl- and carboxylate-containing substrates, and this Account aims to highlight my research group's contributions to this field. In our initial 2014 communication, we reported that the bis(imino)pyridine-supported compound ( Ph2PPr PDI)Mn mediates ketone hydrosilylation with exceptional activity under solvent-free conditions. Silanes including Ph 2 SiH 2 , (EtO) 3 SiH, (EtO) 2 MeSiH, and (EtO)Me 2 SiH were found to partially reduce cyclohexanone in the presence of ( Ph2PPr PDI)Mn, while turnover frequencies of up to 1280 min -1 were observed using PhSiH 3 . This led us to evaluate the hydrosilylation of 11 additional ketones and allowed for the atom-efficient preparation of tertiary and quaternary silanes. At that time, it was also discovered that ( Ph2PPr PDI)Mn catalyzes the dihydrosilylation of esters (by way of acyl C-O bond hydrosilylation) to yield a mixture of silyl ethers with modest activity. Earlier this year, the scope of these transformations was extended to aldehydes and formates, and the observed hydrosilylation activities are among the highest obtained for any transition-metal catalyst. The effectiveness of three related catalysts has also been evaluated: ( Ph2PPr PDI)MnH, ( PyEt PDEA)Mn, and [( Ph2PEt PDI)Mn] 2 . To our surprise, ( Ph2PPr PDI)MnH was found to exhibit higher carboxylate dihydrosilylation activity than ( Ph2PPr PDI)Mn, while ( PyEt PDEA)Mn demonstrated remarkable carbonyl hydrosilylation activity considering that it lacks a redox-active supporting ligand. The evaluation of [( Ph2PEt PDI)Mn] 2 revealed

  18. Coccolithophores in the equatorial Atlantic Ocean

    DEFF Research Database (Denmark)

    Kinkel, Hanno; Baumann, K.-H.; Cepek, M.

    2000-01-01

    with each other. In general, the living coccolithophores in the surface and subsurface waters show considerable variation in cell numbers and distribution patterns. Cell densities reached a maximum of up to 300 x 10 coccospheres/l in the upwelling area of the equatorial Atlantic. Here, Emiliania huxleyi...

  19. Electromagnetic properties of carbonyl iron and their microwave ...

    Indian Academy of Sciences (India)

    Administrator

    The aim of this paper is to develop a novel thin micro- wave absorber with good absorbing performance in wide bandwidth and lightweight. So we investigated the micro- wave absorbing characterization of silicone rubber using carbonyl iron as filler. Carbonyl iron can be widely used in the field of electromagnetic shielding ...

  20. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini

    2014-07-01

    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  1. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  2. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  3. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...... modifications are isobaric to carbonylation and it is often challenging to detect the weaker signal from carbonylated peptides necessitating enrichment step. We here present an optimized method for the enrichment of carbonylated peptides....

  4. Catalyst Initiation in the Oscillatory Carbonylation Reaction

    Directory of Open Access Journals (Sweden)

    Katarina Novakovic

    2011-01-01

    Full Text Available Palladium(II iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II iodide within this oscillatory reaction. The species researched include methanol, palladium(II iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

  5. 3,6-Bis(2-pyrazinyl)-1,2,4,5-tetrazin: Ein neuer mehrfunktioneller Ligand und sein syn,fac-konfigurierter Bis(tricarbonylchlororhenium)-Komplex

    Czech Academy of Sciences Publication Activity Database

    Sarkar, B.; Kaim, W.; Schleid, T.; Hartenbach, I.; Fiedler, Jan

    2003-01-01

    Roč. 629, - (2003), s. 1353-1357 ISSN 0044-2313 R&D Projects: GA MŠk OC D14.20; GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : carbonyl ligands * heterocyclic ligands * rhenium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.127, year: 2003

  6. Carbonyl[4-(2,6-dimethylphenylaminopent-3-en-2-onato-κ2N,O](triphenylphosphine-κPrhodium(I acetone hemisolvate

    Directory of Open Access Journals (Sweden)

    Andreas Roodt

    2009-12-01

    Full Text Available In the title compound, [Rh(C13H16NO(C18H15P(CO]·0.5C3H6O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenylphosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-molecule, lying about an inversion center, of the acetone solvate. Intermolecular C—H...O hydrogen bonds are observed between a C—H group of the triphenylphosphine unit and a carbonyl O atom and between the methyl group of the enaminoketonato backbone and the solvent O atom. In addition, an intramolecular interaction is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonato ligand.

  7. High throughput assay for evaluation of reactive carbonyl scavenging capacity.

    Science.gov (United States)

    Vidal, N; Cavaille, J P; Graziani, F; Robin, M; Ouari, O; Pietri, S; Stocker, P

    2014-01-01

    Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  8. High throughput assay for evaluation of reactive carbonyl scavenging capacity

    Directory of Open Access Journals (Sweden)

    N. Vidal

    2014-01-01

    Full Text Available Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  9. Long wavelength irregularities in the equatorial electrojet

    OpenAIRE

    Kudeki, E.; Farley, D. T.; Fejer, Bela G.

    1982-01-01

    We have used the radar interferometer technique at Jicamarca to study in detail irregularities with wavelengths of a few kilometers generated in the unstable equatorial electrojet plasma during strong type 1 conditions. In-situ rocket observations of the same instability process are discussed in a companion paper. These large scale primary waves travel essentially horizontally and have large amplitudes. The vertical electron drift velocities driven by the horizontal wave electric fields reach...

  10. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund

    2012-12-01

    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  11. High altitude flights in equatorial regions

    Science.gov (United States)

    Redkar, R. T.

    A thorough analysis of balloon flights made from Hyderabad, India (Latitude 17°28'N, Longitude 78°35'E), and other equatorial sites has been made. It has been shown that limited success is expected for flights made from equatorial latitudes with balloons made out of natural colour polyethylene film, since the best known balloon film in the world today viz. Winzen Stratofilm is tested for low temperature brittleness only at -80°C., whereas the tropopause temperatures over equatorial latitudes vary between -80°C and -90°C. The success becomes even more critical when flights are made with heavy payloads and larger balloons particularly at night when in the absence of solar radiation the balloon film becomes more susceptible to low temperature brittle failure. It is recommended that in case of capped balloons longer caps should be used to fully cover the inflated protion of the balloon at the higher level equatorial tropopause. It is also advised that the conditions such as wind shears in the tropopause should be critically studied before launching and a day with the tropopause temperature nearer to -80°C should be chosen. Special care also should be taken while handling the balloon on ground and during launching phase. Properties of Winzen Stratofilm have been critically studied and fresh mandates have been recommended on the basis of limiting values of film stresses which caused balloon failures in the equatorial tropopause. It is also emphasized that the data on such flights is still meagre especially for flights with heavy payloads and larger balloons. It has been also shown that it is safest to use balloons made out of grey coloured film which retains its flexibility with the absorption of solar radiation, the success obtained with such balloons so far being 100%. The drawback, however, is that these balloons cannot be used for night flights. Stratospheric wind regimes over Hyderabad are also discussed with a view to determine the period over which long

  12. Synthesis, structure and photoluminescence of novel lanthanide (Tb(III), Gd(III)) complexes with 6-diphenylamine carbonyl 2-pyridine carboxylate

    International Nuclear Information System (INIS)

    An Baoli; Gong Menglian; Cheah, Kok-Wai; Wong, Wai-Kwok; Zhang Jiming

    2004-01-01

    A novel organic ligand, 6-diphenylamine carbonyl 2-pyridine carboxylic acid (HDPAP), and the corresponding lanthanide complexes, tris(6-diphenylamine carbonyl 2-pyridine carboxylato) terbium(III) (Tb-DPAP) and tris(6-diphenylamine carbonyl 2-pyridine carboxylato) gadolinium(III) (Gd-DPAP) have been designed and synthesized. The crystal structure and photoluminescence of Tb-DPAP and Gd-DPAP have been studied. The results showed that the lanthanide complexes have electroneutral structures, and the solid terbium complex emits characteristic green fluorescence of Tb(III) ions at room temperature while the gadolinium complex emits the DPAP ligand phosphorescence. The lowest triplet level of DPAP ligand was calculated from the phosphorescence spectrum of Gd-DPAP in N,N-dimethyl formamide (DMF) dilute solution determined at 77 K, and the energy transfer mechanisms in the lanthanide complexes were discussed. The lifetimes of the 5 D 4 levels of Tb 3+ ions in the terbium complex were examined using time-resolved spectroscopy, and the values are 0.0153±0.0001 ms for solid Tb(DPAP) 3 ·11.5H 2 O and 0.074±0.007 ms for 2.5x10 -5 mol/l Tb-DPAP ethanol solution

  13. Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

    Science.gov (United States)

    Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2010-11-04

    Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

  14. Structural insights into the neuroprotective-acting carbonyl reductase Sniffer of Drosophila melanogaster.

    Science.gov (United States)

    Sgraja, Tanja; Ulschmid, Julia; Becker, Katja; Schneuwly, Stephan; Klebe, Gerhard; Reuter, Klaus; Heine, Andreas

    2004-10-01

    In vivo studies with the fruit-fly Drosophila melanogaster have shown that the Sniffer protein prevents age-dependent and oxidative stress-induced neurodegenerative processes. Sniffer is a NADPH-dependent carbonyl reductase belonging to the enzyme family of short-chain dehydrogenases/reductases (SDRs). The crystal structure of the homodimeric Sniffer protein from Drosophila melanogaster in complex with NADP+ has been determined by multiple-wavelength anomalous dispersion and refined to a resolution of 1.75 A. The observed fold represents a typical dinucleotide-binding domain as detected for other SDRs. With respect to the cofactor-binding site and the region referred to as substrate-binding loop, the Sniffer protein shows a striking similarity to the porcine carbonyl reductase (PTCR). This loop, in both Sniffer and PTCR, is substantially shortened compared to other SDRs. In most enzymes of the SDR family this loop adopts a well-defined conformation only after substrate binding and remains disordered in the absence of any bound ligands or even if only the dinucleotide cofactor is bound. In the structure of the Sniffer protein, however, the conformation of this loop is well defined, although no substrate is present. Molecular modeling studies provide an idea of how binding of substrate molecules to Sniffer could possibly occur.

  15. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Southwest Sciences proposes to develop small, low power instrumentation for the real-time direct measurement of carbonyl sulfide (OCS) in the atmosphere, especially...

  16. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — In this Phase II SBIR program, Southwest Sciences will continue the development of small, low power instrumentation for real-time direct measurement of carbonyl...

  17. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili; Bao, Junwei Lucas; Wang, Zhandong; Zhang, Feng; Truhlar, Donald G.

    2017-01-01

    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere

  18. Equatorial westward electrojet impacting equatorial ionization anomaly development during the 6 April 2000 superstorm

    Science.gov (United States)

    Horvath, Ildiko; Lovell, Brian C.

    2013-11-01

    investigate the forward plasma fountain and the equatorial ionosphere in the topside region during the 6 April 2000 superstorm in the Australian sector at ~0900 LT. Space- and ground-based multi-instrument measurements, Coupled Thermosphere-Ionosphere-Plasmasphere Electrodynamics (CTIPe) simulations, and field-aligned observations comprise our results. These reveal an unusual storm development during which the eastward prompt penetration electric (E) field (PPEF) developed and operated under the continuous effects of the westward disturbance dynamo E-field (DDEF) while large-scale traveling ionospheric disturbances (TIDs) traveled equatorward and generated strong equatorward wind surges. We have identified the eastward PPEF by the superfountain effect causing the equatorial ionization anomaly (EIA)'s development with crests situated at ~±28°N (geomagnetic) in the topside ionosphere at ~840 km altitude. The westward DDEF's occurrence is confirmed by mapping the "anti-Sq" current system wherein the equatorial westward current created a weak long-lasting westward electrojet event. Line plots of vertical drift data tracked large-scale TIDs. Four scenarios, covering ~3.5 h in universal time, demonstrate that the westward DDEF became superimposed on the eastward PPEF. As these E-fields of different origins became mapped into the F region, they could interact. Consequently, the eastward PPEF-related equatorial upward E × B drift became locally reduced by up to 75 m/s near the dip equator by the westward DDEF-related equatorial downward E × B drift. Meanwhile, the EIA displayed a better development as equatorial wind surges, reproduced by CTIPe, increased from 501 to 629 m/s, demonstrating the crucial role of mechanical wind effects keeping plasma density high.

  19. DNA damage by carbonyl stress in human skin cells

    International Nuclear Information System (INIS)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L.

    2003-01-01

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the α-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N ε -(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress

  20. DNA damage by carbonyl stress in human skin cells

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L

    2003-01-28

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the {alpha}-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N{sup {epsilon}}-(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress.

  1. Propheromones that release pheromonal carbonyl compounds in light.

    Science.gov (United States)

    Liu, X; Macaulay, E D; Pickett, J A

    1984-05-01

    Pheromonal carbonyl compounds; (Z)-11-hexadecanal, (E)-citral, and 2-heptanone were treated with six alcohols to give acetals or ketals, some of which acted as propheromones by releasing the pheromonal carbonyl compounds in ultraviolet or simulated sunlight. Highest yields of pheromone were obtained from adducts prepared witho-nitrobenzyl alcohol ando-nitrophenylethane-1,2-diol. Adducts from (Z)-11-hexadecenal and these two alcohols were employed in lures to catch diamondback moths,Plutella xylostella (L.).

  2. Dansyl labeling and bidimensional mass spectrometry to investigate protein carbonylation.

    Science.gov (United States)

    Palmese, Angelo; De Rosa, Chiara; Marino, Gennaro; Amoresano, Angela

    2011-01-15

    Carbonylation is a non-enzymatic irreversible post-translational modification. The adduction of carbonyl groups to proteins is due to the presence of excess of ROS in cells. Carbonylation of specific amino acid side chains is one of the most abundant consequences of oxidative stress; therefore, the determination of carbonyl groups content in proteins is regarded as a reliable way to estimate the cellular damage caused by oxidative stress. This paper reports a novel RIGhT (Reporter Ion Generating Tag) (A. Amoresano, G. Monti, C. Cirulli, G. Marino. Rapid Commun. Mass Spectrom. 2006, 20, 1400) approach for selective labeling of carbonyl groups in proteins using dansylhydrazide, coupled with selective analysis by bidimensional mass spectrometry. We first applied this approach to ribonuclease A and lysozyme as model proteins. According to the so-called 'gel-free procedures', the analysis is carried out at the level of peptides following tryptic digest of the whole protein mixture. Modified RNaseA was analyzed in combined MS(2) and MS(3) scan mode, to specifically select the dansylated species taking advantage of the dansyl-specific fragmentation pathways. This combination allowed us to obtain a significant increase in signal/noise ratio and a significant increase in sensitivity of analysis, due to the reduction of duty cycle of the mass spectrometer. The unique signal obtained was correlated to peptide 1-10 of RNaseA carbonylated and labeled by dansylhydrazide. This strategy represents the first method leading to the direct identification of the carbonylation sites in proteins, thus indicating the feasibility of this strategy to investigate protein carbonylation in a proteomic approach. Copyright © 2010 John Wiley & Sons, Ltd.

  3. Geomagnetic storms and electric fields in the equatorial ionosphere

    International Nuclear Information System (INIS)

    Rastogi, R.G.

    1977-01-01

    Using direct measurements of equatorial electric field during a geomagnetic storm it is shown that the large decrease in the field observed near the dip equator is due to the reversal of the equatorial electrojet current. This is caused by the imposition of an additional westward electric field on the equatorial ionosphere which was originated by the interaction of solar wind with the interplanetary magnetic field. (author)

  4. Cobalt Carbonyl Hydrides with 1,1´-Diphosphinylferrocene Ligands - Structural and Electrochemical Diversity

    Czech Academy of Sciences Publication Activity Database

    Krafft, M. J.; Lissner, F.; Fiedler, Jan; Kaim, W.

    2017-01-01

    Roč. 643, č. 23 (2017), s. 1971-1977 ISSN 0044-2313 Institutional support: RVO:61388955 Keywords : 1,1´-bis(diorganophosphanyl)ferrocenes * cobalt * electrochemistry Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 1.144, year: 2016

  5. MACSAT - A Near Equatorial Earth Observation Mission

    Science.gov (United States)

    Kim, B. J.; Park, S.; Kim, E.-E.; Park, W.; Chang, H.; Seon, J.

    MACSAT mission was initiated by Malaysia to launch a high-resolution remote sensing satellite into Near Equatorial Orbit (NEO). Due to its geographical location, Malaysia can have large benefits from NEO satellite operation. From the baseline circular orbit of 685 km altitude with 7 degrees of inclination, the neighboring regions around Malaysian territory can be frequently monitored. The equatorial environment around the globe can also be regularly observed with unique revisit characteristics. The primary mission objective of MACSAT program is to develop and validate technologies for a near equatorial orbit remote sensing satellite system. MACSAT is optimally designed to accommodate an electro-optic Earth observation payload, Medium-sized Aperture Camera (MAC). Malaysian and Korean joint engineering teams are formed for the effective implementation of the satellite system. An integrated team approach is adopted for the joint development for MACSAT. MAC is a pushbroom type camera with 2.5 m of Ground Sampling Distance (GSD) in panchromatic band and 5 m of GSD in four multi-spectral bands. The satellite platform is a mini-class satellite. Including MAC payload, the satellite weighs under 200 kg. Spacecraft bus is designed optimally to support payload operations during 3 years of mission life. The payload has 20 km of swath width with +/- 30 o of tilting capability. 32 Gbits of solid state recorder is implemented as the mass image storage. The ground element is an integrated ground station for mission control and payload operation. It is equipped with S- band up/down link for commanding and telemetry reception as well as 30 Mbps class X-band down link for image reception and processing. The MACSAT system is capable of generating 1:25,000-scale image maps. It is also anticipated to have capability for cross-track stereo imaging for Digital elevation Model (DEM) generation.

  6. The equatorial F-layer: progress and puzzles

    Directory of Open Access Journals (Sweden)

    H. Rishbeth

    Full Text Available This work reviews some aspects of the ionospheric F-layer in the vicinity of the geomagnetic equator. Starting with a historical introduction, brief summaries are given of the physics that makes the equatorial ionosphere so interesting, concentrating on the large-scale structure rather than the smaller-scale instability phenomena. Several individual topics are then discussed, including eclipse effects, the asymmetries of the `equatorial trough', variations with longitude, the semiannual variation, the effects of the global thermospheric circulation, and finally the equatorial neutral thermosphere, including `superrotation' and possible topographic influences.

    Keyword: Ionosphere (equatorial ionosphere

  7. An equatorial coronal hole at solar minimum

    Science.gov (United States)

    Bromage, B. J. I.; DelZanna, G.; DeForest, C.; Thompson, B.; Clegg, J. R.

    1997-01-01

    The large transequatorial coronal hole that was observed in the solar corona at the end of August 1996 is presented. It consists of a north polar coronal hole called the 'elephant's trunk or tusk'. The observations of this coronal hole were carried out with the coronal diagnostic spectrometer onboard the Solar and Heliospheric Observatory (SOHO). The magnetic field associated with the equatorial coronal hole is strongly connected to that of the active region at its base, resulting in the two features rotating at almost the same rate.

  8. Reduction of dinitrogen ligands

    International Nuclear Information System (INIS)

    Richards, R.L.

    1983-01-01

    Processes of dinitrogen ligand reduction in complexes of transition metals are considered. The basic character of the dinitrogen ligand is underlined. Data on X-ray photoelectronic spectroscopy and intensities of bands ν (N 2 ) in IR-spectra of nitrogen complexes are given. The mechanism of protonation of an edge dinitrogen ligand is discussed. Model systems and mechanism of nitrogenogenase are compared

  9. Ozone Effects on Protein Carbonyl Content in the Frontal ...

    Science.gov (United States)

    Oxidative stress (OS) plays an important role in susceptibility and disease in old age. Understanding age-related susceptibility is a critical part of community-based human health risk assessment of chemical exposures. There is growing concern over a common air pollutant, ozone (03), and adverse health effects including dysfunction of the pulmonary, cardiac, and nervous systems. The objective of this study was to test whether OS plays a role in the adverse effects caused by 03 exposure, and if so, if effects were age-dependent. We selected protein carbonyl as an indicator of OS because carbonyl content of cells is a useful indicator of oxidative protein damage and has been linked to chemical-induced adverse effects. Male Brown Norway rats (4, 12, and 24 months) were exposed to 03 (0,0.25 or 1 ppm) via inhalation for 6 h/day, 2 days per week for 13 weeks. Frontal cortex (FC) and cerebellum (CB) were dissected, quick frozen on dry ice, and stored at -80°C. Protein carbonyls were assayed using commercial kits. Hydrogen peroxide, a positive control, increased protein carbonyls in cortical tissue in vitro in a concentration-dependent manner. Significant effects of age on protein carbonyls in FC and a significant effect of age and 03 dose on protein carbonyls in CB were observed. In control rats, there was an age-dependent increase in protein carbonyls indicating increased OS in 12 and 24 month old rats compared to 4 month old rats. Although 03 increase

  10. Preliminary report: STOIC CGCM intercomparison - equatorial sections

    International Nuclear Information System (INIS)

    Davey, M; Huddleston, M; Sperber, K R.

    1999-01-01

    An intercomparison and assessment of the tropical behaviour of coupled general circulation models (CGCMs) is being carried out, to identify common strengths and weaknesses and thus guide future CGCM development. The work is being carried out as part of the CLIVAR climate research programme, as a WG-SIP (Working Group on Seasonal to Interannual Prediction) project called STOIC (Study of Tropical Oceans In CGCMs), organised by Michael Davey. This project complements a companion sub-project called ENSIP (El Ni no Simulation Intercomparison Project) organised by Mojib Latif (Max- Planck-Institute for Meteorology) that focusses on equatorial Pacific CGCM behaviour (Latif et al. 1999). Previous coupled model assessments (Mechoso et al. 1995, Neelin et al. 1992, and ENSIP) have focussed on tropical Pacific behaviour. The aim of STOIC is to look at model performance in all tropical ocean regions. This status report contains a sample of the STOIC assessment work, highlighting mean and inter- annual equatorial sea surface temperatures and zonal windstresses. The intention is to submit STOIC and ENSIP papers in mid-1999 for publication together in a refereed journal

  11. Nighttime ionospheric D region: Equatorial and nonequatorial

    Science.gov (United States)

    Thomson, Neil R.; McRae, Wayne M.

    2009-08-01

    Nighttime ionospheric D region parameters are found to be generally well modeled by the traditional H‧ and β as used by Wait and by the U.S. Navy in their Earth-ionosphere VLF radio waveguide programs. New comparisons with nonequatorial, mainly all-sea VLF path observations reported over several decades are shown to be consistent with the previously determined height H‧ ˜ 85.0 km and sharpness β ˜ 0.63 km-1. These paths include NPM (Hawaii) to Washington, D. C., Omega Hawaii and NLK (Seattle) to Japan, NWC (N.W. Australia) to Madagascar, and NBA (Panama) to Colorado. In marked contrast, transequatorial path observations (even when nearly all-sea) are found to be often not well modeled: for example, for Omega Japan and JJI (Japan) to Dunedin, New Zealand, the observed amplitudes are markedly lower than those which would be expected from H‧ ˜ 85.0 km and β ˜ 0.63 km-1, or any other realistic values of H‧ and β. Other transequatorial observations compared with modeling include NWC to Japan, Omega Hawaii to Dunedin, and NPM (Hawaii) to Dunedin. It is suggested that the effects of irregularities in the equatorial electrojet may extend down into the nighttime D region and so account for the observed equatorial VLF perturbations through scattering or mode conversion.

  12. Midday reversal of equatorial ionospheric electric field

    Directory of Open Access Journals (Sweden)

    R. G. Rastogi

    1997-10-01

    Full Text Available A comparative study of the geomagnetic and ionospheric data at equatorial and low-latitude stations in India over the 20 year period 1956–1975 is described. The reversal of the electric field in the ionosphere over the magnetic equator during the midday hours indicated by the disappearance of the equatorial sporadic E region echoes on the ionograms is a rare phenomenon occurring on about 1% of time. Most of these events are associated with geomagnetically active periods. By comparing the simultaneous geomagnetic H field at Kodaikanal and at Alibag during the geomagnetic storms it is shown that ring current decreases are observed at both stations. However, an additional westward electric field is superimposed in the ionosphere during the main phase of the storm which can be strong enough to temporarily reverse the normally eastward electric field in the dayside ionosphere. It is suggested that these electric fields associated with the V×Bz electric fields originate at the magnetopause due to the interaction of the solar wind and the interplanetary magnetic field.

  13. Central Equatorial Pacific Experiment (CEPEX). Design document

    Energy Technology Data Exchange (ETDEWEB)

    1993-04-01

    The Earth`s climate has varied significantly in the past, yet climate records reveal that in the tropics, sea surface temperatures seem to have been remarkably stable, varying by less than a few degrees Celsius over geologic time. Today, the large warm pool of the western Pacific shows similar characteristics. Its surface temperature always exceeds 27{degree}C, but never 31{degree}C. Heightened interest in this observation has been stimulated by questions of global climate change and the exploration of stabilizing climate feedback processes. Efforts to understand the observed weak sensitivity of tropical sea surface temperatures to climate forcing has led to a number of competing ideas about the nature of this apparent thermostat. Although there remains disagreement on the processes that regulate tropical sea surface temperature, most agree that further progress in resolving these differences requires comprehensive field observations of three-dimensional water vapor concentrations, solar and infrared radiative fluxes, surface fluxes of heat and water vapor, and cloud microphysical properties. This document describes the Central Equatorial Pacific Experiment (CEPEX) plan to collect such observations over the central equatorial Pacific Ocean during March of 1993.

  14. Midday reversal of equatorial ionospheric electric field

    Directory of Open Access Journals (Sweden)

    R. G. Rastogi

    Full Text Available A comparative study of the geomagnetic and ionospheric data at equatorial and low-latitude stations in India over the 20 year period 1956–1975 is described. The reversal of the electric field in the ionosphere over the magnetic equator during the midday hours indicated by the disappearance of the equatorial sporadic E region echoes on the ionograms is a rare phenomenon occurring on about 1% of time. Most of these events are associated with geomagnetically active periods. By comparing the simultaneous geomagnetic H field at Kodaikanal and at Alibag during the geomagnetic storms it is shown that ring current decreases are observed at both stations. However, an additional westward electric field is superimposed in the ionosphere during the main phase of the storm which can be strong enough to temporarily reverse the normally eastward electric field in the dayside ionosphere. It is suggested that these electric fields associated with the V×Bz electric fields originate at the magnetopause due to the interaction of the solar wind and the interplanetary magnetic field.

  15. Determination of Carbonyl Compounds in Exhaled Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Moldoveanu S

    2014-12-01

    Full Text Available This paper presents the findings on a quantitative evaluation of carbonyl levels in exhaled cigarette smoke from human subjects. The cigarettes evaluated include products with 5.0 mg ‘tar’, 10.6 mg ‘tar’ and 16.2 mg ‘tar’, where ‘tar’ is defined as the weight of total wet particulate matter (TPM minus the weight of nicotine and water, and the cigarettes are smoked following U.S. Federal Trade Commission (FTC recommendations. The measured levels of carbonyls in the exhaled smoke were compared with calculated yields of carbonyls in the inhaled smoke and a retention efficiency was obtained. The number of human subjects included a total of ten smokers for the 10.6 mg ‘tar’, five for the 16.2 mg ‘tar’, and five for the 5.0 mg ‘tar’ product, each subject smoking three cigarettes. The analyzed carbonyl compounds included several aldehydes (formaldehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde and n-butyraldehyde, and two ketones (acetone and 2-butanone. The smoke collection from the human subjects was vacuum assisted. Exhaled smoke was collected on Cambridge pads pretreated with a solution of dinitrophenylhydrazine (DNPH followed by high performance liquid chromatography (HPLC analysis of the dinitrophenylhydrazones of the carbonyl compounds. The cigarette butts from the smokers were collected and analyzed for nicotine. The nicotine levels for the cigarette butts from the smokers were used to calculate the level of carbonyls in the inhaled smoke, based on calibration curves. These were generated separately by analyzing the carbonyls in smoke and the nicotine in the cigarette butts obtained by machine smoking under different puffing regimes. The comparison of the level of carbonyl compounds in exhaled smoke with that from the inhaled smoke showed high retention of all the carbonyls. The retention of aldehydes was above 95% for all three different ‘tar’ levels cigarettes. The ketones were retained with a

  16. Emissions of carbonyl compounds from various cookstoves in China

    International Nuclear Information System (INIS)

    Zhang, J.; Smith, K.R.; Univ. of California, Berkeley, CA

    1999-01-01

    This paper presents a new database of carbonyl emission factors for commonly used cookstoves in China. The emission factors, reported both on a fuel-mass basis (mg/kg) and on a defined cooking-task basis (mg/task), were determined using a carbon balance approach for 22 types of fuel/stove combinations. These include various stoves using different species of crop residues and wood, kerosene, and several types of coals and gases. The results show that all the tested cookstoves produced formaldehyde and acetaldehyde and that the vast majority of the biomass stoves produced additional carbonyl compounds such as acetone, acrolein, propionaldehyde, crotonaldehyde, 2-butanone, isobutyraldehyde, butyraldehyde, isovaleraldehyde, valeraldehyde, hexaldehyde, benzaldehyde, o-tolualdehyde, m,p-tolualdehyde, and 2,4-dimethylbenzaldehyde. Carbonyls other than formaldehyde and acetaldehyde, however, were rarely generated by burning coal, coal gas, and natural gas. Kerosene and LPG stoves generated more carbonyl compounds than coal, coal gas, and natural gas stoves, but less than biomass stoves. Indoor levels of carbonyl compounds for typical village houses during cooking hours, estimated using a mass balance model and the measured emission factors, can be high enough to cause acute health effects documented for formaldehyde exposure, depending upon house parameters and individuals' susceptibility

  17. Ligands in PSI structures

    International Nuclear Information System (INIS)

    Kumar, Abhinav; Chiu, Hsiu-Ju; Axelrod, Herbert L.; Morse, Andrew; Elsliger, Marc-André; Wilson, Ian A.; Deacon, Ashley

    2010-01-01

    A survey of the types and frequency of ligands that are bound to PSI structures is analyzed as well as their utility in functional annotation of previously uncharacterized proteins. Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a survey of the types, variety and frequency of ligands that are observed in the PSI structures is also compiled and analyzed, including illustrations of how these bound ligands have provided functional clues for annotation of proteins with little or no previous experimental characterization. Furthermore, a web server was developed as a tool to mine and analyze the PSI structures for bound ligands and other identifying features

  18. The D1 parameter for the equatorial F1 region

    International Nuclear Information System (INIS)

    Adeniyi, J.O.; Radicella, S.M.

    2002-01-01

    This work is a contribution to the effort at improving the representation of the F1 equatorial ionospheric region in the International Reference Ionosphere (IRI) model. The D1 parameter has been proposed for describing the F1 layer. We have therefore produced a maiden table of D1 parameter for an equatorial station. Diurnal and seasonal effects were considered. (author)

  19. Reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2) with isocyanides. 5. Mixed carbonyl-isocyanide and carbonyl-isocyanide-nitrile complexes of stoichiometry (Re2Cl3(dppm)2(CO)(CNR)(L))PF6 (R = t-Bu, xyl (Xylyl); L = t-BuNC, xylNC, MeCN, EtCN). Structural characterization of the cation (Cl2(CO)Re(μ-dppm)2ReCl (CN-t-Bu)2)+

    International Nuclear Information System (INIS)

    Fanwick, P.E.; Price, A.C.; Walton, R.A.

    1988-01-01

    Several dirhenium (II) species that contain mixed sets of carbonyl, isocyanide, and/or nitrile ligands have been prepared from the reactions between Re 2 Cl 4 (dppm) 2 (CO)(CNR) (dppm = Ph 2 PCHPPh 2 ; R = t-Bu, xyl (xylyl)), and the appropriate ligands in the presence of TlPF 6 . The crystal structures of these compounds are reported. The terminally-bound ligand noted in the complexes (Re 2 Cl 3 (dppm) 2 (CO)(CN-t-Bu) 2 )PF 6 and (Re 2 CL 3 (dppm) 2 (CO)(CN-t-Bu)(CNxyl))PF 6 indicates structures that have not been previously reported. Complexes in which there are mixed sets of carbonyl, isocyanide, and nitrile ligands, viz. (Re 2 Cl 3 (dppm) 2 (CO)(CNR)(CNR'))PF 6 are also reported. 20 refs., 1 fig., 5 tabs

  20. Equatorial electrojet and its response to external electromagnetic effects

    Science.gov (United States)

    Bespalov, P. A.; Savina, O. N.

    2012-09-01

    In the quiet low-latitude Earth's ionosphere, a sufficiently developed current system that is responsible for the Sq magnetic-field variations is formed in quiet Sun days under the action of tidal streams. The density of the corresponding currents is maximum in the midday hours at the equatorial latitudes, where the so-called equatorial electrojet is formed. In this work, we discuss the nature of the equatorial electrojet. This paper studies the value of its response to external effects. First of all, it is concerned with estimating the possibility of using the equatorial electrojet for generating low-frequency electromagnetic signals during periodic heating of the ionosphere by the heating-facility radiation. The equatorial electrojet can also produce electrodynamic response to the natural atmospheric processes, e.g., an acoustic-gravity wave.

  1. Catalytic production of metal carbonyls from metal oxides

    Science.gov (United States)

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  2. Long wavelength irregularities in the equatorial electrojet

    International Nuclear Information System (INIS)

    Kudeki, E.; Farley, D.T.; Fejer, B.G.

    1982-01-01

    We have used the radar interferometer technique at Jicamarca to study in detail irregularities with wavelengths of a few kilometers generated in the unstable equatorial electrojet plasma during strong type 1 conditions. In-situ rocket observations of the same instability process are discussed in a companion paper. These large scale primary waves travel essentially horizontally and have large amplitudes. The vertical electron drift velocities driven by the horizontal wave electric fields reach or exceed the ion-acoustic velocity even though the horizontal phase velocity of the wave is considerably smaller. A straightforward extension to the long wavelength regime of the usual linear theory of the electrojet instability explains this and several other observed features of these dominant primary waves

  3. Linear theory of equatorial spread F

    International Nuclear Information System (INIS)

    Hudson, M.K.; Kennel, C.F.

    1975-01-01

    A fluid dispersion relation for the drift and interchange (Rayleigh-Taylor) modes in a collisional plasma forms the basis for a linear theory of equatorial spread F. The collisional drift mode growth rate will exceed the growth rate of the Rayleigh-Taylor mode at short perpendicular wavelengths and density gradient scale lengths, and the drift mode can grow on top side as well as on bottom side density gradients. However, below the F peak, where spread F predominates, it is concluded that both the drift and the Rayleigh-Taylor modes contribute to the total spread F spectrum, the Rayleigh-Taylor mode dominating at long and the drift mode at short perpendicular wavelengths above the ion Larmor radius

  4. Equatorial circular motion in Kerr spacetime

    International Nuclear Information System (INIS)

    Pugliese, Daniela; Quevedo, Hernando; Ruffini, Remo

    2011-01-01

    We analyze the properties of circular orbits of test particles on the equatorial plane of a rotating central mass whose gravitational field is described by the Kerr spacetime. For rotating black holes and naked singularities we explore all the spatial regions where circular orbits can exist and analyze the behavior of the energy and the angular momentum of the corresponding test particles. In particular, we find all the radii at which a test particle can have zero angular momentum due to the repulsive gravity effects generated by naked singularities. We classify all the stability zones of circular orbits. It is shown that the geometric structure of the stability zones of black holes is completely different from that of naked singularities.

  5. Designer ligands. Part 14. Novel Mn(lI), Ni(II) and Zn(II) complexes of benzamide- and biphenyl-derived ligands

    CSIR Research Space (South Africa)

    Wellington, Kevin W

    2009-01-01

    Full Text Available . Results and Discussion The ligands 1a-c (Scheme 1) were prepared by treating benzoic acid with carbonyl diimidazole (CDI)13 in dimethylformamide (DMF), followed by the respective primary amines, histamine, 2- (2-aminoethyl)benzimidazole and 2...-(2-aminoethyl)pyridine. [Histamine had to be released from its dihydrochloride salt by treatment with sodium methoxide, while 2-(2- aminoethyl)benzimidazole was prepared from 1,2-diaminobenzene and β-alanine.16] The synthesis of the biphenyl-derived ligand 2...

  6. Dynamical variability in Saturn Equatorial Atmosphere

    Science.gov (United States)

    Sánchez-Lavega, A.; Pérez-Hoyos, S.; Hueso, R.; Rojas, J. F.; French, R. G.; Grupo Ciencias Planetarias Team

    2003-05-01

    Historical ground-based and recent HST observations show that Saturn's Equatorial Atmosphere is the region where the most intense large-scale dynamical variability took place at cloud level in the planet. Large-scale convective storms (nicknamed the ``Great White Spots") occurred in 1876, 1933 and 1990. The best studied case (the 1990 storm), produced a dramatic change in the cloud aspect in the years following the outburst of September 1990. Subsequently, a new large storm formed in 1994 and from 1996 to 2002 our HST observations showed periods of unusual cloud activity in the southern part of the Equator. This contrast with the aspect observed during the Voyager 1 and 2 encounters in 1980 and 1981 when the Equator was calm, except for some mid-scale plume-like features seen in 1981. Cloud-tracking of the features have revealed a dramatic slow down in the equatorial winds from maximum velocities of ˜ 475 m/s in 1980-1981 to ˜ 275 m/s during 1996-2002, as we have recently reported in Nature, Vol. 423, 623 (2003). We discuss the possibility that seasonal and ring-shadowing effects are involved in generating this activity and variability. Acknowledgements: This work was supported by the Spanish MCYT PNAYA 2000-0932. SPH acknowledges a PhD fellowship from the Spanish MECD and RH a post-doc fellowship from Gobierno Vasco. RGF was supported in part by NASA's Planetary Geology and Geophysics Program NAG5-10197 and STSCI Grant GO-08660.01A.

  7. Proton flux under radiation belts: near-equatorial zone

    International Nuclear Information System (INIS)

    Grigoryan, O.R.; Panasyuk, M.I.; Petrov, A.N.; Kudela, K.

    2005-01-01

    In this work the features of low-energy proton flux increases in near-equatorial region (McIlvein parameter L th the proton flux (with energy from tens keV up to several MeV) increases are registering regularly. However modern proton flux models (for example AP8 model) works at L>1.15 only and does not take into account near-equatorial protons. These fluxes are not too big, but the investigation of this phenomenon is important in scope of atmosphere-ionosphere connections and mechanisms of particles transport in magnetosphere. In according to double charge-exchange model the proton flux in near-equatorial region does not depend on geomagnetic local time (MLT) and longitude. However the Azur satellite data and Kosmos-484, MIR station and Active satellite data revealed the proton flux dependence on longitude. The other feature of near-equatorial proton flux is the dependence on geomagnetic local time revealed in the Sampex satellite experiment and other experiments listed above. In this work the dependences on MLT and longitude are investigated using the Active satellite (30-500 keV) and Sampex satellite (>800 keV). This data confirms that main sources of near-equatorial protons are radiation belts and ring current. The other result is that near-equatorial protons are quasi-trapped. The empirical proton flux dependences on L, B at near-equatorial longitudes are presented. (author)

  8. Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Hall, Gabriel B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chatterjee, Sayandev [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Martin, Thibaut J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wall, Nathalie [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walter, Eric D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-11-24

    Among long-lived radioactive constituents in the Hanford tank waste, Tc presents a unique challenge in that it exists predominantly in the liquid phase, generally in the anionic form of pertechnetate, TcO4-, which is highly volatile at low-activity waste (LAW) vitrification melter temperatures and mobile in the Hanford site’s subsurface environment. The complex behavior of Tc under storage, treatment, and immobilization conditions significantly affects its management options, which to-date remain uncertain. In strongly alkaline environments, Tc exists as pertechnetate, TcO4- (oxidation state +7), and in the reduced forms (oxidation state < +7) collectively known as non-pertechnetate species. Pertechnetate is a well-characterized, anionic Tc species that can be removed from LAW by anion exchange or solvent extraction methods. There is no definitive information on the origin of the non-pertechnetate Tc species, nor is there a comprehensive description of their composition and behavior. It has been recently proposed that the non-pertechnetate species can comprise Tc(I) metal center and carbonyl or mixed carbonyl nitrosyl ligands stabilizing low-valent Tc. Recent work by our group has significantly expanded this previous work, generating a series of Tc(I) carbonyl compounds and demonstrating that they can be generated from reduction of TcO4- in the simulated Hanford tank waste in presence of CO at elevated temperature (Levitskaia et al. 2014). These results are consistent with the previous proposal that [Tc(CO)3]+ species can be present in the Hanford tank waste and suggest that the low Tc(I) oxidation state is stabilized by the π-accepting ability of the CO ligands. The continuation work has been initiated to develop model Tc carbonyl nitrosyl compounds and investigate their potential presence in the Hanford tank wastes. This report summarizes our to-date results.

  9. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  10. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    Science.gov (United States)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  11. Plasma protein carbonyl levels and breast cancer risk

    Czech Academy of Sciences Publication Activity Database

    Rössner ml., Pavel; Terry, M. B.; Gammon, M. D.; Agrawal, M.; Zhang, F. F.; Ferris, J.S.; Teitelbaum, S. L.; Eng, S. M.; Gaudet, M. M.; Neugut, A. I.; Santella, R. M.

    2007-01-01

    Roč. 11, č. 5 (2007), s. 1138-1148 ISSN 1582-1838 Institutional research plan: CEZ:AV0Z50390512 Keywords : oxidative stress * protein carbonyl * breast cancer Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 6.807, year: 2007

  12. Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

    DEFF Research Database (Denmark)

    Zahrtmann, Nanette; Claver, Carmen; Godard, Cyril

    2018-01-01

    A catalytic system for the selective oxidative carbonylation of aniline to diphenylurea based on Pd complexes in combination with imidazolium ionic liquids is presented. Both oxidants, Pd complexes and ionic liquids affect the activity of the reaction while the choice of oxidant determines...

  13. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Unknown

    cited state energy of the olefin must be higher than that of the ketone so that ... the first singlet and triplet1,3 (n, π*) excited state of the carbonyl compounds.3,4 ... of the oxetane via carbon–carbon and carbon–oxygen attacks. They found the ...

  14. Olefination of carbonyl compounds: modern and classical methods

    Energy Technology Data Exchange (ETDEWEB)

    Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2004-10-31

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  15. Olefination of carbonyl compounds: modern and classical methods

    Science.gov (United States)

    Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.

    2004-10-01

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  16. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  17. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili

    2017-10-12

    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons

  18. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    NARCIS (Netherlands)

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be

  19. Ligand intermediates in metal-catalyzed reactions; Annual technical report, August 1, 1992--August 1, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Gladysz, J.A.

    1993-08-10

    Achievements are reported for the following 4 areas: {pi}/{sigma} equillibria in aldehyde and ketone complexes; thermodynamic ligand binding affinities ({alpha},{beta} unsaturated organic carbonyl compounds); (a new form of coordinated carbon) an unsupported C{sub 3} chain that spans two different transition metals; and (a new form of coordinated carbon) an C{sub 3} chain that is anchored by a metal on each end and spanned by a third.

  20. Schiff base ligand

    Indian Academy of Sciences (India)

    Unknown

    Low-temperature stoichiometric Schiff base reaction in air in 3 : 1 mole ratio between benz- aldehyde and triethylenetetramine (trien) in methanol yields a novel tetraaza µ-bis(bidentate) acyclic ligand L. It was .... electrochemical work was performed as reported in ..... change in ligand shape through change in oxidation.

  1. Equatorial wave activity during 2007 over Gadanki, a tropical station

    Indian Academy of Sciences (India)

    been used to investigate the wave activity in the troposphere and lower stratosphere. Waves in the ...... Oltmans S J 2001 Water vapor control at the tropopause by equatorial Kelvin .... observed in UARS microwave limb sounder temperature.

  2. An overview on the equatorial electrojet theoretical grounds

    International Nuclear Information System (INIS)

    Zamlutti, C.J.; Sobral, J.H.A.; Abdu, M.A.

    1988-01-01

    The grounds on which the equatorial electrojet theory is based are reexamined in a way as to suggest specific additional implementations in the existing electrodynamical modeling of this phenomena, making use of now existing improved computer processing speeds. (author) [pt

  3. ITER L 6 equatorial maintenance duct remote handling study

    International Nuclear Information System (INIS)

    Millard, J.

    1996-09-01

    The status and conclusions of a preliminary study of equatorial maintenance duct remote handling is reported. Due to issues with the original duct design a significant portion of the study had to be refocused on equatorial duct layout studies. The study gives an overview of some of the options for design of these ducts and the impact of the design on the equipment to work in the duct. To develop a remote handling concept for creating access through the ducts the following design tasks should be performed: define the operations sequences for equatorial maintenance duct opening and closing; review the remote handling requirements for equatorial maintenance duct opening and closing; design concept for door and pipe handling equipment and to propose preliminary procedures for material handling outsides the duct. 35 figs

  4. Modelling the development of mixing height in near equatorial region

    Energy Technology Data Exchange (ETDEWEB)

    Samah, A.A. [Univ. of Malaya, Air Pollution Research Unit, Kuala Lumpur (Malaysia)

    1997-10-01

    Most current air pollution models were developed for mid-latitude conditions and as such many of the empirical parameters used were based on observations taken in the mid-latitude boundary layer which is physically different from that of the equatorial boundary layer. In the equatorial boundary layer the Coriolis parameter f is small or zero and moisture plays a more important role in the control of stability and the surface energy balance. Therefore air pollution models such as the OMLMULTI or the ADMS which were basically developed for mid-latitude conditions must be applied with some caution and would need some adaptation to properly simulate the properties of equatorial boundary layer. This work elucidates some of the problems of modelling the evolution of mixing height in the equatorial region. The mixing height estimates were compared with routine observations taken during a severe air pollution episodes in Malaysia. (au)

  5. Onset conditions for equatorial spread F

    International Nuclear Information System (INIS)

    Mendillo, M.; Baumgardner, J.; Xiaoqing Pi; Sultan, P.J.; Tsunoda, R.

    1992-01-01

    The problem of day-to-day variability in the occurrence of equatorial spread F (ESF) is addressed using multidiagnostic observations and semiempirical modeling. The observational results are derived from a two-night case study of ESF onset conditions observed at Kwajalein Atoll (Marshall Islands) using the ALTAIR incoherent scatter radar and all-sky optical imaging techniques. The major difference between nights when ESF instabilities did not occur (August 14, 1988) and did occur (August 15, 1988) in the Kwajalein sector was that the northern meridional gradient of 6300-angstrom airglow was reduced on the night of limited ESF activity. Modeling results suggest that this unusual airglow pattern is due to equatorward neutral winds. Previous researchers have shown that transequatorial thermospheric winds can exert a control over ESF seasonal and longitudinal occurrence patterns by inhibiting Rayleigh-Taylor instability growth rates. They present evidence to suggest that this picture can be extended to far shorter time scales, namely, that 'surges' in transequatoral winds acting over characteristic times of a few hours to a day can result in a stabilizing influence upon irregularity growth rates. The seemingly capricious nature of ESF onset may thus be controlled, in part, by the inherent variability of low-latitude thermospheric winds

  6. An equatorial temperature and wind anomaly (ETWA)

    International Nuclear Information System (INIS)

    Raghavarao, R.; Wharton, L.E.; Mayr, H.G.; Brace, L.H.; Spencer, N.W.

    1991-01-01

    Data obtained from the WATS (Wind and Temperature Spectrometer) and LP (Langmuir Probe) experiments on board DE-2 (Dynamic Explorer) during high solar activity show evidence of anomalous latitudinal variations in the zonal winds and temperature at low latitudes. The zonal winds exhibit a broad maximum centered around the dip equator, flanked by minima on either side around 25 degrees; while the temperature exhibits a pronounced bowl-shaped minimum at the dip equator which is flanked by maxima. The two minima in the zonal winds and the corresponding maxima in the temperature are nearly collocated with the crests of the well known Equatorial Ionization Anomaly (EIA). The maximum in the zonal winds and the minimum in the gas temperature are collected with the trough of the EIA. The differences between the maxima and minima in temperature and zonal winds, on many occasions, are observed to exceed 100 K and 100 m/s, respectively. The characteristics of this new phenomenon have eluded present day empirical models of thermospheric temperature and winds. The connection among these variables can be understood from the ion-neutral drag effect on the motions of the neutrals that in turn affect their energy balance

  7. Plasma instabilities multifrequency study in equatorial electrojet

    International Nuclear Information System (INIS)

    Hanuise, C.

    1983-01-01

    In this thesis, multifrequential HF coherent radar results are presented, in the field plasma instabilities in equatorial electrojet. In a first part, characteristics of the irregularities observed either at the 3 meter wavelength by VHF radars, either at other wavelengths during pinpoint experiments, or in-situ by probe rockets are recalled. Theoretical studies progressed and are presented, at the same time with these experimental observations: instability linear theory, non linear theories, HF radar specificity, and problems associated to HF waves propagation and refraction in ionosphere. Original experimental results from Ethiopia are gathered in the second part. Plasma instability has been studied in different geophysical conditions and Doppler spectra characteristics are presented for each one of them. These characteristics are completely different according to the various cases; they are also different according to wether observations are made during the day in normal conditions (electric field pointed to the east at the equator) or in counter-electrojet conditions (electric field pointed to the west). The last part is concerned with theoretical interpretation of the previous results. A comprehensive view of the instability physical mechanisms, according to the geophysical conditions encountered, has been allowed by our results, VHF radar measurements at Jicamarca, or in situ probe measurements on the whole. Irregularities study has been limited to the E region [fr

  8. Condor equatorial electrojet campaign: Radar results

    International Nuclear Information System (INIS)

    Kudeki, E.; Fejer, B.G.; Farley, D.T.; Hanuise, C.

    1987-01-01

    A review of the experimental and theoretical background to the Condor equatorial electrojet compaign is followed by the presentation and discussion of VHF radar interferometer and HF radar backscatter data taken concurrently with two rocket in situ experiments reported in companion papers (Pfaff et al., this issue (a, b). Both experiments were conducted in strongly driven periods with the on-line radar interferometer displaying signatures of what has been interpreted in earlier radar work (Kudeki et al., 1982) as kilometer scale gradient drift waves. Low-frequency density fluctuations detected by in situ rocket sensors confirm the earlier interpretation. VHF radar/rocket data comparisons also indicate the existence of a turbulent layer in the upper portion of the daytime electrojet at about 108 km altitude driven purely by the two-stream instability. Nonlinear mode coupling of linearly growing two-stream waves to linearly damped 3-m vertical modes could account for the radar echoes scattered from this layer, which showed no indication of large-scale gradient drift waves. Nonlinear mode coupling may therefore compete with the wave-induced anomalous diffusion mechanism proposed recently by Sudan (1983) for the saturation of directly excited two-stream waves. Nighttime radar data show a bifurcated layer with the two parts having comparable echo strength but oppositely directed zonal drift velocities. The lower layer shows narrow backscatter spectra; the upper layer is characterized by kilometer scale waves and vertically propagating type 1 waves

  9. Radiation protection in hospitals of Equatorial Guinea

    International Nuclear Information System (INIS)

    Rabat Macambo, P.

    2001-01-01

    With a population of four hundred thousand (400.000) inhabitants and distributed in a territory of 28 thousand (28.000) km 2 , the use of ionizing radiations for medical practice in Equatorial Guinea is few and decreasing. It is used for diagnostic practices in the main hospitals of the country, where the work burden is not over 20 patients per day. The political, social and economical embryonic development of the country until recently had a negative influence on indicators and health organisations, so that even now the country does not have any radiological protection law, this shortness, in addition with the old architectural structure that x ray tools is lodging, as well as dosimetrical lack of employed staff, put this staff under risk of electromagnetic energy. This is to show the present survey of medical activities with ionizing radiation and to request technical support for implementing suitably the basic standards of radiation protection which will help us as basis for the elaboration outline law, on radiological protection in accordance with the new guidelines of the International Atomic Energy Agency. (author)

  10. Sampling and energy evaluation challenges in ligand binding protein design.

    Science.gov (United States)

    Dou, Jiayi; Doyle, Lindsey; Jr Greisen, Per; Schena, Alberto; Park, Hahnbeom; Johnsson, Kai; Stoddard, Barry L; Baker, David

    2017-12-01

    The steroid hormone 17α-hydroxylprogesterone (17-OHP) is a biomarker for congenital adrenal hyperplasia and hence there is considerable interest in development of sensors for this compound. We used computational protein design to generate protein models with binding sites for 17-OHP containing an extended, nonpolar, shape-complementary binding pocket for the four-ring core of the compound, and hydrogen bonding residues at the base of the pocket to interact with carbonyl and hydroxyl groups at the more polar end of the ligand. Eight of 16 designed proteins experimentally tested bind 17-OHP with micromolar affinity. A co-crystal structure of one of the designs revealed that 17-OHP is rotated 180° around a pseudo-two-fold axis in the compound and displays multiple binding modes within the pocket, while still interacting with all of the designed residues in the engineered site. Subsequent rounds of mutagenesis and binding selection improved the ligand affinity to nanomolar range, while appearing to constrain the ligand to a single bound conformation that maintains the same "flipped" orientation relative to the original design. We trace the discrepancy in the design calculations to two sources: first, a failure to model subtle backbone changes which alter the distribution of sidechain rotameric states and second, an underestimation of the energetic cost of desolvating the carbonyl and hydroxyl groups of the ligand. The difference between design model and crystal structure thus arises from both sampling limitations and energy function inaccuracies that are exacerbated by the near two-fold symmetry of the molecule. © 2017 The Authors Protein Science published by Wiley Periodicals, Inc. on behalf of The Protein Society.

  11. Accumulation of carbonyls accelerates the formation of pentosidine, an advanced glycation end product: carbonyl stress in uremia.

    Science.gov (United States)

    Miyata, T; Ueda, Y; Yamada, Y; Izuhara, Y; Wada, T; Jadoul, M; Saito, A; Kurokawa, K; van Ypersele de Strihou, C

    1998-12-01

    Advanced glycation end product (AGE) formation is related to hyperglycemia in diabetes but not in uremia, because plasma AGE levels do not differ between diabetic and nondiabetic hemodialysis patients. The mechanism of this phenomenon remains elusive. Previously, it was suggested that elevation of AGE levels in uremia might result from the accumulation of unknown AGE precursors. The present study evaluates the in vitro generation of pentosidine, a well identified AGE structure. Plasma samples from healthy subjects and nondiabetic hemodialysis patients were incubated under air for several weeks. Pentosidine levels were determined at intervals by HPLC assay. Pentosidine rose to a much larger extent in uremic than in control plasma. Pentosidine yield, i.e., the change in pentosidine level between 0 and 4 wk divided by 28 d, averaged 0.172 nmol/ml per d in uremic versus 0.072 nmol/ml per d in control plasma (P aminoguanidine and OPB-9195, which inhibit the Maillard reaction, lowered pentosidine yield in both uremic and control plasma. When ultrafiltrated plasma was exposed to 2,4-dinitrophenylhydrazine, the yield of hydrazones, formed by interaction with carbonyl groups, was markedly higher in uremic than in control plasma. These observations strongly suggest that the pentosidine precursors accumulated in uremic plasma are carbonyl compounds. These precursors are unrelated to glucose or ascorbic acid, whose concentration is either normal or lowered in uremic plasma. They are also unrelated to 3-deoxyglucosone, a glucose-derived dicarbonyl compound whose level is raised in uremic plasma: Its addition to normal plasma fails to increase pentosidine yield. This study reports an elevated level of reactive carbonyl compounds ("carbonyl stress") in uremic plasma. Most have a lower than 5000 Da molecular weight and are thus partly removed by hemodialysis. Their effect on pentosidine generation can be inhibited by aminoguanidine or OPB-9195. Carbonyl stress might contribute to

  12. Intraseasonal vertical velocity variation caused by the equatorial wave in the central equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Horii, T.; Masumoto, Y.; Ueki, I.; PrasannaKumar, S.; Mizuno, K.

    to the theoretical solution of the equatorial waves [Matsuno, 1966] and the phase speed of the baroclinic mode, the wave that has meridional current on the equator with a quasi-biweekly period is the anti-symmetric mixed Rossby-gravity wave. In the wave... and conclusions are given in section 5. 2. Field Experiment, Data, and Methods 2.1. MISMO Ocean Observation [8] The goal of MISMO was to observe atmospheric conditions and variability associated with intraseasonal disturbances and resulting ocean responses...

  13. Time dependent response of equatorial ionospheric electric fieldsto magnetospheric disturbances

    OpenAIRE

    Fejer, Bela G.; Scherliess, L.

    1995-01-01

    We use extensive radar measurements of F region vertical plasma drifts and auroral electrojet indices to determine the storm time dependence of equatorial zonal electric fields. These disturbance drifts result from the prompt penetration of high latitude electric fields and from the dynamo action of storm time winds which produce largest perturbations a few hours after the onset of magnetic activity. The signatures of the equatorial disturbance electric fields change significantly depending o...

  14. Equatorial ionospheric electric fields during the November 2004 magnetic storm

    OpenAIRE

    Fejer, Bela G.; Jensen, J. W.; Kikuchi, T.; Abdu, M. A.; Chau, J. L.

    2007-01-01

    [1] We use radar measurements from the Jicamarca Radio Observatory, magnetometer observations from the Pacific sector and ionosonde data from Brazil to study equatorial ionospheric electric fields during the November 2004 geomagnetic storm. Our data show very large eastward and westward daytime electrojet current perturbations with lifetimes of about an hour (indicative of undershielding and overshielding prompt penetration electric fields) in the Pacific equatorial region during the November...

  15. Performance evaluation of GPS receiver under equatorial scintillation

    Directory of Open Access Journals (Sweden)

    Alison de Oliveira Moraes

    2009-06-01

    Full Text Available Equatorial scintillation is a phenomenon that occurs daily in the equatorial region after the sunset and affects radio signals that propagate through the ionosphere. Depending on the temporal and spatial situation, equatorial scintillation can represent a problem in the availability and precision of the Global Positioning System (GPS. This work is concerned with evaluating the impact of equatorial scintillation on the performance of GPS receivers. First, the morphology and statistical model of equatorial scintillation is briefly presented. A numerical model that generates synthetic scintillation data to simulate the effects of equatorial scintillation is presented. An overview of the main theoretical principles on GPS receivers is presented. The analytical models that describe the effects of scintillation at receiver level are presented and compared with numerical simulations using a radio software receiver and synthetic data. The results achieved by simulation agreed quite well with those predicted by the analytical models. The only exception is for links with extreme levels of scintillation and when weak signals are received.

  16. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  17. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  18. Authigenic Uranium in Eastern Equatorial Pacific Sediments

    Science.gov (United States)

    Marcantonio, F.; Lyle, M. W.; Loveley, M. R.; Ibrahim, R.

    2014-12-01

    Authigenic U concentrations have been used as an indicator of redox state in marine sediments. Soluble U(VI) in porewaters is reduced to insoluble U(IV) under suboxic conditions setting up a diffusion gradient through which U in bottom waters is supplied to reducing sediments. Researchers have used sedimentary redox enrichment of U as a tool to identify past redox changes, which may be caused by changes in organic carbon rain rates and/or bottom water oxygen levels. Differentiating between these two explanations is important, as the former is tied to the use of authigenic U as a paleoproductivity proxy. We examined sediments from 4 sediment cores retrieved from two different localities in the Panama Basin in the eastern equatorial Pacific. Two cores were retrieved from the northern Panama basin at the Cocos Ridge, (4JC at 5° 44.7'N 85° 45.5' W, 1730 m depth; 8JC at 6° 14.0'N 86° 2.6' W, 1993 m depth), and two were retrieved from the south at the Carnegie Ridge, (11JC at 0° 41.6'S 85° 20.0' W, 2452 m depth; 17JC at 0° 10.8'S 85° 52.0' W, 2846 m depth). Using 230Th systematics and seismic profiling at each of the sites, we've identified significant sediment winnowing (4JC and 11JC) and focusing (8JC and 17JC). At all sites, we believe that changes in age-model-derived sand (i.e., >63µm) mass accumulation rates (MAR) best represent changes in rain rates. Glacial rain rates are higher than those in the Holocene by a factor of 2-3 at both sites. Peak Mn levels (>1%), the brown-to-green color transition (which likely represents the oxic/post-oxic boundary), and peak U concentrations all appear in the same order with increasing depth down core. At the Carnegie sites, where MARs are greater than those at the Cocos sites, increases in authigenic U (up to 4 ppm) occur during the mid- to late Holocene at depths of 10-15 cm. At the Cocos sites, increases in authigenic U (up to 12 ppm) occur lower in the sediment column (25-30 cm) during the late glacial. The decrease

  19. Measurements of carbonyls in a 13-story building.

    Science.gov (United States)

    Báez, Armando P; Padilla, Hugo G; García, Rocío M; Belmont, Raúl D; Torres, Maria del Carmen B

    2004-01-01

    Formaldehyde and acetaldehyde are emitted by many mobile and stationary sources and secondary aldehydes are intermediates in the photo-oxidation of organic compounds in the atmosphere. These aldehydes are emitted indoors by many materials such as furniture, carpets, heating and cooling systems, an by smoking. Carbonyls, mainly formaldehyde and acetaldehyde, have been studied because of their adverse health effects. In addition, formaldehyde is a suspected carcinogen. Therefore, the concentrations of formaldehyde and acetaldehyde were determined to assess the inhalation exposure doses to carbonyls for people who work in a 13-story building and in order to evaluate the cancer hazard. Carbonyl compounds in indoor and outdoor air were measured at a 13-story building located in Mexico City. The mezzanine, fifth and tenth floors, and the third level-parking garage were selected for sampling. Samples were collected in two sampling periods, the first from April 20 to 29, 1998 and the second from December 1 to 20, 1998. Carbonyls were sampled by means of DNHP-coated cartridges at a flow rate of 1 l min(-1) from 9:00 to 19:00 hours, during 2-hour time intervals and analyzed by HPLC with hours, during 2-hour time intervals and analyzed by HPLC with UV/VIS detection. Mean carbonyl concentrations were highest in the 3rd level-parking garage, with the formaldehyde concentration being the highest ranging from 108 to 418 microg m(-3). In working areas, the highest carbonyl arithmetic mean concentrations (AM) were observed on the 5th floor. Acetone and formaldehyde concentrations were highest in April ranging from 161 to 348 microg m(-3) (AM = 226) and from 157 to 270 microg m(-3) (AM = 221), respectively. Propionaldehyde and butyraldehyde were present in smaller concentrations ranging from 2 to 25 and 1 to 28 microg m(-3), respectively, considering all the samples. Mean indoor/outdoor ratios of carbonyls ranged from 1.8 to 9.6. A reduction of inhalation exposure doses of 41% and

  20. Anchoring selenido-carbonyl ruthenium clusters to functionalized silica xerogels

    International Nuclear Information System (INIS)

    Cauzzi, Daniele; Graiff, Claudia; Pattacini, Roberto; Predieri, Giovanni; Tiripicchio, Antonio

    2003-01-01

    Silica Xerogels containing carbonyl Ru 3 Se 2 nido clusters were prepared in three different ways. The simple dispersion of [Ru 3 (μ 3 -Se) 2 (CO) 7 (PPh 3 ) 2 ] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru 3 (μ 3 -Se) 2 (CO) 8 (PPh 3 )] with functionalized xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru 3 (CO) 12 ] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru 3 (CO) 12 ] and dodecyl diphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. (author)

  1. Reactions of α-phosphorylated carbonyl compounds with amino alcohols

    International Nuclear Information System (INIS)

    Moskva, V.V.; Sitdikova, T.Sh.; Zykova, T.V.; Alparova, M.V.; Shagvaleev, F.Sh.

    1986-01-01

    2-Aminoethanol reacts with carbonyl compounds with the formation, depending on the structure of the latter, either of a mixture of azomethines and oxazolidines, or of only azomethines. In the development of investigations on the reactivity of α-phosphorylated carbonyl compounds the authors studied the reactions of a number of amino alcohols with phosphorylated acetaldehyde and acetone. In both cases they observed the formation of compounds of enamine structure, oxazolidines and azomethines were not observed. By means of NMR spectroscopy they established clearly the formation of the E-isomeric products. The 1 H, 31 P, and 13 C NMR spectra were recorded on a WP-80 spectrometer. Chemical shifts of protons and 13 C nuclei are given relative to TMS, and phosphorus nuclei relative to orthophosphoric acid

  2. Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

    Energy Technology Data Exchange (ETDEWEB)

    Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)

    1995-12-31

    A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

  3. A three-membered ring approach to carbonyl olefination.

    Science.gov (United States)

    Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno

    2017-10-23

    The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

  4. Emissions of Toxic Carbonyls in an Electronic Cigarette

    Directory of Open Access Journals (Sweden)

    Guthery William

    2016-01-01

    Full Text Available Electronic cigarettes (e-cigs provide a smoke-free alternative for inhalation of nicotine without the vast array of toxic and carcinogenic combustion products produced by tobacco smoke. Elevated levels of toxic carbonyls may be generated during vaporisation; however, it is unclear whether that is indicative of a fault with the device or is due to the applied conditions of the test. A device, designed and built at this facility, was tested to determine the levels of selected toxic carbonyls. The reservoir was filled with approximately 960 mg of an e-liquid formulation containing 1.8% (w/v nicotine. Devices were puffed 200 times in blocks of 40 using a standardised regime consisting of a 55 mL puff volume; 3 s puff duration; 30 s puff interval; square wave puff profile. Confirmatory testing for nicotine and total aerosol delivery resulted in mean (n = 8 values of 10 mg (RSD 12.3% and 716 mg (RSD 11.2%, respectively. Emissions of toxic carbonyls were highly variable yet were between < 0.1% and 22.9% of expected levels from a Kentucky Reference Cigarette (K3R4F puffed 200 times under Health Canada Intense smoking conditions. It has been shown that a device built to a high specification with relatively consistent nicotine and aerosol delivery emits inconsistent levels of carbonyls. The exposure is greatly reduced when compared with lit tobacco products. However, it was observed that as the reservoirs neared depletion then emission levels were significantly higher

  5. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr

    2015-01-01

    Roč. 169, Jan (2015), s. 24-31 ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant - others:GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.213, year: 2015

  6. Magnetophoretic manipulation in microsystem using carbonyl iron-polydimethylsiloxane microstructures

    OpenAIRE

    Faivre, Magalie; Gelszinnis, Renaud; Degouttes, Jérôme; Terrier, Nicolas; Rivière, Charlotte; Ferrigno, Rosaria; Deman, Anne-Laure

    2014-01-01

    This paper reports the use of a recent composite material, noted hereafter i-PDMS, made of carbonyl iron microparticles mixed in a PolyDiMethylSiloxane (PDMS) matrix, for magnetophoretic functions such as capture and separation of magnetic species. We demonstrated that this composite which combine the advantages of both components, can locally generate high gradients of magnetic field when placed between two permanent magnets. After evaluating the magnetic susceptibility of the material as a ...

  7. Nonlinear bounce resonances between magnetosonic waves and equatorially mirroring electrons

    Science.gov (United States)

    Chen, Lunjin; Maldonado, Armando; Bortnik, Jacob; Thorne, Richard M.; Li, Jinxing; Dai, Lei; Zhan, Xiaoya

    2015-08-01

    Equatorially mirroring energetic electrons pose an interesting scientific problem, since they generally cannot resonate with any known plasma waves and hence cannot be scattered down to lower pitch angles. Observationally it is well known that the flux of these equatorial particles does not simply continue to build up indefinitely, and so a mechanism must necessarily exist that transports these particles from an equatorial pitch angle of 90° down to lower values. However, this mechanism has not been uniquely identified yet. Here we investigate the mechanism of bounce resonance with equatorial noise (or fast magnetosonic waves). A test particle simulation is used to examine the effects of monochromatic magnetosonic waves on the equatorially mirroring energetic electrons, with a special interest in characterizing the effectiveness of bounce resonances. Our analysis shows that bounce resonances can occur at the first three harmonics of the bounce frequency (nωb, n = 1, 2, and 3) and can effectively reduce the equatorial pitch angle to values where resonant scattering by whistler mode waves becomes possible. We demonstrate that the nature of bounce resonance is nonlinear, and we propose a nonlinear oscillation model for characterizing bounce resonances using two key parameters, effective wave amplitude à and normalized wave number k~z. The threshold for higher harmonic resonance is more strict, favoring higher à and k~z, and the change in equatorial pitch angle is strongly controlled by k~z. We also investigate the dependence of bounce resonance effects on various physical parameters, including wave amplitude, frequency, wave normal angle and initial phase, plasma density, and electron energy. It is found that the effect of bounce resonance is sensitive to the wave normal angle. We suggest that the bounce resonant interaction might lead to an observed pitch angle distribution with a minimum at 90°.

  8. Seasonal influence of ENSO on the Atlantic ITCZ and equatorial South America

    Science.gov (United States)

    Münnich, M.; Neelin, J. D.

    2005-11-01

    In late boreal spring, especially May, a strong relationship exists in observations among precipitation anomalies over equatorial South America and the Atlantic intertropical convergence zone (ITCZ), and eastern equatorial Pacific and central equatorial Atlantic sea surface temperature anomalies (SSTA). A chain of correlations of equatorial Pacific SSTA, western equatorial Atlantic wind stress (WEA), equatorial Atlantic SSTA, sea surface height, and precipitation supports a causal chain in which El Niño/Southern Oscillation (ENSO) induces WEA stress anomalies, which in turn affect Atlantic equatorial ocean dynamics. These correlations show strong seasonality, apparently arising within the atmospheric links of the chain. This pathway and the influence of equatorial Atlantic SSTA on South American rainfall in May appear independent of that of the northern tropical Atlantic. Brazil's Nordeste is affected by the northern tropical Atlantic. The equatorial influence lies further to the north over the eastern Amazon and the Guiana Highlands.

  9. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: pangxbyuanj@gmail.com [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: ally.lewis@york.ac.uk [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  10. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    International Nuclear Information System (INIS)

    Pang, Xiaobing; Lewis, Alastair C.

    2011-01-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette -1 (μg cig -1 ) and the particulate carbonyl emissions varied in the range of 23-127 μg cig -1 . Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig -1 gaseous and 141 μg cig -1 particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: → Carbonyl emission factors in both gas (16 species) and

  11. The growth and decay of equatorial backscatter plumes

    Science.gov (United States)

    Tsunoda, R. T.

    1980-02-01

    During the past three years, a series of rocket experiments from the Kwajalein Atoll, Marshall Islands, were conducted to investigate the character of intense, scintillation-producing irregularities that occur in the nighttime equatorial ionosphere. Because the source mechanism of equatorial irregularities, believed to be the Rayleigh-Taylor instability, is analogous to that which generates plasma-density striations in a nuclear-induced environment, there is considerable interest in the underlying physics that controls the characteristics of these irregularities. A primary objective of ALTAIR investigations of equatorial irregularities is to seek an understanding of the underlying physics by establishing the relationship between meter-scale irregularities (detected by ALTAIR), and the large-scale plasma-density depletions (or 'bubbles') that contain the kilometer-scale, scintillation-producing irregularities. We describe the time evolution of backscatter 'plumes' produced by one meter equatorial field-aligned irregularities. Using ALTAIR, a fully steerable backscatter radar, to repeatedly map selected plumes, we characterize the dynamic behavior of plumes in terms of growth and a decay phase. Most of the observed characteristics are found to be consistent with equatorial-irregularity generation predicted by current theories of Rayleigh-Taylor and gradient-drift instabilities. However, other characteristics have been found that suggest key roles played by the eastward neutral wind and by altitude-modulation of the bottomside F layer in establishing the initial conditions for plume growth.

  12. Ambient levels of carbonyl compounds and their sources in Guangzhou, China

    Science.gov (United States)

    Feng, Yanli; Wen, Sheng; Chen, Yingjun; Wang, Xinming; Lü, Huixiong; Bi, Xinhui; Sheng, Guoying; Fu, Jiamo

    Ambient levels of carbonyl compounds and their possible sources, vehicular exhaust and cooking exhaust, were studied at seven places in Guangzhou, including five districts (a residential area, an industrial area, a botanical garden, a downtown area and a semi-rural area), a bus station and a restaurant during the period of June-September 2003. Nineteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Only little changes were found in carbonyl concentration levels in the five different districts because of their dispersion and mixture in the atmosphere in summer. The lower correlations between the carbonyls' concentrations might result from the mixture of carbonyls derived from different sources, including strong photochemical reactions at noon in summer. Formaldehyde and acetaldehyde were the main carbonyls in bus station, while straight-chain carbonyls were comparatively abundant in cooking exhaust. Besides vehicular exhaust, cooking might be another major source of carbonyl compounds in Guangzhou City, especially for high molecular weight carbonyls.

  13. A method of detecting carbonyl compounds in tree leaves in China.

    Science.gov (United States)

    Huang, Juan; Feng, Yanli; Fu, Jiamo; Sheng, Guoying

    2010-06-01

    Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 +/- 3.4 microg g(-1)(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

  14. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

    Science.gov (United States)

    Black, Stuart; Ferrell, Jack R

    2017-02-07

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  15. Effect of geomagnetic storm conditions on the equatorial ionization anomaly and equatorial temperature anomaly

    Science.gov (United States)

    Bharti, Gaurav; Bag, T.; Sunil Krishna, M. V.

    2018-03-01

    The effect of the geomagnetic storm on the equatorial ionization anomaly (EIA) and equatorial temperature anomaly (ETA) has been studied using the atomic oxygen dayglow emissions at 577.7 nm (OI 557.7 nm) and 732.0 nm (OII 732.0 nm). For the purpose of this study, four intense geomagnetic storms during the ascending phase of solar cycle 24 have been considered. This study is primarily based on the results obtained using photochemical models with necessary inputs from theoretical studies and experimental observations. The latest reaction rate coefficients, quantum yields and the corresponding cross-sections have also been incorporated in these models. The volume emission rate of airglow emissions has been calculated using the neutral densities from NRLMSISE-00 and charged densities from IRI-2012 model. The modeled volume emission rate (VER) for OI 557.7 nm shows a positive correlation with the Dst index at 150 km and negative correlation with Dst at 250 and 280 km altitudes. Latitudinal profile of the greenline emission rate at different altitudes show a distinct behaviour similar to what has been observed in EIA with crests on either sides of the equator. The EIA crests are found to show poleward movement in the higher altitude regions. The volume emission rate of 732.0 nm emission shows a strong enhancement during the main phase of the storm. The changes observed in the airglow emission rates are explained with the help of variations induced in neutral densities and parameters related to EIA and ETA. The latitudinal variation of 732.0 nm emission rate is correlated to the variability in EIA during the storm period.

  16. Space Weather Research in the Equatorial Region: A Philosophical Reinforcement

    Science.gov (United States)

    Chukwuma, Victor; Odunaike, Rasaki; Laoye, John

    Investigations using radio waves reflected from the ionosphere, at high-and mid-latitudes indicate that ionospheric absorption can strongly increase following geomagnetic storms; which appears to suggest some definite relationship between ionospheric radio wave absorption and geomagnetic storms at these latitudes. However, corresponding earlier studies in the equatorial region did not appear to show any explicit relationship between ionospheric radio wave absorption and geomagnetic storm activity. This position appeared acceptable to the existing scientific paradigm, until in an act of paradigm shift, by a change of storm selection criteria, some more recent space weather investigations in the low latitudes showed that ionospheric radio wave absorption in the equatorial region clearly increases after intense storms. Given that these results in the equatorial region stood against the earlier results, this paper presently attempts to highlight their philosophical underpinning and posit that they constitute a scientific statement.

  17. Occurrence of Equatorial Plasma Bubbles during Intense Magnetic Storms

    Directory of Open Access Journals (Sweden)

    Chao-Song Huang

    2011-01-01

    Full Text Available An important issue in low-latitude ionospheric space weather is how magnetic storms affect the generation of equatorial plasma bubbles. In this study, we present the measurements of the ion density and velocity in the evening equatorial ionosphere by the Defense Meteorological Satellite Program (DMSP satellites during 22 intense magnetic storms. The DMSP measurements show that deep ion density depletions (plasma bubbles are generated after the interplanetary magnetic field (IMF turns southward. The time delay between the IMF southward turning and the first DMSP detection of plasma depletions decreases with the minimum value of the IMF Bz, the maximum value of the interplanetary electric field (IEF Ey, and the magnitude of the Dst index. The results of this study provide strong evidence that penetration electric field associated with southward IMF during the main phase of magnetic storms increases the generation of equatorial plasma bubbles in the evening sector.

  18. Molecular characterization of Cryptosporidium isolates from humans in Equatorial Guinea.

    Science.gov (United States)

    Blanco, María Alejandra; Iborra, Asunción; Vargas, Antonio; Nsie, Eugenia; Mbá, Luciano; Fuentes, Isabel

    2009-12-01

    The aim of the study was to perform a molecular characterization of clinical isolates of Cryptosporidium species from Equatorial Guinea. Standard laboratory methods were used to identify 35 cryptosporidiosis cases among 185 patients. PCR-RFLP successfully identified 34 Cryptosporidium species from these 35 cases, comprising C. parvum (52.9%), C. hominis (44.1%) and C. meleagridis (2.9%); over 90% of the species were isolated from HIV-positive patients. This is the first report of the molecular characterization of Cryptosporidium species isolated from humans in Equatorial Guinea and shows that zoonotic and anthroponotic transmission is present in this country.

  19. Longitudinal Variation and Waves in Jupiter's South Equatorial Wind Jet

    Science.gov (United States)

    Simon-Miller, A. A.; Rogers, John H.; Gierasch, Peter J.; Choi, David; Allison, Michael; Adamoli, Gianluigi; Mettig, Hans-Joerg

    2012-01-01

    We have conducted a detailed study of the cloud features in the strong southern equatorial wind jet near 7.5 S planetographic latitude. To understand the apparent variations in average zonal wind jet velocity at this latitude [e.g.. 1,2,3], we have searched for variations iIi both feature latitude and velocity with longitude and time. In particular, we focused on the repetitive chevron-shaped dark spots visible on most dates and the more transient large anticyclonic system known as the South Equatorial Disturbance (SED). These small dark spots are interpreted as cloud holes, and are often used as material tracers of the wind field.

  20. Instability of equatorial protons in Jupiter's mid-magnetosphere

    International Nuclear Information System (INIS)

    Northrop, T.G.; Schardt, A.W.

    1980-01-01

    Two different models for the distribution function are fit to the Jovian protons seen by Pioneer 10 inbound. The models reproduce the observed energy and angular distributions. These models are then used to assess the collisionless mirror instability. Because of the pancake proton angular distributions in the equatorial ring current region, the ring current particle population appears to be mirror unstable at times, with instability growth rates of approx.10 min. Such a time is consistent with observed proton flux autocorrelation times. An instability such as this (there are other candidates) may be responsible for the previously established proton flux flowing parallel to the magnetic field away from the equatorial region

  1. Carbonyl Compounds Produced by Vaporizing Cannabis Oil Thinning Agents.

    Science.gov (United States)

    Troutt, William D; DiDonato, Matthew D

    2017-11-01

    Cannabis use has increased in the United States, particularly the use of vaporized cannabis oil, which is often mixed with thinning agents for use in vaporizing devices. E-cigarette research shows that heated thinning agents produce potentially harmful carbonyls; however, similar studies have not been conducted (1) with agents that are commonly used in the cannabis industry and (2) at temperatures that are appropriate for cannabis oil vaporization. The goal of this study was to determine whether thinning agents used in the cannabis industry produce potentially harmful carbonyls when heated to a temperature that is appropriate for cannabis oil vaporization. Four thinning agents (propylene glycol [PG], vegetable glycerin [VG], polyethylene glycol 400 [PEG 400], and medium chain triglycerides [MCT]) were heated to 230°C and the resulting vapors were tested for acetaldehyde, acrolein, and formaldehyde. Each agent was tested three times. Testing was conducted in a smoking laboratory. Carbonyl levels were measured in micrograms per puff block. Analyses showed that PEG 400 produced significantly higher levels of acetaldehyde and formaldehyde than PG, MCT, and VG. Formaldehyde production was also significantly greater in PG compared with MCT and VG. Acrolein production did not differ significantly across the agents. PG and PEG 400 produced high levels of acetaldehyde and formaldehyde when heated to 230°C. Formaldehyde production from PEG 400 isolate was particularly high, with one inhalation accounting for 1.12% of the daily exposure limit, nearly the same exposure as smoking one cigarette. Because PG and PEG 400 are often mixed with cannabis oil, individuals who vaporize cannabis oil products may risk exposure to harmful formaldehyde levels. Although more research is needed, consumers and policy makers should consider these potential health effects before use and when drafting cannabis-related legislation.

  2. Determination of Carbonyl Compounds in Cigarette Mainstream Smoke. The CORESTA 2010 Collaborative Study and Recommended Method

    Directory of Open Access Journals (Sweden)

    Intorp M

    2014-12-01

    Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected carbonyl compounds (acetaldehyde, formaldehyde, acetone, acrolein, methyl ethyl ketone, crotonaldehyde, propionaldehyde and butyraldehyde in cigarette mainstream smoke. The method involved smoke collection in impinger traps, derivatisation of carbonyls with 2,4-dinitrophenylhydrazine (DNPH, separation of carbonyl hydrazones by reversed phase high performance liquid chromatography and detection by ultra violet or diode array.

  3. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.

    1995-09-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetone+acrolein. Three different types of samples (rural, urban, petrol emission) were successfully analyzed

  4. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.

    1995-01-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs

  5. Magnetic properties of carbonyl iron particles in magnetorheological fluids

    International Nuclear Information System (INIS)

    Gorodkin, S R; James, R O; Kordonski, W I

    2009-01-01

    Knowledge of the magnetic properties of dispersed magnetic particles is a prerequisite to the design an MR fluid with desired performance. A term specific susceptibility is introduced for characterization of particle susceptibility. The study was performed with the Bartington MS2B magnetic susceptibility system on small samples volume. Specific magnetic susceptibility of iron particles was found to be a linear function of median particle size. Structural change in the fluid, including particle organization, led to susceptibility drift and may affect fluid performance. It was shown that susceptibility data can be used for evaluation of the concentration of carbonyl iron particles in MR fluids.

  6. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma

    DEFF Research Database (Denmark)

    Havelund, Jesper F; Wojdyla, Katarzyna; Davies, Michael J

    2017-01-01

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues...... in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine...

  7. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

    2017-12-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  8. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  9. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    International Nuclear Information System (INIS)

    Arnold, John

    2015-01-01

    The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  10. Upper ocean circulation modulation by phytoplankton concentration in the Equatorial Pacific and the Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Nakamoto, S.; PrasannaKumar, S.; Oberhuber, J.M.; Sammarco, P.; Muneyama, K.; Sato, T.; AjoyKumar, A.; Frouin, R.

    gradient in the upper ocean. This strengthens the geostrophically balanced westward currents in both side of the equatorial wave-guide (within 5 degree bands). Once these currents reach the western Pacific coast, they feed the Equatorial undercurrent (EUC...

  11. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA...

  12. Ocean dynamics, not dust, have controlled equatorial Pacific productivity over the past 500,000 years

    OpenAIRE

    Winckler, Gisela; Anderson, Robert F.; Jaccard, Samuel L.; Marcantonio, Franco

    2016-01-01

    Biological productivity in the equatorial Pacific is relatively high compared with other low latitude regimes especially east of the dateline where divergence driven by the trade winds brings nutrient rich waters of the Equatorial Undercurrent to the surface. The equatorial Pacific is one of the three principal high nutrient low chlorophyll ocean regimes where biological utilization of nitrate and phosphate is limited in part by the availability of iron. Throughout most of the equatorial Paci...

  13. Iron sources and pathways into the Pacific Equatorial Undercurrent

    NARCIS (Netherlands)

    Qin, Xuerong; Menviel, Laurie; Sen Gupta, Alex; van Sebille, Erik

    2016-01-01

    Using a novel observationally constrained Lagrangian iron model forced by outputs from an eddy-resolving biogeochemical ocean model, we examine the sensitivity of the Equatorial Undercurrent (EUC) iron distribution to EUC source region iron concentrations. We find that elevated iron concentrations

  14. Equatorial electrojet in the Indian region during the geomagnetic ...

    Indian Academy of Sciences (India)

    1998-11-14

    Nov 14, 1998 ... In the recovery phase of the storm, the electric field due to shielding layer penetrates to equatorial latitudes as an overshielding electric field with opposite polarity, westward during day- side and eastward during night side (Kelley et al. 1979). In addition to the prompt penetration elec- tric fields, there are ...

  15. Climate regulation of fire emissions and deforestation in equatorial Asia

    NARCIS (Netherlands)

    van der Werf, G. R.; Dempewolf, J.; Trigg, S. N.; Randerson, J. T.; Kasibhatla, P. S.; Giglio, L.; Murdiyarso, D.; Peters, W.; Morton, D. C.; Collatz, G. J.; Dolman, A. J.; Defries, R. S.

    2008-01-01

    Drainage of peatlands and deforestation have led to large-scale fires in equatorial Asia, affecting regional air quality and global concentrations of greenhouse gases. Here we used several sources of satellite data with biogeochemical and atmospheric modeling to better understand and constrain fire

  16. Backscatter measurements of 11-cm equatorial spread-F irregularities

    International Nuclear Information System (INIS)

    Tsunoda, R.T.

    1980-01-01

    In the equatorial F-region ionosphere, a turbulent cascade process has been found to exist that extends from irregularity spatial wavelengths longer than tens of kilometers down to wavelengths as short as 36 cm. To investigate the small-scale regime of wavelengths less than 36 cm, an equatorial radar experiment was conducted using a frequency of 1320 MHz that corresponds to an irregularity wavelength of 11 cm. The first observations of radar backscatter from 11-cm field-aligned irregularities (FAI) are described. These measurements extend the spatial wavelength regime of F-region FAI to lengths that approach both electron gyroradius and the Debye length. Agreement of these results with the theory of high-frequency drift waves suggests that these observations may be unique to the equatorial ionosphere. That is, the requirement of low electron densities for which the theroy calls may preclude the existence of 11-cm FAI elsewhere in the F-region ionosphere, except in equatorial plasma bubbles

  17. Characterisation of tectonic lineaments in the Central Equatorial ...

    African Journals Online (AJOL)

    Characterisation of tectonic lineaments in the Central Equatorial Atlantic region of Africa using Bouguer anomaly gravity data. ... Ife Journal of Science ... 3-D standard Euler deconvolution analysis was carried out on Bouguer anomaly gravity data for configuration definition and approximate depth estimate of tectonic ...

  18. Planktonic foraminifera from core tops of western equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Naidu, P.D.; Guptha, M.V.S.

    distributional pattern showing upward trend in its abundance from 38 per cent at 21 degrees S latitude to 0.8 per cent at 6 degrees N latitude. Sub-tropical fauna is sparsely distributed in the Equatorial Indian Ocean. Based on these studies it is interpreted...

  19. equatorial electrojet strength in the african sector during high

    African Journals Online (AJOL)

    Preferred Customer

    shown to be consistent with the earlier similar work carried out for the American and ... reference to the quiet day night time level of H, ... February and July, and shifts equator ward to 27°N ... effect of the equatorial electrojet along this line is.

  20. Radar observation of the equatorial counter-electrojet

    International Nuclear Information System (INIS)

    Hanuise, C.; Crochet, M.; Gouin, P.; Ogubazghi, Ghebrebrhan

    1979-01-01

    Electron drift velocity in the equatorial electrojet has been measured for a few years by coherent radar techniques in Africa. For the first time such measurements were performed during a strong reversal of the ionospheric current dubbed 'counter-electrojet'. These observations agree with the theories of the plasma instabilities at the origin of the electron density irregularities giving the radar echoes

  1. Composition of amino acid using carbon monoxide. Amide carbonylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Izawa, Kunisuke (Ajinomoto Co., Inc., Tokyo (Japan))

    1989-02-01

    Amide carbonylation reaction is a method to compose N-acyl-{alpha}-amino acid from aldehyde, carboxylic acid amide, and carbon monoxide in a phase and with high yield. Unlike the conventional Strecker reaction, this method does not use HCN which is in question on public pollution and does not require hydrolysis. This amide carbonylation reaction was discovered by Wakamatsu and others of Ajinomoto Co.,Ltd. Present application examples of this method are the composition of N-acetyl amino acid from the aldehyde class, the composition of N-Acyl amino acid from olefin, the composition of N-acyl or acetyl amino acid from the raw material of alcohol and the halide class, the composition of N-acyl or acetyl amino acid via the isomerization of epoxide and allyl alcohol, the composition of amino dicarboxylic acid, applying deoxidation of ring acid anhydride, the composition of N-acyl amino acid from the raw material of the amine class, the stereoselective composition of -substitution ring-{alpha}-amino acid, and the composition of amino aldehyde. 24 refs., 2 figs., 2 tabs.

  2. Synthesis of dimethyl carbonate by oxidative carbonylation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.G.; Han, M.S.; Kim, H.S.; Ahn, B.S.; Park, K.Y.

    1999-07-01

    Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities was intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological change of catalysts during the reaction was also compared by X-ray diffraction and SEM analysis. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120--130 C. The reaction rate was too slow below 100 C, while too many by-products were produced above 150 C. Among the various catalysts employed, CuCl{sub 2}/NaOH/AC catalyst with the mole ratio of OH/Cu = 0.5--1.0 has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu{sub 2}(OH){sub 3}Cl.

  3. Post-midnight occurrence of equatorial plasma bubbles

    Science.gov (United States)

    Ajith, K. K.; Otsuka, Yuichi; Yamamoto, Mamoru; Yokoyama, Tatsuhiro; Tulasiram, S.

    2016-07-01

    The equatorial plasma bubbles (EPBs)/equatorial spread F (ESF) irregularities are an important topic of space weather interest because of their impact on transionospheric radio communications, satellite-based navigation and augmentation systems. This local plasma depleted structures develop at the bottom side F layer through Rayleigh-Taylor instability and rapidly grow to topside ionosphere via polarization electric fields within them. The steep vertical gradients due to quick loss of bottom side ionization and rapid uplift of equatorial F layer via prereversal enhancement (PRE) of zonal electric field makes the post-sunset hours as the most preferred local time for the formation of EPBs. However, there is a different class of irregularities that occurs during the post-midnight hours of June solstice reported by the previous studies. The occurrence of these post-midnight EPBs maximize during the low solar activity periods. The growth characteristics and the responsible mechanism for the formation of these post-midnight EPBs are not yet understood. Using the rapid beam steering ability of 47 MHz Equatorial Atmosphere Radar (EAR) at Kototabang (0.2°S geographic latitude, 100.3°E geographic longitude, and 10.4°S geomagnetic latitude), Indonesia, the spatial and temporal evolution of equatorial plasma bubbles (EPBs) were examined to classify the evolutionary-type EPBs from those which formed elsewhere and drifted into the field of view of radar. The responsible mechanism for the genesis of summer time post-midnight EPBs were discussed in light of growth rate of Rayleigh-Taylor instability using SAMI2 model.

  4. Lagrangian mixed layer modeling of the western equatorial Pacific

    Science.gov (United States)

    Shinoda, Toshiaki; Lukas, Roger

    1995-01-01

    Processes that control the upper ocean thermohaline structure in the western equatorial Pacific are examined using a Lagrangian mixed layer model. The one-dimensional bulk mixed layer model of Garwood (1977) is integrated along the trajectories derived from a nonlinear 1 1/2 layer reduced gravity model forced with actual wind fields. The Global Precipitation Climatology Project (GPCP) data are used to estimate surface freshwater fluxes for the mixed layer model. The wind stress data which forced the 1 1/2 layer model are used for the mixed layer model. The model was run for the period 1987-1988. This simple model is able to simulate the isothermal layer below the mixed layer in the western Pacific warm pool and its variation. The subduction mechanism hypothesized by Lukas and Lindstrom (1991) is evident in the model results. During periods of strong South Equatorial Current, the warm and salty mixed layer waters in the central Pacific are subducted below the fresh shallow mixed layer in the western Pacific. However, this subduction mechanism is not evident when upwelling Rossby waves reach the western equatorial Pacific or when a prominent deepening of the mixed layer occurs in the western equatorial Pacific or when a prominent deepening of the mixed layer occurs in the western equatorial Pacific due to episodes of strong wind and light precipitation associated with the El Nino-Southern Oscillation. Comparison of the results between the Lagrangian mixed layer model and a locally forced Eulerian mixed layer model indicated that horizontal advection of salty waters from the central Pacific strongly affects the upper ocean salinity variation in the western Pacific, and that this advection is necessary to maintain the upper ocean thermohaline structure in this region.

  5. Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

    Science.gov (United States)

    Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

    2016-08-19

    Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    International Nuclear Information System (INIS)

    Cao, Xiao Guo; Ren, Hao; Zhang, Hai Yan

    2015-01-01

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range

  7. Comparison of carbonyl compounds emissions from diesel engine fueled with biodiesel and diesel

    Science.gov (United States)

    He, Chao; Ge, Yunshan; Tan, Jianwei; You, Kewei; Han, Xunkun; Wang, Junfang; You, Qiuwen; Shah, Asad Naeem

    The characteristics of carbonyl compounds emissions were investigated on a direct injection, turbocharged diesel engine fueled with pure biodiesel derived from soybean oil. The gas-phase carbonyls were collected by 2,4-dinitrophenylhydrazine (DNPH)-coated silica cartridges from diluted exhaust and analyzed by HPLC with UV detector. A commercial standard mixture including 14 carbonyl compounds was used for quantitative analysis. The experimental results indicate that biodiesel-fueled engine almost has triple carbonyls emissions of diesel-fueled engine. The weighted carbonyls emission of 8-mode test cycle of biodiesel is 90.8 mg (kW h) -1 and that of diesel is 30.7 mg (kW h) -1. The formaldehyde is the most abundant compound of carbonyls for both biodiesel and diesel, taking part for 46.2% and 62.7% respectively. The next most significant compounds are acetaldehyde, acrolein and acetone for both fuels. The engine fueled with biodiesel emits a comparatively high content of propionaldehyde and methacrolein. Biodiesel, as an alternative fuel, has lower specific reactivity (SR) caused by carbonyls compared with diesel. When fueled with biodiesel, carbonyl compounds make more contribution to total hydrocarbon emission.

  8. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients

    Directory of Open Access Journals (Sweden)

    Vaishali Kolgiri

    2017-01-01

    Conclusions: Carbonyl content may has a role as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients.

  9. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing; Zhang, Mengying; Wang, Limu; Li, Weihua; Sheng, Ping; Wen, Weijia

    2010-01-01

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested

  10. Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

    International Nuclear Information System (INIS)

    Hollingsworth, W.E.

    1982-11-01

    A flowing afterglow apparatus was used to study the metal fluorescence resulting from the quenching of metastable rare-gas states by metal carbonyls. The data from the quenching or argon, neon, and helium by iron and nickel carbonyl agreed well with a restricted degree of freedom model indicating a concerted bond-breaking dissociation

  11. rac-Carbonyl{1-[(diphenylphosphinomethyl]ethanethiolato}(triphenylphosphinerhodium(I

    Directory of Open Access Journals (Sweden)

    Simón Hernández-Ortega

    2008-11-01

    Full Text Available The title compound, [Rh(C15H16PS(C18H15P(CO], was synthesized from the reaction of the ligand rac-[Ph2PCH2CH(CH3SH] with trans-[Rh(F(CO(PPh32] in a 1:1 molar ratio in toluene. The Rh atom is four-coordinated in a distorted square-planar geometry with the P—S ligand [Ph2PCH2CH(CH3S] acting as a chelate and the PPh3 and disordered CO [site occupation factors of 0.61 (5 and 0.39 (5] ligands completing the coordination.

  12. AMPA receptor ligands

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Mellor, Ian

    2004-01-01

    Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player in the f......Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player...... in the formation of memory. Hence, ligands affecting AMPARs are highly important for the study of the structure and function of this receptor, and in this regard polyamine-based ligands, particularly polyamine toxins, are unique as they selectively block Ca2+ -permeable AMPARs. Indeed, endogenous intracellular...

  13. Radiobiology with DNA ligands

    International Nuclear Information System (INIS)

    Weinreich, R.; Argentini, M.; Guenther, I.; Koziorowski, J.; Larsson, B.; Nievergelt-Egido, M.C.; Salt, C.; Wyer, L.; Dos Santos, D.F.; Hansen, H.J.

    1997-01-01

    The paper deals with the following topics: labelling of DNA ligands and other tumour-affinic compounds with 4.15-d 124 I, radiotoxicity of Hoechst 33258 and 33342 and of iodinated Hoechst 33258 in cell cultures, preparation of 76 Br-, 123 I-, and 221 At-labelled 5-halo-2'-deoxyuridine, chemical syntheses of boron derivatives of Hoechst 33258.III., Gadolinium neutron capture therapy

  14. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  15. Development of an automatic sampling device for the continuous measurement of atmospheric carbonyls compounds

    International Nuclear Information System (INIS)

    Perraud, V.

    2007-12-01

    Two sampling strategies were studied to develop an automatic instrument for the continuous measurement of atmospheric carbonyl compounds. Because of its specificity towards carbonyls compounds, sampling by using a transfer of gaseous phase in a liquid phase associated with a simultaneous chemical derivatization of the trapped compounds was first studied. However, this method do not allow a quantitative sampling of all studied carbonyl compounds, nor a continuous measurement in the field. To overcome the difficulties, a second strategy was investigated: the cryogenic adsorption onto solid adsorbent followed by thermodesorption and a direct analysis by GC/MS. Collection efficiency using different solid adsorbents was found greater than 95% for carbonyl compounds consisting of 1 to 7 carbons. This work is a successful first step towards the realization of the automatic sampling device for a continuous measurement of atmospheric carbonyls compounds. (author)

  16. Impact of HVAC filter on indoor air quality in terms of ozone removal and carbonyls generation

    Science.gov (United States)

    Lin, Chi-Chi; Chen, Hsuan-Yu

    2014-06-01

    This study aims at detecting ozone removal rates and corresponding carbonyls generated by ozone reaction with HVAC filters from various building, i.e., shopping mall, school, and office building. Studies were conducted in a small-scale environmental chamber. By examining dust properties including organic carbon proportion and specific surface area of dusts adsorbed on filters along with ozone removal rates and carbonyls generation rate, the relationship among dust properties, ozone removal rates, and carbonyls generation was identified. The results indicate a well-defined positive correlation between ozone removal efficiency and carbonyls generation on filters, as well as a positive correlation among the mass of organic carbon on filters, ozone removal efficiency and carbonyls generations.

  17. Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Scurrell, M S

    1977-01-01

    In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

  18. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

    2006-07-01

    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  19. Integration of a semi-rigid proline ligand and 4,4'-bipyridine in the synthesis of homochiral metal-organic frameworks with helices.

    Science.gov (United States)

    Xu, Zhong-Xuan; Kang, Yao; Han, Min-Le; Li, Dong-Sheng; Zhang, Jian

    2015-06-28

    A pair of 3-D homochiral metal-organic frameworks (HMOFs) based on a mixed semi-rigid 5-(2-carboxypyrrolidine-1-carbonyl)isophthalate (PIA) ligand and rigid 4,4'-bipyridine (bipy), [Co3((R)-PIA)2(bipy)3]·6H2O (1-D) and [Co3((S)-PIA)2(bipy)3]·6H2O (1-L) are synthesized and structurally characterized. They are enantiomers and exhibit three-dimensional open frameworks. In each structure, the PIA ligands link the Co centers into homochiral frameworks with large open channels that are occupied by the bipy ligands. Interesting helical chains built from the connectivity between PIA ligands and Co centers are presented. Antiferromagnetic coupling is observed in 1-D. These results demonstrated that the mixed ligand approach is successful for the construction of HMOFs.

  20. Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl

    International Nuclear Information System (INIS)

    Pyykkoe, P.; Li, J.; Runeberg, N.

    1994-01-01

    The calculated trends of geometries and vibrational frequencies of several uranyl isoelectronic species, like the known NUN and CUO, and the unknown CUN - , NUO + , and NUF 2+ , are reported. The NUN and CUO results support the matrix spectroscopic assignments. The simplest example of equatorial coordination to uranyl is the C 2d species UO 3 . Its calculated vibrational frequencies also support matrix spectroscopic ones. We earlier suggested that the large range of uranyl bond lengths in UO 6 6- -type systems could be interpreted in terms of a open-quotes frozen, soft e g vibrational modeclose quotes. Further studies on UF 6 , U(OH) 6 , [(OUO)(F eq ) n ] (n-2) -, [(OUO)(NO 3 ) 3 ] - , and [(OUO)(CO 3 ) 3 ] 4- show only small variation of R ax as function of R eq . Thus, the all-oxide case is a special one, where all ligands are capable of single and multiple bonding. 44 refs., 10 figs., 7 tabs

  1. Global mode of Pi2 waves in the equatorial region

    International Nuclear Information System (INIS)

    Kitamura, Tai-ichi; Saka, Ousuke; Shimoizumi, Masashi

    1988-01-01

    Fluxgate magnetometers with accurate timing data logger were set up at two equatorial stations (Garous-Marous and Huancayo), and also at a middle latitude station (Kuju). The phase of Pi2 waves is compared among these stations. It is found that 1) Pi2 pulsations in low and equatorial latitudes are linearly polarized approximately along the magnetic meridian, 2) phase difference of the H component of Pi2 waves at different stations is much less than 1 - 10 of the pulsation period despite a large longitudinal separation (∼ 90 deg) of the stations, showing the so-called azimuthal wave number, m, to be much less than unity and 3) phase difference of the D component at different stations is variable. (author)

  2. Ongoing Analysis of Jupiter's Equatorial Hotspots and Plumes from Cassini

    Science.gov (United States)

    Choi, D. S.; Showmwn, A. P.; Vasavada, A. R.; Simon-Miller, A. A.

    2012-01-01

    We present updated results from our ongoing analysis of Cassini observations of Jupiter's equatorial meteorology. For two months preceding the spacecraft's closest approach of the planet, the ISS instrument onboard Cassini regularly imaged the atmosphere of Jupiter. We created time-lapse movies from this period that show the complex activity and interactions of the equatorial atmosphere. During this period, hot spots exhibited significant variations in size and shape over timescales of days and weeks. Some of these changes appear to be a result of interactions with passing vortex systems in adjacent latitudes. Strong anticyclonic gyres to the southeast of the dark areas converge with flow from the west and appear to circulate into a hot spot at its southwestern corner.

  3. Bottomside sinusoidal irregularities in the equatorial F region

    Science.gov (United States)

    Valladares, C. E.; Hanson, W. B.; Mcclure, J. P.; Cragin, B. L.

    1983-01-01

    By using the Ogo 6 satellite, McClure and Hanson (1973) have discovered sinusoidal irregularities in the equatorial F region ion number density. In the present investigation, a description is provided of the properties of a distinct category of sinusoidal irregularities found in equatorial data from the AE-C and AE-E satellites. The observed scale sizes vary from about 300 m to 3 km in the direction perpendicular to B, overlapping with and extending the range observed by using Ogo 6. Attention is given to low and high resolution data, a comparison with Huancayo ionograms, the confinement of 'bottomside sinusoidal' (BSS) irregularities essentially to the bottomside of the F layer, spectral characteristics, and BSS, scintillation, and ionosonde observations.

  4. Nonlinearly coupled dynamics of irregularities in the equatorial electrojet

    Energy Technology Data Exchange (ETDEWEB)

    Atul, J.K., E-mail: jkatulphysics@gmail.com [Department of Physics, College of Commerce under Magadh University, Patna 800020 (India); Sarkar, S. [FCIPT, Institute for Plasma Research, Gandhinagar 382428 (India); Singh, S.K. [Department of Physics, College of Commerce under Magadh University, Patna 800020 (India)

    2016-04-01

    Kinetic wave description is used to study the nonlinear influence of background Farley Buneman (FB) modes on the Gradient Drift (GD) modes in the equatorial electrojet ionosphere. The dominant nonlinearity is mediated through the electron flux term in the governing fluid equation which further invokes a turbulent current into the system. Electron dynamics reveals the modification in electron collision frequency and inhomogeneity scale length. It is seen that the propagation and growth rate of GD modes get modified by the background FB modes. Also, a new quasimode gets excited through the quadratic dispersion relation. Physical significance of coupled dynamics between the participating modes is also discussed. - Highlights: • Nonlinear influence of Farley Buneman mode on the Gradient drift mode, is investigated. • Electron collision frequency and density gradient scale length get modified. • A new quasimode gets excited due to the competition between these modes. • It seems to be important for modelling of Equatorial Electrojet current system.

  5. Equatorial enhancement of the nighttime OH mesospheric infrared airglow

    International Nuclear Information System (INIS)

    Baker, D J; Thurgood, B K; Harrison, W K; Mlynczak, M G; Russell, J M

    2007-01-01

    Global measurements of the hydroxyl mesospheric airglow over an extended period of time have been made possible by the NASA SABER infrared sensor aboard the TIMED satellite which has been functioning since December of 2001. The orbital mission has continued over a significant portion of a solar cycle. Experimental data from SABER for several years have exhibited equatorial enhancements of the nighttime mesospheric OH (Δv=2) airglow layer consistent with the high average diurnal solar flux. The brightening of the OH airglow typically means more H+O 3 is being reacted. At both the spring and autumn seasonal equinoxes when the equatorial solar UV irradiance mean is greatest, the peak volume emission rate (VER) of the nighttime Meinel infrared airglow typically appears to be both significantly brighter plus lower in altitude by several kilometres at low latitudes compared with midlatitude findings

  6. Nonlinearly coupled dynamics of irregularities in the equatorial electrojet

    International Nuclear Information System (INIS)

    Atul, J.K.; Sarkar, S.; Singh, S.K.

    2016-01-01

    Kinetic wave description is used to study the nonlinear influence of background Farley Buneman (FB) modes on the Gradient Drift (GD) modes in the equatorial electrojet ionosphere. The dominant nonlinearity is mediated through the electron flux term in the governing fluid equation which further invokes a turbulent current into the system. Electron dynamics reveals the modification in electron collision frequency and inhomogeneity scale length. It is seen that the propagation and growth rate of GD modes get modified by the background FB modes. Also, a new quasimode gets excited through the quadratic dispersion relation. Physical significance of coupled dynamics between the participating modes is also discussed. - Highlights: • Nonlinear influence of Farley Buneman mode on the Gradient drift mode, is investigated. • Electron collision frequency and density gradient scale length get modified. • A new quasimode gets excited due to the competition between these modes. • It seems to be important for modelling of Equatorial Electrojet current system.

  7. Saturn's equatorial jet structure from Cassini/ISS

    Science.gov (United States)

    García-Melendo, Enrique; Legarreta, Jon; Sánchez-Lavega, Agustín.; Pérez-Hoyos, Santiago; Hueso, Ricardo

    2010-05-01

    Detailed wind observations of the equatorial regions of the gaseous giant planets, Jupiter and Saturn, are crucial for understanding the basic problem of the global circulation and obtaining new detailed information on atmospheric phenomena. In this work we present high resolution data of Saturn's equatorial region wind profile from Cassini/ISS images. To retrieve wind measurements we applied an automatic cross correlator to image pairs taken by Cassini/ISS with the MT1, MT2, MT3 filters centred at the respective three methane absorbing bands of 619nm, 727nm, and 889nm, and with the adjacent continuum CB1, CB2, and CB3 filters. We obtained a complete high resolution coverage of Saturn's wind profile in the equatorial region. The equatorial jet displays an overall symmetric structure similar to that shown the by same region in Jupiter. This result suggests that, in accordance to some of the latest compressible atmosphere computer models, probably global winds in gaseous giants are deeply rooted in the molecular hydrogen layer. Wind profiles in the methane absorbing bands show the effect of strong vertical shear, ~40m/s per scale height, confirming previous results and an important decay in the wind intensity since the Voyager era (~100 m/s in the continuum and ~200 m/s in the methane absorbing band). We also report the discovery of a new feature, a very strong and narrow jet on the equator, about only 5 degrees wide, that despite the vertical shear maintains its intensity (~420 m/s) in both, the continuum and methane absorbing band filters. Acknowledgements: Work supported by the Spanish MICIIN AYA2009-10701 with FEDER and Grupos Gobierno Vasco IT-464-07.

  8. Meteorology of Jupiter's Equatorial Hot Spots and Plumes from Cassini

    Science.gov (United States)

    Choi, David Sanghun; Showman, Adam P.; Vasavada, Ashwin R.; Simon-Miller, Amy A.

    2013-01-01

    We present an updated analysis of Jupiter's equatorial meteorology from Cassini observations. For two months preceding the spacecraft's closest approach, the Imaging Science Subsystem (ISS) onboard regularly imaged the atmosphere. We created time-lapse movies from this period in order to analyze the dynamics of equatorial hot spots and their interactions with adjacent latitudes. Hot spots are relatively cloud-free regions that emit strongly at 5 lm; improved knowledge of these features is crucial for fully understanding Galileo probe measurements taken during its descent through one. Hot spots are quasistable, rectangular dark areas on visible-wavelength images, with defined eastern edges that sharply contrast with surrounding clouds, but diffuse western edges serving as nebulous boundaries with adjacent equatorial plumes. Hot spots exhibit significant variations in size and shape over timescales of days and weeks. Some of these changes correspond with passing vortex systems from adjacent latitudes interacting with hot spots. Strong anticyclonic gyres present to the south and southeast of the dark areas appear to circulate into hot spots. Impressive, bright white plumes occupy spaces in between hot spots. Compact cirrus-like 'scooter' clouds flow rapidly through the plumes before disappearing within the dark areas. These clouds travel at 150-200 m/s, much faster than the 100 m/s hot spot and plume drift speed. This raises the possibility that the scooter clouds may be more illustrative of the actual jet stream speed at these latitudes. Most previously published zonal wind profiles represent the drift speed of the hot spots at their latitude from pattern matching of the entire longitudinal image strip. If a downward branch of an equatorially-trapped Rossby wave controls the overall appearance of hot spots, however, the westward phase velocity of the wave leads to underestimates of the true jet stream speed.

  9. Equatorial noise emissions with quasiperiodic modulation of wave intensity

    Czech Academy of Sciences Publication Activity Database

    Němec, F.; Santolík, Ondřej; Hrbáčková, Zuzana; Pickett, J. S.; Cornilleau-Wehrlin, N.

    2015-01-01

    Roč. 120, č. 4 (2015), s. 2649-2661 ISSN 2169-9380 R&D Projects: GA MŠk(CZ) LH11122 Institutional support: RVO:68378289 Keywords : equatorial noise * magnetosonic waves * quasiperiodic modulation Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.318, year: 2015 http://onlinelibrary.wiley.com/doi/10.1002/2014JA020816/full

  10. Increases of equatorial total electron content (TEC) during magnetic storms

    International Nuclear Information System (INIS)

    Yeboah-Amankwah, D.

    1976-01-01

    This paper is a report on the analysis of equatorial electron content, TEC, during magnetic storms. Storms between 1969 and 1972 have been examined as part of an on-going study of TEC morphology during magnetically disturbed days. The published magnetic Ksup(p) indices and TEC data from the Legon abservatory have been employed. The general picture arising from the analysis is that the total electron content of the ionosphere is significantly enhanced during magnetic storms. (author)

  11. Bexarotene ligand pharmaceuticals.

    Science.gov (United States)

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  12. Electrochemical Behaviour, IR Spectroelectrochemistry and Theoretical Studies of Tetracobalt Carbonyl Cluster Complexes with a Facial Cyclooctatetraene Ligand

    Czech Academy of Sciences Publication Activity Database

    Fiedler, Jan; Nervi, C.; Osella, D.; Calhorda, M. J.; Godinho, S. M. C.; Merkel, R.; Wadepohl, H.

    - (2002), s. 3705-3711 ISSN 1472-7773 R&D Projects: GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroelectrochemistry * electron-transfer reactions Subject RIV: CG - Electrochemistry Impact factor: 3.023, year: 2002

  13. Active control of methanol carbonylation selectivity over Au/carbon anode by electrochemical potential.

    Science.gov (United States)

    Funakawa, Akiyasu; Yamanaka, Ichiro; Otsuka, Kiyoshi

    2005-05-12

    Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO(2). Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au(3+), methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au(0) is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (selective DMC formation by indirect electrochemical carbonylation through Au(3+)/Au(+) redox at high potentials (>+1.3 V).

  14. Protein carbonylation sites in bovine raw milk and processed milk products.

    Science.gov (United States)

    Milkovska-Stamenova, Sanja; Mnatsakanyan, Ruzanna; Hoffmann, Ralf

    2017-08-15

    During thermal treatment of milk, proteins are oxidized, which may reduce the nutritional value of milk, abolish protein functions supporting human health, especially important for newborns, and yield potentially harmful products. The side chains of several amino acids can be oxidized to reactive carbonyls, which are often used to monitor oxidative stress in organisms. Here we mapped protein carbonylation sites in raw milk and different brands of pasteurized, ultra high temperature (UHT) treated milk, and infant formulas (IFs) after digesting the precipitated proteins with trypsin. Reactive carbonyls were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine to enrich the modified peptides by avidin-biotin affinity chromatography and analyze them by nanoRP-UPLC-ESI-MS. Overall, 53 unique carbonylated peptides (37 carbonylation sites, 15 proteins) were identified. Most carbonyls were derived from dicarbonyls (mainly glyoxal). The number of carbonylation sites increased with the harsher processing from raw milk (4) to pasteurized (16) and UHT milk (16) and to IF (24). Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Crystal structure of di-μ-chlorido-bis[dichloridobis(methanol-κOiridium(III] dihydrate: a surprisingly simple chloridoiridium(III dinuclear complex with methanol ligands

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola

    2015-05-01

    Full Text Available The reaction between IrCl3·xH2O in methanol led to the formation of small amounts of the title compound, [Ir2Cl6(CH3OH4]·2H2O, which consists of two IrCl4O2 octahedra sharing an edge via chloride bridges. The molecule lies across an inversion center. Each octahedron can be envisioned as being comprised of four chloride ligands in the equatorial plane with methanol ligands in the axial positions. A lattice water molecule is strongly hydrogen-bonded to the coordinating methanol ligands and weak interactions with coordinating chloride ligands lead to the formation of a three-dimensional network. This is a surprising structure given that, while many reactions of iridium chloride hydrate are carried out in alcoholic solvents, especially methanol and ethanol, this is the first structure of a chloridoiridium compound with only methanol ligands.

  16. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    OpenAIRE

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be carried out under rather mild reaction conditions, such as 0–100 °C and 0–2.5 MPa. We studied the conversion of benzyl chloride to phenyl acetic methyl ester in a semi-batch reactor in which one of the...

  17. Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite.

    Science.gov (United States)

    Boronat, Mercedes; Martínez, Cristina; Corma, Avelino

    2011-02-21

    The activity and selectivity towards carbonylation presented by Brønsted acid sites located inside the 8MR pockets or in the main 12MR channels of mordenite is studied by means of quantum-chemical calculations, and the mechanistic differences between methanol and DME carbonylation are investigated. The selectivity towards carbonylation is higher inside the 8MR pockets, where the competitive formation of DME and hydrocarbons that finally leads to catalyst deactivation is sterically impeded. Moreover, inclusion of dispersion interactions in the calculations leads to agreement between the calculated activation barriers for the rate determining step and the experimentally observed higher reactivity of methoxy groups located inside the 8MR channels.

  18. Formation of neutral and charged gold carbonyls on highly facetted gold nanostructures

    Science.gov (United States)

    Chau, Thoi-Dai; Visart de Bocarmé, Thierry; Kruse, Norbert; Wang, Richard L. C.; Kreuzer, Hans Jürgen

    2003-12-01

    We show that gold mono- and di-carbonyls are formed on gold field emitter tips during interaction with carbon monoxide gas at room temperature and in the presence of high electrostatic fields. The experiments are done in a time-of-flight atom probe to obtain mass spectra. The yield of monocarbonyl cations is about twice that of di-carbonyl ions. Density functional theory calculations are reported that explain the field stabilization of adsorbed carbonyls and the desorption yield of their cations.

  19. Carbonylation of 1-hexene in the presence of palladium-anion-exchange resin catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Pirozhkov, S.D.; Buiya, M.A.; Lunin, A.F.; Karapetyan, L.P.; Saldadze, K.M.

    1986-06-20

    Activated charcoal, silica gel, and zeolites containing palladium are active in the carbonylation of lower olefins by carbon monoxide. In the present work, they studied the carbonylation of 1-hexene in the presence of a series of palladium catalysts containing An-221, An-251, and AN-511 anion-exchange catalysts produced in the USSR as the supports. A catalyst obtained by the deposition of palladium(II) on weakly basic anion-exchange resins displays high efficiency in the carbonylation of 1-hexene with the formation of a nixture of enanthoic and 2-methylcaproic acids.

  20. Flow carbonylation of sterically hindered ortho-substituted iodoarenes

    Directory of Open Access Journals (Sweden)

    Carl J. Mallia

    2016-07-01

    Full Text Available The flow synthesis of ortho-substituted carboxylic acids, using carbon monoxide gas, has been studied for a number of substrates. The optimised conditions make use of a simple catalyst system compromising of triphenylphosphine as the ligand and palladium acetate as the pre-catalyst. Carbon monoxide was introduced via a reverse “tube-in-tube” flow reactor at elevated pressures to give yields of carboxylated products that are much higher than those obtained under normal batch conditions.

  1. Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

    International Nuclear Information System (INIS)

    Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

    2011-01-01

    Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

  2. Ligand Depot: a data warehouse for ligands bound to macromolecules.

    Science.gov (United States)

    Feng, Zukang; Chen, Li; Maddula, Himabindu; Akcan, Ozgur; Oughtred, Rose; Berman, Helen M; Westbrook, John

    2004-09-01

    Ligand Depot is an integrated data resource for finding information about small molecules bound to proteins and nucleic acids. The initial release (version 1.0, November, 2003) focuses on providing chemical and structural information for small molecules found as part of the structures deposited in the Protein Data Bank. Ligand Depot accepts keyword-based queries and also provides a graphical interface for performing chemical substructure searches. A wide variety of web resources that contain information on small molecules may also be accessed through Ligand Depot. Ligand Depot is available at http://ligand-depot.rutgers.edu/. Version 1.0 supports multiple operating systems including Windows, Unix, Linux and the Macintosh operating system. The current drawing tool works in Internet Explorer, Netscape and Mozilla on Windows, Unix and Linux.

  3. Thermal characterization of magnetically aligned carbonyl iron/agar composites.

    Science.gov (United States)

    Diaz-Bleis, D; Vales-Pinzón, C; Freile-Pelegrín, Y; Alvarado-Gil, J J

    2014-01-01

    Composites of magnetic particles into polymeric matrices have received increasing research interest due to their capacity to respond to external magnetic or electromagnetic fields. In this study, agar from Gelidium robustum has been chosen as natural biocompatible polymer to build the matrix of the magnetic carbonyl iron particles (CIP) for their uses in biomedical fields. Heat transfer behavior of the CIP-agar composites containing different concentrations (5, 10, 15, 20, 25 and 30% w/w) of magnetically aligned and non-aligned CIP in the agar matrix was studied using photothermal radiometry (PTR) in the back-propagation emission configuration. The morphology of the CIP-agar composites with aligned and non-aligned CIP under magnetic field was also evaluated by scanning electron microscopy (SEM). The results revealed a dominant effect of CIP concentration over the alignment patterns induced by the magnetic field, which agrees with the behavior of the thermal diffusivity and thermal conductivity. Agar served as a perfect matrix to be used with CIP, and CIP-agar composites magnetically aligned at 20% CIP concentration can be considered as promising 'smart' material for hyperthermia treatments in the biomedical field. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.

    1994-12-31

    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  5. Plant Uptake of Atmospheric Carbonyl Sulfide in Coast Redwood Forests

    Science.gov (United States)

    Campbell, J. E.; Whelan, M. E.; Berry, J. A.; Hilton, T. W.; Zumkehr, A.; Stinecipher, J.; Lu, Y.; Kornfeld, A.; Seibt, U.; Dawson, T. E.; Montzka, S. A.; Baker, I. T.; Kulkarni, S.; Wang, Y.; Herndon, S. C.; Zahniser, M. S.; Commane, R.; Loik, M. E.

    2017-12-01

    The future resilience of coast redwoods (Sequoia sempervirens) is now of critical concern due to the detection of a 33% decline in California coastal fog over the 20th century. However, ecosystem-scale measurements of photosynthesis and stomatal conductance are challenging in coast redwood forests, making it difficult to anticipate the impacts of future changes in fog. To address this methodological problem, we explore coastal variations in atmospheric carbonyl sulfide (COS or OCS), which could potentially be used as a tracer of these ecosystem processes. We conducted atmospheric flask campaigns in coast redwood sites, sampling at surface heights and in the canopy ( 70 m), at the University of California Landels-Hill Big Creek Reserve and Big Basin State Park. We simulated COS atmosphere-biosphere exchange with a high-resolution 3-D model to interpret these data. Flask measurements indicated a persistent daytime drawdown between the coast and the downwind forest (45 ± 6 ppt COS) that is consistent with the expected relationship between COS plant uptake, stomatal conductance, and gross primary production. Other sources and sinks of COS that could introduce noise to the COS tracer technique (soils, anthropogenic activity, nocturnal plant uptake, and surface hydrolysis on leaves) are likely to be small relative to daytime COS plant uptake. These results suggest that COS measurements may be useful for making ecosystem-scale estimates of carbon, water, and energy exchange in coast redwood forests.

  6. Catalytic hydrogenation of carbonyl group for deuterated compound production

    International Nuclear Information System (INIS)

    Gluhoi, C. Andreea; Marginean, P.; Lazar, Diana; Almasan, V.

    1999-01-01

    The total deuterated isopropyl alcohol can be produced starting from acetone. The developed technology comprises two steps: Deuteration of acetone by H/D isotopic exchange between acetone and heavy water in homogeneous catalysis. Reduction of the deuterated acetone with deuterium in presence of a metal/support catalyst. H/D isotopic exchange reaction of the H atoms from CH 3 groups is easy to occur because carbonyl group weakens C-H bond (ceto-enolyc tautomery). The big difference between boiling points of acetone and water permits an easy separation of acetone by distillation method. The reduction of acetone with deuterium was performed in a dynamic reactor by passing a deuterium flow saturated with acetone vapour through a supported nickel catalyst bed. The reaction products were analysed on-line using a flame ionisation detector. The supported nickel catalysts were checked for this reaction. By using nickel over different supports the selectivity for isopropyl alcohol was about 100%. The propane was detected only as traces. The catalytic activity depends strongly on the support nature: the Ni/SiO 2 is less active, while the Ni/TiO 2 presents the larger value for the intrinsic activity. (authors)

  7. Global gridded anthropogenic emissions inventory of carbonyl sulfide

    Science.gov (United States)

    Zumkehr, Andrew; Hilton, Tim W.; Whelan, Mary; Smith, Steve; Kuai, Le; Worden, John; Campbell, J. Elliott

    2018-06-01

    Atmospheric carbonyl sulfide (COS or OCS) is the most abundant sulfur containing gas in the troposphere and is an atmospheric tracer for the carbon cycle. Gridded inventories of global anthropogenic COS are used for interpreting global COS measurements. However, previous gridded anthropogenic data are a climatological estimate based on input data that is over three decades old and are not representative of current conditions. Here we develop a new gridded data set of global anthropogenic COS sources that includes more source sectors than previously available and uses the most current emissions factors and industry activity data as input. Additionally, the inventory is provided as annually varying estimates from years 1980-2012 and employs a source specific spatial scaling procedure. We estimate a global source in year 2012 of 406 Gg S y-1 (range of 223-586 Gg S y-1), which is highly concentrated in China and is twice as large as the previous gridded inventory. Our large upward revision in the bottom-up estimate of the source is consistent with a recent top-down estimate based on air-monitoring and Antarctic firn data. Furthermore, our inventory time trends, including a decline in the 1990's and growth after the year 2000, are qualitatively consistent with trends in atmospheric data. Finally, similarities between the spatial distribution in this inventory and remote sensing data suggest that the anthropogenic source could potentially play a role in explaining a missing source in the global COS budget.

  8. Relationship between laparoscopic cholecystectomy operative time and carbonyl hemoglobin content

    Directory of Open Access Journals (Sweden)

    ZHANG Qi

    2013-06-01

    Full Text Available ObjectiveTo investigate whether operative time of laparoscopic cholecystectomy impacts the carbonyl hemoglobin (COHb concentration in peripheral blood. MethodsForty patients with gallstones and indications for laparoscopic cholecystectomy were enrolled in the study. Peripheral venous blood samples were collected at the beginning and end of the operative procedure. COHb concentration was measured by UV spectroscopy. The significance of changes in COHb concentration in relation to time of the operative procedure (rounded to the nearest minute was assessed by statistical correlation coefficient test. ResultsThe laparoscopic procedure was completed in 38 cases, and two patients required conversion to laparotomy. The content of COHb in peripheral venous blood had significantly increased during the laparoscopic operation (operation beginning: 11.07%±1.18% vs. operation end: 1.44%±0.26%, P<0.05. The change was positively correlated with operation time (r=0.85. ConclusionCarbon monoxide produced during the laparoscopic cholecystectomy procedure can lead to an increase in peripheral venous blood COHb. The longer the operation lasts, the greater the increase in COHb.

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

    KAUST Repository

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

    2014-01-01

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

  10. Structure and Bonding in Binuclear Metal Carbonyls. Classical Paradigms vs. Insights from Modern Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert

    2015-01-01

    Roč. 1053, SI (2015), s. 195-213 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : binuclear metal carbonyls * DAFH analysis * 18-electron rule Subject RIV: CC - Organic Chemistry Impact factor: 1.403, year: 2015

  11. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

    2015-01-01

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  12. Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

    International Nuclear Information System (INIS)

    Marling, J.B.

    1981-01-01

    A deuterium-enriched material is produced by selective photoinduced dissociation of a gas phase organic carbonyl compound containing at least one hydrogen atom bonded to an atom adjacent to a carbonyl group. Alkyl carbonyl compounds such as acetone, acetaldehyde, trifluoroacetic acid, cyclobutanone, cyclopentanone, methyl acetate, 3,3-dimethyl-2-butanone, 2,4-pentanedione, and 4-methyl-2-pentanone are preferred. The carbonyl compound is subjected to intense infrared radiation from one laser, or two lasers operating at different frequencies, to selectively dissociate the deuterated molecules into stable products. The undissociated compound may be redeuterated by direct aqueous liquid phase H/D exchange, or by indirect liquid phase exchange using an alkanol in an intermediate step

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

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

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

  14. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Science.gov (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  15. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Matthias, E-mail: matthias.schindler@physik.uni-erlangen.de; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-15

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO{sub 2} and reduced to graphite to determine {sup 14}C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  16. Melatonin: functions and ligands.

    Science.gov (United States)

    Singh, Mahaveer; Jadhav, Hemant R

    2014-09-01

    Melatonin is a chronobiotic substance that acts as synchronizer by stabilizing bodily rhythms. Its synthesis occurs in various locations throughout the body, including the pineal gland, skin, lymphocytes and gastrointestinal tract (GIT). Its synthesis and secretion is controlled by light and dark conditions, whereby light decreases and darkness increases its production. Thus, melatonin is also known as the 'hormone of darkness'. Melatonin and analogs that bind to the melatonin receptors are important because of their role in the management of depression, insomnia, epilepsy, Alzheimer's disease (AD), diabetes, obesity, alopecia, migraine, cancer, and immune and cardiac disorders. In this review, we discuss the mechanism of action of melatonin in these disorders, which could aid in the design of novel melatonin receptor ligands. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Synthesis and characterization of bisoxazolines- and pybox-copper(II) complexes and their application in the coupling of α-carbonyls with functionalized amines

    KAUST Repository

    Jia, Weiguo

    2014-01-01

    Binuclear complexes [{(DMOX)CuCl}2(μ-Cl)2] (1), mononuclear complexes [(DMOX)CuBr2] (2) (DMOX = 4,5-dihydro-2-(4,5- dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyloxazole) and the pybox Cu(ii) complex [(Dm-Pybox)CuBr2] (3) (Dm-Pybox = 2,6-bis[4′,4′- dimethyloxazolin-2′-yl]pyridine) were obtained by reactions of CuX 2 (X = Cl, Br) with DMOX and Dm-Pybox ligands, respectively. The molecular structures of 1, 2 and 3 have been determined by single-crystal X-ray diffraction analyses. The complexes 2 and 3 are efficient in catalyzing α-amination of ketones and esters through α-bromo carbonyl intermediate. The procedures are environmentally benign methods using molecular oxygen as an oxidant with water as the only byproduct. This journal is © the Partner Organisations 2014.

  18. Synthesis of silyl iron hydride via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides.

    Science.gov (United States)

    Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

    2018-03-28

    The hydrido silyl iron complex (o-Ph 2 PC 6 H 4 SiMe 2 )Fe(PMe 3 ) 3 H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph 2 P(C 6 H 4 )SiMe 2 H (1) by Fe(PMe 3 ) 4 . 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

  19. Longitudinal Variation of the Lunar Tide in the Equatorial Electrojet

    Science.gov (United States)

    Yamazaki, Yosuke; Stolle, Claudia; Matzka, Jürgen; Siddiqui, Tarique A.; Lühr, Hermann; Alken, Patrick

    2017-12-01

    The atmospheric lunar tide is one known source of ionospheric variability. The subject received renewed attention as recent studies found a link between stratospheric sudden warmings and amplified lunar tidal perturbations in the equatorial ionosphere. There is increasing evidence from ground observations that the lunar tidal influence on the ionosphere depends on longitude. We use magnetic field measurements from the CHAMP satellite during July 2000 to September 2010 and from the two Swarm satellites during November 2013 to February 2017 to determine, for the first time, the complete seasonal-longitudinal climatology of the semidiurnal lunar tidal variation in the equatorial electrojet intensity. Significant longitudinal variability is found in the amplitude of the lunar tidal variation, while the longitudinal variability in the phase is small. The amplitude peaks in the Peruvian sector (˜285°E) during the Northern Hemisphere winter and equinoxes, and in the Brazilian sector (˜325°E) during the Northern Hemisphere summer. There are also local amplitude maxima at ˜55°E and ˜120°E. The longitudinal variation is partly due to the modulation of ionospheric conductivities by the inhomogeneous geomagnetic field. Another possible cause of the longitudinal variability is neutral wind forcing by nonmigrating lunar tides. A tidal spectrum analysis of the semidiurnal lunar tidal variation in the equatorial electrojet reveals the dominance of the westward propagating mode with zonal wave number 2 (SW2), with secondary contributions by westward propagating modes with zonal wave numbers 3 (SW3) and 4 (SW4). Eastward propagating waves are largely absent from the tidal spectrum. Further study will be required for the relative importance of ionospheric conductivities and nonmigrating lunar tides.

  20. New Measurements Of Jupiter's Equatorial Region In Visible Wavelengths

    Science.gov (United States)

    Rojas, Jose; Arregi, J.; García-Melendo, E.; Barrado-Izagirre, N.; Hueso, R.; Gómez-Forrellad, J. M.; Pérez-Hoyos, S.; Sanz-Requena, J. F.; Sánchez-Lavega, A.

    2010-10-01

    We have studied the equatorial region of Jupiter, between 15ºS and 15ºN, on Cassini ISS images obtained during the Jupiter flyby at the end of 2000 and on HST images acquired in May and July 2008. We have found significant longitudinal variations in the intensity of the 6ºN eastward jet, up to 60 m s-1 in Cassini and HST observations. In the HST case we found that these longitudinal variations are associated to different cloud morphology. Photometric and radiative transfer analysis of the cloud features used as tracers in HST images shows that there is only a small height difference, no larger than 0.5 - 1 scale heights at most, between the slow ( 100 m s-1) and fast ( 150 m s-1) moving features. This suggests that speed variability at 6ºN is not dominated by vertical wind shears and we propose that Rossby wave activity is the responsible for the zonal variability. After removing this variability we found that Jupiter's equatorial jet is actually symmetric relative to the equator with two peaks of 140 - 150 m s-1 located at latitudes 6ºN and 6ºS and at a similar pressure level. We also studied a large, long-lived feature called the White Spot (WS) located at 6ºS that turns to form and desapear. The internal flow field in the White Spot indicates that it is a weakly rotating quasi-equatorial anticyclone relative to the ambient meridionally sheared flow. Acknowledgements: This work was supported by the Spanish MICIIN AYA2009-10701 with FEDER and Grupos Gobierno Vasco IT-464-07.

  1. Discovery Of A Rossby Wave In Jupiter's South Equatorial Region

    Science.gov (United States)

    Simon-Miller, Amy A.; Choi, D. S.; Rogers, J. H.; Gierasch, P. J.

    2012-01-01

    A detailed study of the chevron-shaped dark spots on the strong southern equatorial wind jet near 7.5 deg S planetographic latitude shows variations in velocity with longitude and time. The chevrons move with velocities near the maximum wind jet velocity of approx.140 m/s, as deduced by the history of velocities at this latitude and the magnitude of the symmetric wind jet near 7 deg N latitude. Their repetitive nature is consistent with an inertia-gravity wave (n = 75-100) with phase speed up to 25 m/s, relative to the local flow, but the identity of this wave mode is not well constrained. However, high spatial resolution movies from Cassini images show that the chevrons oscillate in latitude with a approx.7-day period. This oscillating motion has a wavelength of approx.20 deg and a speed of approx.100 m/s, following a pattern similar to that seen in the Rossby wave plumes of the North Equatorial Zone, and possibly reinforced by it, though they are not perfectly in phase. The transient anticyclonic South Equatorial Disturbance (SED) may be a similar wave feature, but moves at slower velocity. All data show chevron latitude variability, but it is unclear if this Rossby wave is present during other epochs, without time series movies that fully delineate it. In the presence of multiple wave modes, the difference in dominant cloud appearance between 7 deg N and 7.5 deg S may be due to the presence of the Great Red Spot, either through changes in stratification and stability or by acting as a wave boundary.

  2. Regulation of primary productivity rate in the equatorial Pacific

    International Nuclear Information System (INIS)

    Barber, R.T.; Chavez, F.P.

    1991-01-01

    Analysis of the Chl-specific rate of primary productivity (P B ) as a function of subsurface nutrient concentration at >300 equatorial stations provides an answer to the question: What processes regulate primary productivity rate in the high-nutrient, low-chlorophyll waters of the equatorial Pacific? In the western Pacific where there is a gradient in 60-m [NO 3 ] from 0 to ∼12 μM, the productivity rate is a linear function of nutrient concentration; in the eastern Pacific where the gradient is from 12 to 28 μM, the productivity rate is independent of nutrient concentration and limited to ∼36 mg C(mg Chl) -1 d -1 , or a mean euphotic zone C-specific growth rate (μ) of 0.47 d -1 . However, rates downstream of the Galapagos Islands are not limited; they are 46.4 mg C(mg Chl) -1 d -1 and μ = 0.57 d -1 , very close to the predicted nutrient-regulated rates in the absence of other limitation. This pattern of rate regulation can be accounted for by a combination of eolian Fe, subsurface nutrients, and sedimentary Fe derived from the Galapagos platform. In the low-nutrient western Pacific the eolian supply of Fe is adequate to allow productivity rate to be set by subsurface nutrient concentration. In the nutrient-rich easter equatorial region eolian Fe is inadequate to support productivity rates proportional to the higher nutrient concentrations, so in this region eolian Fe is rate limiting. Around the Galapagos Islands productivity rates reach levels consistent with nutrient concentrations; sedimentary Fe from the Galapagos platform seems adequate to support increased nutrient-regulated productivity rates in this region

  3. Propagation of EMIC triggered emissions toward the magnetic equatorial plane

    Science.gov (United States)

    Grison, B.; Santolik, O.; Pickett, J. S.; Omura, Y.; Engebretson, M. J.; Dandouras, I. S.; Masson, A.; Decreau, P.; Cornilleau-Wehrlin, N.

    2011-12-01

    EMIC triggered emissions are observed close to the equatorial plane of the magnetosphere at locations where EMIC waves are commonly observed: close to the plasmapause region and in the dayside magnetosphere close to the magnetopause. Their overall characteristics (frequency with time dispersion, generation mechanism) make those waves the EMIC analogue of rising frequency whistler-mode chorus emissions. In our observations the Poynting flux of these emissions is usually clearly arriving from the equatorial region direction, especially when observations take place at more than 5 degrees of magnetic latitude. Simulations have also confirmed that the conditions of generation by interaction with energetic ions are at a maximum at the magnetic equator (lowest value of the background magnetic field along the field line). However in the Cluster case study presented here the Poynting flux of EMIC triggered emissions is propagating toward the equatorial region. The large angle between the wave vector and the background magnetic field is also unusual for this kind of emission. The rising tone starts just above half of the He+ gyrofrequency (Fhe+) and it disappears close to Fhe+. At the time of detection, the spacecraft magnetic latitude is larger than 10 degrees and L shell is about 4. The propagation sense of the emissions has been established using two independent methods: 1) sense of the parallel component of the Poynting flux for a single spacecraft and 2) timing of the emission detections at each of the four Cluster spacecraft which were in a relatively close configuration. We propose here to discuss this unexpected result considering a reflection of this emission at higher latitude.

  4. Equatorial storm sudden commencements and interplanetary magnetic field

    International Nuclear Information System (INIS)

    Rastogi, R.G.

    1980-01-01

    A comparison is made of the signatures of interplanetary (IP) shocks in the B and theta plots of interplanetary magnetic field (IMF) data of satellites Explorer 33, 34 and 35 and in the H magnetograms at ground observatories within the equatorial electrojet belt, Huancayo, Addis Ababa and Trivandrum associated with major storm sudden commencements during 1967-70. The IP shocks showing sudden increase of the scalar value of IMF, i.e. B without any change of the latitude theta or with the southward turning of theta, were followed by a purely positive sudden increase of H, at any of the magnetic observatories, either on the dayside or the nightside of the earth. The IP shocks identified by a sudden increase of B and with the northward turning of the latitude theta (positive ΔBsub(z)) were associated with purely positive sudden commencement (SC) at the observatories in the nightside, but at the equatorial observatories in the dayside of the earth the signature of the shock was a SC in H with a preliminary negative impulse followed by the main positive excursion (SC-+). It is suggested that the SCs in H at low latitudes are composed of two effects, viz. (i) one due to hydromagnetic pressure on the magnetosphere by the solar plasma and (ii) the other due to the induced electric field associated with the solar wind velocity, V and the Z-component of the IP magnetic field (E = - V x Bsub(z)). The effect of magnetosphere electric field is faster than the effect due to the compression of the magnetosphere by the impinging solar plasma. The negative impulse of SC-+ at low latitude is seen at stations close to the dip equator and only during daytime due to the existence of high ionospheric conductivities in the equatorial electrojet region. (author)

  5. Macrocyclic G-quadruplex ligands

    DEFF Research Database (Denmark)

    Nielsen, M C; Ulven, Trond

    2010-01-01

    are macrocyclic structures which have been modeled after the natural product telomestatin or from porphyrin-based ligands discovered in the late 1990s. These two structural classes of G-quadruplex ligands are reviewed here with special attention to selectivity and structure-activity relationships, and with focus...

  6. Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

    Science.gov (United States)

    Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

    2017-01-20

    The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

  7. Structure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of Alcohols

    OpenAIRE

    Briggs, Daniel Neal

    2010-01-01

    AbstractStructure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of AlcoholsbyDaniel Neal BriggsDoctor of Philosophy in Chemical EngineeringUniversity of California, BerkeleyProfessor Alexis T. Bell, Chair The oxidative carbonylation of alcohols to produce dialkyl carbonates is a process that takes place commercially in a slurry of cuprous chloride in the appropriate alcohol. While this process is chemically efficient, it incurs costs in terms of ene...

  8. Chemoselective Reduction and Alkylation of Carbonyl Functions Using Phosphonium Salts as an in Situ Protecting Groups.

    Science.gov (United States)

    Ohta, Reiya; Fujioka, Hiromichi

    2017-01-01

    Recent progress in the chemoselective reduction and alkylation of carbonyl functions using our in situ protection method is described. Methods that enable reversal or control of the reactivity of a carbonyl functional group are potentially useful. They open up new areas of synthetic organic chemistry and change the concept of retrosynthesis because they remove the need for complicated protection/deprotection sequences. In this account, we discuss the strategy and applications of our in situ protection method using phosphonium salts.

  9. Cytoprotective Effects of Pumpkin (Cucurbita Moschata) Fruit Extract against Oxidative Stress and Carbonyl Stress.

    Science.gov (United States)

    Shayesteh, Reyhaneh; Kamalinejad, Mohammad; Adiban, Hasan; Kardan, Azin; Keyhanfar, Fariborz; Eskandari, Mohammad Reza

    2017-10-01

    Background Diabetes mellitus is a chronic endocrine disorder that is associated with significant mortality and morbidity due to microvascular and macrovascular complications. Diabetes complications accompanied with oxidative stress and carbonyl stress in different organs of human body because of the increased generation of free radicals and impaired antioxidant defense systems. In the meantime, reactive oxygen species (ROS) and reactive carbonyl species (RCS) have key mediatory roles in the development and progression of diabetes complications. Therapeutic strategies have recently focused on preventing such diabetes-related abnormalities using different natural and chemical compounds. Pumpkin ( Cucurbita moschata ) is one of the most important vegetables in the world with a broad-range of pharmacological activities such as antihyperglycemic effect. Methods In the present study, the cytoprotective effects of aqueous extract of C. moschata fruit on hepatocyte cytotoxicity induced by cumene hydroperoxide (oxidative stress model) or glyoxal (carbonylation model) were investigated using freshly isolated rat hepatocytes. Results The extract of C. moschata (50 μg/ml) excellently prevented oxidative and carbonyl stress markers, including hepatocyte lysis, ROS production, lipid peroxidation, glutathione depletion, mitochondrial membrane potential collapse, lysosomal damage, and cellular proteolysis. In addition, protein carbonylation was prevented by C. moschata in glyoxal-induced carbonyl stress. Conclusion It can be concluded that C. moschata has cytoprotective effects in oxidative stress and carbonyl stress models and this valuable vegetable can be considered as a suitable herbal product for the prevention of toxic subsequent of oxidative stress and carbonyl stress seen in chronic hyperglycemia. © Georg Thieme Verlag KG Stuttgart · New York.

  10. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    International Nuclear Information System (INIS)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young

    2017-01-01

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields

  11. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young [Dept. of Energy Systems Research, Ajou University, Suwon (Korea, Republic of)

    2017-03-15

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields.

  12. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    OpenAIRE

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, P. (Petra); Filip, P. (Petr); Vesel, A.

    2011-01-01

    The aim of this paper is to document suitability of plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids. Surface-modified carbonyl iron particles were prepared via their exposure to 50% argon and 50% octafluorocyclobutane plasma. The X-ray photoelectron spectroscopy was used for analysis of chemical bonding states in the surface layer. Plasma-treated particles were adopted for a dispersed phase in magnetorheological (MR) fluids, and the MR behaviour was in...

  13. An endogenous aryl hydrocarbon receptor ligand inhibits proliferation and migration of human ovarian cancer cells.

    Science.gov (United States)

    Wang, Kai; Li, Yan; Jiang, Yi-Zhou; Dai, Cai-Feng; Patankar, Manish S; Song, Jia-Sheng; Zheng, Jing

    2013-10-28

    The aryl hydrocarbon receptor (AhR), a ligand-activated transcription factor mediates many biological processes. Herein, we investigated if 2-(1'H-indole-3'-carbonyl)-thiazole-4-carboxylic acid methyl ester (ITE, an endogenous AhR ligand) regulated proliferation and migration of human ovarian cancer cells via AhR. We found that AhR was widely present in many histotypes of ovarian cancer tissues. ITE suppressed OVCAR-3 cell proliferation and SKOV-3 cell migration in vitro, which were blocked by AhR knockdown. ITE also suppressed OVCAR-3 cell growth in mice. These data suggest that the ITE might potentially be used for therapeutic intervention for at least a subset of human ovarian cancer. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  14. Variability in equatorial B0 and B1

    International Nuclear Information System (INIS)

    Adeniyi, J.O.; Radicella, S.M.

    2002-01-01

    Variability of ionospheric profile parameters B0 and B1, below the F2 peak is investigated for an equatorial station at two levels of solar activities. The whole 24 hours of the day and the four seasons of the year are covered. Absolute and relative variability indices were utilized in the study. Some evidences of correlations of variability index and profiles parameters were observed. Daytime values of relative variability in B1 at solar minimum were found to be greater than those of solar maximum. (author)

  15. Role of protein-bound carbonyl groups in the formation of advanced glycation endproducts.

    Science.gov (United States)

    Liggins, J; Furth, A J

    1997-08-22

    Several mechanisms have been postulated for the formation of advanced glycation endproducts (AGEs) from glycated proteins; they all feature protein-bound carbonyl intermediates. Using 2,4-dinitrophenylhydrazine (DNPH), we have detected these intermediates on bovine serum albumin, lysozyme and beta-lactoglobulin after in vitro glycation by glucose or fructose. Carbonyls were formed in parallel with AGE-fluorophores, via oxidative Maillard reactions. Neither Amadori nor Heyns products contributed to the DNPH reaction. Fluorophore and carbonyl yields were much enhanced in lipid-associated proteins, but both groups could also be detected in lipid-free proteins. When pre-glycated proteins were incubated in the absence of free sugar, carbonyl groups were rapidly lost in a first-order reaction, while fluorescence continued to develop beyond the 21 days of incubation. Another unexpected finding was that not all carbonyl groups were blocked by aminoguanidine, although there was complete inhibition of reactions leading to AGE-fluorescence. It is suggested that carbonyls acting as fluorophore precursors react readily with aminoguanidine, while others are resistant to this hydrazine, possibly because they are involved in ring closure. Factors influencing the relative rates of acyclisation and hydrazone formation are discussed, together with possible implications for antiglycation therapy.

  16. Carbonyl Emissions in E-cigarette Aerosol: A Systematic Review and Methodological Considerations

    Directory of Open Access Journals (Sweden)

    Konstantinos E. Farsalinos

    2018-01-01

    Full Text Available Carbonyl emissions from tobacco cigarettes represent a substantial health risk contributing to smoking-related morbidity and mortality. As expected, this is an important research topic for tobacco harm reduction products, in an attempt to compare the relative risk of these products compared to tobacco cigarettes. In this study, a systematic review of the literature available on PubMed was performed analyzing the studies evaluating carbonyl emissions from e-cigarettes. A total of 32 studies were identified and presented. We identified a large diversity of methodologies, with substantial discrepancies in puffing patterns, aerosol collection and analytical methods as well as reported units of measurements. Such discrepancies make comparisons difficult, and in some cases the accuracy of the findings cannot be determined. Importantly, control for the generation of dry puffs was not performed in the vast majority of studies, particularly in studies using variable power devices, which could result in testing conditions and reported carbonyl levels that have no clinical relevance or context. Some studies have been replicated, verifying the presence of dry puff conditions. Whenever realistic use conditions were ensured, carbonyl emissions from e-cigarettes were substantially lower than tobacco cigarette smoke, while newer generation (bottom-coil, cotton wick atomizers appeared to emit minimal levels of carbonyls with questionable clinical significance in terms of health risk. However, extremely high levels of carbonyl emissions were reported in some studies, and all these studies need to be replicated because of potentially important health implications.

  17. Predicting personal exposure to airborne carbonyls using residential measurements and time/activity data

    Science.gov (United States)

    Liu, Weili; Zhang, Junfeng (Jim); Korn, Leo R.; Zhang, Lin; Weisel, Clifford P.; Turpin, Barbara; Morandi, Maria; Stock, Tom; Colome, Steve

    As a part of the Relationships of Indoor, Outdoor, and Personal Air (RIOPA) study, 48 h integrated residential indoor, outdoor, and personal exposure concentrations of 10 carbonyls were simultaneously measured in 234 homes selected from three US cities using the Passive Aldehydes and Ketones Samplers (PAKS). In this paper, we examine the feasibility of using residential indoor concentrations to predict personal exposures to carbonyls. Based on paired t-tests, the means of indoor concentrations were not different from those of personal exposure concentrations for eight out of the 10 measured carbonyls, indicating indoor carbonyls concentrations, in general, well predicted the central tendency of personal exposure concentrations. In a linear regression model, indoor concentrations explained 47%, 55%, and 65% of personal exposure variance for formaldehyde, acetaldehyde, and hexaldehyde, respectively. The predictability of indoor concentrations on cross-individual variability in personal exposure for the other carbonyls was poorer, explainingexposure concentrations. It was found that activities related to driving a vehicle and performing yard work had significant impacts on personal exposures to a few carbonyls.

  18. COMPARATIVE STUDY OF EFFICACY OF FERROUS SULPHATE AND CARBONYL IRON IN ANEMIA OF ANTENATAL WOMEN

    Directory of Open Access Journals (Sweden)

    Radhika

    2015-03-01

    Full Text Available Iron deficiency anemia is the most common and important public health problem all over the world in the risk group of antenatal women. Research is going on to improve the iron status of the pregnant women with different forms of iron available. In this regard, Carbonyl Iron is showing promising results in improving the red cell mass with better compliance. 120 antenatal women were recruited in this study. The study comprised of 6weeks for each patient. They were given Carbonyl Iron 100 mg/day and FeS04 100gm/day . Before and after treatment all the baseline and specific investigations were one. Results were tabulated, comparison and significance were tested by unpaired student ’s’ test and their 'p' value was calculated. Results were shown graphically also. Carbonyl Iron showed improvement in hemoglobin, PCV and better than ferrous Sulphate (P <0.001. Incidence of side effects were less with Carbonyl Iron than Ferrous Sulphate, better compliance was seen with Carbonyl Iron. In conclusion, the present study s howed that Carbonyl Iron had better efficacy and safety in the management of Iron deficiency anemia in antenatal women than ferrous Sulphate

  19. Protein carbonylation associated to high-fat, high-sucrose diet and its metabolic effects.

    Science.gov (United States)

    Méndez, Lucía; Pazos, Manuel; Molinar-Toribio, Eunice; Sánchez-Martos, Vanesa; Gallardo, José M; Rosa Nogués, M; Torres, Josep L; Medina, Isabel

    2014-12-01

    The present research draws a map of the characteristic carbonylation of proteins in rats fed high-caloric diets with the aim of providing a new insight of the pathogenesis of metabolic diseases derived from the high consumption of fat and refined carbohydrates. Protein carbonylation was analyzed in plasma, liver and skeletal muscle of Sprague-Dawley rats fed a high-fat, high-sucrose (HFHS) diet by a proteomics approach based on carbonyl-specific fluorescence-labeling, gel electrophoresis and mass spectrometry. Oxidized proteins along with specific sites of oxidative damage were identified and discussed to illustrate the consequences of protein oxidation. The results indicated that long-term HFHS consumption increased protein oxidation in plasma and liver; meanwhile, protein carbonyls from skeletal muscle did not change. The increment of carbonylation by HFHS diet was singularly selective on specific target proteins: albumin from plasma and liver, and hepatic proteins such as mitochondrial carbamoyl-phosphate synthase (ammonia), mitochondrial aldehyde dehydrogenase, argininosuccinate synthetase, regucalcin, mitochondrial adenosine triphosphate synthase subunit beta, actin cytoplasmic 1 and mitochondrial glutamate dehydrogenase 1. The possible consequences that these specific protein carbonylations have on the excessive weight gain, insulin resistance and nonalcoholic fatty liver disease resulting from HFHS diet consumption are discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Line profile analyses of rhodium metal obtained by decomposition of rhodium carbonyl

    International Nuclear Information System (INIS)

    Chandra, D.; Mandalia, H.; Garner, M.L.; Blakely, M.K.; Lau, K.H.

    1995-01-01

    Metal carbonyls are important for chemical vapor deposition (CVD) of metals and alloys and formation of high surface area metallic particles which have potential applications as catalysts. Rhodium carbonyl [Rh 6 (CO) 16 ] produces high surface area metallic particles whose structure has been reported as monoclinic (I2/a) with lattice dimensions, a=17.00(±0.03)Angstrom, b=9.78(±0.02)Angstrom, c=17.53(±0.03)Angstrom and Β=121 degrees 45' ± 30' at room temperature. Generally, metal carbonyl crystals dissociate under vacuum as carbonyl gas and decompose to metallic crystals and carbon monoxide at higher temperatures. However, the behavior of rhodium carbonyl crystals is different; they decompose directly to metallic rhodium without the formation of rhodium carbonyl gas in vacuum. Several residual fine grains of rhodium metal are found after the decomposition in vacuum at relatively low temperatures. The metallic samples of rhodium were obtained from vapor pressure experiments using torsion Knudsen-effusion apparatus. X-ray diffraction analyses performed on these gains showed severely broadened Bragg reflections indicative of small particle size and/or lattice microgram. In this study, a comparison of lattice strains and domain sizes obtained by integral breadth and Fourier methods has been made. In addition a comparison of the lattice strains and domain sizes has been made between the Cauchy, Gaussian, Cauchy-Gaussian and Aqua integral breadth methods

  1. Characteristics of carbonyl compounds in public vehicles of Beijing city: Concentrations, sources, and personal exposures

    Science.gov (United States)

    Pang, Xiaobing; Mu, Yujing

    The characteristics of carbonyl compounds (carbonyls) including concentrations, major sources, and personal exposure were investigated for 29 vehicles including taxi, bus and subway in Beijing. It was found that the taxis (Xiali, TA) and buses (Huanghe, BA) fueled by gasoline with longer service years had the higher indoor carbonyl levels (178±42.7 and 188±31.6 μg m -3) while subways energized by electricity without exhaust and the jingwa buses (BB) driven in the suburb had the lower levels with total concentrations of 98.5±26.3 and 92.1±20.3 μg m -3, respectively. Outdoor carbonyls of taxi cars and buses were nearly at the same level with their total concentrations varying from 80 to 110 μg m -3. The level of outdoor subways carbonyls was equal with the ambient air levels. Exhaust leakage, indoor material emissions, photochemical formation, and infiltration of outdoor air were considered to be the major sources to in-vehicle carbonyls. Personal exposures and cancer risk to formaldehyde and acetaldehyde were calculated for professional bus and taxi drivers, respectively. Taxi drivers had the highest cancer risk with personal exposure to formaldehyde and acetaldehyde of 212 and 243 μg day -1, respectively. The public concern should pay considerable attention to professional drivers' health.

  2. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    Science.gov (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  3. Use of PET and the radioligand [carbonyl-11C]WAY-100635 in psychotropic drug development

    International Nuclear Information System (INIS)

    Andree, Bengt; Halldin, Christer; Thorberg, Seth-Olov; Sandell, Johan; Farde, Lars

    2000-01-01

    Positron-emission tomography (PET) provides potential in neuropsychiatric drug development by expanding knowledge of drug action in the living human brain and reducing time consumption and costs. The 5-hydroxytryptamine 1A (5-HT 1A ) receptor is of central interest as a target for the treatment of anxiety, depression, and schizophrenia. Research on the clinical significance of the 5-HT 1A receptor now benefits from the highly selective radioligand [carbonyl- 11 C]WAY-100635 (WAY) for quantitative determination of 5-HT 1A receptors in the primate and human brain in vivo using PET. In this paper, three studies are reviewed to demonstrate the suitability of WAY as radioligand for quantification of central 5-HT 1A receptors in brain and as an applicable tool for drug development. In the first study a monkey model was used to characterize WAY binding. It was confirmed that the reference ligand 8-OH-DPAT and psychoactive drugs such as buspirone and pindolol occupies 5-HT 1A receptors in the primate brain. Pindolol is an β-adrenoreceptor antagonist with a high affinity to 5-HT 1A receptors. This drug has been suggested in combination with selective serotonin reuptake inhibitors for the treatment of depression and was given to healthy males in the second study. Pindolol induced a marked inhibition of central 5-HT 1A receptors as calculated by the ratio-analysis method and simplified reference tissue model, 2 h after administration of 10 mg as a single oral dose. This observation suggests that pindolol may have a role for the suggested potentiation of selective serotonin reuptake inhibitor treatment of depression. The third study was on robalzotan (NAD-299), a recently developed 5-HT 1A receptor antagonist and putative drug with implications for the treatment of depression. In the cynomolgus monkey brain, robalzotan in the dose range 2-100 μg/kg IV occupied 5-HT 1A receptors in a dose-dependent and saturable manner with a maximal calculated occupancy of 70-80%. The

  4. Vertical Rise Velocity of Equatorial Plasma Bubbles Estimated from Equatorial Atmosphere Radar Observations and High-Resolution Bubble Model Simulations

    Science.gov (United States)

    Yokoyama, T.; Ajith, K. K.; Yamamoto, M.; Niranjan, K.

    2017-12-01

    Equatorial plasma bubble (EPB) is a well-known phenomenon in the equatorial ionospheric F region. As it causes severe scintillation in the amplitude and phase of radio signals, it is important to understand and forecast the occurrence of EPBs from a space weather point of view. The development of EPBs is presently believed as an evolution of the generalized Rayleigh-Taylor instability. We have already developed a 3D high-resolution bubble (HIRB) model with a grid spacing of as small as 1 km and presented nonlinear growth of EPBs which shows very turbulent internal structures such as bifurcation and pinching. As EPBs have field-aligned structures, the latitude range that is affected by EPBs depends on the apex altitude of EPBs over the dip equator. However, it was not easy to observe the apex altitude and vertical rise velocity of EPBs. Equatorial Atmosphere Radar (EAR) in Indonesia is capable of steering radar beams quickly so that the growth phase of EPBs can be captured clearly. The vertical rise velocities of the EPBs observed around the midnight hours are significantly smaller compared to those observed in postsunset hours. Further, the vertical growth of the EPBs around midnight hours ceases at relatively lower altitudes, whereas the majority of EPBs at postsunset hours found to have grown beyond the maximum detectable altitude of the EAR. The HIRB model with varying background conditions are employed to investigate the possible factors that control the vertical rise velocity and maximum attainable altitudes of EPBs. The estimated rise velocities from EAR observations at both postsunset and midnight hours are, in general, consistent with the nonlinear evolution of EPBs from the HIRB model.

  5. Fast retrievals of tropospheric carbonyl sulfide with IASI

    Science.gov (United States)

    Vincent, R. Anthony; Dudhia, Anu

    2017-02-01

    Iterative retrievals of trace gases, such as carbonyl sulfide (OCS), from satellites can be exceedingly slow. The algorithm may even fail to keep pace with data acquisition such that analysis is limited to local events of special interest and short time spans. With this in mind, a linear retrieval scheme was developed to estimate total column amounts of OCS at a rate roughly 104 times faster than a typical iterative retrieval. This scheme incorporates two concepts not utilized in previously published linear estimates. First, all physical parameters affecting the signal are included in the state vector and accounted for jointly, rather than treated as effective noise. Second, the initialization point is determined from an ensemble of atmospheres based on comparing the model spectra to the observations, thus improving the linearity of the problem. All of the 2014 data from the Infrared Atmospheric Sounding Interferometer (IASI), instruments A and B, were analysed and showed spatial features of OCS total columns, including depletions over tropical rainforests, seasonal enhancements over the oceans, and distinct OCS features over land. Error due to assuming linearity was found to be on the order of 11 % globally for OCS. However, systematic errors from effects such as varying surface emissivity and extinction due to aerosols have yet to be robustly characterized. Comparisons to surface volume mixing ratio in situ samples taken by NOAA show seasonal correlations greater than 0.7 for five out of seven sites across the globe. Furthermore, this linear scheme was applied to OCS, but may also be used as a rapid estimator of any detectable trace gas using IASI or similar nadir-viewing instruments.

  6. Plasma protein carbonyl responses to anaerobic exercise in female cyclists

    Directory of Open Access Journals (Sweden)

    M.E Afzalpour

    2016-03-01

    Full Text Available Single bouts of aerobic exercise may leads to oxidative stress due to the use of oxygen for metabolism and the generation of reactive oxygen. In athletes, oxidative stress can lead to several deleterious performance effects, such as muscular oxidative damage, muscle soreness, loss of skeletal muscle force production and/or inflammation. However, little is known regarding the severity and duration of oxidative stress arising from intensive anaerobic modes of exercise in aerobically-trained athletes. The purpose of this study was to investigate the effect of a single bout of intensive anaerobic exercise on plasma protein carbonyl (PC in aerobically-trained women. Aerobically-trained, provincial female cyclists [n = 18, age: 24.2±2.7 years; stature: 163.6±4.6 cm; body mass: 53.4±4.2 kg] were randomly assigned into either a non-exercising control (CON; n = 9 or experimental (EXP; n = 9 group that underwent a 30-second anaerobic (Wingate cycle ergometer exercise session. Blood sampling took place before exercise, immediately after the exercise (IE, and 24 hours following the exercise (24HR bout. In the EXP, results indicated significant (P ≤ 0.05 differences in PC levels between the pre-test and IE (0.010±0.0124 to 0.0149±0.0420 mmol/milt; P = 0.010, and IE and 24HR (0.0149±0.0420 to 0.0111±0.0183 mmol/milt; P = 0.013. No significant differences were observed between pre-test and 24HR (0.010±0.0124 to 0.0111±0.0183 mmol/milt; P = 0.371. These results indicate that oxidative protein damage, as indicated by PC levels, rises immediately with the onset of anaerobic exercise, but returns to resting levels within 24 hours following exercise in aerobically-trained women.

  7. Hydroxylamine-induced oxidation of ferrous carbonylated truncated hemoglobins from Mycobacterium tuberculosis and Campylobacter jejuni is limited by carbon monoxide dissociation.

    Science.gov (United States)

    Ascenzi, Paolo; Ciaccio, Chiara; Gasperi, Tecla; Pesce, Alessandra; Caporaso, Lucia; Coletta, Massimo

    2017-08-01

    Hydroxylamine (HA) is an oxidant of ferrous globins and its action has been reported to be inhibited by CO, even though this mechanism has not been clarified. Here, kinetics of the HA-mediated oxidation of ferrous carbonylated Mycobacterium tuberculosis truncated hemoglobin N and O (Mt-trHbN(II)-CO and Mt-trHbO(II)-CO, respectively) and Campylobacter jejuni truncated hemoglobin P (Cj-trHbP(II)-CO), at pH 7.2 and 20.0 °C, are reported. Mixing Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO solution with the HA solution brings about absorption spectral changes reflecting the disappearance of the ferrous carbonylated derivatives with the concomitant formation of the ferric species. HA oxidizes irreversibly Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO with the 1:2 stoichiometry. The dissociation of CO turns out to be the rate-limiting step for the oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO by HA. Values of the second-order rate constant for HA-mediated oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO range between 8.8 × 10 4 and 8.6 × 10 7 M -1 s -1 , reflecting different structural features of the heme distal pocket. This study (1) demonstrates that the inhibitory effect of CO is linked to the dissociation of this ligand, giving a functional basis to previous studies, (2) represents the first comparative investigation of the oxidation of ferrous carbonylated bacterial 2/2 globins belonging to the N, O, and P groups by HA, (3) casts light on the correlation between kinetics of HA-mediated oxidation and carbonylation of globins, and (4) focuses on structural determinants modulating the HA-induced oxidation process.

  8. Preface: The International Reference Ionosphere (IRI) at equatorial latitudes

    Science.gov (United States)

    Reinisch, Bodo; Bilitza, Dieter

    2017-07-01

    This issue of Advances in Space Research includes papers that report and discuss improvements of the International Reference Ionosphere (IRI). IRI is the international standard for the representation of the plasma in Earth's ionosphere and recognized as such by the Committee on Space Research (COSPAR), the International Union of Radio Science (URSI), the International Telecommunication Union (ITU), and the International Standardization Organization (ISO). As requested, particularly by COSPAR and URSI, IRI is an empirical model relying on most of the available and reliable ground and space observations of the ionosphere. As new data become available and as older data sources are fully exploited the IRI model undergoes improvement cycles to stay as close to the existing data record as possible. The latest episode of this process is documented in the papers included in this issue using data from the worldwide network of ionosondes, from a few of the incoherent scatter radars, from the Alouette and ISIS topside sounders, and from the Global Navigation Satellite Systems (GNSS). The focus of this issue is on the equatorial and low latitude region that is of special importance for ionospheric physics because it includes the largest densities and steep density gradients in the double hump latitudinal structure, the Equatorial Ionization Anomaly (EIA), which is characteristic for this region.

  9. The Plasma Environment Associated With Equatorial Ionospheric Irregularities

    Science.gov (United States)

    Smith, Jonathon M.; Heelis, R. A.

    2018-02-01

    We examine the density structure of equatorial depletions referred to here as equatorial plasma bubbles (EPBs). Data recorded by the Ion Velocity Meter as part of the Coupled Ion Neutral Dynamics Investigation (CINDI) aboard the Communication/Navigation Outage Forecasting System (C/NOFS) satellite are used to study EPBs from 1600 to 0600 h local time at altitudes from 350 to 850 km. The data are taken during the 7 years from 2008 to 2014, more than one half of a magnetic solar cycle, that include solar minimum and a moderate solar maximum. Using a rolling ball algorithm, EPBs are identified by profiles in the plasma density, each having a depth measured as the percent change between the background and minimum density (ΔN/N). During solar moderate activity bubbles observed in the topside postsunset sector are more likely to have large depths compared to those observed in the topside postmidnight sector. Large bubble depths can be observed near 350 km in the bottomside F region in the postsunset period. Conversely at solar minimum the distribution of depths is similar in the postsunset and postmidnight sectors in all longitude sectors. Deep bubbles are rarely observed in the topside postsunset sector and never in the bottomside above 400 km in altitude. We suggest that these features result from the vertical drift of the plasma for these two solar activity levels. These drift conditions affect both the background density in which bubbles are embedded and the growth rate of perturbations in the bottomside where bubbles originate.

  10. Solvothermal synthesis of tetravalent uranium with isophthalate or pyromellitate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Falaise, Clement; Delille, Jason; Volkringer, Christophe; Loiseau, Thierry [Contribution from Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille, USTL-ENSCL, Villeneuve d' Ascq (France)

    2015-06-15

    Three new coordination polymers bearing tetravalent uranium have been isolated with the O-donor ligands such as isophthalate (1,3-bdc) or pyromellitate (btec). The compounds 1 and 3 have been solvothermally synthesized in N,N-dimethylformamide (DMF). The crystal structure of U(1,3-bdc){sub 2}(DMF) (1) is built up from discrete tricapped trigonal-primastic UO{sub 9} units, for which one carbonyl oxygen atom from DMF is bound to uranium. The connection of the UO{sub 9} units with the isophthalate linkers occurs in a chelating and bidentate fashion and gives rise to the formation of a 3D framework, delimiting narrow channels running along the [101] direction. Upon heating, the DMF molecules are removed, generating the second phase U(1,3-bdc){sub 2} (2) compound, closely related to 1. Indeed, the coordination environment of uranium is reduced to eight with a distorted square-antiprismatic geometry. This transition induces the relative shrinkage of the network (ΔV = 23 %). The structure of the compound U(btec)(DMF){sub 2} (3) also exhibits a 3D framework composed of an isolated bicapped square-antiprismatic UO{sub 10} unit, for which two carbonyl oxygen atoms from DMF are bonded to uranium. Pyromellitate ensures the connection of the UO{sub 10} units through the carboxylate arms in a chelating mode. This results in the formation of a network with diamond-shaped channels, developed along the c axis and encapsulating the DMF molecules. In contrast to 1, no stable phase is observed upon removing the DMF species by heating. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Two novel mixed-ligand complexes containing organosulfonate ligands.

    Science.gov (United States)

    Li, Mingtian; Huang, Jun; Zhou, Xuan; Fang, Hua; Ding, Liyun

    2008-07-01

    The structures reported herein, viz. bis(4-aminonaphthalene-1-sulfonato-kappaO)bis(4,5-diazafluoren-9-one-kappa(2)N,N')copper(II), [Cu(C(10)H(8)NO(3)S)(2)(C(11)H(6)N(2)O)(2)], (I), and poly[[[diaquacadmium(II)]-bis(mu-4-aminonaphthalene-1-sulfonato)-kappa(2)O:N;kappa(2)N:O] dihydrate], {[Cd(C(10)H(8)NO(3)S)(2)(H(2)O)(2)].2H(2)O}(n), (II), are rare examples of sulfonate-containing complexes where the anion does not fulfill a passive charge-balancing role, but takes an active part in coordination as a monodentate and/or bridging ligand. Monomeric complex (I) possesses a crystallographic inversion center at the Cu(II) atom, and the asymmetric unit contains one-half of a Cu atom, one complete 4-aminonaphthalene-1-sulfonate (ans) ligand and one 4,5-diazafluoren-9-one (DAFO) ligand. The Cu(II) atom has an elongated distorted octahedral coordination geometry formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO molecules. Complex (II) is polymeric and its crystal structure is built up by one-dimensional chains and solvent water molecules. Here also the cation (a Cd(II) atom) lies on a crystallographic inversion center and adopts a slightly distorted octahedral geometry. Each ans anion serves as a bridging ligand linking two Cd(II) atoms into one-dimensional infinite chains along the [010] direction, with each Cd(II) center coordinated by four ans ligands via O and N atoms and by two aqua ligands. In both structures, there are significant pi-pi stacking interactions between adjacent ligands and hydrogen bonds contribute to the formation of two- and three-dimensional networks.

  12. Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries.

    Science.gov (United States)

    Zhao, Qing; Zhu, Zhiqiang; Chen, Jun

    2017-12-01

    Organic carbonyl electrode materials that have the advantages of high capacity, low cost and being environmentally friendly, are regarded as powerful candidates for next-generation stationary and redox flow rechargeable batteries (RFBs). However, low carbonyl utilization, poor electronic conductivity and undesired dissolution in electrolyte are urgent issues to be solved. Here, we summarize a molecular engineering approach for tuning the capacity, working potential, concentration of active species, kinetics, and stability of stationary and redox flow batteries, which well resolves the problems of organic carbonyl electrode materials. As an example, in stationary batteries, 9,10-anthraquinone (AQ) with two carbonyls delivers a capacity of 257 mAh g -1 (2.27 V vs Li + /Li), while increasing the number of carbonyls to four with the formation of 5,7,12,14-pentacenetetrone results in a higher capacity of 317 mAh g -1 (2.60 V vs Li + /Li). In RFBs, AQ, which is less soluble in aqueous electrolyte, reaches 1 M by grafting -SO 3 H with the formation of 9,10-anthraquinone-2,7-disulphonic acid, resulting in a power density exceeding 0.6 W cm -2 with long cycling life. Therefore, through regulating substituent groups, conjugated structures, Coulomb interactions, and the molecular weight, the electrochemical performance of carbonyl electrode materials can be rationally optimized. This review offers fundamental principles and insight into designing advanced carbonyl materials for the electrodes of next-generation rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhenlie [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Department of Toxicology, Guangdong Prevention and Treatment Center for Occupational Diseases, Guangzhou 510‐300 (China); Ichihara, Sahoko [Graduate School of Regional Innovation Studies, Mie University, Tsu 514‐8507 (Japan); Oikawa, Shinji [Department of Environmental and Molecular Medicine, Mie University Graduate School of Medicine, Mie 514‐8507 (Japan); Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Ichihara, Gaku, E-mail: gak@med.nagoya-u.ac.jp [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan)

    2012-08-15

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  14. Variability in the origins and pathways of Pacific Equatorial Undercurrent water

    NARCIS (Netherlands)

    Qin, Xuerong; Sen Gupta, Alex; Van Sebille, Erik

    2015-01-01

    The Pacific Equatorial Undercurrent (EUC) transports water originating from a number of distinct source regions, eastward across the Pacific Ocean. It is responsible for supplying nutrients to the productive eastern Equatorial Pacific Ocean. Of particular importance is the transport of iron by the

  15. A study on ionospheric scintillation near the EIA crest in relation to equatorial electrodynamics

    Science.gov (United States)

    Chatterjee, S.; Chakraborty, S. K.; Veenadhari, B.; Banola, S.

    2014-02-01

    Equatorial electrojet (EEJ) data, which are considered as a proxy index of equatorial electric field, are analyzed in conjunction with equatorial ionosonde, total electron content (TEC) and scintillation data near the equatorial ionization anomaly (EIA) crest for the equinoctial months of high solar activity years (2011-2012) to identify any precursor index of postsunset evolution of equatorial electron density irregularities and subsequent occurrence of scintillation near the northern EIA crest. Only geomagnetically quiet and normal electrojet days are considered. The diurnal profiles of EEJ on the scintillation days exhibit a secondary enhancement in the afternoon to presunset hours following diurnal peaks. A series of electrodynamical processes conducive for generation of irregularities emerge following secondary enhancement of EEJ. Latitudinal profile of TEC exhibits resurgence in EIA structure around the postsunset period. Diurnal TEC profile near the EIA crest resembles postsunset secondary enhancement on the days with afternoon enhancement in EEJ. Occurrence of equatorial spread F and postsunset scintillation near the EIA crest seems to follow the secondary enhancement events in EEJ. Both the magnitude and duration of enhanced EEJ are found to be important for postsunset intensification of EIA structure and subsequent occurrence of equatorial irregularities. A critical value combining the two may be considered an important precursor for postsunset occurrence of scintillation near the EIA crest. The results are validated using archived data for the years 1989-1990 and explained in terms of modulation effects of enhanced equatorial fountain.

  16. Influence of biomass burning emissions on precipitation chemistry in the equatorial forests of Africa

    International Nuclear Information System (INIS)

    Lacaux, J.P.; Lefeivre, B.; Delmas, R.A.; Cros, B.; Andreae, M.O.

    1991-01-01

    As part of the DESCAFE program (Dynamics and Chemistry of the Atmosphere in Equatorial Forest), measurements of precipitation chemistry were made at two sampling sites of the equatorial forest in the Republic of Congo. The measurements were made in order to identify and compare atmospheric sources of gases and particles (mainly biogenic sources and emissions from burning vegetation)

  17. Correcting ligands, metabolites, and pathways

    NARCIS (Netherlands)

    Ott, M.A.; Vriend, G.

    2006-01-01

    BACKGROUND: A wide range of research areas in bioinformatics, molecular biology and medicinal chemistry require precise chemical structure information about molecules and reactions, e.g. drug design, ligand docking, metabolic network reconstruction, and systems biology. Most available databases,

  18. Seasonal-longitudinal variability of equatorial plasma bubbles

    Directory of Open Access Journals (Sweden)

    W. J. Burke

    2004-09-01

    Full Text Available We compare seasonal and longitudinal distributions of more than 8300 equatorial plasma bubbles (EPBs observed during a full solar cycle from 1989-2000 with predictions of two simple models. Both models are based on considerations of parameters that influence the linear growth rate, γRT, of the generalized Rayleigh-Taylor instability in the context of finite windows of opportunity available during the prereversal enhancement near sunset. These parameters are the strength of the equatorial magnetic field, Beq, and the angle, α, it makes with the dusk terminator line. The independence of α and Beq from the solar cycle phase justifies our comparisons.

    We have sorted data acquired during more than 75000 equatorial evening-sector passes of polar-orbiting Defense Meteorological Satellite Program (DMSP satellites into 24 longitude and 12 one-month bins, each containing ~250 samples. We show that: (1 in 44 out of 48 month-longitude bins EPB rates are largest within 30 days of when α=0°; (2 unpredicted phase shifts and asymmetries appear in occurrence rates at the two times per year when α≈0°; (3 While EPB occurrence rates vary inversely with Beq, the relationships are very different in regions where Beq is increasing and decreasing with longitude. Results (2 and (3 indicate that systematic forces not considered by the two models can become important. Damping by interhemispheric winds appears to be responsible for phase shifts in maximum rates of EPB occurrence from days when α=0°. Low EPB occurrence rates found at eastern Pacific longitudes suggest that radiation belt electrons in the drift loss cone reduce γRT by enhancing E-layer Pedersen conductances. Finally, we analyze an EPB event observed during a magnetic storm at a time and place where α≈-27°, to illustrate how electric-field penetration from

  19. Spread F – an old equatorial aeronomy problem finally resolved?

    Directory of Open Access Journals (Sweden)

    R. F. Woodman

    2009-05-01

    Full Text Available One of the oldest scientific topics in Equatorial Aeronomy is related to Spread-F. It includes all our efforts to understand the physical mechanisms responsible for the existence of ionospheric F-region irregularities, the spread of the traces in a night-time equatorial ionogram – hence its name – and all other manifestations of the same. It was observed for the first time as an abnormal ionogram in Huancayo, about 70 years ago. But only recently are we coming to understand the physical mechanisms responsible for its occurrence and its capricious day to day variability. Several additional techniques have been used to reveal the spatial and temporal characteristics of the F-region irregularities responsible for the phenomenon. Among them we have, in chronological order, radio star scintillations, trans-equatorial radio propagation, satellite scintillations, radar backscatter, satellite and rocket in situ measurements, airglow, total electron content techniques using the propagation of satellite radio signals and, recently, radar imaging techniques. Theoretical efforts are as old as the observations. Nevertheless, 32 years after their discovery, Jicamarca radar observations showed that none of the theories that had been put forward could explain them completely. The observations showed that irregularities were detected at altitudes that were stable according to the mechanisms proposed. A breakthrough came a few years later, again from Jicamarca, by showing that some of the "stable" regions had become unstable by the non-linear propagation of the irregularities from the unstable to the stable region of the ionosphere in the form of bubbles of low density plasma. A problem remained, however; the primary instability mechanism proposed, an extended (generalized Rayleigh-Taylor instability, was too slow to explain the rapid development seen by the observations. Gravity waves in the neutral background have been proposed as a seeding mechanism to

  20. Extraction complexes of Pu(IV) with carbamoylmethylphosphine oxide ligands. A relativistic density functional study

    International Nuclear Information System (INIS)

    Wang, Cong-Zhi; Lan, Jian-Hui; Feng, Yi-Xiao; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun; Wei, Yue-Zhou

    2014-01-01

    The extraction complexes of Pu(IV) with n-octyl(phenyl)-N,N-diisobutyl-methylcarbamoyl phosphine oxide (CMPO) and diphenyl-N,N-diisobutyl carbamoyl phosphine oxide (Ph 2 CMPO) have been studied by using density functional theory (DFT) combined with relativistic small-core pseudopotentials. For most complexes, the CMPO and Ph 2 CMPO molecules are coordinated as bidentate chelating ligands through the carbonyl oxygen and phosphoric oxygen atoms. The metal-ligand bonding is mainly ionic for all of these complexes. The neutral PuL(NO 3 ) 4 and PuL 2 (NO 3 ) 4 complexes are predicted to be the most thermodynamically stable molecules according to the metal-ligand complexation reactions. In addition, hydration energies may also play a significant role in the extractability of CMPO and Ph 2 CMPO for the plutonium cations. In most cases, the complexes with CMPO possess qualitatively similar geometries and electron structures to those with Ph 2 CMPO, and they also have comparable metal-ligand binding energies. Thus, replacement of alkyl groups by phenyl groups at the phosphorus atom of CMPO seems to have no obvious influence on the extraction of Pu(IV). (orig.)

  1. Role of interannual Kelvin wave propagations in the equatorial Atlantic on the Angola Benguela Current system

    Science.gov (United States)

    Imbol Koungue, Rodrigue Anicet; Illig, Serena; Rouault, Mathieu

    2017-06-01

    The link between equatorial Atlantic Ocean variability and the coastal region of Angola-Namibia is investigated at interannual time scales from 1998 to 2012. An index of equatorial Kelvin wave activity is defined based on Prediction and Research Moored Array in the Tropical Atlantic (PIRATA). Along the equator, results show a significant correlation between interannual PIRATA monthly dynamic height anomalies, altimetric monthly Sea Surface Height Anomalies (SSHA), and SSHA calculated with an Ocean Linear Model. This allows us to interpret PIRATA records in terms of equatorial Kelvin waves. Estimated phase speed of eastward propagations from PIRATA equatorial mooring remains in agreement with the linear theory, emphasizing the dominance of the second baroclinic mode. Systematic analysis of all strong interannual equatorial SSHA shows that they precede by 1-2 months extreme interannual Sea Surface Temperature Anomalies along the African coast, which confirms the hypothesis that major warm and cold events in the Angola-Benguela current system are remotely forced by ocean atmosphere interactions in the equatorial Atlantic. Equatorial wave dynamics is at the origin of their developments. Wind anomalies in the Western Equatorial Atlantic force equatorial downwelling and upwelling Kelvin waves that propagate eastward along the equator and then poleward along the African coast triggering extreme warm and cold events, respectively. A proxy index based on linear ocean dynamics appears to be significantly more correlated with coastal variability than an index based on wind variability. Results show a seasonal phasing, with significantly higher correlations between our equatorial index and coastal SSTA in October-April season.

  2. Enhanced microwave absorption in ZnO/carbonyl iron nano-composites by coating dielectric material

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Chang [School of Physics and Material Science, Anhui University, Hefei 230036 (China); Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China); Fang Qingqing, E-mail: physfangqq@126.com [School of Physics and Material Science, Anhui University, Hefei 230036 (China) and Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China); Yan Fangliang; Wang Weina; Wu Keyue; Liu Yanmei; Lv Qingrong; Zhang Hanming; Zhang Qiping; Li Jinguang; Ding Qiongqiong [School of Physics and Material Science, Anhui University, Hefei 230036 (China); Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China)

    2012-05-15

    The microwave absorption properties of zinc oxide/carbonyl iron composite nanoparticles fabricated by high energy ball milling were studied at 0-20 GHz. Experiments showed that ZnO as a kind of dielectric material coating carbonyl iron particles made the bandwidth of reflection loss (RL)<-5 dB expanding to the low frequency, and enhanced absorption effect obviously. For a 3 mm thickness absorber of ZnO/carbonyl iron after 30 h milling, the values of RL<-5 dB and RL<-8 dB were obtained in the frequency range from 7.0 GHz to 17.8 GHz and from 9.8 dB to 14.9 dB, respectively, and its strongest RL peak was -29.34 dB at 13.59 GHz. The magnetic loss of carbonyl iron particles and the dielectric loss of ZnO particles were the main mechanisms of microwave absorption for the composites. - Highlights: Black-Right-Pointing-Pointer We fabricated zinc oxide/carbonyl iron composites by high energy ball milling. Black-Right-Pointing-Pointer ZnO dielectric property increased absorption effect and absorption bandwidth. Black-Right-Pointing-Pointer Absorbing frequence of composites is expanding to low frequency direction. Black-Right-Pointing-Pointer The craft of high energy ball milling is easy to realize commerce production.

  3. Enhanced microwave absorption in ZnO/carbonyl iron nano-composites by coating dielectric material

    International Nuclear Information System (INIS)

    Zhou Chang; Fang Qingqing; Yan Fangliang; Wang Weina; Wu Keyue; Liu Yanmei; Lv Qingrong; Zhang Hanming; Zhang Qiping; Li Jinguang; Ding Qiongqiong

    2012-01-01

    The microwave absorption properties of zinc oxide/carbonyl iron composite nanoparticles fabricated by high energy ball milling were studied at 0–20 GHz. Experiments showed that ZnO as a kind of dielectric material coating carbonyl iron particles made the bandwidth of reflection loss (RL)<−5 dB expanding to the low frequency, and enhanced absorption effect obviously. For a 3 mm thickness absorber of ZnO/carbonyl iron after 30 h milling, the values of RL<−5 dB and RL<−8 dB were obtained in the frequency range from 7.0 GHz to 17.8 GHz and from 9.8 dB to 14.9 dB, respectively, and its strongest RL peak was −29.34 dB at 13.59 GHz. The magnetic loss of carbonyl iron particles and the dielectric loss of ZnO particles were the main mechanisms of microwave absorption for the composites. - Highlights: ► We fabricated zinc oxide/carbonyl iron composites by high energy ball milling. ► ZnO dielectric property increased absorption effect and absorption bandwidth. ► Absorbing frequence of composites is expanding to low frequency direction. ► The craft of high energy ball milling is easy to realize commerce production.

  4. Catalytic reactions of synthesis gas. Part 2. Methanol carbonylation and homologation

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M.

    1993-01-01

    The aim of the review is to evaluate the applicability of methanol hydrocarbonylation as a second test reaction to study the nondissociative activation of CO by heterogeneous rhodium and cobalt catalysts. The main emphasis in methanol (hydro)carbonylation chemistry has been on homogeneous reactions. These systems have been seen advantageous in selectivity, activity and ease of modification. The heterogenization attempts have been carried out to obtain easier separation of the catalyst and the product. The activity of cobalt, rhodium and other metals supported on different materials have been studied in heterogeneous methanol (hydro)carbonylation. The observed activities have been considerably influenced by the support. The most effective catalyst support has been activated carbon. Good carbonylation activities and selectivities have also been observed in conjunction with zeolite supports. The literature study indicates that the typical experimental conditions of methanol (hydro)carbonylation do not exceed the constructional and operational limits of the available reactor system, i.e. 500 C and 50 bar. The reaction is suitable for testing Co and Rh precursors, since both cobalt and rhodium compounds have shown carbonylation activity.

  5. Enhanced antioxidation and microwave absorbing properties of SiO2-coated flaky carbonyl iron particles

    Science.gov (United States)

    Zhou, Yingying; Xie, Hui; Zhou, Wancheng; Ren, Zhaowen

    2018-01-01

    SiO2 was successfully coated on the surface of flaky carbonyl iron particles using a chemical bath deposition method in the presence of 3-aminopropyl triethoxysilane (APTES). The morphologies, composition, valence states of elements, as well as antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and microwave network analyzer. TG curve shows the obvious weight gain of carbonyl iron was deferred to 360 °C after SiO2-coated, which can be ascribed to the exits of SiO2 overlayer. Compared with the raw carbonyl iron, SiO2-coated sample shows good wave absorption performance due to its impedance matching. The electromagnetic properties of raw and SiO2-coated carbonyl iron particles were characterized in X band before and after heat treatment at 250 °C for 10 h. It was established that SiO2-coated carbonyl iron demonstrate good thermal stability, indicating SiO2-coating is useful in the usage of microwave absorbers operating at temperature up to 250 °C.

  6. Proteomic evaluation of myofibrillar carbonylation in chilled fish mince and its inhibition by catechin.

    Science.gov (United States)

    Pazos, Manuel; Maestre, Rodrigo; Gallardo, José M; Medina, Isabel

    2013-01-01

    The present study investigates the susceptibility of individual myofibrillar proteins from mackerel (Scomber scombrus) mince to undergo carbonylation reactions during chilled storage, and the antioxidant capacity of (+)-catechin to prevent oxidative processes of proteins. The carbonylation of each particular protein was quantified by combining the labelling of protein carbonyls by fluorescein-5-thiosemicarbazide (FTSC) with 1-D or 2-D gel electrophoresis. Alpha skeletal actin, glycogen phosphorylase, unnamed protein product (UNP) similar to enolase, pyruvate kinase, isoforms of creatine kinase, aldolase A and an isoform of glyceraldehyde 3-phosphate dehydrogenase (G3PDH) showed elevated oxidation in chilled non-supplemented mince. Myosin heavy chain (MHC) was not carbonylated in chilled muscle, but an extensive MHC degradation was observed in those samples. The supplementation of catechin reduced protein oxidation and lipid oxidation in a concentration-dependent manner: control>25>100≈200ppm. Therefore, the highest catechin concentrations (100 and 200ppm) exhibited the strongest antioxidant activity. Catechin (200ppm) reduced significantly carbonylation of protein spots identified as glycogen phosphorylase, pyruvate kinase muscle isozyme, isoforms of creatine kinase. Conversely, catechin was ineffective to inhibit the oxidation of actin and UNP similar to enolase. These results draw attention to the inefficiency of catechin to prevent actin oxidation, in contrast to the extremely high efficiency of catechin in inhibiting oxidation of lipids and other proteins. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Multistation digisonde observations of equatorial spread F in South America

    Directory of Open Access Journals (Sweden)

    B. W. Reinisch

    2004-09-01

    Full Text Available Directional ionogram and F-region drift observations were conducted at seven digisonde stations in South America during the COPEX campaign from October to December 2002. Five stations in Brazil, one in Argentina, and one in Peru, monitored the ionosphere across the continent to study the onset and development of F-region density depletions that cause equatorial spread F (ESF. New ionosonde techniques quantitatively describe the prereversal uplifting of the F layer at the magnetic equator and the eastward motion of the depletions over the stations. Three of the Brazilian stations were located along a field line with a 350-km apex over the equator to investigate the relation of the occurrence of ESF and the presence of sporadic E-layers at the two E-region intersections of the field line. No simple correlation was found.

  8. Observers in Kerr spacetimes. The ergoregion on the equatorial plane

    Energy Technology Data Exchange (ETDEWEB)

    Pugliese, D. [Silesian University in Opava, Faculty of Philosophy and Science, Institute of Physics, Opava (Czech Republic); Quevedo, H. [Universita di Roma ' ' La Sapienza' ' , Dipartimento di Fisica, Rome (Italy); Universidad Nacional Autonoma de Mexico, Instituto de Ciencias Nucleares, Mexico, DF (Mexico); Kazakh National University, Department of Theoretical and Nuclear Physics, Almaty (Kazakhstan)

    2018-01-15

    We perform a detailed analysis of the properties of stationary observers located on the equatorial plane of the ergosphere in a Kerr spacetime, including light-surfaces. This study highlights crucial differences between black hole and the super-spinner sources. In the case of Kerr naked singularities, the results allow us to distinguish between ''weak'' and ''strong'' singularities, corresponding to spin values close to or distant from the limiting case of extreme black holes, respectively. We derive important limiting angular frequencies for naked singularities. We especially study very weak singularities as resulting from the spin variation of black holes. We also explore the main properties of zero angular momentum observers for different classes of black hole and naked singularity spacetimes. (orig.)

  9. Seeding and layering of equatorial spread F by gravity waves

    International Nuclear Information System (INIS)

    Hysell, D.L.; Kelley, M.C.; Swartz, W.E.; Woodman, R.F.

    1990-01-01

    Studies dating back more than 15 years have presented evidence that atmospheric gravity waves play a role in initiating nighttime equatorial F region instabilities. This paper analyzes a spectabular spread F event that for the first time demonstrates a layering which, the authors argue, is controlled by a gravity wave effect. The 50-km vertical wavelength of a gravity wave which they have found is related theoretically to a plasma layering irregularity that originated at low altitudes and then was convected, intact, to higher altitudes. Gravity waves also seem to have determined bottomside intermediate scale undulations, although this fact is not as clear in the data. The neutral wind dynamo effect yields wave number conditions on the gravity wave's ability to modulate the Rayleigh-Taylor instaiblity process. Finally, after evaluating the gravity wave dispersion relation and spatial resonance conditions, we estimate the properties of the seeding wave

  10. Solar cycle signatures in the NCEP equatorial annual oscillation

    Science.gov (United States)

    Mayr, H. G.; Mengel, J. G.; Huang, F. T.; Nash, E. R.

    2009-08-01

    Our analysis of temperature and zonal wind data (1958 to 2006) from the National Center for Atmospheric Research (NCAR) reanalysis (Re-1), supplied by the National Centers for Environmental Prediction (NCEP), shows that the hemispherically symmetric 12-month equatorial annual oscillation (EAO) contains spectral signatures with periods around 11 years. Moving windows of 44 years show that, below 20 km, the 11-year modulation of the EAO is phase locked to the solar cycle (SC). The spectral features from the 48-year data record reveal modulation signatures of 9.6 and 12 years, which produce EAO variations that mimic in limited altitude regimes the varying maxima and minima of the 10.7 cm flux solar index. Above 20 km, the spectra also contain modulation signatures with periods around 11 years, but the filtered variations are too irregular to suggest that systematic SC forcing is the principal agent.

  11. Is there a hole in the topside, equatorial ionosphere?

    Directory of Open Access Journals (Sweden)

    D. Gallagher

    Full Text Available A paper in 2000 (Huba, 2000 found a depression in electron density in the topside ionosphere near the magnetic equator, based on the SAMI-2 physical ionospheric model. The model showed, for the first time, the formation of a hole in electron density in the altitude range 1500–2500 km at geomagnetic equatorial latitudes. The model produced the hole because of transhemispheric O+ flows that collisionally couple to H+, transporting it to lower altitudes, and thereby reducing the electron density at high altitudes. At that time and until now, no published observations have been reported to confirm or refute this numerical result. Recent, new analysis of Dynamics Explorer 1 Retarding Ion Mass Spectrometer measurements provides the first tentative experimental support for this model result. Keywords: Ionosphere, Topside, Magnetic equator, Plasmasphere

  12. Solar cycle signatures in the NCEP equatorial annual oscillation

    Directory of Open Access Journals (Sweden)

    H. G. Mayr

    2009-08-01

    Full Text Available Our analysis of temperature and zonal wind data (1958 to 2006 from the National Center for Atmospheric Research (NCAR reanalysis (Re-1, supplied by the National Centers for Environmental Prediction (NCEP, shows that the hemispherically symmetric 12-month equatorial annual oscillation (EAO contains spectral signatures with periods around 11 years. Moving windows of 44 years show that, below 20 km, the 11-year modulation of the EAO is phase locked to the solar cycle (SC. The spectral features from the 48-year data record reveal modulation signatures of 9.6 and 12 years, which produce EAO variations that mimic in limited altitude regimes the varying maxima and minima of the 10.7 cm flux solar index. Above 20 km, the spectra also contain modulation signatures with periods around 11 years, but the filtered variations are too irregular to suggest that systematic SC forcing is the principal agent.

  13. Combined radar observations of equatorial electrojet irregularities at Jicamarca

    Directory of Open Access Journals (Sweden)

    D. L. Hysell

    2007-03-01

    Full Text Available Daytime equatorial electrojet plasma irregularities were investigated using five distinct radar diagnostics at Jicamarca including range-time-intensity (RTI mapping, Faraday rotation, radar imaging, oblique scattering, and multiple-frequency scattering using the new AMISR prototype UHF radar. Data suggest the existence of plasma density striations separated by 3–5 km and propagating slowly downward. The striations may be caused by neutral atmospheric turbulence, and a possible scenario for their formation is discussed. The Doppler shifts of type 1 echoes observed at VHF and UHF frequencies are compared and interpreted in light of a model of Farley Buneman waves based on kinetic ions and fluid electrons with thermal effects included. Finally, the up-down and east-west asymmetries evident in the radar observations are described and quantified.

  14. The earth's equatorial principal axes and moments of inertia

    Science.gov (United States)

    Liu, H. S.; Chao, B. F.

    1991-01-01

    The earth's equatorial principal moments of inertia are given as A and B, where A is less than B, and the corresponding principal axes are given as a and b. Explicit formulas are derived for determining the orientation of a and b axes and the difference B - A using C(22) and S(22), the two gravitational harmonic coefficients of degree 2 and order 2. For the earth, the a axis lies along the (14.93 deg W, 165.07 deg E) diameter, and the b axis lies perpendicular to it along the (75.07 deg E, 104.93 deg W) diameter. The difference B - A is 7.260 x 10 to the -6th MR2. These quantities for other planets are contrasted, and geophysical implications are discussed.

  15. A Generalized Equatorial Model for the Accelerating Solar Wind

    Science.gov (United States)

    Tasnim, S.; Cairns, Iver H.; Wheatland, M. S.

    2018-02-01

    A new theoretical model for the solar wind is developed that includes the wind's acceleration, conservation of angular momentum, deviations from corotation, and nonradial velocity and magnetic field components from an inner boundary (corresponding to the onset of the solar wind) to beyond 1 AU. The model uses a solution of the time-steady isothermal equation of motion to describe the acceleration and analytically predicts the Alfvénic critical radius. We fit the model to near-Earth observations of the Wind spacecraft during the solar rotation period of 1-27 August 2010. The resulting data-driven model demonstrates the existence of noncorotating, nonradial flows and fields from the inner boundary (r = rs) outward and predicts the magnetic field B = (Br,Bϕ), velocity v = (vr,vϕ), and density n(r,ϕ,t), which vary with heliocentric distance r, heliolatitude ϕ, and time t in a Sun-centered standard inertial plane. The description applies formally only in the equatorial plane. In a frame corotating with the Sun, the transformed velocity v' and a field B' are not parallel, resulting in an electric field with a component Ez' along the z axis. The resulting E'×B'=E'×B drift lies in the equatorial plane, while the ∇B and curvature drifts are out of the plane. Together these may lead to enhanced scattering/heating of sufficiently energetic particles. The model predicts that deviations δvϕ from corotation at the inner boundary are common, with δvϕ(rs,ϕs,ts) comparable to the transverse velocities due to granulation and supergranulation motions. Abrupt changes in δvϕ(rs,ϕs,ts) are interpreted in terms of converging and diverging flows at the cell boundaries and centers, respectively. Large-scale variations in the predicted angular momentum demonstrate that the solar wind can drive vorticity and turbulence from near the Sun to 1 AU and beyond.

  16. A tropospheric ozone maximum over the equatorial Southern Indian Ocean

    Directory of Open Access Journals (Sweden)

    L. Zhang

    2012-05-01

    Full Text Available We examine the distribution of tropical tropospheric ozone (O3 from the Microwave Limb Sounder (MLS and the Tropospheric Emission Spectrometer (TES by using a global three-dimensional model of tropospheric chemistry (GEOS-Chem. MLS and TES observations of tropospheric O3 during 2005 to 2009 reveal a distinct, persistent O3 maximum, both in mixing ratio and tropospheric column, in May over the Equatorial Southern Indian Ocean (ESIO. The maximum is most pronounced in 2006 and 2008 and less evident in the other three years. This feature is also consistent with the total column O3 observations from the Ozone Mapping Instrument (OMI and the Atmospheric Infrared Sounder (AIRS. Model results reproduce the observed May O3 maximum and the associated interannual variability. The origin of the maximum reflects a complex interplay of chemical and dynamic factors. The O3 maximum is dominated by the O3 production driven by lightning nitrogen oxides (NOx emissions, which accounts for 62% of the tropospheric column O3 in May 2006. We find the contribution from biomass burning, soil, anthropogenic and biogenic sources to the O3 maximum are rather small. The O3 productions in the lightning outflow from Central Africa and South America both peak in May and are directly responsible for the O3 maximum over the western ESIO. The lightning outflow from Equatorial Asia dominates over the eastern ESIO. The interannual variability of the O3 maximum is driven largely by the anomalous anti-cyclones over the southern Indian Ocean in May 2006 and 2008. The lightning outflow from Central Africa and South America is effectively entrained by the anti-cyclones followed by northward transport to the ESIO.

  17. Observations of EMIC Triggered Emissions off the Magnetic Equatorial Plane

    Science.gov (United States)

    Grison, B.; Breuillard, H.; Santolik, O.; Cornilleau-Wehrlin, N.

    2016-12-01

    On 19/08/2005 Cluster spacecraft had their perigee close to the dayside of the Earth magnetic equatorial plane, at about 14 hours Magnetic Local Time. The spacecraft crossed the equator from the southern hemisphere toward the northern hemisphere. In the Southern hemisphere, at about -23° magnetic latitude (MLAT) and at distance of 5.25 Earth Radii from Earth, Cluster 3 observes an EMIC triggered emission between the He+ and the proton local gyrofrequencies. The magnetic waveform (STAFF instrument data) is transformed into the Fourier space for a study based on single value decomposition (SVD) analysis. The emission lasts about 30s. The emission frequency rises from 1Hz up to 1.9Hz. The emission polarization is left-hand, its coherence value is high and the propagation angle is field aligned (lower than 30º). The Poynting flux orientation could not be established. Based on previous study results, these properties are indicative of an observation in vicinity of the source region of the triggered emission. From our knowledge this is the first time that EMIC triggered emission are observed off the magnetic equator. In order to identify the source region we study two possibilities: a source region at higher latitudes than the observations (and particles orbiting in "Shabansky" orbits) and a source region close to the magnetic equatorial plane, as reported in previous studies. We propose to identify the source region from ray tracing analysis and to compare the observed propagation angle in several frequency ranges to the ray tracing results.

  18. Priority areas for large mammal conservation in Equatorial Guinea.

    Science.gov (United States)

    Murai, Mizuki; Ruffler, Heidi; Berlemont, Antoine; Campbell, Genevieve; Esono, Fidel; Agbor, Anthony; Mbomio, Domingo; Ebana, Agustín; Nze, Antonio; Kühl, Hjalmar S

    2013-01-01

    Hunting is one of the main driving forces behind large mammal density distribution in many regions of the world. In tropical Africa, urban demand for bushmeat has been shown to dominate over subsistence hunting and its impact often overrides spatial-ecological species characteristics. To effectively protect remaining mammal populations the main factors that influence their distribution need to be integrated into conservation area prioritisation and management plans. This information has been lacking for Río Muni, Equatorial Guinea, as prior studies have been outdated or have not systematically covered the continental region of the country. In this study we evaluated: 1) the relative importance of local vs. commercial hunting; 2) wildlife density of protected vs. non-protected areas; and 3) the importance of ecological factors vs. human influence in driving mammal density distribution in Río Muni. We adopted a systematic countrywide line transect approach with particular focus on apes and elephants, but also including other mammal species. For analysis of field data we used generalised linear models with a set of predictor variables representing ecological conditions, anthropogenic pressure and protected areas. We estimate that there are currently 884 (437-1,789) elephants and 11,097 (8,719-13,592) chimpanzees and gorillas remaining in Río Muni. The results indicate strong hunting pressures on both local and commercial levels, with roads demonstrating a negative impact on elephants and overall mammal body mass. Protected areas played no role in determining any of the mammal species distributions and significant human hunting signs were found inside these protected areas, illustrating the lack of environmental law enforcement throughout the country. Río Muni is currently under-represented in conservation efforts in Western Equatorial Africa, and we recommend a focus on cross-boundary conservation, in particular in the Monte Alén-Monts de Cristal and Río Campo

  19. Characteristics of Volcanic Stratospheric Aerosol Layer Observed by CALIOP and Ground Based Lidar at Equatorial Atmosphere Radar Site

    Science.gov (United States)

    Abo, Makoto; Shibata, Yasukuni; Nagasawa, Chikao

    2018-04-01

    We investigated the relation between major tropical volcanic eruptions in the equatorial region and the stratospheric aerosol data, which have been collected by the ground based lidar observations at at Equatorial Atmosphere Radar site between 2004 and 2015 and the CALIOP observations in low latitude between 2006 and 2015. We found characteristic dynamic behavior of volcanic stratospheric aerosol layers over equatorial region.

  20. Influence of the Dielectric Medium on the Carbonyl Infrared Absorption Peak of Acetylferrocene

    Directory of Open Access Journals (Sweden)

    F. López-Linares

    2005-02-01

    Full Text Available The solvent effect on the position of the carbonyl vibrational stretching ofacetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in thisorganometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO proposed by Kolling. In contrast to the established trends for carbonyl groupsin organic systems, the results suggest that the continuum models for the reaction field arenot adequate and that the influence of dipolarity-polarizability described by aninhomogeneous coupling function θ (ε L(n 2 that assumes optical dielectric saturation isresponsible for the carbonyl band shift and, there is empirical evidence that the effect offield-induced intermolecular interaction on band shift, interpreted in terms of the van derWaals forces from the solvent, have a important contribution to this phenomena.

  1. Coal and biomass-based chemicals via carbonylation, hydroformylation and homologation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sunavala, P.D.; Raghunath, B.

    The paper emphasizes the importance of carbonylation, hydroformylation and homologation reactions in the manufacture of organic chemicals (such as acetic acid, acetic anhydride, cellulose acetate, vinyl acetate monomer, aliphatic amines, isocyanates, methanol, ethanol, n-butanol, ethylene glycol, acrylic acid, etc.) from coal and biomass feedstocks. Topics covered are: synthesis of acetic acid; manufacture of acetic anhydride; synthesis of vinyl acetate monomer by carbonylation; synthesis of aliphatic amines by hydroformylation; synthesis of organic diisocyanates; ethanol synthesis by homologation of methanol; synthesis of ethylene glycol via hydroformylation of formaldehyde; synthesis of n- butanol and n-butyraldehyde by propylene formylation; synthesis of acrylic acid; homologation reaction of carboxylic acid esters with ruthenium catalysts; and synthesis of phenyl isocyanate from nitrobenzene by reductive carbonylation. 26 refs.

  2. Effect of carbonyl iron particles composition on the physical characteristics of MR grease

    Energy Technology Data Exchange (ETDEWEB)

    Mohamad, Norzilawati, E-mail: mnorzilawati@gmail.com; Mazlan, Saiful Amri, E-mail: amri.kl@utm.my [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Ubaidillah, E-mail: ubaidillah@uns.ac.id [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Mechanical Engineering Department, Faculty of Engineering, Universitas Sebelas Maret, Jl. Ir. Sutami 36A, Kentingan, Surakarta, 57126, Central Java, Surakarta (Indonesia)

    2016-03-29

    Magnetorheological (MR) grease is an extension of the study of magnetorheological materials. The MR grease can help to reduce the particles sedimentation problem occurred in the MR fluids. Within this study, an effort has been taken to investigate the effect of different weight compositions of carbonyl iron particles on the physical and chemical characteristics of the MR grease under off-state condition (no magnetic field). The MR grease is prepared by mixing carbonyl iron particles having a size range of 1 to 10 µm with commercial NPC Highrex HD-3 grease. Characterizations of MR grease are investigated using Vibrating Sample Magnetometer (VSM), Environmental Scanning Electron Microscopy (ESEM), Differential Scanning Calorimeter (DSC) and rheometer. The dependency of carbonyl iron particles weight towards the magnetic properties of MR grease and other characterizations are investigated.

  3. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

    Science.gov (United States)

    Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

    2017-01-09

    Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Unprecedented twofold intramolecular hydroamination in diam(m)ine-dicarboxylatodichloridoplatinum(IV) complexes - ethane-1,2-diamine vs. ammine ligands.

    Science.gov (United States)

    Reithofer, Michael R; Galanski, Markus; Arion, Vladimir B; Keppler, Bernhard K

    2008-03-07

    Reaction of (OC-6-13)-bis(2Z-3-carboxyacrylato)dichlorido(ethane-1,2-diamine)platinum(IV) and (OC-6-13)-diamminebis(2Z-3-carboxyacrylato)dichloridoplatinum(IV) with propylamine in the presence of 1,1'-carbonyl diimidazole afforded not the expected amides; instead, beside amide formation, a twofold intramolecular attack of the am(m)ine ligand at the C[double bond, length as m-dash]C bonds was observed involving either both (ethane-1,2-diamine) or only one (ammine) coordinated nitrogen atom(s).

  6. CONVECTIVE BURSTS AND THE COUPLING OF SATURN'S EQUATORIAL STORMS AND INTERIOR ROTATION

    International Nuclear Information System (INIS)

    Heimpel, Moritz; Aurnou, Jonathan M.

    2012-01-01

    Temporal variations of Saturn's equatorial jet and magnetic field hint at rich dynamics coupling the atmosphere and the deep interior. However, it has been assumed that rotation of the interior dynamo must be steady over tens of years of modern observations. Here we use a numerical convection model and scaling estimates to show how equatorial convective bursts can transfer angular momentum to the deeper interior. The numerical model allows angular momentum transfer between a fluid outer spherical shell and a rigid inner sphere. Convection drives a prograde equatorial jet exhibiting quasiperiodic bursts that fill the equatorial volume outside the tangent cylinder. For each burst strong changes in the equatorial surface velocity are associated with retrograde torque on the inner sphere. Our results suggest that Saturn's Great White Spot, a giant storm that was observed to fill the equatorial region in 1990, could mobilize a volume of fluid carrying roughly 15% of Saturn's moment of inertia. Conservation of angular momentum then implies that a 20% change in the equatorial jet angular velocity could change the average interior rotation rate by about 0.1%—roughly an order of magnitude less than the apparent rotation rate changes associated with Saturn's kilometric radio (SKR) signal. However, if the SKR signal originates outside the liquid metal core in a 'planetary tachocline' that separates the layer of fast zonal flow from the magnetically controlled and slowly convecting deep interior, then convective bursts can provide a possible mechanism for the observed ∼1% SKR changes.

  7. The streaming-trapped ion interface in the equatorial inner magnetosphere

    Science.gov (United States)

    Lin, J.; Horwitz, J. L.; Gallagher, D.; Pollock, C. J.

    1994-01-01

    Spacecraft measurements of core ions on L=4-7 field-lines typically show trapped ion distributions near the magnetic equator, and frequently indicate field-aligned ion streams at higher latitudes. The nature of the transition between them may indicate both the microphysics of hot-cold plasma interactions and overall consequences for core plasma evolution. We have undertaken a statistical analysis and characterization of this interface and its relation to the equatorial region of the inner magnetosphere. In this analysis, we have characterized such features as the equatorial ion flux anisotropy, the penetration of field-aligned ionospheric streams into the equatorial region, the scale of the transition into trapped ion populations, and the transition latitude. We found that most transition latitudes occur within 13 deg of the equator. The typical values of equatorial ion anisotropies are consistent with bi-Maxwellian temperature ratios of T(sub perpendicular)/T(sub parallel) in the range of 3-5. The latitudinal scales for the edges of the trapped ion populations display a rather strong peak in the 2-3 deg range. We also found that there is a trend for the penetration ratio, the anisotropy half width, and the transition scale length to decrease with a higher equatorial ion anisotropy. We may interpret these features in terms of Liouville mapping of equatorially trapped ions and the reflection of the incoming ionospheric ion streams from the equatorial potential peaks associated with such trapped ions.

  8. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  9. Reaction of acid esters of methylenebis(phosphonous acid) with carbonyl compounds

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Odinets, I.L.; Lutsenko, I.F.

    1987-01-01

    The reaction of methylenebis(phosphonites) containing two hydrophosphoryl groupings with aliphatic and aromatic aldehydes and ketones in the presence of alkali metal fluorides leads to methylenebis(α-hydroxyalkylphosphinates). The reaction of methylenebis(phosphonites) containing one hydrophosphoryl groupings with carbonyl compounds in the presence of alkali metal fluorides proceeds with the formation of a new type of heterocyclic phosphorus compound, viz., 1,2λ 3 ,4λ 5 -oxadiphospholanes. The reaction of acid esters of methylenebis(phosphonous) acid with carbonyl compounds in the presence of alkali metal alkoxides or a tertiary amine is accompanied by phosphinate-phosphonate rearrangement of the intermediately formed α-hydroxylalkylphosphinates

  10. Impaired cardiac SIRT1 activity by carbonyl stress contributes to aging-related ischemic intolerance.

    Directory of Open Access Journals (Sweden)

    Chunhu Gu

    Full Text Available Reactive aldehydes can initiate protein oxidative damage which may contribute to heart senescence. Sirtuin 1 (SIRT1 is considered to be a potential interventional target for I/R injury management in the elderly. We hypothesized that aldehyde mediated carbonyl stress increases susceptibility of aged hearts to ischemia/reperfusion (I/R injury, and elucidate the underlying mechanisms with a focus on SIRT1. Male C57BL/6 young (4-6 mo and aged (22-24 mo mice were subjected to myocardial I/R. Cardiac aldehyde dehydrogenase (ALDH2, SIRT1 activity and protein carbonyls were assessed. Our data revealed that aged heart exhibited increased endogenous aldehyde/carbonyl stress due to impaired ALDH2 activity concomitant with blunted SIRT1 activity (P<0.05. Exogenous toxic aldehydes (4-HNE exposure in isolated cardiomyocyte verified that aldehyde-induced carbonyl modification on SIRT1 impaired SIRT1 activity leading to worse hypoxia/reoxygenation (H/R injury, which could all be rescued by Alda-1 (ALDH2 activator (all P<0.05. However, SIRT1 inhibitor blocked the protective effect of Alda-1 on H/R cardiomyocyte. Interestingly, myocardial I/R leads to higher carbonylation but lower activity of SIRT1 in aged hearts than that seen in young hearts (P<0.05. The application of Alda-1 significantly reduced the carbonylation on SIRT1 and markedly improved the tolerance to in vivo I/R injury in aged hearts, but failed to protect Sirt1(+/- knockout mice against myocardial I/R injury. This was verified by Alda-1 treatment improved postischemic contractile function recovery in ex vivo perfused aged but not in Sirt1(+/- hearts. Thus, aldehyde/carbonyl stress is accelerated in aging heart. These results provide a new insight that impaired cardiac SIRT1 activity by carbonyl stress plays a critical role in the increased susceptibility of aged heart to I/R injury. ALDH2 activation can restore this aging-related myocardial ischemic intolerance.

  11. Nicotine and Carbonyl Emissions From Popular Electronic Cigarette Products: Correlation to Liquid Composition and Design Characteristics.

    Science.gov (United States)

    El-Hellani, Ahmad; Salman, Rola; El-Hage, Rachel; Talih, Soha; Malek, Nathalie; Baalbaki, Rima; Karaoghlanian, Nareg; Nakkash, Rima; Shihadeh, Alan; Saliba, Najat A

    2018-01-05

    Available in hundreds of device designs and thousands of flavors, electronic cigarette (ECIG) may have differing toxicant emission characteristics. This study assesses nicotine and carbonyl yields in the most popular brands in the U.S. market. These products included disposable, prefilled cartridge, and tank-based ECIGs. Twenty-seven ECIG products of 10 brands were procured and their power outputs were measured. The e-liquids were characterized for pH, nicotine concentration, propylene glycol/vegetable glycerin (PG/VG) ratio, and water content. Aerosols were generated using a puffing machine and nicotine and carbonyls were, respectively, quantified using gas chromatograph and high-performance liquid chromatography. A multiregression model was used to interpret the data. Nicotine yields varied from 0.27 to 2.91 mg/15 puffs, a range corresponding to the nicotine yield of less than 1 to more than 3 combustible cigarettes. Nicotine yield was highly correlated with ECIG type and brand, liquid nicotine concentration, and PG/VG ratio, and to a lower significance with electrical power, but not with pH and water content. Carbonyls, including the carcinogen formaldehyde, were detected in all ECIG aerosols, with total carbonyl concentrations ranging from 3.72 to 48.85 µg/15 puffs. Unlike nicotine, carbonyl concentrations were mainly correlated with power. In 15 puffs, some ECIG devices emit nicotine quantities that exceed those of tobacco cigarettes. Nicotine emissions vary widely across products but carbonyl emissions showed little variations. In spite of that ECIG users are exposed to toxicologically significant levels of carbonyl compounds, especially formaldehyde. Regression analysis showed the importance of design and e-liquid characteristics as determinants of nicotine and carbonyl emissions. Periodic surveying of characteristics of ECIG products available in the marketplace is valuable for understanding population-wide changes in ECIG use patterns over time. © The

  12. Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination.

    Science.gov (United States)

    Breit, Bernhard

    1998-03-02

    Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  13. Determining the magnitude and direction of photoinduced ligand field switching in photochromic metal-organic complexes: molybdenum-tetracarbonyl spirooxazine complexes.

    Science.gov (United States)

    Paquette, Michelle M; Patrick, Brian O; Frank, Natia L

    2011-07-06

    The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.

  14. Model studies of the Cu(B) site of cytochrome c oxidase utilizing a Zn(II) complex containing an imidazole-phenol cross-linked ligand.

    Science.gov (United States)

    Pesavento, Russell P; Pratt, Derek A; Jeffers, Jerry; van der Donk, Wilfred A

    2006-07-21

    Cytochrome c oxidase, the enzyme complex responsible for the four-electron reduction of O2 to H2O, contains an unusual histidine-tyrosine cross-link in its bimetallic heme a3-CuB active site. We have synthesised an unhindered, tripodal chelating ligand, BPAIP, containing the unusual ortho-imidazole-phenol linkage, which mimics the coordination environment of the CuB center. The ligand was used to investigate the physicochemical (pKa, oxidation potential) and coordination properties of the imidazole-phenol linkage when bound to a dication. Zn(II) coordination lowers the pKa of the phenol by 0.6 log units, and increases the potential of the phenolate/phenoxyl radical couple by approximately 50 mV. These results are consistent with inductive withdrawal of electron density from the phenolic ring. Spectroscopic data and theoretical calculations (DFT) were used to establish that the cationic complex [Zn(BPAIP)Br]+ has an axially distorted trigonal bipyramidal structure, with three coordinating nitrogen ligands (two pyridine and one imidazole) occupying the equatorial plane and the bromide and the tertiary amine nitrogen of the tripod in the axial positions. Interestingly, the Zn-Namine bonding interaction is weak or absent in [Zn(BPAIP)Br]+ and the complex gains stability in basic solutions, as indicated by 1H NMR spectroscopy. These observations are supported by theoretical calculations (DFT), which suggest that the electron-donating capacity of the equatorial imidazole ligand can be varied by modulation of the protonation and/or redox state of the cross-linked phenol. Deprotonation of the phenol makes the equatorial imidazole a stronger sigma-donor, resulting in an increased Zn-Nimd interaction and thereby leading to distortion of the axial ligand axis toward a more tetrahedral geometry.

  15. Spatial relationship of 1-meter equatorial spread-F irregularities and depletions in total electron content

    International Nuclear Information System (INIS)

    Tsunoda, R.T.; Towle, D.M.

    1979-01-01

    An experiment was conducted at Kwajalein Atoll, Marshall Islands to investigate the spatial relationship of 1-m equatorial spread-F irregularities to total electron content (TEC) depletions. A high-power radar was operated (1) in a backscatter scan mode to spatially map the distribution of 1-m irregularities, and (2) in a dual-frequency, satellite-track mode to obtain the longitudinal TEC variations. We show that radar backscatter ''plumes'' found in the disturbed, nighttime equatorial ionosphere are longitudinally coincident with TEC depletions. We suggest that the TEC depletions are probably due to the presence of plasma ''bubbles'' in the equatorial F layer

  16. The physical and theoretical basis of solar-terrestrial relationships 1. Equatorial locations

    International Nuclear Information System (INIS)

    Njau, E.C.

    1988-07-01

    The theory of solar-terrestrial relationships developed earlier by the author is extended to incorporate expressions that represent the non-linear responses of the earth-atmosphere system to incoming solar radiation in a more detailed manner. Application of the extended theory to equatorial locations leads to new and interesting features that are consistent with past observations. It also predicts the existence of new oscillations in the equatorial atmosphere whose causative physical processes are given and explained. Non-equatorial locations are treated along similar lines in Part 2 of the series. (author). 44 refs

  17. Enthalpies of ligand substitution for [Mo(η5C5H5)(CO)2(NO)] – The role of π-bonding effects in metal–ligand bond strengths

    International Nuclear Information System (INIS)

    Majumdar, Subhojit; Captain, Burjor; Cazin, Catherine S.J.; Nolan, Steven P.; Hoff, Carl D.

    2014-01-01

    Graphical abstract: - Highlights: • Enthalpies of ligand substitution are measured for Mo(C 5 H 5 )(CO) 2 (NO). • Phosphines and N-heterocyclic carbenes are stronger ligands and displace CO. • Backbonding to π ∗ orbitals is an important part of complex stability. • FTIR studies show shifts to lower wavenumbers of ν-CO and ν-NO. • Structural studies show lengthening of the C-O and N-O bonds. - Abstract: Enthalpies of ligand substitution for [Mo(η 5 -C 5 H 5 )(CO) 2 (NO)] producing [Mo(η 5 -C 5 H 5 )Mo(CO)(L)(NO)] have been measured by solution calorimetry at 30 °C in THF for L = P(OMe) 3 2 2 Ph 3 (SIPr = 1,3-bis(2,6-bis(diisopropylphenyl)imidazolinylidene; IPr = 1,3-bis(2,6-bis(diisopropylphenyl)-imidazol-2-ylidene)). The accepting metal fragment [Mo(η 5 -C 5 H 5 )(CO)(NO)] has a vacant site containing strongly π-accepting carbonyl and nitrosyl ligands and this is shown to influence the stability of the product complex. Infrared studies of both ν CO and ν NO show that metal-to-ligand backbonding increases in the order P(OMe) 3 3 5 -C 5 H 5 )(CO)(IPr)(NO)] and [Mo(η 5 -C 5 H 5 )(CO)(SIPr)(NO)] are reported

  18. LigandRFs: random forest ensemble to identify ligand-binding residues from sequence information alone

    KAUST Repository

    Chen, Peng; Huang, Jianhua Z; Gao, Xin

    2014-01-01

    Protein-ligand binding is important for some proteins to perform their functions. Protein-ligand binding sites are the residues of proteins that physically bind to ligands. Despite of the recent advances in computational prediction

  19. DEMETER Observations of Equatorial Plasma Depletions and Related Ionospheric Phenomena

    Science.gov (United States)

    Berthelier, J.; Malingre, M.; Pfaff, R.; Jasperse, J.; Parrot, M.

    2008-12-01

    DEMETER, the first micro-satellite of the CNES MYRIAD program, was launched from Baikonour on June 29, 2004 on a nearly circular, quasi helio-synchronous polar orbit at ~ 715 km altitude. The DEMETER mission focuses primarily on the search for a possible coupling between seismic activity and ionospheric disturbances as well as on the effects of natural phenomena such as tropospheric thunderstorms and man-made activities on the ionosphere. The scientific payload provides fairly complete measurements of the ionospheric plasma, energetic particles above ~ 70 keV, and plasma waves, up to 20 kHz for the magnetic and 3.3 MHz for the electric components. Several studies related to space weather and ionospheric physics have been conducted over the past years. Following a brief description of the payload and the satellite modes of operation, this presentation will focus on a set of results that provide a new insight into the physics of instabilities in the night-time equatorial ionosphere. The observations were performed during the major magnetic storm of November 2004. Deep plasma depletions were observed on several night-time passes at low latitudes characterized by the decrease of the plasma density by nearly 3 orders of magnitude relative to the undisturbed plasma, and a significant abundance of molecular ions. These features can be best interpreted as resulting from the rise of the F-layer above the satellite altitude over an extended region of the ionosphere. In one of the passes, DEMETER was operated in the Burst mode and the corresponding high resolution data allowed for the discovery of two unexpected phenomena. The first one is the existence of high intensity monochromatic wave packets at the LH frequency that develop during the decay phase of intense bursts of broadband LH turbulence. The broadband LH turbulence is triggered by whistlers emitted by lightning from atmospheric thunderstorms beneath the satellite. The second unexpected feature is the detection of a

  20. An endogenous aryl hydrocarbon receptor ligand acts on dendritic cells and T cells to suppress experimental autoimmune encephalomyelitis

    Science.gov (United States)

    Quintana, Francisco J.; Murugaiyan, Gopal; Farez, Mauricio F.; Mitsdoerffer, Meike; Tukpah, Ann-Marcia; Burns, Evan J.; Weiner, Howard L.

    2010-01-01

    The ligand-activated transcription factor aryl hydrocarbon receptor (AHR) participates in the differentiation of FoxP3+ Treg, Tr1 cells, and IL-17–producing T cells (Th17). Most of our understanding on the role of AHR on the FoxP3+ Treg compartment results from studies using the toxic synthetic chemical 2,3,7,8-tetrachlorodibenzo-p-dioxin. Thus, the physiological relevance of AHR signaling on FoxP3+ Treg in vivo is unclear. We studied mice that carry a GFP reporter in the endogenous foxp3 locus and a mutated AHR protein with reduced affinity for its ligands, and found that AHR signaling participates in the differentiation of FoxP3+ Treg in vivo. Moreover, we found that treatment with the endogenous AHR ligand 2-(1′H-indole-3′-carbonyl)-thiazole-4-carboxylic acid methyl ester (ITE) given parenterally or orally induces FoxP3+ Treg that suppress experimental autoimmune encephalomyelitis. ITE acts not only on T cells, but also directly on dendritic cells to induce tolerogenic dendritic cells that support FoxP3+ Treg differentiation in a retinoic acid-dependent manner. Thus, our work demonstrates that the endogenous AHR ligand ITE promotes the induction of active immunologic tolerance by direct effects on dendritic and T cells, and identifies nontoxic endogenous AHR ligands as potential unique compounds for the treatment of autoimmune disorders. PMID:21068375

  1. An Analysis of Unseasonal Equatorial Plasma Bubbles in July 2014

    Science.gov (United States)

    Carter, B. A.; Currie, J. L.; Pradipta, R.; Groves, K. M.; Caton, R. G.; Yokoyama, T.

    2017-12-01

    In the equatorial ionosphere, the Raleigh-Taylor (RT) plasma instability in the post sunset region is known to cause plasma depletions, known as equatorial plasma bubbles (EPBs). These EPBs can have adverse effects on satellite-reliant technologies by causing scintillations in the phase and amplitude of Global Navigation Satellite System (GNSS) signals. The effect of EPBs on satellite-reliant technologies highlights a need for reliable forecasting of EPBs in the low-latitude regions, which requires a solid understanding of their climatology and daily variability. The climatology of EPB occurrence is known to correlate with the angle between the magnetic field and solar terminator. This angle controls the longitudinal E-region conductivity gradient across the day-night terminator, which influences the strength of the pre-reversal enhancement in the upward plasma drift, a dominant term in the linear RT growth rate. This relationship is well established from ground-based GNSS and satellite-based studies. However, reliable forecasts have not been developed by space weather forecasting agencies due to the lack of understanding of EPB daily variability. During July, EPB occurrence is small in the South-East Asia longitude sector due to the relatively large angle between the magnetic field and solar terminator. As a result, the pre-reversal enhancement in the upward plasma drift is typically low during this period, creating less favourable conditions for EPB growth. However, despite the typically low pre-reversal enhancement strength, this analysis reveals that July 2014 is not devoid of EPB events above South-East Asia. These unseasonal EPB events during July 2014 are studied in the context of the prevalently low solar and geomagnetic activity conditions. Given the lack of solar and geomagnetic control, the influence of the lower atmosphere on EPB generation (e.g., via atmospheric gravity wave seeding) is explored. These events provide a unique opportunity to investigate

  2. Priority areas for large mammal conservation in Equatorial Guinea.

    Directory of Open Access Journals (Sweden)

    Mizuki Murai

    Full Text Available Hunting is one of the main driving forces behind large mammal density distribution in many regions of the world. In tropical Africa, urban demand for bushmeat has been shown to dominate over subsistence hunting and its impact often overrides spatial-ecological species characteristics. To effectively protect remaining mammal populations the main factors that influence their distribution need to be integrated into conservation area prioritisation and management plans. This information has been lacking for Río Muni, Equatorial Guinea, as prior studies have been outdated or have not systematically covered the continental region of the country. In this study we evaluated: 1 the relative importance of local vs. commercial hunting; 2 wildlife density of protected vs. non-protected areas; and 3 the importance of ecological factors vs. human influence in driving mammal density distribution in Río Muni. We adopted a systematic countrywide line transect approach with particular focus on apes and elephants, but also including other mammal species. For analysis of field data we used generalised linear models with a set of predictor variables representing ecological conditions, anthropogenic pressure and protected areas. We estimate that there are currently 884 (437-1,789 elephants and 11,097 (8,719-13,592 chimpanzees and gorillas remaining in Río Muni. The results indicate strong hunting pressures on both local and commercial levels, with roads demonstrating a negative impact on elephants and overall mammal body mass. Protected areas played no role in determining any of the mammal species distributions and significant human hunting signs were found inside these protected areas, illustrating the lack of environmental law enforcement throughout the country. Río Muni is currently under-represented in conservation efforts in Western Equatorial Africa, and we recommend a focus on cross-boundary conservation, in particular in the Monte Alén-Monts de Cristal

  3. Snowball Earth termination by destabilization of equatorial permafrost methane clathrate.

    Science.gov (United States)

    Kennedy, Martin; Mrofka, David; von der Borch, Chris

    2008-05-29

    The start of the Ediacaran period is defined by one of the most severe climate change events recorded in Earth history--the recovery from the Marinoan 'snowball' ice age, approximately 635 Myr ago (ref. 1). Marinoan glacial-marine deposits occur at equatorial palaeolatitudes, and are sharply overlain by a thin interval of carbonate that preserves marine carbon and sulphur isotopic excursions of about -5 and +15 parts per thousand, respectively; these deposits are thought to record widespread oceanic carbonate precipitation during postglacial sea level rise. This abrupt transition records a climate system in profound disequilibrium and contrasts sharply with the cyclical stratigraphic signal imparted by the balanced feedbacks modulating Phanerozoic deglaciation. Hypotheses accounting for the abruptness of deglaciation include ice albedo feedback, deep-ocean out-gassing during post-glacial oceanic overturn or methane hydrate destabilization. Here we report the broadest range of oxygen isotope values yet measured in marine sediments (-25 per thousand to +12 per thousand) in methane seeps in Marinoan deglacial sediments underlying the cap carbonate. This range of values is likely to be the result of mixing between ice-sheet-derived meteoric waters and clathrate-derived fluids during the flushing and destabilization of a clathrate field by glacial meltwater. The equatorial palaeolatitude implies a highly volatile shelf permafrost pool that is an order of magnitude larger than that of the present day. A pool of this size could have provided a massive biogeochemical feedback capable of triggering deglaciation and accounting for the global postglacial marine carbon and sulphur isotopic excursions, abrupt unidirectional warming, cap carbonate deposition, and a marine oxygen crisis. Our findings suggest that methane released from low-latitude permafrost clathrates therefore acted as a trigger and/or strong positive feedback for deglaciation and warming. Methane hydrate

  4. Rosetta Ligand docking with flexible XML protocols.

    Science.gov (United States)

    Lemmon, Gordon; Meiler, Jens

    2012-01-01

    RosettaLigand is premiere software for predicting how a protein and a small molecule interact. Benchmark studies demonstrate that 70% of the top scoring RosettaLigand predicted interfaces are within 2Å RMSD from the crystal structure [1]. The latest release of Rosetta ligand software includes many new features, such as (1) docking of multiple ligands simultaneously, (2) representing ligands as fragments for greater flexibility, (3) redesign of the interface during docking, and (4) an XML script based interface that gives the user full control of the ligand docking protocol.

  5. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  6. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins

    DEFF Research Database (Denmark)

    Weber, Daniela; Davies, Michael J.; Grune, Tilman

    2015-01-01

    Protein oxidation is involved in regulatory physiological events as well as in damage to tissues and is thought to play a key role in the pathophysiology of diseases and in the aging process. Protein-bound carbonyls represent a marker of global protein oxidation, as they are generated by multiple...

  7. Femtosecond Fluorescence and Intersystem Crossing in Rhenium(I) Carbonyl-Bipyridine Complexes

    Czech Academy of Sciences Publication Activity Database

    Cannizzo, A.; Blanco-Rodríguez, A. M.; Nahhas, A. E.; Šebera, Jakub; Záliš, Stanislav; Vlček, Antonín; Chergui, M.

    2008-01-01

    Roč. 130, č. 28 (2008), s. 8967-8974 ISSN 0002-7863 R&D Projects: GA MŠk 1P05OC068 Institutional research plan: CEZ:AV0Z40400503 Keywords : rhenium(I) * carbonyl-bipyridine * intersystem crossing Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  8. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    DEFF Research Database (Denmark)

    Poppendieck, D.G.; Hubbard, H.F.; Weschler, Charles J.

    2007-01-01

    at concentrations of 1000 ppm in the inlet stream of experimental chambers. Fifteen target carbonyls were selected and measured as building ozonation by-products (BOBPs). During the 36 h that include the 16 h ozonation and 20 h persistence phase, the total BOBP mass released from flooring and wall coverings ranged...

  9. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

    Science.gov (United States)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

    2006-03-07

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

  10. Unsuitability of using the DNPH-coated solid sorbent cartridge for determination of airborne unsaturated carbonyls

    Science.gov (United States)

    Ho, Steven Sai Hang; Ho, K. F.; Liu, W. D.; Lee, S. C.; Dai, W. T.; Cao, J. J.; Ip, H. S. S.

    2011-01-01

    Measurements of aldehydes and ketones are typically conducted by derivatization using sorbent cartridges coated with 2,4-dinitrophenylhydrazine (DNPH). The collected samples are eluted with acetonitrile and analyzed by high-pressure liquid chromatography coupled with an ultra-violet detector (HPLC/UV). This paper intends to examine artifacts about its suitability in identification of unsaturated carbonyls. Kinetic tests for acrolein, crotonaldehyde, methacrolein and methyl vinyl ketone (MVK) showed formations of carbonyl-DNP-hydrazone during sampling, which could further react with DNPH, resulting in undesired UV absorption products [e.g., carbonyl-DNP-hydrazone-DNPH (dimer) and 2(carbonyl-DNP-hydrazone)-DNPH (trimer)]. The dimerization and trimerization occurred for acrolein and MVK whereas only dimerization for crotonaldehyde and methacrolein. The polymerization products undoubtedly affect the integrity of the chromatogram, leading to misidentification and inaccurate quantification. Whether precautions taken during sampling and/or sample treatment could avoid or minimize this artifact has not been thoughtfully investigated. More often, such artifacts are usually overlooked by scientists when the data are reported.

  11. Antioxidative potential of Perna viridis and its protective role against ROS induced lipidperoxidation and protein carbonyl

    Digital Repository Service at National Institute of Oceanography (India)

    Jena, K.B.; Jagtap, T.G.; Verlecar, X.N.

    ) such as hydrogen peroxide (H2O2) and hydroxyl radical (OH•), and inhibition of lipid peroxidation (LPX) and protein carbonyl (PC). The scavenging activity of DPPH radical, H sub(2) O sub(2) and OH• radicals increased in dose dependent manner. The reducing power...

  12. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  13. Mechanism of stimulation of endogenous fermentation in yeast by carbonyl cyanide m-chlorophenylhydrazone

    NARCIS (Netherlands)

    Noshiro, A.; Purwin, C.; Laux, M.; Nicolaij, K.; Scheffers, W.A.; Holzer, H.

    1987-01-01

    Addition of the uncoupler and protonophore carbonyl cyanide m-chlorophenylhydrazone (CCCP) to starved yeast cells starts endogenous alcoholic fermentation lasting about 20 min. Hexose 6-phosphates, fructose 2,6-bisphosphate, and pyruvate accumulate in less than 2 min after addition of CCCP from

  14. Efficient Conversion of Oximes to the Corresponding Carbonyl Compounds with Tetrabutylammonium Chromate under Aprotic Conditions

    International Nuclear Information System (INIS)

    Pourali, Ali Reza; Goli, Arezou

    2006-01-01

    The solubility in several solvents, mildness, simple work-up and absence of side reactions provide advantages of using TBAC in deoximation reactions. This is an efficient and selective method for homogeneous deoximation of structurally different compounds under the moderately acidic and aprotic conditions in high yields. Regeneration of ketones and aldehydes from their oximes has assumed added importance since the discovery of the Barton reaction in which oximes are produced at non-activated hydrocarbon sites. Also, their synthesis from non-carbonyl compounds, such as by nitrosation of an active methylene group, nitrosation of an α-halo carbonyl compound and condensation of a nitro-alkene with an aldehyde provides a valid alternative pathway to carbonyl compounds. Therefore, there has been a continued interest in the effective regeneration of carbonyl compounds from the corresponding oximes especially under mild conditions. Oxidative and reductive methods have been found to show advantages over the classical hydrolytic methods. Although many oxidizing agents have been used, only a limited number of methods are efficient because of the low solubility of these metallic reagents in most organic solvents

  15. Iron Dextran treatment does not induce serum protein carbonyls in the newborn pig

    Science.gov (United States)

    Oxidation of serum proteins can lead to carbonyl formation which alters their function and is often associated with stress-related diseases. Since it is recommended that all pigs reared in modern production facilities be given supplemental iron at birth to prevent anemia, and metals can catalyze th...

  16. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    International Nuclear Information System (INIS)

    Guan, Jiwen; Hu, Yongjun; Xie, Min; Bernstein, Elliot R.

    2012-01-01

    Highlights: ► The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. ► Acetone molecules in the dimer are stacked with an antiparallel way. ► The structure of the acetone trimer and the tetramer are the cyclic structures. ► The carbonyl groups would interact with the methyl groups in acetone clusters. ► These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR–VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 ∼ 3550 cm −1 of neutral acetone and its clusters (CH 3 COCH 3 ) n (n = 1–4). Features around 3440 cm −1 in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm −1 as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  17. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    2009-01-01

    Roč. 11, - (2009), s. 8795-8703 ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  18. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  19. 10Be/230Th ratios as proxy for particle flux in the equatorial Pacific ocean

    International Nuclear Information System (INIS)

    Anderson, R.F.; Fleisher, M.Q.; Kubik, P.W.; Suter, M.

    1997-01-01

    Particulate 10 Be/ 230 Th ratios collected by sediment traps in the central equatorial Pacific Ocean exhibit a positive correlation with particle flux, but little or no correlation with particle composition. (author) 1 fig., 4 refs

  20. Determination of vertical velocities in the equatorial part of the western Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Bahulayan, N.; Varadachari, V.V.R.

    Using steady state two-dimensional turbulent diffusion equations of salt and heat some important characteristics of vertical circulation in the equatorial part of the Indian Ocean have been evaluated and discussed. Upwelling and sinking velocities...

  1. Bacterial Diversity in Deep-Sea Sediments from Afanasy Nikitin Seamount, Equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Khandeparker, R.; Meena, R.M.; Deobagkar, D.D.

    Deep-sea sediments can reveal much about the last 200 million years of Earth history, including the history of ocean life and climate. Microbial diversity in Afanasy Nikitin seamount located at Equatorial East Indian Ocean (EEIO) was investigated...

  2. Surface currents in the equatorial Indian Ocean during spring and fall - An altimetry based analysis

    Digital Repository Service at National Institute of Oceanography (India)

    Antony, M.K.; Somayajulu, Y.K.

    This communication presents the results of a study aimed at investigating the nature and variability of surface currents in the equatorial Indian Ocean between 5 degrees N and 5 degrees S during spring and fall seasons. Geostrophic surface currents...

  3. Observational evidence of lower-frequency Yanai waves in the central equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    David, D.T.; PrasannaKumar, S.; Byju, P.; Sarma, M.S.S.; Suryanarayana, A.; Murty, V.S.N.

    created by the northward shifting and strengthening of the westward flowing south equatorial current associated with positive IOD and the eastward flowing southwest monsoon current provides energy for the generation of lower-frequency Yanai waves. Vertical...

  4. Weight Percentage of Calcium Carbonate for 17 Equatorial Pacific Cores from Brown University

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Weight percentages of calcium carbonate in this file were compiled by J. Farrell and W. L. Prell of Brown University for 17 equatorial Pacific Ocean sediment cores....

  5. Detection and Characterization of Equatorial Scintillation for Real-Time Operational Support

    National Research Council Canada - National Science Library

    McNeil, W

    1997-01-01

    The Phillips Laboratory Scintillation Network Decision Aid (PL-SCINDA) is a software tool which uses real-time data from remote sites to model ionospheric plasma depletions in the equatorial region...

  6. Electronic transitions and bonding properties in a series of five-coordinate "16-electron" complexes [Mn(CO)3(L2)]- (L2 = chelating redox-active .pi.-donor ligand)

    Czech Academy of Sciences Publication Activity Database

    Hartl, F.; Rosa, P.; Ricard, L.; Le Floch, P.; Záliš, Stanislav

    2007-01-01

    Roč. 251, 3-4 (2007), s. 557-576 ISSN 0010-8545 R&D Projects: GA MŠk 1P05OC068; GA AV ČR 1ET400400413 Institutional research plan: CEZ:AV0Z40400503 Keywords : manganese carbonyl * .pi.-donor ligand * electronic delocalization * Five-coordinate complex Subject RIV: CG - Electrochemistry Impact factor: 8.568, year: 2007

  7. Investigations of equatorial ionosphere nighttime mode conversion at VLF

    Science.gov (United States)

    Hildebrand, Verne

    1993-05-01

    VLF Radiowave propagation provides one of the few viable tools for exploring the properties of the lower D-region ionosphere. Conversely, VLF communications coverage analysis and prediction is directly dependent on the quality of models for the D-region ionosphere. The VLF Omega navigation signals are an excellent and under-utilized resource for conducting D-region research in direct support of VLF communications. Stations are well placed for investigating polar, mid latitude, and equatorial phenomena. Much can be learned by fully utilizing the very stable signals radiated at five frequencies, available from each of the eight transmitters, and taking full advantage of modal structure. While the Omega signals, 10.2 to 13.6 kHz, are well below the VLF communications band, we contend that much of the knowledge gained on D-region characteristics can be directly applied at the higher frequencies. The opportunity offered by Omega needs to be exploited. With the Global Positioning System (GPS) coming onboard as the prime means for global navigation, pressure is mounting to phase out Omega. In this paper we describe how we are using Omega along with computer codes of full wave VLF propagation, provided to us by the U.S. Naval Ocean Systems Center (NOSC), for ionosphere research and by example illustrate the potential for other investigations.

  8. Equatorial segment of the mid-atlantic ridge

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The Equatorial Segment of the Mid-Atlantic Ridge is a part of this mid-oceanic ridge limited by a cluster of fracture zones - Cape Verde, Marathon, Mercury, Vema, Doldrums, Vernadsky and Sierra Leone - in the North, and a similar cluster of fracture zones - St Paul, Romanche and Chain - in the South. During recent decades, following the publication of the 5. edition of the General Bathymetric Chart of the Oceans (GEBCO), there has been a great deal of geological-geophysical research and mapping of the World Ocean. The results have led to the development of a number of theories concerning the essential heterogeneity of the structure of the ocean floor and, in particular, the heterogeneity of the structure and segmentation of mid-oceanic ridges. Research on the nature of such segmentation is of great importance for an understanding of the processes of development of such ridges and oceanic basins as a whole. Chapter 20 is dedicated to the study of the atlantic ocean mantle by using (Th.U)Th, (Th/U)pb and K/Ti systematics 380 refs.

  9. Equatorial segment of the mid-atlantic ridge

    International Nuclear Information System (INIS)

    1996-01-01

    The Equatorial Segment of the Mid-Atlantic Ridge is a part of this mid-oceanic ridge limited by a cluster of fracture zones - Cape Verde, Marathon, Mercury, Vema, Doldrums, Vernadsky and Sierra Leone - in the North, and a similar cluster of fracture zones - St Paul, Romanche and Chain - in the South. During recent decades, following the publication of the 5. edition of the General Bathymetric Chart of the Oceans (GEBCO), there has been a great deal of geological-geophysical research and mapping of the World Ocean. The results have led to the development of a number of theories concerning the essential heterogeneity of the structure of the ocean floor and, in particular, the heterogeneity of the structure and segmentation of mid-oceanic ridges. Research on the nature of such segmentation is of great importance for an understanding of the processes of development of such ridges and oceanic basins as a whole. Chapter 20 is dedicated to the study of the atlantic ocean mantle by using (Th.U)Th, (Th/U)pb and K/Ti systematics

  10. A Cenozoic record of the equatorial Pacific carbonate compensation depth.

    Science.gov (United States)

    Pälike, Heiko; Lyle, Mitchell W; Nishi, Hiroshi; Raffi, Isabella; Ridgwell, Andy; Gamage, Kusali; Klaus, Adam; Acton, Gary; Anderson, Louise; Backman, Jan; Baldauf, Jack; Beltran, Catherine; Bohaty, Steven M; Bown, Paul; Busch, William; Channell, Jim E T; Chun, Cecily O J; Delaney, Margaret; Dewangan, Pawan; Dunkley Jones, Tom; Edgar, Kirsty M; Evans, Helen; Fitch, Peter; Foster, Gavin L; Gussone, Nikolaus; Hasegawa, Hitoshi; Hathorne, Ed C; Hayashi, Hiroki; Herrle, Jens O; Holbourn, Ann; Hovan, Steve; Hyeong, Kiseong; Iijima, Koichi; Ito, Takashi; Kamikuri, Shin-ichi; Kimoto, Katsunori; Kuroda, Junichiro; Leon-Rodriguez, Lizette; Malinverno, Alberto; Moore, Ted C; Murphy, Brandon H; Murphy, Daniel P; Nakamura, Hideto; Ogane, Kaoru; Ohneiser, Christian; Richter, Carl; Robinson, Rebecca; Rohling, Eelco J; Romero, Oscar; Sawada, Ken; Scher, Howie; Schneider, Leah; Sluijs, Appy; Takata, Hiroyuki; Tian, Jun; Tsujimoto, Akira; Wade, Bridget S; Westerhold, Thomas; Wilkens, Roy; Williams, Trevor; Wilson, Paul A; Yamamoto, Yuhji; Yamamoto, Shinya; Yamazaki, Toshitsugu; Zeebe, Richard E

    2012-08-30

    Atmospheric carbon dioxide concentrations and climate are regulated on geological timescales by the balance between carbon input from volcanic and metamorphic outgassing and its removal by weathering feedbacks; these feedbacks involve the erosion of silicate rocks and organic-carbon-bearing rocks. The integrated effect of these processes is reflected in the calcium carbonate compensation depth, which is the oceanic depth at which calcium carbonate is dissolved. Here we present a carbonate accumulation record that covers the past 53 million years from a depth transect in the equatorial Pacific Ocean. The carbonate compensation depth tracks long-term ocean cooling, deepening from 3.0-3.5 kilometres during the early Cenozoic (approximately 55 million years ago) to 4.6 kilometres at present, consistent with an overall Cenozoic increase in weathering. We find large superimposed fluctuations in carbonate compensation depth during the middle and late Eocene. Using Earth system models, we identify changes in weathering and the mode of organic-carbon delivery as two key processes to explain these large-scale Eocene fluctuations of the carbonate compensation depth.

  11. A mantle plume model for the Equatorial Highlands of Venus

    Science.gov (United States)

    Kiefer, Walter S.; Hager, Bradford H.

    1991-01-01

    The possibility that the Equatorial Highlands are the surface expressions of hot upwelling mantle plumes is considered via a series of mantle plume models developed using a cylindrical axisymmetric finite element code and depth-dependent Newtonian rheology. The results are scaled by assuming whole mantle convection and that Venus and the earth have similar mantle heat flows. The best model fits are for Beta and Atla. The common feature of the allowed viscosity models is that they lack a pronounced low-viscosity zone in the upper mantle. The shape of Venus's long-wavelength admittance spectrum and the slope of its geoid spectrum are also consistent with the lack of a low-viscosity zone. It is argued that the lack of an asthenosphere on Venus is due to the mantle of Venus being drier than the earth's mantle. Mantle plumes may also have contributed to the formation of some smaller highland swells, such as the Bell and Eistla regions and the Hathor/Innini/Ushas region.

  12. Improved design of an ITER equatorial EC launcher

    International Nuclear Information System (INIS)

    Takahashi, K.; Kajiwara, K.; Kobayashi, N.; Kasugai, A.; Sakamoto, K.

    2008-01-01

    New design improvements for an ITER equatorial EC launcher are described. A design of the front shield modules was evaluated analytically. The results indicate that these modules can withstand the electromagnetic forces induced by plasma disruption and vertical plasma motion. The steering mirror mock-up including the spiral cooling tubes was fabricated based on the present design with application of the hot isostatic pressing technique to bond the copper alloy mirror body and the embedded stainless steel cooling tubes. The test of water flow was carried out and the expected flow rate was successfully obtained. A quasi-optical (QO) transmission layout has been proposed instead of the waveguide lines. The advantage of this option is possibly to increase the reliability in terms of fabrication and refurbishment. According to the beam propagation analysis, it is verified that transmission loss at the QO region is 1.1%-2.2%, which is comparable to the reference design. The peak heat load on the steering mirror surface could be reduced by 55%, which relaxes the mirror design

  13. Mismo field experiment in the equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Masumoto, Y.; Kuroda, Y.; Katsumata, M.; Mizuno, K.; Takayabu, Y.N.; Yoshizaki, M.; Shareef, A.; Fujiyoshi, Y.; McPhaden, M.J.; Murty, V.S.N.; Shirooka, R; Yasunaga, K.; Yamada, H.; Sato, N.; Ushiyama, T.; Moteki, Q.; Seiki, A.; Fujita, M.; Ando, K.; Hase, H.; Ueki, I; Horii, T.; Yokoyama, C.; Miyakawa, T.

    MISMO FIELD EXPERIMENT IN THE EQUATORIAL INDIAN OCEAN * b y Ku n i o yo n e y a m a , yu K i o ma s u m o t o , yo s h i f u m i Ku r o d a , ma s a K i Ka t s u m a t a , Ke i s u K e mi z u n o , yu K a r i n. ta K a y a b u , ma s a n o r i... yo s h i z a K i , al i sh a r e e f, ya s u s h i fu j i y o s h i , mi c h a e l j. mcPh a d e n , V. s. n. mu r t y , ry u i c h i sh i r o o K a , Ka z u a K i ya s u n a g a , hi r o y u K i ya m a d a , na o K i sa t o , to m o K i us...

  14. Bottom-type scattering layers and equatorial spread F

    Directory of Open Access Journals (Sweden)

    D. L. Hysell

    2004-12-01

    Full Text Available Jicamarca radar observations of bottom-type coherent scattering layers in the post-sunset bottomside F-region ionosphere are presented and analyzed. The morphology of the primary waves seen in radar images of the layers supports the hypothesis of kudeki+bhattacharyya-1999 that wind-driven gradient drift instabilities are operating. In one layer event when topside spread F did not occur, irregularities were distributed uniformly in space throughout the layers. In another event when topside spread F did eventually occur, the irregularities within the pre-existing bottom-type layers were horizontally clustered, with clusters separated by about 30km. The same horizontal periodicity was evident in the radar plumes and large-scale irregularities that emerged later in the event. We surmise that horizontal periodicity in bottom-type layer irregularity distribution is indicative of large-scale horizontal waves in the bottomside F-region that may serve as seed waves for large-scale Rayleigh Taylor instabilities. Key words. Ionosphere (equatorial ionosphere; ionospheric irregularties; plasma waves and instabilities

  15. Asymptotic approach for the nonlinear equatorial long wave interactions

    International Nuclear Information System (INIS)

    Ramirez Gutierrez, Enver; Silva Dias, Pedro L; Raupp, Carlos

    2011-01-01

    In the present work we use an asymptotic approach to obtain the long wave equations. The shallow water equation is put as a function of an external parameter that is a measure of both the spatial scales anisotropy and the fast to slow time ratio. The values given to the external parameters are consistent with those computed using typical values of the perturbations in tropical dynamics. Asymptotically, the model converge toward the long wave model. Thus, it is possible to go toward the long wave approximation through intermediate realizable states. With this approach, the resonant nonlinear wave interactions are studied. To simplify, the reduced dynamics of a single resonant triad is used for some selected equatorial trios. It was verified by both theoretical and numerical results that the nonlinear energy exchange period increases smoothly as we move toward the long wave approach. The magnitude of the energy exchanges is also modified, but in this case depends on the particular triad used and also on the initial energy partition among the triad components. Some implications of the results for the tropical dynamics are discussed. In particular, we discuss the implications of the results for El Nino and the Madden-Julian in connection with other scales of time and spatial variability.

  16. Equatorial spread F: a review of recent experimental results

    International Nuclear Information System (INIS)

    Kelley, M.C.

    1979-01-01

    In this paper the authors review an intense research effort aimed at understanding the large scale disruption of the equatorial F layer which often commences just after sunset, and lasts for most of the night. A very attractive explanation for the phenomena, although one not universally accepted, is that the F layer is unstable to the classic Rayleigh-Taylor condition in which a heavy fluid, the plasma, is supported against gravity by a light 'fluid', the Earth's magnetic field. It is concluded that a reasonable case has been made for this explanation provided that the concept is extended to include nonlinear Rayleigh-Taylor like buoyancy effects above the F peak where linear process is stable. Internal gravity waves in neutral atmosphere seem to play an important role in seeding the Rayleigh-Taylor process with large scale finite amplitude perturbations. One of the remarkable features of this phenomena is the nearly simultaneous generation of structure with scale sizes spanning five orders of magnitude. These results may have applications in astrophysical processes where the Rayleigh-Taylor instability is thought to play a role. (Auth.)

  17. Equatorial insolation: from precession harmonics to eccentricity frequencies

    Directory of Open Access Journals (Sweden)

    A. Berger

    2006-01-01

    Full Text Available Since the paper by Hays et al. (1976, spectral analyses of climate proxy records provide substantial evidence that a fraction of the climatic variance is driven by insolation changes in the frequency ranges of obliquity and precession variations. However, it is the variance components centered near 100 kyr which dominate most Upper Pleistocene climatic records, although the amount of insolation perturbation at the eccentricity driven periods close to 100-kyr (mainly the 95 kyr- and 123 kyr-periods is much too small to cause directly a climate change of ice-age amplitude. Many attempts to find an explanation to this 100-kyr cycle in climatic records have been made over the last decades. Here we show that the double maximum which characterizes the daily irradiation received in tropical latitudes over the course of the year is at the origin in equatorial insolation of not only strong 95 kyr and 123 kyr periods related to eccentricity, but also of a 11-kyr and a 5.5-kyr periods related to precession.

  18. Equatorial circular orbits in the Kerr-de Sitter spacetimes

    International Nuclear Information System (INIS)

    Stuchlik, Zdenek; Slany, Petr

    2004-01-01

    Equatorial motion of test particles in Kerr-de Sitter spacetimes is considered. Circular orbits are determined, their properties are discussed for both black-hole and naked-singularity spacetimes, and their relevance for thin accretion disks is established. The circular orbits constitute two families that coalesce at the so-called static radius. The orientation of the motion along the circular orbits is, in accordance with case of asymptotically flat Kerr spacetimes, defined by relating the motion to the locally nonrotating frames. The minus-family orbits are all counterrotating, while the plus-family orbits are usually corotating relative to these frames. However, the plus-family orbits become counterrotating in the vicinity of the static radius in all Kerr-de Sitter spacetimes, and they become counterrotating in the vicinity of the ring singularity in Kerr-de Sitter naked-singularity spacetimes with a low enough rotational parameter. In such spacetimes, the efficiency of the conversion of the rest energy into heat energy in the geometrically thin plus-family accretion disks can reach extremely high values exceeding the efficiency of the annihilation process. The transformation of a Kerr-de Sitter naked singularity into an extreme black hole due to accretion in the thin disks is briefly discussed for both the plus-family and minus-family disks. It is shown that such a conversion leads to an abrupt instability of the innermost parts of the plus-family accretion disks that can have strong observational consequences

  19. Equatorial segment of the mid-atlantic ridge

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-12-31

    The Equatorial Segment of the Mid-Atlantic Ridge is a part of this mid-oceanic ridge limited by a cluster of fracture zones - Cape Verde, Marathon, Mercury, Vema, Doldrums, Vernadsky and Sierra Leone - in the North, and a similar cluster of fracture zones - St Paul, Romanche and Chain - in the South. During recent decades, following the publication of the 5. edition of the General Bathymetric Chart of the Oceans (GEBCO), there has been a great deal of geological-geophysical research and mapping of the World Ocean. The results have led to the development of a number of theories concerning the essential heterogeneity of the structure of the ocean floor and, in particular, the heterogeneity of the structure and segmentation of mid-oceanic ridges. Research on the nature of such segmentation is of great importance for an understanding of the processes of development of such ridges and oceanic basins as a whole. Chapter 20 is dedicated to the study of the atlantic ocean mantle by using (Th.U)Th, (Th/U)pb and K/Ti systematics 380 refs.

  20. Tree rings and rainfall in the equatorial Amazon

    Science.gov (United States)

    Granato-Souza, Daniela; Stahle, David W.; Barbosa, Ana Carolina; Feng, Song; Torbenson, Max C. A.; de Assis Pereira, Gabriel; Schöngart, Jochen; Barbosa, Joao Paulo; Griffin, Daniel

    2018-05-01

    The Amazon basin is a global center of hydroclimatic variability and biodiversity, but there are only eight instrumental rainfall stations with continuous records longer than 80 years in the entire basin, an area nearly the size of the coterminous US. The first long moisture-sensitive tree-ring chronology has been developed in the eastern equatorial Amazon of Brazil based on dendrochronological analysis of Cedrela cross sections cut during sustainable logging operations near the Rio Paru. The Rio Paru chronology dates from 1786 to 2016 and is significantly correlated with instrumental precipitation observations from 1939 to 2016. The strength and spatial scale of the precipitation signal vary during the instrumental period, but the Rio Paru chronology has been used to develop a preliminary reconstruction of February to November rainfall totals from 1786 to 2016. The reconstruction is related to SSTs in the Atlantic and especially the tropical Pacific, similar to the stronger pattern of association computed for the instrumental rainfall data from the eastern Amazon. The tree-ring data estimate extended drought and wet episodes in the mid- to late-nineteenth century, providing a valuable, long-term perspective on the moisture changes expected to emerge over the Amazon in the coming century due to deforestation and anthropogenic climate change.

  1. Modeling Global Ocean Biogeochemistry With Physical Data Assimilation: A Pragmatic Solution to the Equatorial Instability

    Science.gov (United States)

    Park, Jong-Yeon; Stock, Charles A.; Yang, Xiaosong; Dunne, John P.; Rosati, Anthony; John, Jasmin; Zhang, Shaoqing

    2018-03-01

    Reliable estimates of historical and current biogeochemistry are essential for understanding past ecosystem variability and predicting future changes. Efforts to translate improved physical ocean state estimates into improved biogeochemical estimates, however, are hindered by high biogeochemical sensitivity to transient momentum imbalances that arise during physical data assimilation. Most notably, the breakdown of geostrophic constraints on data assimilation in equatorial regions can lead to spurious upwelling, resulting in excessive equatorial productivity and biogeochemical fluxes. This hampers efforts to understand and predict the biogeochemical consequences of El Niño and La Niña. We develop a strategy to robustly integrate an ocean biogeochemical model with an ensemble coupled-climate data assimilation system used for seasonal to decadal global climate prediction. Addressing spurious vertical velocities requires two steps. First, we find that tightening constraints on atmospheric data assimilation maintains a better equatorial wind stress and pressure gradient balance. This reduces spurious vertical velocities, but those remaining still produce substantial biogeochemical biases. The remainder is addressed by imposing stricter fidelity to model dynamics over data constraints near the equator. We determine an optimal choice of model-data weights that removed spurious biogeochemical signals while benefitting from off-equatorial constraints that still substantially improve equatorial physical ocean simulations. Compared to the unconstrained control run, the optimally constrained model reduces equatorial biogeochemical biases and markedly improves the equatorial subsurface nitrate concentrations and hypoxic area. The pragmatic approach described herein offers a means of advancing earth system prediction in parallel with continued data assimilation advances aimed at fully considering equatorial data constraints.

  2. Biogeochemical impact of a model western iron source in the Pacific Equatorial Undercurrent

    OpenAIRE

    Slemons, L.; Gorgues, T.; Aumont, Olivier; Menkès, Christophe; Murray, J. W.

    2009-01-01

    Trace element distributions in the source waters of the Pacific Equatorial Undercurrent (EUC) show the existence of elevated total acid-soluble iron concentrations. This region has been suggested to contribute enough bioavailable iron to regulate interannual and interglacial variability in biological productivity downstream in the high-nitrate low-chlorophyll upwelling zone of the eastern equatorial Pacific. We investigated the advection and first-order biogeochemical impact of an imposed, da...

  3. The effect of J2 on equatorial and halo orbits around a magnetic planet

    International Nuclear Information System (INIS)

    Inarrea, Manuel; Lanchares, Victor; Palacian, Jesus F.; Pascual, Ana I.; Pablo Salas, J.; Yanguas, Patricia

    2009-01-01

    We calculate equatorial and halo orbits around a non-spherical (both oblate and prolate) magnetic planet. It is known that circular equatorial and halo orbits exist for a dust grain orbiting a spherical magnetic planet. However, the frequency of the orbit is constrained by the charge-mass ratio of the particle. If the non-sphericity of the planet is taken into account this constraint is modified or, in some cases, it disappears.

  4. Understanding the Longitudinal Variability of Equatorial Electrodynamics using integrated Ground- and Space-based Observations

    Science.gov (United States)

    Yizengaw, E.; Moldwin, M.; Zesta, E.

    2015-12-01

    The currently funded African Meridian B-Field Education and Research (AMBER) magnetometer array comprises more than thirteen magnetometers stationed globally in the vicinity of geomagnetic equator. One of the main objectives of AMBER network is to understand the longitudinal variability of equatorial electrodynamics as function of local time, magnetic activity, and season. While providing complete meridian observation in the region and filling the largest land-based gap in global magnetometer coverage, the AMBER array addresses two fundamental areas of space physics: first, the processes governing electrodynamics of the equatorial ionosphere as a function of latitude (or L-shell), local time, longitude, magnetic activity, and season, and second, ULF pulsation strength at low/mid-latitude regions and its connection with equatorial electrojet and density fluctuation. The global AMBER network can also be used to augment observations from space-based instruments, such us the triplet SWARM mission and the upcoming ICON missions. Thus, in coordination with space-based and other ground-based observations, the AMBER magnetometer network provides a great opportunity to understand the electrodynamics that governs equatorial ionosphere motions. In this paper we present the longitudinal variability of the equatorial electrodynamics using the combination of instruments onboard SWARM and C/NOFS satellites and ground-based AMBER network. Both ground- and pace-based observations show stronger dayside and evening sector equatorial electrodynamics in the American and Asian sectors compared to the African sector. On the other hand, the African sector is home to stronger and year-round ionospheric bubbles/irregularities compared to the American and Asian sectors. This raises the question if the evening sector equatorial electrodynamics (vertical drift), which is believed to be the main cause for the enhancement of Rayleigh-Taylor (RT) instability growth rate, is stronger in the

  5. Impact of convection over the equatorial trough on the summer monsoon activity over India

    Digital Repository Service at National Institute of Oceanography (India)

    RameshKumar, M.R.; Shenoi, S.S.C.; Schulz, J.

    . There have been studies (Cadet and Olory Togbe, 1981; Sadhuram and Sastry, 1987) on the role of Equatorial Trough (ET) as well as Southern Hemispheric Equatorial Trough (SHET) on the rainfall over central India. Most of these studies are related... the ET, WET and EET behave in a similar fashion during different monsoon and El Nino conditions ? c) What role do the synoptic systems play during the BM over the Indian subcontinent? 2. Data and Methodology The pentad precipitation data used...

  6. The effect of J{sub 2} on equatorial and halo orbits around a magnetic planet

    Energy Technology Data Exchange (ETDEWEB)

    Inarrea, Manuel [Universidad de la Rioja, Area de Fisica, 26006 Logrono (Spain); Lanchares, Victor [Dpto. de Matematicas y Computacion, CIEMUR: Centro de Investigacion en Informatica, Estadistica y Matematicas, Universidad de la Rioja, 26004 Logrono (Spain)], E-mail: vlancha@unirioja.es; Palacian, Jesus F. [Universidad Publica de Navarra, Departamento de Ingenieria Matematica e Informatica, 31006 Pamplona (Spain); Pascual, Ana I. [Dpto. de Matematicas y Computacion, CIEMUR: Centro de Investigacion en Informatica, Estadistica y Matematicas, Universidad de la Rioja, 26004 Logrono (Spain); Pablo Salas, J. [Universidad de la Rioja, Area de Fisica, 26006 Logrono (Spain); Yanguas, Patricia [Universidad Publica de Navarra, Departamento de Ingenieria Matematica e Informatica, 31006 Pamplona (Spain)

    2009-10-15

    We calculate equatorial and halo orbits around a non-spherical (both oblate and prolate) magnetic planet. It is known that circular equatorial and halo orbits exist for a dust grain orbiting a spherical magnetic planet. However, the frequency of the orbit is constrained by the charge-mass ratio of the particle. If the non-sphericity of the planet is taken into account this constraint is modified or, in some cases, it disappears.

  7. Gas-phase chemistry of Mo, Ru, W, and Os metal carbonyl complexes

    International Nuclear Information System (INIS)

    Wang, Y.; Qin, Z.; Fan, F.L.

    2014-01-01

    Metal carbonyl complexes were used for studying the gas-phase chemical behavior of Mo, Ru, W and Os isotopes with an on-line low temperature isothermal gas chromatography apparatus. Short-lived Mo and Ru isotopes were produced by a 252 Cf spontaneous fission source. Short-lived nuclides of W and Os were produced using the heavy ion reactions 19 F + 159 Tb and 165 Ho, respectively. Short-lived products were thermalized in a recoil chamber filled with a gas mixture of helium and carbon monoxide. The carbonyls formed were then transported through capillaries to an isothermal chromatography column for study of the adsorption behavior as a function of temperature. On-line isothermal chromatography (IC) experiments on Teflon (PTFE) and quartz surfaces showed that short-lived isotopes of the listed elements can form carbonyl complexes which are very volatile and interact most likely in physical sorption processes. Deduced adsorption enthalpies of Mo and Ru carbonyls were -38 ± 2 kJ/mol and -36 ± 2 kJ/mol, respectively. These values are in good agreement with literature data, partly obtained with different chromatographic techniques. A validation of the applied Monte Carlo model to deduce adsorption enthalpies with Mo isotopes of different half-lives proved the validity of the underlying adsorption model. The investigations using a gas-jet system coupled to a heavy ion accelerator without any preseparator clearly showed the limitations of the approach. The He and CO gas mixture, which was directly added into the chamber, will result in decomposition of CO gas and produce some aerosol particles. After the experiment of 173 W and 179 Os in the heavy ion experiments, the Teflon column was covered by a yellowish deposit; the adsorption enthalpy of W and Os carbonyls could therefore not be properly deduced using Monte Carlo simulations. (orig.)

  8. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients.

    Science.gov (United States)

    Kolgiri, Vaishali; Patil, Vinayak Wamanrao

    The major complications of "treated" Human Immunodeficiency Virus (HIV) infection are cardiovascular disease, malignancy, renal disease, liver disease, bone disease, and perhaps neurological complications, which are phenomena of the normal aging process occurring at an earlier age in the HIV-infected population. The present study is aimed to explore protein carbonyl content as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. To investigate the potential of carbonyl content as a biomarker for detecting oxidative Deoxyribonucleic acid (DNA) damage induced Antiretroviral Theraphy (ART) toxicity and/or accelerated aging in HIV/AIDS patients. In this case-control study a total 600 subjects were included. All subjects were randomly selected and grouped as HIV-negative (control group) (n=300), HIV-infected ART naive (n=100), HIV-infected on first line ART (n=100), and HIV-infected on second line ART (n=100). Seronegative control subjects were age- and sex-matched with the ART naive patients and the two other groups. Carbonyl protein was determined by the method described in Levine et al. DNA damage marker 8-OH-dG was determined using 8-hydroxy-2-deoxy Guanosine StressXpress ELA Kit by StressMarq Biosciences. Protein carbonyl content levels and oxidative DNA damage were significantly higher (paging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients. Copyright © 2016 Sociedade Brasileira de Infectologia. Published by Elsevier Editora Ltda. All rights reserved.

  9. Equatorial electrojet as part of the global circuit: a case-study from the IEEY

    Directory of Open Access Journals (Sweden)

    A. T. Kobea

    1998-06-01

    Full Text Available Geomagnetic storm-time variations often occur coherently at high latitude and the day-side dip equator where they affect the normal eastward Sq field. This paper presents an analysis of ground magnetic field and ionospheric electrodynamic data related to the geomagnetic storm which occured on 27 May 1993 during the International Equatorial Electrojet Year (IEEY experiment. This storm-signature analysis on the auroral, mid-latitude and equatorial ground field and ionospheric electrodynamic data leads to the identification of a sensitive response of the equatorial electrojet (EEJ to large-scale auroral return current: this response consists in a change of the eastward electric field during the pre-sunrise hours (0400-0600 UT coherently to the high-, mid-, and equatorial-latitude H decrease and the disappearance of the EEJ irregularities between the time-interval 0800-0950 UT. Subsequent to the change in h'F during pre-sunrise hours, the observed foF2 increase revealed an enhancement of the equatorial ionization anomaly (EIA caused by the high-latitude penetrating electric field. The strengthening of these irregularities attested by the Doppler frequency increase tracks the H component at the equator which undergoes a rapid increase around 0800 UT. The ∆H variations observed at the equator are the sum of the following components: SR, DP, DR, DCF and DT.Keywords. Equatorial electrojet · Magnetosphere-ionosphere interactions · Electric fields and currents · Auroral ionosphere · Ionospheric disturbances

  10. Crystallization of protein–ligand complexes

    International Nuclear Information System (INIS)

    Hassell, Anne M.; An, Gang; Bledsoe, Randy K.; Bynum, Jane M.; Carter, H. Luke III; Deng, Su-Jun J.; Gampe, Robert T.; Grisard, Tamara E.; Madauss, Kevin P.; Nolte, Robert T.; Rocque, Warren J.; Wang, Liping; Weaver, Kurt L.; Williams, Shawn P.; Wisely, G. Bruce; Xu, Robert; Shewchuk, Lisa M.

    2007-01-01

    Methods presented for growing protein–ligand complexes fall into the categories of co-expression of the protein with the ligands of interest, use of the ligands during protein purification, cocrystallization and soaking the ligands into existing crystals. Obtaining diffraction-quality crystals has long been a bottleneck in solving the three-dimensional structures of proteins. Often proteins may be stabilized when they are complexed with a substrate, nucleic acid, cofactor or small molecule. These ligands, on the other hand, have the potential to induce significant conformational changes to the protein and ab initio screening may be required to find a new crystal form. This paper presents an overview of strategies in the following areas for obtaining crystals of protein–ligand complexes: (i) co-expression of the protein with the ligands of interest, (ii) use of the ligands during protein purification, (iii) cocrystallization and (iv) soaks

  11. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui; Hu, Jinsong; Huang, Kuo-Wei

    2017-01-01

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  12. -Pincer Ligand Family through Ligand Post-Modification

    KAUST Repository

    Huang, Mei-Hui

    2017-10-02

    A series of air-stable nickel complexes containing triazine-based PN3P-pincer ligands were synthesized and fully characterized. Complex 3 contains a de-aromatized central triazine ring from the deprotonation of one of the N–H arms. With a post-modification strategy, the Me-PN3P*NiCl complex (3) could be converted into a new class of diimine–traizine PN3P-pincer nickel complexes.

  13. Reactivity of halide and pseudohalide ligands

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

  14. Ocean Color and the Equatorial Annual Cycle in the Pacific

    Science.gov (United States)

    Hammann, A. C.; Gnanadesikan, A.

    2012-12-01

    The presence of chlorophyll, colored dissolved organic matter (CDOM) and other scatterers in ocean surface waters affect the flux divergence of solar radiation and thus the vertical distribution of radiant heating of the ocean. While this may directly alter the local mixed-layer depth and temperature (Martin 1985; Strutton & Chavez 2004), non-local changes are propagated through advection (Manizza et al. 2005; Murtugudde et al. 2002; Nakamoto et al. 2001; Sweeny et al. 2005). In and coupled feedbacks (Lengaigne et al. 2007; Marzeion & Timmermann 2005). Anderson et al. (2007), Anderson et al. (2009) and Gnanadesikan & Anderson (2009) have performed a series of experiments with a fully coupled climate model which parameterizes the e-folding depth of solar irradiance in terms of surface chlorophyll-a concentration. The results have so far been discussed with respect to the climatic mean state and ENSO variability in the tropical Pacific. We extend the discussion here to the Pacific equatorial annual cycle. The focus of the coupled experiments has been the sensitivity of the coupled system to regional differences in chlorophyll concentration. While runs have been completed with realistic SeaWiFS-derived monthly composite chlorophyll ('green') and with a globally chlorophyll-free ocean ('blue'), the concentrations in two additional runs have been selectively set to zero in specific regions: the oligotrophic subtropical gyres ('gyre') in one case and the mesotrophic gyre margins ('margin') in the other. The annual cycle of ocean temperatures exhibits distinctly reduced amplitudes in the 'blue' and 'margin' experiments, and a slight reduction in 'gyre' (while ENSO variability almost vanishes in 'blue' and 'gyre', but amplifies in 'margin' - thus the frequently quoted inverse correlation between ENSO and annual amplitudes holds only for the 'green' / 'margin' comparison). It is well-known that on annual time scales, the anomalous divergence of surface currents and vertical

  15. Coral settlement on a highly disturbed equatorial reef system.

    Science.gov (United States)

    Bauman, Andrew G; Guest, James R; Dunshea, Glenn; Low, Jeffery; Todd, Peter A; Steinberg, Peter D

    2015-01-01

    Processes occurring early in the life stages of corals can greatly influence the demography of coral populations, and successful settlement of coral larvae that leads to recruitment is a critical life history stage for coral reef ecosystems. Although corals in Singapore persist in one the world's most anthropogenically impacted reef systems, our understanding of the role of coral settlement in the persistence of coral communities in Singapore remains limited. Spatial and temporal patterns of coral settlement were examined at 7 sites in the southern islands of Singapore, using settlement tiles deployed and collected every 3 months from 2011 to 2013. Settlement occurred year round, but varied significantly across time and space. Annual coral settlement was low (~54.72 spat m(-2) yr(-1)) relative to other equatorial regions, but there was evidence of temporal variation in settlement rates. Peak settlement occurred between March-May and September-November, coinciding with annual coral spawning periods (March-April and October), while the lowest settlement occurred from December-February during the northeast monsoon. A period of high settlement was also observed between June and August in the first year (2011/12), possibly due to some species spawning outside predicted spawning periods, larvae settling from other locations or extended larval settlement competency periods. Settlement rates varied significantly among sites, but spatial variation was relatively consistent between years, suggesting the strong effects of local coral assemblages or environmental conditions. Pocilloporidae were the most abundant coral spat (83.6%), while Poritidae comprised only 6% of the spat, and Acroporidae coral spat. These results indicate that current settlement patterns are reinforcing the local adult assemblage structure ('others'; i.e. sediment-tolerant coral taxa) in Singapore, but that the replenishment capacity of Singapore's reefs appears relatively constrained, which could lead

  16. Modeling Tides, Planetary Waves, and Equatorial Oscillations in the MLT

    Science.gov (United States)

    Mengel, J. G.; Mayr, H. G.; Drob, D. P.; Porter, H. S.; Bhartia, P. K. (Technical Monitor)

    2001-01-01

    Applying Hines Doppler Spread Parameterization for gravity waves (GW), our 3D model reproduces some essential features that characterize the observed seasonal variations of tides and planetary waves in the upper mesosphere. In 2D, our model also reproduces the large Semi-Annual Oscillation (SAO) and Quasi Biennial Oscillation (QBO) observed in this region at low latitudes. It is more challenging to describe these features combined in a more comprehensive self consistent model, and we give a progress report that outlines the difficulties and reports some success. In 3D, the GW's are partially absorbed by tides and planetary waves to amplify them. Thus the waves are less efficient in generating the QBO and SAO at equatorial latitudes. Some of this deficiency is compensated by the fact that the GW activity is observed to be enhanced at low latitudes. Increasing the GW source has the desired effect to boost the QBO, but the effect is confined primarily to the stratosphere. With increasing altitude, the meridional circulation becomes more important in redistributing the momentum deposited in the background flow by the GW's. Another factor involved is the altitude at which the GW's originate, which we had originally chosen to be the surface. Numerical experiments show that moving this source altitude to the top of the troposphere significantly increases the efficiency for generating the QBO without affecting much the tides and planetary waves in the model. Attention to the details in which the GW source comes into play thus appears to be of critical importance in modeling the phenomenology of the MLT. Among the suite of numerical experiments reported, we present a simulation that produced significant variations of tides and planetary waves in the upper mesosphere. The effect is related to the QBO generated in the model, and GW filtering is the likely cause.

  17. Magnetospheric conditions near the equatorial footpoints of proton isotropy boundaries

    Directory of Open Access Journals (Sweden)

    V. A. Sergeev

    2015-12-01

    Full Text Available Data from a cluster of three THEMIS (Time History of Events and Macroscale Interactions during Substorms spacecraft during February–March 2009 frequently provide an opportunity to construct local data-adaptive magnetospheric models, which are suitable for the accurate mapping along the magnetic field lines at distances of 6–9 Re in the nightside magnetosphere. This allows us to map the isotropy boundaries (IBs of 30 and 80 keV protons observed by low-altitude NOAA POES (Polar Orbiting Environmental Satellites to the equatorial magnetosphere (to find the projected isotropy boundary, PIB and study the magnetospheric conditions, particularly to evaluate the ratio KIB (Rc/rc; the magnetic field curvature radius to the particle gyroradius in the neutral sheet at that point. Special care is taken to control the factors which influence the accuracy of the adaptive models and mapping. Data indicate that better accuracy of an adaptive model is achieved when the PIB distance from the closest spacecraft is as small as 1–2 Re. For this group of most accurate predictions, the spread of KIB values is still large (from 4 to 32, with the median value KIB ~13 being larger than the critical value Kcr ~ 8 expected at the inner boundary of nonadiabatic angular scattering in the current sheet. It appears that two different mechanisms may contribute to form the isotropy boundary. The group with K ~ [4,12] is most likely formed by current sheet scattering, whereas the group having KIB ~ [12,32] could be formed by the resonant scattering of low-energy protons by the electromagnetic ion-cyclotron (EMIC waves. The energy dependence of the upper K limit and close proximity of the latter event to the plasmapause locations support this conclusion. We also discuss other reasons why the K ~ 8 criterion for isotropization may fail to work, as well as a possible relationship between the two scattering mechanisms.

  18. Engineering activities on the ITER representative diagnostic equatorial port plug

    International Nuclear Information System (INIS)

    Meunier, L.; Doceul, L.; Salasca, S.; Martins, J.-P.; Jullien, F.; Dechelle, Christian; Bidaud, Pierre; Pilard, Vincent; Terra, Alexis; Ogea, Mathieu; Ciattaglia, Emanuela; Walker, Christopher

    2009-01-01

    Most of ITER diagnostic systems are integrated in port plugs, which are water cooled stainless steel structures inserted into the vacuum vessel ports. The port plug must provide basic functions such as neutron and gamma shielding, supporting the first wall armour (BSM), closing the vacuum vessel ports, while supporting the diagnostic equipments. ITER diagnostic port plug must resist a severe environment like high temperature due to neutron interaction with the structures and high electromechanical loading during disruptions events. CEA has contributed to the design and integration tasks in the frame of the representative equatorial port plug EQ no. 01, in particular on the engineering, structural and thermal finite element analysis. These detailed analyses have highlighted some design issues which were worked out through different solutions. This paper contains a description of the engineering activities performed such as: -The static mechanical calculations of the top plate closure system under disruption load. -The static mechanical calculations of the BSM attachment to the port plug. These two first studies led to design changes proposals which significantly improved the behaviour of the structures but also showed that the safety margin with respect to design limits is quite low. -The design of a Diagnostic Shield Module (DSM) integrated inside the port plug and a proposition of attachment scheme, with respect to disruption loads. The manufacturing of the DSM has been taken into account, as well as diagnostic integration inside the structure and maintenance aspects. -The thermal assessment of the port plug under neutronic load during normal operation, with the optimization of the cooling system. The maximum temperature calculated in normal operation has been reduced from 900 deg. C to less than 400 deg. C in the front plate; and the cooling arrangement at the back of the port plug has been simplified without important temperature increase.

  19. Engineering activities on the ITER representative diagnostic equatorial port plug

    Energy Technology Data Exchange (ETDEWEB)

    Meunier, L. [Association Euratom CEA, CEA/DSM/IRFM (France)], E-mail: lmeunier@cea.fr; Doceul, L.; Salasca, S.; Martins, J.-P.; Jullien, F.; Dechelle, Christian; Bidaud, Pierre; Pilard, Vincent; Terra, Alexis; Ogea, Mathieu [Association Euratom CEA, CEA/DSM/IRFM (France); Ciattaglia, Emanuela [EFDA CSU, Garching (Germany); Walker, Christopher [ITER International Organisation (France)

    2009-06-15

    Most of ITER diagnostic systems are integrated in port plugs, which are water cooled stainless steel structures inserted into the vacuum vessel ports. The port plug must provide basic functions such as neutron and gamma shielding, supporting the first wall armour (BSM), closing the vacuum vessel ports, while supporting the diagnostic equipments. ITER diagnostic port plug must resist a severe environment like high temperature due to neutron interaction with the structures and high electromechanical loading during disruptions events. CEA has contributed to the design and integration tasks in the frame of the representative equatorial port plug EQ no. 01, in particular on the engineering, structural and thermal finite element analysis. These detailed analyses have highlighted some design issues which were worked out through different solutions. This paper contains a description of the engineering activities performed such as: -The static mechanical calculations of the top plate closure system under disruption load. -The static mechanical calculations of the BSM attachment to the port plug. These two first studies led to design changes proposals which significantly improved the behaviour of the structures but also showed that the safety margin with respect to design limits is quite low. -The design of a Diagnostic Shield Module (DSM) integrated inside the port plug and a proposition of attachment scheme, with respect to disruption loads. The manufacturing of the DSM has been taken into account, as well as diagnostic integration inside the structure and maintenance aspects. -The thermal assessment of the port plug under neutronic load during normal operation, with the optimization of the cooling system. The maximum temperature calculated in normal operation has been reduced from 900 deg. C to less than 400 deg. C in the front plate; and the cooling arrangement at the back of the port plug has been simplified without important temperature increase.

  20. Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

    Science.gov (United States)

    Guo, H; Lee, S C; Louie, P K K; Ho, K F

    2004-12-01

    Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas

  1. Ligand-regulated peptide aptamers.

    Science.gov (United States)

    Miller, Russell A

    2009-01-01

    The peptide aptamer approach employs high-throughput selection to identify members of a randomized peptide library displayed from a scaffold protein by virtue of their interaction with a target molecule. Extending this approach, we have developed a peptide aptamer scaffold protein that can impart small-molecule control over the aptamer-target interaction. This ligand-regulated peptide (LiRP) scaffold, consisting of the protein domains FKBP12, FRB, and GST, binds to the cell-permeable small-molecule rapamycin and the binding of this molecule can prevent the interaction of the randomizable linker region connecting FKBP12 with FRB. Here we present a detailed protocol for the creation of a peptide aptamer plasmid library, selection of peptide aptamers using the LiRP scaffold in a yeast two-hybrid system, and the screening of those peptide aptamers for a ligand-regulated interaction.

  2. Ligand binding by PDZ domains

    DEFF Research Database (Denmark)

    Chi, Celestine N.; Bach, Anders; Strømgaard, Kristian

    2012-01-01

    , for example, are particularly rich in these domains. The general function of PDZ domains is to bring proteins together within the appropriate cellular compartment, thereby facilitating scaffolding, signaling, and trafficking events. The many functions of PDZ domains under normal physiological as well...... as pathological conditions have been reviewed recently. In this review, we focus on the molecular details of how PDZ domains bind their protein ligands and their potential as drug targets in this context....

  3. The Role of Reversed Equatorial Zonal Transport in Terminating an ENSO Event

    Science.gov (United States)

    Chen, H. C.; Hu, Z. Z.; Huang, B.; Sui, C. H.

    2016-02-01

    In this study, we demonstrate that a sudden reversal of anomalous equatorial zonal current at the peaking ENSO phase triggers the rapid termination of an ENSO event. Throughout an ENSO cycle, the anomalous equatorial zonal current is strongly controlled by the concavity of the anomalous thermocline meridional structure near the equator. During the ENSO developing phase, the anomalous zonal current in the central and eastern Pacific generally enhances the ENSO growth through its zonal SST advection. In the mature phase of ENSO, however, the equatorial thermocline depth anomalies are reflected in the eastern Pacific and slowly propagate westward off the equator in both hemispheres. As a result, the concavity of the thermocline anomalies near the equator is reversed, i.e., the off-equatorial thermocline depth anomalies become higher than that on the equator for El Niño events and lower for La Niño events. This meridional change of thermocline structure reverses zonal transport rapidly in the central-to-eastern equatorial Pacific, which weakens the ENSO SST anomalies by reversed advection. More importantly, the reversed zonal mass transport weakens the existing zonal tilting of equatorial thermocline and suppresses the thermocline feedback. Both processes are concentrated in the eastern equatorial Pacific and can be effective on subseasonal time scales. These current reversal effects are built-in to the ENSO peak phase and independent of the zonal wind effect on thermocline slope. It functions as an oceanic control on ENSO evolution during both El Niño and La Niña events.

  4. The role of the Indonesian Throughflow in equatorial Pacific thermocline ventilation

    Science.gov (United States)

    Rodgers, Keith B.; Cane, Mark A.; Naik, Naomi H.; Schrag, Daniel P.

    1999-09-01

    The role of the Indonesian Throughflow (ITF) in the thermocline circulation of the low-latitude Pacific Ocean is explored using a high-resolution primitive equation ocean circulation model. Seasonally forced runs for a domain with an open Indonesian passage are compared with seasonally forced runs for a closed Pacific domain. Three cases are considered: one with no throughflow, one with 10 Sv of imposed ITF transport, and one with 20 Sv of ITF transport. Two idealized tracers, one that tags northern component subtropical water and another that tags southern component subtropical water, are used to diagnose the mixing ratio of northern and southern component waters in the equatorial thermocline. It is found that the mixing ratio of north/south component waters in the equatorial thermocline is highly sensitive to whether the model accounts for an ITF. Without an ITF, the source of equatorial undercurrent water is primarily of North Pacific origin, with the ratio of northern to southern component water being approximately 2.75 to 1. The ratio of northern to southern component water in the Equatorial Undercurrent with 10 Sv of ITF is approximately 1.4 to 1, and the ratio with 20 Sv of imposed ITF is 1 to 1.25. Estimates from data suggest a mean mixing ratio of northern to southern component water of less than 1 to 1. Assuming that the mixing ratio changes approximately linearly as the ITF transport varies between 10 and 20 Sv, an approximate balance between northern and southern component water is reached when the ITF transport is approximately 16 Sv. It is also shown that for the isopycnal surfaces within the core of the equatorial undercurrent, a 2°C temperature front exists across the equator in the western equatorial Pacific, beneath the warm pool. The implications of the model results and the temperature data for the heat budget of the equatorial Pacific are considered.

  5. Multiple embryos, multiple nepionts and multiple equatorial layers in Cycloclypeus carpenteri.

    Science.gov (United States)

    Briguglio, Antonino; Kinoshita, Shunichi; Wolfgring, Erik; Hohenegger, Johann

    2016-04-01

    In this study, 17 specimens of Cycloclypeus carpenteri have been analyzed by means of microCT scanning. We used CT scanning technique as it enables the visualization and the quantifications of internal structures of hollow specimens without their destruction. It has been observed that many specimens possessing the natural morphology of this taxon, actually contain multiple embryos (up to 16 in one single specimen) and, in some few cases, multiple nepionts each with its own heterosteginid chambers (up to three separated nepionts). The diameter of each proloculus has been measured, and as a result, they are very variable even within the same specimen, therefore questioning the long known theory that schizonts have smaller proloculi than gamonts and also questioning the fact that proloculi in the same species should all have comparable size. Furthermore, we have observed the presence of additional equatorial planes on several specimens. Such additional planes are always connected to what seems to be the main equatorial plane. Such connections are T-shaped and are located at the junction between two equatorial layers; these junctions are made by a chamberlet, which possesses an unusually higher number of apertures. The connections between equatorial planes are always perfectly synchronized with the relative growth step and the same chamber can be therefore followed along the multiple equatorial planes. Apparently there is a perfect geometric relationship between the creation of additional equatorial planes and the position of the nepionts. Whenever the nepionts are positioned on different planes, additional planes are created and the angle of the nepionts is related to the banding angle of the equatorial planes. The presence of additional planes do not hamper the life of the cell, on the contrary, it seems that the cell is still able to build nicely shaped chamberlets and, after volumetric calculations, it seems all specimens managed to keep their logistic growth

  6. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    of orthosteric binding sites. Bitopic ligands have been employed to address the selectivity problem by combining (linking) an orthosteric ligand with an allosteric modulator, theoretically leading to high-affinity subtype selective ligands. However, it remains a challenge to identify suitable allosteric binding...... that have been reported to date, this type of bitopic ligands would be composed of two identical pharmacophores. Herein, we outline the concept of bitopic ligands, review metastable binding sites, and discuss their potential as a new source of allosteric binding sites....

  7. Radioiodinated ligands for dopamine receptors

    International Nuclear Information System (INIS)

    Kung, H.F.

    1994-01-01

    The dopamine receptor system is important for normal brain function; it is also the apparent action site for various neuroleptic drugs for the treatment of schizophrenia and other metal disorders. In the past few years radioiodinated ligands for single photon emission tomography (SPECT) have been successfully developed and tested in humans: [ 123 I]TISCH for D1 dopamine receptors; [ 123 I]IBZM, epidepride, IBF and FIDA2, four iodobenzamide derivatives, for D2/D3 dopamine receptors. In addition, [ 123 I]β-CIT (RTI-55) and IPT, cocaine derivatives, for the dopamine reuptake site are potentially useful for diagnosis of loss of dopamine neurons. The first iodinated ligand, (R)trans-7-OH-PIPAT, for D3 dopamine receptors, was synthesized and characterized with cloned cell lines (Spodoptera frugiperda, Sf9) expressing the D2 and D3 dopamine receptors and with rat basal forebrain membrane preparations. Most of the known iodobenzamides displayed similar potency in binding to both D2 and D3 dopamine receptors expressed in the cell lines. Initial studies appear to suggest that by fine tuning the structures it may be possible to develop agents specific for D2 and D3 dopamine receptors. It is important to investigate D2/D3 selectivity for this series of potent ligands

  8. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    DEFF Research Database (Denmark)

    Dimitrovski, Darko; Abu-Samha, Mahmoud; Madsen, Lars Bojer

    2011-01-01

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molec......We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction......-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron...

  9. Influence of gamma radiation reaction on the hydroesterification of butenes catalyzed by metal carbonyls

    International Nuclear Information System (INIS)

    Velde, J. van der.

    1976-01-01

    In the hydro carboxylation reaction, which first has been studied by Reppe, olefine and acetylene compounds are processed with carbon monoxide and water at high pressures and high temperatures in the presence of metal carbonyls. This reaction can be enhanced considerably by application of ionizing radiation. Lower pressures and in particular lower temperatures can be used if gamma irradiation is performed during carboxylation. For the experiments a mixture of buten-1 and buten-2 as well as pure buten-1 and pure buten-2 has been used to study the behaviour of these olefines with respect to the isomerization of the reaction products and to the olefines not transformed in the reaction process. Replacing water, methanol has been used as a reaction component, thus obtaining directly the respective carbonyl acid esters, which can be analysed quantitatively and qualitatively with respect to their isomeric composition by gaschromatography. (orig./HK) [de

  10. Spectroscopic and theoretical studies on the aromaticity of pyrrol-2-yl-carbonyl conformers

    Science.gov (United States)

    Dubis, Alina T.; Wojtulewski, Sławomir; Filipkowski, Karol

    2013-06-01

    The aromaticity of s-cis and s-trans pyrrol-2-yl carbonyl conformers was studied by FT-IR, 1H NMR spectroscopy and DFT calculations at the B3LYP/6-311++G(d,p) level of theory. The Harmonic Oscillator Model of Aromaticity (HOMA) and Nucleus Independent Chemical Shift (NICS) indices were calculated to estimate π-electron delocalization in the pyrrole ring. The usefulness of infrared spectroscopy in the evaluation of the aromaticity of the homogeneous set of pyrroles is discussed. The influence of 2-substitution on different aspects of aromaticity and stability of the pyrrol-2-yl carbonyl conformers is also discussed. It is concluded that the substitution effect of the title pyrrole derivatives can be explained on the basis of theoretical and experimental measurements of π-electron delocalization, including IR data.

  11. Contribution to radiation-chemically catalyzed hydroformylation of butenes in the presence of metal carbonyls

    International Nuclear Information System (INIS)

    Joosten, L.

    1976-01-01

    In this paper a study is presented of the influence of gamma-radiation on the catalytic hydroformylation of olefines. As model olefines buten-1 and buten-2 as well as their mixtures have been used together with the catalysts di-cobalt octacarbonyle and rhodium (I) tristri phenyl-phosphine carbonyle hydride. In addition the catalytic activity of the VI. side group carbonyles Cr(CO) 6 , Mo(CO) 6 and W(CO) 6 has been studied under radiation chemical conditions. For this purpose a mixture of olefine, solvent (cyclo hexane) and calalyst has been pressurized and processed in a mixing autoklave together with a Co and H 2 (1:1) mixture, variing the reaction variables within certain limits. (orig.) [de

  12. Age-related carbonylation of fibrocartilage structural proteins drives tissue degenerative modification.

    Science.gov (United States)

    Scharf, Brian; Clement, Cristina C; Yodmuang, Supansa; Urbanska, Aleksandra M; Suadicani, Sylvia O; Aphkhazava, David; Thi, Mia M; Perino, Giorgio; Hardin, John A; Cobelli, Neil; Vunjak-Novakovic, Gordana; Santambrogio, Laura

    2013-07-25

    Aging-related oxidative stress has been linked to degenerative modifications in different organs and tissues. Using redox proteomic analysis and illustrative tandem mass spectrometry mapping, we demonstrate oxidative posttranslational modifications in structural proteins of intervertebral discs (IVDs) isolated from aging mice. Increased protein carbonylation was associated with protein fragmentation and aggregation. Complementing these findings, a significant loss of elasticity and increased stiffness was measured in fibrocartilage from aging mice. Studies using circular dichroism and intrinsic tryptophan fluorescence revealed a significant loss of secondary and tertiary structures of purified collagens following oxidation. Collagen unfolding and oxidation promoted both nonenzymatic and enzymatic degradation. Importantly, induction of oxidative modification in healthy fibrocartilage recapitulated the biochemical and biophysical modifications observed in the aging IVD. Together, these results suggest that protein carbonylation, glycation, and lipoxidation could be early events in promoting IVD degenerative changes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing

    2010-10-12

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested to determine the influence of CI concentration. The magnetic and mechanical properties of the magnetic elastomers were characterized, respectively, by vibrating-sample magnetometer and by tensile testing using a mechanical analyzer. The elastomer was found to exhibit high magnetization and good mechanical flexibility. The morphology and deformation of the CI-PDMS membrane also were observed. A magnetically actuated microfluidic mixer (that is, a micromixer) integrated with CI-PDMS elastomer membranes was successfully designed and fabricated. The high efficiency and quality of the mixing makes possible the impressive potential applications of this unique CI-PDMS material in microfluidic systems. © Springer-Verlag 2010.

  14. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

    2012-11-15

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

  15. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    International Nuclear Information System (INIS)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

    2012-01-01

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

  16. Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyltrimethylsilane and triphenylphosphine

    Directory of Open Access Journals (Sweden)

    Fei Wang

    2014-02-01

    Full Text Available Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods.Results: The combination of (chlorodifluoromethyltrimethylsilane (TMSCF2Cl and triphenylphosphine (PPh3 can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyltrimethylsilane (TMSCF2Br and (trifluoromethyltrimethylsilane (TMSCF3 in this reaction.Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.

  17. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  18. Analysis of protein carbonylation - pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, A.; Wojdyla, K.; Nedic, O.

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  19. Analysis of protein carbonylation-pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, Adelina; Wojdyla, K; Nedić, O

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  20. No iron fertilization in the equatorial Pacific Ocean during the last ice age.

    Science.gov (United States)

    Costa, K M; McManus, J F; Anderson, R F; Ren, H; Sigman, D M; Winckler, G; Fleisher, M Q; Marcantonio, F; Ravelo, A C

    2016-01-28

    The equatorial Pacific Ocean is one of the major high-nutrient, low-chlorophyll regions in the global ocean. In such regions, the consumption of the available macro-nutrients such as nitrate and phosphate is thought to be limited in part by the low abundance of the critical micro-nutrient iron. Greater atmospheric dust deposition could have fertilized the equatorial Pacific with iron during the last ice age--the Last Glacial Period (LGP)--but the effect of increased ice-age dust fluxes on primary productivity in the equatorial Pacific remains uncertain. Here we present meridional transects of dust (derived from the (232)Th proxy), phytoplankton productivity (using opal, (231)Pa/(230)Th and excess Ba), and the degree of nitrate consumption (using foraminifera-bound δ(15)N) from six cores in the central equatorial Pacific for the Holocene (0-10,000 years ago) and the LGP (17,000-27,000 years ago). We find that, although dust deposition in the central equatorial Pacific was two to three times greater in the LGP than in the Holocene, productivity was the same or lower, and the degree of nitrate consumption was the same. These biogeochemical findings suggest that the relatively greater ice-age dust fluxes were not large enough to provide substantial iron fertilization to the central equatorial Pacific. This may have been because the absolute rate of dust deposition in the LGP (although greater than the Holocene rate) was very low. The lower productivity coupled with unchanged nitrate consumption suggests that the subsurface major nutrient concentrations were lower in the central equatorial Pacific during the LGP. As these nutrients are today dominantly sourced from the Subantarctic Zone of the Southern Ocean, we propose that the central equatorial Pacific data are consistent with more nutrient consumption in the Subantarctic Zone, possibly owing to iron fertilization as a result of higher absolute dust fluxes in this region. Thus, ice-age iron fertilization in the

  1. Novel Routes to Ethylene Glycol Synthesis via Acid-Catalyzed Carbonylation of Formaldehyde and Dimethoxymethane

    OpenAIRE

    Celik, Fuat Emin

    2010-01-01

    Carbon-carbon bond forming carbonylation reactions were investigated as candidates to replace ethene epoxidation as the major source of ethylene glycol production. This work was motivated by the potentially lower cost of carbon derived from synthesis gas as compared to ethylene. Synthesis gas can be produced from relatively abundant and cheap natural gas, coal, and biomass resources whereas ethylene is derived from increasingly scarce and expensive crude oil. From synthesis gas, a range of...

  2. Characterization of Carbonyl Compounds in the Ambient Air of an Industrial City in Korea

    Directory of Open Access Journals (Sweden)

    Sung-Ok Baek

    2011-01-01

    Full Text Available The purpose of this study was to characterize spatial and temporal variations of carbonyl compounds in Gumi city, where a number of large electronic-industrial complexes are located. Carbonyl samples were collected at five sites in the Gumi area: three industrial, one commercial, and one residential area. Sampling was carried out throughout a year from December 2003 to November 2004. At one industrial site, samples were taken every six days, while those of the other sites were for seven consecutive days in every season. Each sample was collected for 150 minutes and at intervals of three times a day (morning, afternoon, and evening. A total of 476 samples were analyzed to determine 15 carbonyl compounds by the USEPA TO-11A (DNPH-cartridge/HPLC method. In general, acetaldehyde appeared to be the most abundant compound, followed by formaldehyde, and acetone+acrolein. Mean concentrations of acetaldehyde were two to three times higher in the industrial sites than in the other sites, with its maximum of 77.7 ppb. In contrast, ambient levels of formaldehyde did not show any significant difference between the industrial and non-industrial groups. Its concentrations peaked in summer probably due to the enhanced volatilization and photochemical reactivity. These results indicate significant emission sources of acetaldehyde in the Gumi industrial complexes. Mean concentrations of organic solvents (such as acetone+acrolein and methyl ethyl ketone were also significantly high in industrial areas. In conclusion, major sources of carbonyl compounds, including acetaldehyde, are strongly associated with industrial activities in the Gumi city area.

  3. Carbonylative Heck Reactions Using CO Generated ex Situ in a Two-Chamber System

    DEFF Research Database (Denmark)

    Hermange, Philippe; Gøgsig, Thomas; Lindhardt, Anders Thyboe

    2011-01-01

    A carbonylative Heck reaction of aryl iodides and styrene derivatives employing a two-chamber system using a stable, crystalline, and nontransition metal based carbon monoxide source is reported. By applying near-stoichiometric amounts of the carbon monoxide precursor, an effective exploitation o...... of the hazardous CO gas is obtained affording chalcone derivatives in good yields. Application to isotope labeling, incorporating 13CO, was further established....

  4. The magnetorheological fluid of carbonyl iron suspension blended with grafted MWCNT or graphene

    Science.gov (United States)

    Rwei, Syang-Peng; Ranganathan, Palraj; Chiang, Whe-Yi; Wang, Tza-Yi

    2017-12-01

    In this work, the magnetorheological (MR) fluids containing MWCNT/CI (carbonyl iron) complex and graphene/CI complex were prepared and have the better dispersity in silicone oil than CI powders alone. 1, 4-Aminobenzoic acid (PABA) was used as a grafting agent to modify CI powders to have NH2-end-group so that such nanoparticles can adsorb to acid-treated MWCNT or graphene via attraction of NH2 and COOH groups. The MWCNT/CI complex and graphene/CI complex have a structure of carbonyl iron nanoparticles adsorbed to MWCNT and graphene by self assembly, respectively. Because the carbonyl iron particles possessing magnetic permeability in nanometer scale adsorb to MWCNT or graphene which usually has a nanometer-scaled diameter and a micrometer-scaled length in this work, the dispersity of MWCNT/CI or graphene/CI complex in silicone oil is superior than the previous report [15] that the micrometer-scaled carbonyl iron microspheres were coated with multiwalled carbon nanotubes. Among CI (unmodified), MWCNT/CI and graphene/CI, graphene/CI has the best dispersity while MWCNT/CI still has the better dispersity than unmodified CI. At the temperature T = 300 K, the saturation magnetizations of CI, MWCNT/CI, graphene/CI are 208, 211 emu/g, and 204 emu/g, respectively, indicating that MWCNT/CI complex and graphene/CI complex still maintain the saturation magnetization as high as CI without being interfered by the blended MWCNT or graphene. A wide dynamic range of the yield stress adjusted through varying the electric current can be achieved by the MR fluids containing 69 wt% MWCNT/CI and graphene/CI which is useful in a shock absorber or damper. The result of the yield stress indicates the suspended MWCNT/CI particles are oriented more easily toward the direction perpendicular to the flow direction to block the flow stream lines.

  5. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    OpenAIRE

    Worawan Bhanthumnavin; Tirayut Vilaivan

    2010-01-01

    Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects ...

  6. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    Czech Academy of Sciences Publication Activity Database

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, Petra; Filip, Petr; Vesel, A.

    2011-01-01

    Roč. 387, 1-3 (2011), s. 99-103 ISSN 0927-7757 Grant - others:GA ČR(CZ) GD104/09/H080; OP VaVpI(XE) CZ.1.05/2.1.00/03.0111 Program:GD Institutional research plan: CEZ:AV0Z20600510 Keywords : carbonyl iron * magnetorheological fluid * plasma * viscoelasticity Subject RIV: BK - Fluid Dynamics Impact factor: 2.236, year: 2011

  7. Guest investigator program study: Physics of equatorial plasma bubbles

    Science.gov (United States)

    Tsunoda, Roland T.

    1994-01-01

    Plasma bubbles are large-scale (10 to 100 km) depletions in plasma density found in the night-time equatorial ionosphere. Their formation has been found to entail the upward transport of plasma over hundreds of kilometers in altitude, suggesting that bubbles play significant roles in the physics of many of the diverse and unique features found in the low-latitude ionosphere. In the simplest scenario, plasma bubbles appear first as perturbations in the bottomside F layer, which is linearly unstable to the gravitationally driven Rayleigh-Taylor instability. Once initiated, bubbles develop upward through the peak of the F layer into its topside (sometimes to altitudes in excess of 1000 km), a behavior predicted by the nonlinear form of the same instability. While good general agreement has been found between theory and observations, little is known about the detailed physics associated with plasma bubbles. Our research activity centered around two topics: the shape of plasma bubbles and associated electric fields, and the day-to-day variability in the occurrence of plasma bubbles. The first topic was pursued because of a divergence in view regarding the nonlinear physics associated with plasma bubble development. While the development of perturbations in isodensity contours in the bottomside F layer into plasma bubbles is well accepted, some believed bubbles to be cylinder-like closed regions of depleted plasma density that floated upward leaving a turbulent wake behind them (e.g., Woodman and LaHoz, 1976; Ott, 1978; Kelley and Ott, 1978). Our results, summarized in a paper submitted to the Journal of Geophysical Research, consisted of incoherent scatter radar measurements that showed unambiguously that the depleted region is wedgelike and not cylinderlike, and a case study and modeling of SM-D electric field instrument (EFI) measurements that showed that the absence of electric-field perturbations outside the plasma-depleted region is a distinct signature of wedge

  8. Reflection of equatorial Kelvin waves at eastern ocean boundaries Part I: hypothetical boundaries

    Directory of Open Access Journals (Sweden)

    J. Soares

    1999-06-01

    Full Text Available A baroclinic shallow-water model is developed to investigate the effect of the orientation of the eastern ocean boundary on the behavior of equatorial Kelvin waves. The model is formulated in a spherical polar coordinate system and includes dissipation and non-linear terms, effects which have not been previously included in analytical approaches to the problem. Both equatorial and middle latitude response are considered given the large latitudinal extent used in the model. Baroclinic equatorial Kelvin waves of intraseasonal, seasonal and annual periods are introduced into the domain as pulses of finite width. Their subsequent reflection, transmission and dissipation are investigated. It is found that dissipation is very important for the transmission of wave energy along the boundary and for reflections from the boundary. The dissipation was found to be dependent not only on the presence of the coastal Kelvin waves in the domain, but also on the period of these coastal waves. In particular the dissipation increases with wave period. It is also shown that the equatorial β-plane approximation can allow an anomalous generation of Rossby waves at higher latitudes. Nonlinearities generally have a small effect on the solutions, within the confines of this model.Key words. Oceanography: general (equatorial oceanography; numerical modeling · Oceanography: physical (eastern boundary currents

  9. Expression, purification, crystallization and preliminary X-ray diffraction analysis of carbonyl reductase from Candida parapsilosis ATCC 7330

    International Nuclear Information System (INIS)

    Aggarwal, Nidhi; Mandal, P. K.; Gautham, Namasivayam; Chadha, Anju

    2013-01-01

    The expression, purification, crystallization, preliminary X-ray diffraction and molecular-replacement studies on C. parapsilosis carbonyl reductase are reported. The NAD(P)H-dependent carbonyl reductase from Candida parapsilosis ATCC 7330 catalyses the asymmetric reduction of ethyl 4-phenyl-2-oxobutanoate to ethyl (R)-4-phenyl-2-hydroxybutanoate, a precursor of angiotensin-converting enzyme inhibitors such as Cilazapril and Benazepril. The carbonyl reductase was expressed in Escherichia coli and purified by GST-affinity and size-exclusion chromatography. Crystals were obtained by the hanging-drop vapour-diffusion method and diffracted to 1.86 Å resolution. The asymmetric unit contained two molecules of carbonyl reductase, with a solvent content of 48%. The structure was solved by molecular replacement using cinnamyl alcohol dehydrogenase from Saccharomyces cerevisiae as a search model

  10. Molybdenum-95 nuclear magnetic resonance of a series of phosphine and phosphite substituted molybdenum carbonyls Mo(CO)sub(6-n)Lsub(n)(n = 1,2,3,4,5)

    International Nuclear Information System (INIS)

    Jaitner, P.; Wohlgenannt, W.

    1982-01-01

    Molybdenum-95 NMR spectra of a series of phosphine and phosphite substituted molybdenum carbonyls Mo(CO)sub(6-n)Lsub(n)n[L = P(OCH 3 ) 3 n = 1,2,3,4,5, L = P(OC 2 H 5 ) 3 n = 1,2,3, L = P(C 6 H 5 ) 3 n = 1] including isomers (cis, trans, fac, mer) are reported. A large range of chemical shifts is found for the title compounds. The coupling constants 1 J( 95 Mo- 31 P) are derived either from 95 Mo-NMR spectra or 31 P-NMR spectra. Syntheses of the measured compounds were performed by thermal or photochemical ligand sustitution. (Author)

  11. Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, B; Scurrell, M S

    1977-01-01

    Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols with carbon monoxide in the presence of the corresponding alkyl iodides as promotors was studied in a glass reactor at approx. 0.05:1 alcohol/carbon monoxide ratio. The 1% by wt rhodium-zeolite catalyst was prepared by immersing a Linde molecular sieve zeolite Type 13X in rhodium trichloride at 80/sup 0/C for 15 hr. Methanol was converted to methyl acetate at 433/sup 0/-513/sup 0/K with selectivites > 90% even at the highest temperatures, and dimethyl ether was by-produced. In the absence of methyl iodide, the carbonylation rate decreased drastically but the dehydration was virtually unaffected. The selectivity for ethanol carbonylation decreased from 99% at 383/sup 0/K to 6% at 523/sup 0/K due to the formation of ethylene (predominant at > 470/sup 0/K) and diethyl ether. The only product of the reaction with propan-2-ol studied at 433/sup 0/ or 473/sup 0/K was propene with 100% conversion at 473/sup 0/K. These results are consistent with the relative ease of reactant dehydration on polar catalysts. Table and 13 references.

  12. Catalytic performance of heterogeneous Rh/C3N4 for the carbonylation of methanol

    Science.gov (United States)

    Budiman, Anatta Wahyu; Choi, Myoung Jae; Nur, Adrian

    2018-02-01

    The excess of water in homogeneous the carbonylation of methanol system could increase the amount of by-products formed through water-gas shift reaction and could accelerate the rusting of equipment. Many scientists tried to decrease the content of water in the carbonylation of methanol system by using lithium and iodide promoter that results a moderate catalytic activity in the water content at 2wt%. The heterogenized catalyst offers several distinct advantages such as it was enables increased catalyst concentration in the reaction mixture, which is directly proportional to acetic acid production rate, without the addition of an alkali iodide salt promoter. The heterogeneous catalyst also results in reduced by-product formation. This study is aimed to produce a novel catalyst (Rh/C3N4) with a high selectivity of acetic acid in a relatively lower water and halide content. This novel catalyst performs high conversion and selectivity of acetic acid as the result of the strong ionic bonding of melamine and rhodium complex species that was caused by the presence of methyl iodide species. The CO2 in feed gas significantly decreases the catalytic activity of Rh-melamine because of its inert characteristics. The kinetic test was performed as that the first order kinetic equation. The kinetic tests revealed the reaction route of the the carbonylation of methanol in this system was performed trough the methyl acetate.

  13. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    International Nuclear Information System (INIS)

    Shikada, T.; Fujimoto, K.; Tominaga, H.O.

    1986-01-01

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (175 0 C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac 2 O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  14. Gas chromatographic analysis of reactive carbonyl compounds formed from lipids upon UV-irradiation

    International Nuclear Information System (INIS)

    Dennis, K.J.; Shibamoto, T.

    1990-01-01

    Peroxidation of lipids produces carbonyl compounds; some of these, e.g., malonaldehyde and 4-hydroxynonenal, are genotoxic because of their reactivity with biological nucleophiles. Analysis of the reactive carbonyl compounds is often difficult. The methylhydrazine method developed for malonaldehyde analysis was applied to simultaneously measure the products formed from linoleic acid, linolenic acid, arachidonic acid, and squalene upon ultraviolet-irradiation (UV-irradiation). The photoreaction products, saturated monocarbonyl, alpha,beta-unsaturated carbonyls, and beta-dicarbonyls, were derivatized with methylhydrazine to give hydrazones, pyrazolines, and pyrazoles, respectively. The derivatives were analyzed by gas chromatography and gas chromatography-mass spectrometry. Lipid peroxidation products identified included formaldehyde, acetaldehyde, acrolein, malonaldehyde, n-hexanal, and 4-hydroxy-2-nonenal. Malonaldehyde levels formed upon 4 hr of irradiation were 0.06 micrograms/mg from squalene, 2.4 micrograms/mg from linolenic acid, and 5.7 micrograms/mg from arachidonic acid. Significant levels of acrolein (2.5 micrograms/mg) and 4-hydroxy-2-nonenal (0.17 micrograms/mg) were also produced from arachidonic acid upon 4 hr irradiation

  15. A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

    Science.gov (United States)

    Regazzoni, Luca; de Courten, Barbora; Garzon, Davide; Altomare, Alessandra; Marinello, Cristina; Jakubova, Michaela; Vallova, Silvia; Krumpolec, Patrik; Carini, Marina; Ukropec, Jozef; Ukropcova, Barbara; Aldini, Giancarlo

    2016-06-01

    Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, which is one of the most toxic and reactive compounds among reactive carbonyl species. However, neither carnosine nor adducts have been detected in plasma. Urinary excretion of adducts and carnosine showed a positive correlation although a high variability of individual response to carnosine supplementation was observed. Interestingly, treated subjects showed a significant decrease in the percentage of excreted adducts in reduced form, accompanied by a significant increase of the urinary excretion of both carnosine and carnosine-acrolein adducts. Altogether, data suggest that acrolein is entrapped in vivo by carnosine although the response to its supplementation is possibly influenced by individual diversities in terms of carnosine dietary intake, metabolism and basal production of reactive carbonyl species.

  16. Nitrite promotes protein carbonylation and Strecker aldehyde formation in experimental fermented sausages: are both events connected?

    Science.gov (United States)

    Villaverde, A; Ventanas, J; Estévez, M

    2014-12-01

    The role played by curing agents (nitrite, ascorbate) on protein oxidation and Strecker aldehyde formation is studied. To fulfill this objective, increasing concentrations of nitrite (0, 75 and 150ppm) and ascorbate (0, 250 and 500ppm) were added to sausages subjected to a 54day drying process. The concurrence of intense proteolysis, protein carbonylation and formation of Strecker aldehydes during processing of sausages suggests that α-aminoadipic semialdehyde (AAS) and γ-glutamic semialdehyde (GGS) may be implicated in the formation of Strecker aldehydes. The fact that nitrite (150ppm, ingoing amount) significantly promoted the formation of protein carbonyls at early stages of processing and the subsequent formation of Strecker aldehydes provides strength to this hypothesis. Ascorbate (125 and 250ppm) controlled the overall extent of protein carbonylation in sausages without declining the formation of Strecker aldehydes. These results may contribute to understanding the chemistry fundamentals of the positive influence of nitrite on the flavor and overall acceptability of cured muscle foods. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Seasonal behavior of carbonyls and source characterization of formaldehyde (HCHO) in ambient air

    Science.gov (United States)

    Lui, K. H.; Ho, Steven Sai Hang; Louie, Peter K. K.; Chan, C. S.; Lee, S. C.; Hu, Di; Chan, P. W.; Lee, Jeffrey Chi Wai; Ho, K. F.

    2017-03-01

    Gas-phase formaldehyde (HCHO) is an intermediate and a sensitive indicator for volatile organic compounds (VOCs) oxidation, which drives tropospheric ozone production. Effective photochemical pollution control strategies demand a thorough understanding of photochemical oxidation precursors, making differentiation between sources of primary and secondary generated HCHO inevitable. Spatial and seasonal variations of airborne carbonyls based on two years of measurements (2012-2013), coupled with a correlation-based HCHO source apportionment analysis, were determined for three sampling locations in Hong Kong (denoted HT, TC, and YL). Formaldehyde and acetaldehyde were the two most abundant compounds of the total quantified carbonyls. Pearson's correlation analysis (r > 0.7) implies that formaldehyde and acetaldehyde possibly share similar sources. The total carbonyl concentration trends (HT rural). A regression analysis further quantifies the relative primary HCHO source contributions at HT (∼13%), TC (∼21%), and YL (∼40%), showing more direct vehicular emissions in urban than rural areas. Relative secondary source contributions at YL (∼36%) and TC (∼31%) resemble each other, implying similar urban source contributions. Relative background source contributions at TC could be due to a closed structure microenvironment that favors the trapping of HCHO. Comparable seasonal differences are observed at all stations. The results of this study will aid in the development of a new regional ozone (O3) control policy, as ambient HCHO can enhance O3 production and also be produced from atmospheric VOCs oxidation (secondary HCHO).

  18. Role of Protein Carbonylation in Skeletal Muscle Mass Loss Associated with Chronic Conditions

    Directory of Open Access Journals (Sweden)

    Esther Barreiro

    2016-05-01

    Full Text Available Muscle dysfunction, characterized by a reductive remodeling of muscle fibers, is a common systemic manifestation in highly prevalent conditions such as chronic heart failure (CHF, chronic obstructive pulmonary disease (COPD, cancer cachexia, and critically ill patients. Skeletal muscle dysfunction and impaired muscle mass may predict morbidity and mortality in patients with chronic diseases, regardless of the underlying condition. High levels of oxidants may alter function and structure of key cellular molecules such as proteins, DNA, and lipids, leading to cellular injury and death. Protein oxidation including protein carbonylation was demonstrated to modify enzyme activity and DNA binding of transcription factors, while also rendering proteins more prone to proteolytic degradation. Given the relevance of protein oxidation in the pathophysiology of many chronic conditions and their comorbidities, the current review focuses on the analysis of different studies in which the biological and clinical significance of the modifications induced by reactive carbonyls on proteins have been explored so far in skeletal muscles of patients and animal models of chronic conditions such as COPD, disuse muscle atrophy, cancer cachexia, sepsis, and physiological aging. Future research will elucidate the specific impact and sites of reactive carbonyls on muscle protein content and function in human conditions.

  19. Carbonyl compounds and PAH emissions from CNG heavy-duty engine

    International Nuclear Information System (INIS)

    Gambino, M.; Cericola, R.; Corbo, P.; Iannaccone, S.

    1993-01-01

    Previous works carried out in Istituto Motori laboratories have shown that natural gas is a suitable fuel for general means of transportation. This is because of its favorable effects on engine performance and pollutant emissions. The natural gas fueled engine provided the same performance as the diesel engine, met R49 emission standards, and showed very low smoke levels. On the other hand, it is well known that internal combustion engines emit some components that are harmful for human health, such as carbonyl compounds and polycyclic aromatic hydrocarbons (PAH). This paper shows the results of carbonyl compounds and PAH emissions analysis for a heavy-duty Otto cycle engine fueled with natural gas. The engine was tested using the R49 cycle that is used to measure the regulated emissions. The test analysis has been compared with an analysis of a diesel engine, tested under the same conditions. Total PAH emissions from the CNG engine were about three orders of magnitude lower than from the diesel engine. Formaldehyde emission from the CNG engine was about ten times as much as from the diesel engine, while emissions of other carbonyl compounds were comparable

  20. Effect of fiber material on ozone removal and carbonyl production from carpets

    Science.gov (United States)

    Abbass, Omed A.; Sailor, David J.; Gall, Elliott T.

    2017-01-01

    Indoor air quality is affected by indoor materials such as carpets that may act as sources and/or sinks of gas-phase air pollutants. Heterogeneous reactions of ozone with carpets may result in potentially harmful products. In this study, indoor residential carpets of varying fiber types were tested to evaluate their ability to remove ozone, and to assess their role in the production of carbonyls when exposed to elevated levels of ozone. Tests were conducted with six types of new unused carpets. Two sets of experiments were conducted, the first measured ozone removal and ozone deposition velocities, and the second measured primary carbonyl production and secondary production as a result of exposure to ozone. The tests were conducted using glass chambers with volume of 52 L each. Air exchange rates for all tests were 3 h-1. The ozone removal tests show that, for the conditions tested, the polyester carpet sample had the lowest ozone removal (40%), while wool carpet had the greatest ozone removal (65%). Most carpet samples showed higher secondary than primary carbonyl emissions, with carpets containing polypropylene fibers being a notable exception. Carpets with polyester fibers had both the highest primary and secondary emissions of formaldehyde among all samples tested. While it is difficult to make blanket conclusions about the relative air quality merits of various carpet fiber options, it is clear that ozone removal percentages and emissions of volatile organic compounds can vary drastically as a function of fiber type.

  1. Excited state characterization of carbonyl containing carotenoids: a comparison between single and multireference descriptions

    Science.gov (United States)

    Spezia, Riccardo; Knecht, Stefan; Mennucci, Benedetta

    Carotenoids can play multiple roles in biological photoreceptors thanks to their rich photophysics. In the present work, we have investigated six of the most common carbonyl containing carotenoids: Echinenone, Canthaxanthin, Astaxanthin, Fucoxanthin, Capsanthin and Capsorubin. Their excitation properties are investigated by means of a hybrid density functional theory (DFT) and multireference configuration interaction (MRCI) approach to elucidate the role of the carbonyl group: the bright transition is of {\\pi}{\\pi}* character, as expected, but the presence of a C=O moiety reduces the energy of n{\\pi}* transitions which may become closer to the {\\pi}{\\pi}* transition, in particular as the conjugation chain decreases. This can be related to the presence of a low-lying charge transfer state typical of short carbonyl- containing carotenoids. The DFT/MRCI results are finally used to benchmark single- reference time-dependent DFT-based methods: among the investigated functionals, the meta- GGA (and in particular M11L and MN12L) functionals show to perform the best for all six investigated systems.

  2. Dormancy alleviation by NO or HCN leading to decline of protein carbonylation levels in apple (Malus domestica Borkh.) embryos.

    Science.gov (United States)

    Krasuska, Urszula; Ciacka, Katarzyna; Dębska, Karolina; Bogatek, Renata; Gniazdowska, Agnieszka

    2014-08-15

    Deep dormancy of apple (Malus domestica Borkh.) embryos can be overcome by short-term pre-treatment with nitric oxide (NO) or hydrogen cyanide (HCN). Dormancy alleviation of embryos modulated by NO or HCN and the first step of germination depend on temporary increased production of reactive oxygen species (ROS). Direct oxidative attack on some amino acid residues or secondary reactions via reactive carbohydrates and lipids can lead to the formation of protein carbonyl derivatives. Protein carbonylation is a widely accepted covalent and irreversible modification resulting in inhibition or alteration of enzyme/protein activities. It also increases the susceptibility of proteins to proteolytic degradation. The aim of this work was to investigate protein carbonylation in germinating apple embryos, the dormancy of which was removed by pre-treatment with NO or HCN donors. It was performed using a quantitative spectrophotometric method, while patterns of carbonylated protein in embryo axes were analyzed by immunochemical techniques. The highest concentration of protein carbonyl groups was observed in dormant embryos. It declined in germinating embryos pre-treated with NO or HCN, suggesting elevated degradation of modified proteins during seedling formation. A decrease in the concentration of carbonylated proteins was accompanied by modification in proteolytic activity in germinating apple embryos. A strict correlation between the level of protein carbonyl groups and cotyledon growth and greening was detected. Moreover, direct in vitro carbonylation of BSA treated with NO or HCN donors was analyzed, showing action of both signaling molecules as protein oxidation agents. Copyright © 2014 Elsevier GmbH. All rights reserved.

  3. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kazuhiko, E-mail: takedaq@hiroshima-u.ac.jp [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Katoh, Shinya; Mitsui, Yumi; Nakano, Shinichi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Nakatani, Nobutake [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Department of Environmental and Symbiotic Sciences, Rakuno Gakuen University, 582 Bunkyodai-Midorimachi, Ebetsu, Hokkaido 069-8501 (Japan); Sakugawa, Hiroshi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan)

    2014-09-15

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area.

  4. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    International Nuclear Information System (INIS)

    Takeda, Kazuhiko; Katoh, Shinya; Mitsui, Yumi; Nakano, Shinichi; Nakatani, Nobutake; Sakugawa, Hiroshi

    2014-01-01

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area

  5. Synthesis of a Bis(thiophenolate)pyridine Ligand and Its Titanium, Zirconium, and Tantalum Complexes

    KAUST Repository

    Lenton, Taylor N.

    2012-11-12

    A precursor to a new tridentate LX 2 type ligand, bis(thiophenol)pyridine ((SNS)H 2 = (2-C 6H 4SH) 2-2,6-C 5H 3N), was prepared. Bis(thiophenolate)pyridine complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex (SNS)Zr(NMe 2) 2 (4) displays C 2 symmetry in the solid state, unlike a related bis(phenolate)pyridine compound, C s-symmetric (ONO)Ti(NMe 2) 2. This change is likely the result of strain about the sulfur atom in the six-membered chelate with longer metal-sulfur and carbon-sulfur bonds. Solid-state structures of tantalum complexes (SNS)Ta(NMe 2) 3 (5) and (SNS)TaCl(NEt 2) 2 (6) also display pronounced C 2 twisting of the SNS ligand. 1D and 2D NMR experiments show that 5 is fluxional, with rotation about the Ta-N(amide) bonds occurring on the NMR time scale that interchange the equatorial amide methyl groups (ΔG ‡ 393 = 25.0(3) kcal/mol). The fluxional behavior of 6 in solution was also studied by variable-temperature 1H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR time scale in one diastereomeric conformation at temperatures below -50 °C, fast rotation about the equatorial amide Ta-N bonds occurs at higher temperature (ΔG ‡ 393 = 13.4(3) kcal/mol), and exchange of diastereomeric methylene protons occurs via inversion at Ta that interconverts antipodes (ΔG ‡ 393 ≈ 14(1) kcal/mol). © 2012 American Chemical Society.

  6. Time and dose effects of cigarette smoke and acrolein on protein carbonyl formation in HaCaT keratinocytes.

    Science.gov (United States)

    Avezov, K; Reznick, A Z; Aizenbud, D

    2015-01-01

    Cigarette smoke (CS) is an important environmental source of human exposure to a highly toxic and chemically active α,β-unsaturated aldehyde: acrolein. It is capable of causing protein carbonylation and dysfunction, especially in oral tissues of smokers, constantly exposed to CS toxic constituents. The foremost damage is considered to be cumulative, but even a short exposure can be potentially harmful. The objectives of the current study were to examine the short time and dose effects of direct CS and acrolein exposure on intracellular protein carbonylation in epithelial cells. HaCaT-keratinocytes were exposed to different doses of acrolein and whole phase CS using a unique smoking simulator apparatus that mimics the exposure in smokers. The rate of intracellular protein carbonyl modification was examined 10-60 min after the exposure by Western blot. In addition, the effect of pre-incubation with a thiol scavenger N-acetylcysteine (NAC) was also assessed. We found that intracellular protein carbonyls increased as fast as 10 min after CS exposure and their concentration doubled after 20 min, with a slight elevation afterwards. Also, carbonyl levels increased gradually as CS and acrolein doses were elevated. Addition of 1 mM NAC neutralized part of the damage. We conclude that CS and acrolein intracellular protein carbonylation is dose- and time- dependent. Even a short time exposure to CS and its aldehydic constituents can be potentially harmful.

  7. Nonlinear Rayleigh-Taylor instability in partially ionized plasma and the equatorial spread - F

    International Nuclear Information System (INIS)

    Jain, R.K.; Das, A.C.

    1978-01-01

    The nonlinear evolution of the collisional gravitation induced Rayleigh-Taylor (R-T) instability in the equatorial F region is investigated taking into account the finite Larmor radius (FLR) effects and the complete ion inertial term in ion equation of motion. A special class of coherent weakly nonlinear modes as solutions to the wave equation describing R-T instability driven modes is obtained. The leading nonlinear effects in the wave equation are found to appear through Vsub(L), the ion diamagnetic drift which essentially gives the FLR corrections. It is shown that the R-T modes in the equatorial F region can evolve into coherent, nonlinear, almost sinusoidal, stationary wave structures. These structures are found to travel with a constant phase velocity and to have slightly distorted sinusoidal shapes. These results seem to have a good agreement with many of the recent rocket and satellite observations of the equatorial spread F irregularities. (author)

  8. Typical disturbances of the daytime equatorial F region observed with a high-resolution HF radar

    Directory of Open Access Journals (Sweden)

    E. Blanc

    1998-06-01

    Full Text Available HF radar measurements were performed near the magnetic equator in Africa (Korhogo 9°24'63''N–5°37'38''W during the International Equatorial Electrojet Year (1993–1994. The HF radar is a high-resolution zenithal radar. It gives ionograms, Doppler spectra and echo parameters at several frequencies simultaneously. This paper presents a comparative study of the daytime ionospheric structures observed during 3 days selected as representative of different magnetic conditions, given by magnetometer measurements. Broad Doppler spectra, large echo width, and amplitude fluctuations revealed small-scale instability processes up to the F-region peak. The height variations measured at different altitudes showed gravity waves and larger-scale disturbances related to solar daytime influence and equatorial electric fields. The possibility of retrieving the ionospheric electric fields from these Doppler or height variation measurements in the presence of the other possible equatorial ionospheric disturbances is discussed.

  9. Detection of radiation from a heated and modulated equatorial electrojet current system

    International Nuclear Information System (INIS)

    Lunnen, R.J.; Lee, H.S.; Ferraro, A.J.; Collins, T.W.

    1984-01-01

    In May 1983, ionospheric heating experiments were conducted using the very high frequency radar facility at Lima, Peru. Experiments involving high frequency heating of the ionosphere were successfully conducted during 1982 at Islote, Puerto Rico. These local experiments had characterized the signal radiated from a heated and modulated ionospheric current system near the mid-latitudes. A long-path signal had also been received in September 1982 at Salinas, Puerto Rico from a mid-day equatorial electrojet, heated and modulated by the Jicamarca facility. The authors have investigated the characteristics of the local signal that would be radiated from a strong equatorial electrojet when heated and modulated, and report here that at the geomagnetic equator they were similar to, but less intense than, those observed at Arecibo, Puerto Rico due to parameter differences. This radiation is believed to be the first detected from a heated and modulated equatorial electrojet current system in the Western Hemisphere. (author)

  10. Anthropogenic 236U recorded in annually banded coral skeleton at Majuro atoll, the equatorial Pacific

    International Nuclear Information System (INIS)

    Sakaguchi, Aya; Eto, Asuka; Takahashi, Yoshio; Steier, Peter; Yamazaki, Atsuko; Watanabe, Tsuyoshi; Sasaki, Keiichi; Yamano, Hiroya

    2013-01-01

    Historical 236 U/ 238 U atom ratio and concentration of 236 U were determined by Accelerator Mass Spectrometry (AMS) in skeletons of dated modern coral core sample collected from Majuro atoll, equatorial Pacific, to reconstruct anthropogenic 236 U inputs to the Equatorial Pacific. The maximum hydrogen bomb-pulses of 236 U/ 238 U and 236 U concentration, 2.83x10 -9 and 1.85x10 7 atom/g, in an annually resolved coral core were captured in 1954 (Operation Castle at Bikini and Enewetok atolls). The values were abruptly decreased in a few years, and they have been gradually decreased over time. Our results allow studies of not only the present distribution pattern, but gives access to the temporal evolution of 236 U in surface seawater of North Equatorial Current which is introduced to the Japan Sea and the North West Pacific Ocean as Kuroshio and Tsushima currents over the past decades. (author)

  11. Effects of the equatorial ionosphere on L-band Earth-space transmissions

    Science.gov (United States)

    Smith, Ernest K.; Flock, Warren L.

    1993-01-01

    Ionosphere scintillation can effect satellite telecommunication up to Ku-band. Nighttime scintillation can be attributed to large-scale inhomogeneity in the F-region of the ionosphere predominantly between heights of 200 and 600 km. Daytime scintillation has been attributed to sporadic E. It can be thought of as occurring in three belts: equatorial, high-latitude, and mid-latitude, in order of severity. Equatorial scintillation occurs between magnetic latitudes +/- 25 degrees, peaking near +/- 10 degrees. It commonly starts abruptly near 2000 local time and dies out shortly after midnight. There is a strong solar cycle dependence and a seasonal preference for the equinoxes, particularly the vernal one. Equatorial scintillation occurs more frequently on magnetically quiet than on magnetically disturbed days in most longitudes. At the peak of the sunspot cycle scintillation depths as great as 20 dB were observed at L-band.

  12. Larger CO2 source at the equatorial Pacific during the last deglaciation

    Science.gov (United States)

    Kubota, Kaoru; Yokoyama, Yusuke; Ishikawa, Tsuyoshi; Obrochta, Stephen; Suzuki, Atsushi

    2014-01-01

    While biogeochemical and physical processes in the Southern Ocean are thought to be central to atmospheric CO2 rise during the last deglaciation, the role of the equatorial Pacific, where the largest CO2 source exists at present, remains largely unconstrained. Here we present seawater pH and pCO2 variations from fossil Porites corals in the mid equatorial Pacific offshore Tahiti based on a newly calibrated boron isotope paleo-pH proxy. Our new data, together with recalibrated existing data, indicate that a significant pCO2 increase (pH decrease), accompanied by anomalously large marine 14C reservoir ages, occurred following not only the Younger Dryas, but also Heinrich Stadial 1. These findings indicate an expanded zone of equatorial upwelling and resultant CO2 emission, which may be derived from higher subsurface dissolved inorganic carbon concentration. PMID:24918354

  13. Geology of the Venus equatorial region from Pioneer Venus radar imaging

    International Nuclear Information System (INIS)

    Senske, D.A.; Head, J.W.

    1989-01-01

    The surface characteristics and morphology of the equatorial region of Venus were first described by Masursky et al. who showed this part of the planet to be characterized by two topographic provinces, rolling plains and highlands, and more recently by Schaber who described and interpreted tectonic zones in the highlands. Using Pioneer Venus (PV) radar image data (15 deg S to 45 deg N), Senske and Head examined the distribution, characteristics, and deposits of individual volcanic features in the equatorial region, and in addition classified major equatorial physiographic and tectonic units on the basis of morphology, topographic signature, and radar properties derived from the PV data. Included in this classification are: plains (undivided), inter-highland tectonic zones, tectonically segmented linear highlands, upland rises, tectonic junctions, dark halo plains, and upland plateaus. In addition to the physiographic units, features interpreted as coronae and volcanic mountains have also been mapped. The latter four of the physiographic units along with features interpreted to be coronae

  14. Sensitivity of equatorial Pacific and Indian Ocean watermasses to the position of the Indonesian Throughflow

    Science.gov (United States)

    Rodgers, Keith B.; Latif, Mojib; Legutke, Stephanie

    2000-09-01

    The sensitivity of the thermal structure of the equatorial Pacific and Indian Ocean pycnoclines to a model's representation of the Indonesian Straits connecting the two basins is investigated. Two integrations are performed using the global HOPE ocean model. The initial conditions and surface forcing for both cases are identical; the only difference between the runs is that one has an opening for the Indonesian Straits which spans the equator on the Pacific side, and the other has an opening which lies fully north of the equator. The resulting sensitivity throughout much of the upper ocean is greater than 0.5°C for both the equatorial Indian and Pacific. A realistic simulation of net Indonesian Throughflow (ITF) transport (measured in Sverdrups) is not sufficient for an adequate simulation of equatorial watermasses. The ITF must also contain a realistic admixture of northern and southern Pacific source water.

  15. Equatorial electrojet as part of the global circuit: a case-study from the IEEY

    Directory of Open Access Journals (Sweden)

    A. T. Kobea

    Full Text Available Geomagnetic storm-time variations often occur coherently at high latitude and the day-side dip equator where they affect the normal eastward Sq field. This paper presents an analysis of ground magnetic field and ionospheric electrodynamic data related to the geomagnetic storm which occured on 27 May 1993 during the International Equatorial Electrojet Year (IEEY experiment. This storm-signature analysis on the auroral, mid-latitude and equatorial ground field and ionospheric electrodynamic data leads to the identification of a sensitive response of the equatorial electrojet (EEJ to large-scale auroral return current: this response consists in a change of the eastward electric field during the pre-sunrise hours (0400-0600 UT coherently to the high-, mid-, and equatorial-latitude H decrease and the disappearance of the EEJ irregularities between the time-interval 0800-0950 UT. Subsequent to the change in h'F during pre-sunrise hours, the observed foF2 increase revealed an enhancement of the equatorial ionization anomaly (EIA caused by the high-latitude penetrating electric field. The strengthening of these irregularities attested by the Doppler frequency increase tracks the H component at the equator which undergoes a rapid increase around 0800 UT. The ∆H variations observed at the equator are the sum of the following components: SR, DP, DR, DCF and DT.

    Keywords. Equatorial electrojet · Magnetosphere-ionosphere interactions · Electric fields and currents · Auroral ionosphere · Ionospheric disturbances

  16. Use of PET and the radioligand [carbonyl-{sup 11}C]WAY-100635 in psychotropic drug development

    Energy Technology Data Exchange (ETDEWEB)

    Andree, Bengt; Halldin, Christer; Thorberg, Seth-Olov; Sandell, Johan; Farde, Lars

    2000-07-01

    Positron-emission tomography (PET) provides potential in neuropsychiatric drug development by expanding knowledge of drug action in the living human brain and reducing time consumption and costs. The 5-hydroxytryptamine{sub 1A} (5-HT{sub 1A}) receptor is of central interest as a target for the treatment of anxiety, depression, and schizophrenia. Research on the clinical significance of the 5-HT{sub 1A} receptor now benefits from the highly selective radioligand [carbonyl-{sup 11}C]WAY-100635 (WAY) for quantitative determination of 5-HT{sub 1A} receptors in the primate and human brain in vivo using PET. In this paper, three studies are reviewed to demonstrate the suitability of WAY as radioligand for quantification of central 5-HT{sub 1A} receptors in brain and as an applicable tool for drug development. In the first study a monkey model was used to characterize WAY binding. It was confirmed that the reference ligand 8-OH-DPAT and psychoactive drugs such as buspirone and pindolol occupies 5-HT{sub 1A} receptors in the primate brain. Pindolol is an {beta}-adrenoreceptor antagonist with a high affinity to 5-HT{sub 1A} receptors. This drug has been suggested in combination with selective serotonin reuptake inhibitors for the treatment of depression and was given to healthy males in the second study. Pindolol induced a marked inhibition of central 5-HT{sub 1A} receptors as calculated by the ratio-analysis method and simplified reference tissue model, 2 h after administration of 10 mg as a single oral dose. This observation suggests that pindolol may have a role for the suggested potentiation of selective serotonin reuptake inhibitor treatment of depression. The third study was on robalzotan (NAD-299), a recently developed 5-HT{sub 1A} receptor antagonist and putative drug with implications for the treatment of depression. In the cynomolgus monkey brain, robalzotan in the dose range 2-100 {mu}g/kg IV occupied 5-HT{sub 1A} receptors in a dose-dependent and saturable

  17. The use of biodiesel blends on a non-road generator and its impacts on ozone formation potentials based on carbonyl emissions

    International Nuclear Information System (INIS)

    Chai, Ming; Lu, Mingming; Liang, Fuyan; Tzillah, Aisha; Dendramis, Nancy; Watson, Libya

    2013-01-01

    In this study, emissions of carbonyl compounds from the use B50 and B100 were measured with a non-road diesel generator. A total of 25 carbonyl compounds were identified in the exhaust, including 10 with laboratory-synthesized standards. Formaldehyde, acetaldehyde, and acrolein were found as the most abundant carbonyl compounds emitted for both diesel and biodiesel. The sulphur content of diesel fuels and the source of biodiesel fuels were not found to have a significant impact on the emission of carbonyl compounds. The overall maximum incremental reactivity (MIR) was the highest at 0 kW and slightly increased from 25 to 75 kW. The MIR of B100 was the highest, followed by diesel and B50, which is consistent with the emission rates of total carbonyl compounds. This suggests that the use of biodiesel blends may be more beneficial to the environment than using pure biodiesel. -- Highlights: •Carbonyl compound emission from biodiesel blends combustion on a non-road generator. •25 compounds were identified, including 10 by laboratory-synthesized standards. •Sources of biodiesel have insignificant impacts on carbonyl compounds emission. •Sulphur contents have insignificant impacts on carbonyl compounds emission. •MIR of emitted carbonyls decreases in the following order: B100, diesel, B50. -- The study found that B50 resulted in lower total carbonyl emission rates and ozone formation potential resultant from these compounds, whereas both increased with B100

  18. Insights into an original pocket-ligand pair classification: a promising tool for ligand profile prediction.

    Directory of Open Access Journals (Sweden)

    Stéphanie Pérot

    Full Text Available Pockets are today at the cornerstones of modern drug discovery projects and at the crossroad of several research fields, from structural biology to mathematical modeling. Being able to predict if a small molecule could bind to one or more protein targets or if a protein could bind to some given ligands is very useful for drug discovery endeavors, anticipation of binding to off- and anti-targets. To date, several studies explore such questions from chemogenomic approach to reverse docking methods. Most of these studies have been performed either from the viewpoint of ligands or targets. However it seems valuable to use information from both ligands and target binding pockets. Hence, we present a multivariate approach relating ligand properties with protein pocket properties from the analysis of known ligand-protein interactions. We explored and optimized the pocket-ligand pair space by combining pocket and ligand descriptors using Principal Component Analysis and developed a classification engine on this paired space, revealing five main clusters of pocket-ligand pairs sharing specific and similar structural or physico-chemical properties. These pocket-ligand pair clusters highlight correspondences between pocket and ligand topological and physico-chemical properties and capture relevant information with respect to protein-ligand interactions. Based on these pocket-ligand correspondences, a protocol of prediction of clusters sharing similarity in terms of recognition characteristics is developed for a given pocket-ligand complex and gives high performances. It is then extended to cluster prediction for a given pocket in order to acquire knowledge about its expected ligand profile or to cluster prediction for a given ligand in order to acquire knowledge about its expected pocket profile. This prediction approach shows promising results and could contribute to predict some ligand properties critical for binding to a given pocket, and conversely

  19. Insights into an original pocket-ligand pair classification: a promising tool for ligand profile prediction.

    Science.gov (United States)

    Pérot, Stéphanie; Regad, Leslie; Reynès, Christelle; Spérandio, Olivier; Miteva, Maria A; Villoutreix, Bruno O; Camproux, Anne-Claude

    2013-01-01

    Pockets are today at the cornerstones of modern drug discovery projects and at the crossroad of several research fields, from structural biology to mathematical modeling. Being able to predict if a small molecule could bind to one or more protein targets or if a protein could bind to some given ligands is very useful for drug discovery endeavors, anticipation of binding to off- and anti-targets. To date, several studies explore such questions from chemogenomic approach to reverse docking methods. Most of these studies have been performed either from the viewpoint of ligands or targets. However it seems valuable to use information from both ligands and target binding pockets. Hence, we present a multivariate approach relating ligand properties with protein pocket properties from the analysis of known ligand-protein interactions. We explored and optimized the pocket-ligand pair space by combining pocket and ligand descriptors using Principal Component Analysis and developed a classification engine on this paired space, revealing five main clusters of pocket-ligand pairs sharing specific and similar structural or physico-chemical properties. These pocket-ligand pair clusters highlight correspondences between pocket and ligand topological and physico-chemical properties and capture relevant information with respect to protein-ligand interactions. Based on these pocket-ligand correspondences, a protocol of prediction of clusters sharing similarity in terms of recognition characteristics is developed for a given pocket-ligand complex and gives high performances. It is then extended to cluster prediction for a given pocket in order to acquire knowledge about its expected ligand profile or to cluster prediction for a given ligand in order to acquire knowledge about its expected pocket profile. This prediction approach shows promising results and could contribute to predict some ligand properties critical for binding to a given pocket, and conversely, some key pocket

  20. Observation of low energy particle precipitation at low altitude in the equatorial zone

    Science.gov (United States)

    Miah, M. A.

    1989-01-01

    Precipitation of protons in the equatorial zone was investigated by the Phoenix-1 experiment on the S81-1 mission from May to November, 1982. The protons show a precipitation peak along the line of minimum magnetic field strength with a FWHM of 13 deg. The index of equatorial pitch angle distribution is about 19. The peak proton flux shows a fifth-power altitude dependence, and the proton flux shows approximately a factor of 3 times increase in 1982 compared to that in 1969 due, possibly, to the stronger solar maximum conditions of 10.7-cm radiation in 1982.

  1. Concept development for the ITER equatorial port visible/infrared wide angle viewing system

    International Nuclear Information System (INIS)

    Reichle, R.; Beaumont, B.; Boilson, D.; Bouhamou, R.; Direz, M.-F.; Encheva, A.; Henderson, M.; Kazarian, F.; Lamalle, Ph.; Lisgo, S.; Mitteau, R.; Patel, K. M.; Pitcher, C. S.; Pitts, R. A.; Prakash, A.; Raffray, R.; Schunke, B.; Snipes, J.; Diaz, A. Suarez; Udintsev, V. S.

    2012-01-01

    The ITER equatorial port visible/infrared wide angle viewing system concept is developed from the measurement requirements. The proposed solution situates 4 viewing systems in the equatorial ports 3, 9, 12, and 17 with 4 views each (looking at the upper target, the inner divertor, and tangentially left and right). This gives sufficient coverage. The spatial resolution of the divertor system is 2 times higher than the other views. For compensation of vacuum-vessel movements, an optical hinge concept is proposed. Compactness and low neutron streaming is achieved by orienting port plug doglegs horizontally. Calibration methods, risks, and R and D topics are outlined.

  2. Instabilities associated with the equatorial spread-F phenomenon and their north-south asymmetry

    International Nuclear Information System (INIS)

    Beghin, C.; Pandey, R.; Roux, D.

    1985-01-01

    Six North to South passes of AUREOL/ARCAD 3 satellite through the equatorial electron density depletion at variable altitude between 400 and 550 km, at night, during a two weeks period, exhibit a similar feature in plasma density irregularities which are thought to be associated with spread F phenomenon. The irregularities are found to be quasi-sinusoidal with a scale size of about 2 km along the satellite trajectory and occur only on the Northern edge of the equatorial electron density depletion. This implies a violation of the generally believed principle of conjugate mapping for those wavelengths. These observations are analysed and discussed in terms of different known generation mechanisms

  3. Collisional Rayleigh-Taylor instability and shear-flow in equatorial Spread-F plasma

    Directory of Open Access Journals (Sweden)

    N. Chakrabarti

    2003-05-01

    Full Text Available Collisional Rayleigh-Taylor (RT instability is considered in the bottom side of the equatorial F-region. By a novel nonmodal calculation it is shown that for an applied shear flow in equilibrium, the growth of the instability is considerably reduced. Finite but small amounts of diffusion enhances the stabilization process. The results may be relevant to the observations of long-lived irregularities at the bottom-side of the F-layer.Key words. Ionosphere (ionospheric irregularities, equatorial ionosphere, plasma waves and instabilities

  4. The physical and theoretical basis of solar-terrestrial relationships 2. Non-equatorial locations

    International Nuclear Information System (INIS)

    Njau, E.C.

    1988-07-01

    The basic formulations presented in Part 1 of this series (hereinafter simply referred to as ''Paper 1'') are modified in order to mathematically represent the expected solar-terrestrial influences in non-equatorial regions. Analysis and interpretation of these formulations lead to the establishment of several new periodicities as well as other features associated with the non-equatorial atmosphere. Besides, we show through suitable examples that the physical processes that cause and influence some previously observed climatic and upper atmospheric variations in temperate and polar regions are easily deduced from our formulations. (author). 35 refs

  5. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  6. Development of immobilized ligands for actinide separations

    International Nuclear Information System (INIS)

    Paine, R.T.

    1994-01-01

    Primary goals during this grant period were to (1) synthesize new bifunctional chelating ligands, (2) characterize the structural features of the Ln and An coordination complexes formed by these ligands, (3) use structural data to iteratively design new classes of multifunctional ligands, and (4) explore additional routes for attachment of key ligands to solid supports that could be useful for chromatographic separations. Some highlights of recently published work as well as a summary of submitted, unpublished and/or still in progress research are outlined

  7. Global equatorial sea-surface temperatures over the last 150,000 years: An update from foraminiferal elemental analysis

    Digital Repository Service at National Institute of Oceanography (India)

    Saraswat, R.

    for the warmest waters. However, how the equatorial SST affects global climate, is still not clear. Long-term past seawater temperature records are required to understand the effect of temporal changes in equatorial SST on the global climate. Various techniques...

  8. Simple knowledge-based descriptors to predict protein-ligand interactions. Methodology and validation

    Science.gov (United States)

    Nissink, J. Willem M.; Verdonk, Marcel L.; Klebe, Gerhard

    2000-11-01

    A new type of shape descriptor is proposed to describe the spatial orientation for non-covalent interactions. It is built from simple, anisotropic Gaussian contributions that are parameterised by 10 adjustable values. The descriptors have been used to fit propensity distributions derived from scatter data stored in the IsoStar database. This database holds composite pictures of possible interaction geometries between a common central group and various interacting moieties, as extracted from small-molecule crystal structures. These distributions can be related to probabilities for the occurrence of certain interaction geometries among different functional groups. A fitting procedure is described that generates the descriptors in a fully automated way. For this purpose, we apply a similarity index that is tailored to the problem, the Split Hodgkin Index. It accounts for the similarity in regions of either high or low propensity in a separate way. Although dependent on the division into these two subregions, the index is robust and performs better than the regular Hodgkin index. The reliability and coverage of the fitted descriptors was assessed using SuperStar. SuperStar usually operates on the raw IsoStar data to calculate propensity distributions, e.g., for a binding site in a protein. For our purpose we modified the code to have it operate on our descriptors instead. This resulted in a substantial reduction in calculation time (factor of five to eight) compared to the original implementation. A validation procedure was performed on a set of 130 protein-ligand complexes, using four representative interacting probes to map the properties of the various binding sites: ammonium nitrogen, alcohol oxygen, carbonyl oxygen, and methyl carbon. The predicted `hot spots' for the binding of these probes were compared to the actual arrangement of ligand atoms in experimentally determined protein-ligand complexes. Results indicate that the version of SuperStar that applies to

  9. Protein conjugated with aldehydes derived from lipid peroxidation as an independent parameter of the carbonyl stress in the kidney damage

    Directory of Open Access Journals (Sweden)

    Medina-Navarro Rafael

    2011-11-01

    Full Text Available Abstract Background One of the well-defined and characterized protein modifications usually produced by oxidation is carbonylation, an irreversible non-enzymatic modification of proteins. However, carbonyl groups can be introduced into proteins by non-oxidative mechanisms. Reactive carbonyl compounds have been observed to have increased in patients with renal failure. In the present work we have described a procedure designed as aldehyde capture to calculate the protein carbonyl stress derived solely from lipid peroxidation. Methods Acrolein-albumin adduct was prepared as standard at alkaline pH. Rat liver microsomal membranes and serum samples from patients with diabetic nephropathy were subjected to the aldehyde capture procedure and aldol-protein formation. Before alkalinization and incubation, samples were precipitated and redisolved in 6M guanidine. The absorbances of the samples were read with a spectrophotometer at 266 nm against a blank of guanidine. Results Evidence showed abundance of unsaturated aldehydes derived from lipid peroxidation in rat liver microsomal membranes and in the serum of diabetic patients with advanced chronic kidney disease. Carbonyl protein and aldol-proteins resulted higher in the diabetic nephropathy patients (p Conclusion The aldehyde-protein adduct represents a non oxidative component of carbonyl stress, independent of the direct amino acid oxidation and could constitute a practical and novelty strategy to measure the carbonyl stress derived solely from lipid peroxidation and particularly in diabetic nephropathy patients. In addition, we are in a position to propose an alternative explanation of why alkalinization of urine attenuates rhabdomyolysis-induced renal dysfunction.

  10. Characterisation and optimisation of a method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

    Science.gov (United States)

    Rodigast, M.; Mutzel, A.; Iinuma, Y.; Haferkorn, S.; Herrmann, H.

    2015-01-01

    Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds (VOC). Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. Thus a method was systematically characterised and improved to quantify carbonyl compounds. Quantification with the present method can be carried out for each carbonyl compound sampled in the aqueous phase regardless of their source. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). The main advantage of the improved method presented in this study is the low detection limit in the range of 0.01 and 0.17 μmol L-1 depending on carbonyl compounds. Furthermore best results were found for extraction with dichloromethane for 30 min followed by derivatisation with PFBHA for 24 h with 0.43 mg mL-1 PFBHA at a pH value of 3. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione.

  11. Cross-talk between lipid and protein carbonylation in a dynamic cardiomyocyte model of mild nitroxidative stress

    Directory of Open Access Journals (Sweden)

    Eva Griesser

    2017-04-01

    Full Text Available Reactive oxygen and nitrogen species (ROS/RNS play an important role in the regulation of cardiac function. Increase in ROS/RNS concentration results in lipid and protein oxidation and is often associated with onset and/or progression of many cardiovascular disorders. However, interplay between lipid and protein modifications has not been simultaneously studied in detail so far. Biomolecule carbonylation is one of the most common biomarkers of oxidative stress. Using a dynamic model of nitroxidative stress we demonstrated rapid changes in biomolecule carbonylation in rat cardiomyocytes. Levels of carbonylated species increased as early as 15 min upon treatment with the peroxynitrite donor, 3-morpholinosydnonimine (SIN-1, and decreased to values close to control after 16 h. Total (lipids+proteins vs. protein-specific carbonylation showed different dynamics, with a significant increase in protein-bound carbonyls at later time points. Treatment with SIN-1 in combination with inhibitors of proteasomal and autophagy/lysosomal degradation pathways allowed confirmation of a significant role of the proteasome in the degradation of carbonylated proteins, whereas lipid carbonylation increased in the presence of autophagy/lysosomal inhibitors. Electrophilic aldehydes and ketones formed by lipid peroxidation were identified and relatively quantified using LC-MS/MS. Molecular identity of reactive species was used for data-driven analysis of their protein targets. Combination of different enrichment strategies with LC-MS/MS analysis allowed identification of more than 167 unique proteins with 332 sites modified by electrophilic lipid peroxidation products. Gene ontology analysis of modified proteins demonstrated enrichment of several functional categories including proteins involved in cytoskeleton, extracellular matrix, ion channels and their regulation. Using calcium mobilization assays, the effect of nitroxidative stress on the activity of several ion

  12. Manganese(I-Based CORMs with 5-Substituted 3-(2-PyridylPyrazole Ligands

    Directory of Open Access Journals (Sweden)

    Ralf Mede

    2017-01-01

    Full Text Available The reaction of [(OC5MnBr] with substituted 3-(2-pyridylpyrazoles 2-PyPzRH (1a-l in methanol or diethyl ether yields the yellow to orange manganese(I complexes [(OC3Mn(Br(2-PyPzRH] (2a-l, the substituents R being phenyl (a, 1-naphthyl (b, 2-anthracenyl (c, 1-pyrenyl (d, 4-bromophenyl (e, 3-bromophenyl (f, duryl (g, 2-pyridyl (h, 2-furanyl (i, 2-thienyl (j, ferrocenyl (k, and 1-adamantyl (l. The carbonyl ligands are arranged facially, leading to three chemically different CO ligands due to different trans-positioned Lewis donors. The diversity of the substituent R demonstrates that this photoCORM backbone can easily be varied with a negligible influence on the central (OC3MnBr fragment, because the structural parameters and the spectroscopic data of this unit are very similar for all these derivatives. Even the ferrocenyl complex 2k shows a redox potential for the ferrocenyl subunit which is identical to the value of the free 5-ferrocenyl-3-(2-pyridylpyrazole (1k. The ease of variation of the starting 5-substituted 3-(2-pyridylpyrazoles offers a modular system to attach diverse substituents at the periphery of the photoCORM complex.

  13. Macrocyclic ligands for uranium complexation

    International Nuclear Information System (INIS)

    Potts, K.T.

    1991-04-01

    A highly preorganized 24-macrocycle containing biuret, thiobiuret and pyridine subunits has been prepared by high dilution ring-closure procedures. Intermediate products to this macrocycle have been utilized to extend this synthetic route to include further representatives where solubility and stability will be influenced by substituent variation. A 1:1 complex has been formed from uranyl acetate and a quinquepyridine derivative, this representing a new type of ligand for the uranyl ion. A very convenient synthetic procedure that will allow the incorporation of these macrocycles into polymeric systems has been developed for the introduction of a vinyl substituent into the 4-position of the pyridine ring. Using triflate, vinyltributyltin and Pd 0 chemistry, this procedure should make a variety of substituted 4-vinylpyridines available for the first time. 3 refs

  14. Surface temperature of the equatorial Pacific Ocean and the Indian rainfall

    Digital Repository Service at National Institute of Oceanography (India)

    Gopinathan, C.K.

    The time variation of the monthly mean surface temperature of the equatorial Pacific Ocean during 1982-1987 has been studied in relation to summer monsoon rainfall over India The ENSO events of 1982 and 1987 were related to a significant reduction...

  15. A study of Sq(H) variations over equatorial electrojet regions | Okeke ...

    African Journals Online (AJOL)

    The newly established geomagnetic field observations in Japan, have enabled us to analyse the 1998 data of Huancayo, Kiritimati (Christmas Island) and Pohnpei where the geomagnetic Sq(H) variations of equatorial electrojet have been studied. The diurnal variation of the monthly means of Sq(H) on the five international ...

  16. Equatorial Indian Ocean productivity during the last 33 kyr and possible linkage to Westerly Jet variability

    Digital Repository Service at National Institute of Oceanography (India)

    Punyu, V.R.; Banakar, V.K.; Garg, A.

    The top 1 m radiocarbon dated section of a 5.6 m long sediment core retrieved from the Equatorial Indian Ocean is studied for productivity changes in response to climate variability that have taken place during the last ~33 kyr. The robust...

  17. Interannual variability of the Equatorial Jets in the Indian Ocean from the merged altimetry data

    Digital Repository Service at National Institute of Oceanography (India)

    Somayajulu, Y.K.; Murty, V.S.N.; Neelima, C.; Jagadeesh, P.S.V.

    The merged ERS-1/2, TOPEX/Poseidon and Jason-1 altimeter weekly sea level anomalies (SLAs) for the period 1997- 2005 were analyzed to study the variability of sea level and computed geostrophic currents in relation to the equatorial jets...

  18. Seasonal Variation of Diurnal Cycle of Rainfall in the Eastern Equatorial Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    RameshKumar, M.R.; Pednekar, S.; Katsumata, M.; Antony, M.K.; Kuroda, Y.; Unnikrishnan, A.S.

    The diurnal cycle of rainfall over the eastern equatorial Indian Ocean is studied for the period 23rd October 2001 to 31st October 2003 using the hourly data from the Triton buoy positioned at 1.5°S and 90°E. An analysis of the active and weak...

  19. Westward equatorial electrojet during daytime hours. [relation to geomagnetic horizontal field depression

    Science.gov (United States)

    Rastogi, R. G.

    1974-01-01

    The phenomenon of the depression of the geomagnetic horizontal field during the daytime hours of magnetically quiet days at equatorial stations is described. These events are generally seen around 0700 and 1600 LT, being more frequent during the evening than the morning hours. The evening events are more frequent during periods of low solar activity and in the longitude region of weak equatorial electrojet currents. The latitudinal extent of the phenomenon is limited to the normal equatorial electrojet region, and on some occasions the phenomenon is not seen at both stations, separated by only a few hours in longitude. During such an event, the latitudinal profile of the geomagnetic vertical field across the equator is reversed, the ionospheric drift near the equator is reversed toward the east, the q type of sporadic E layer is completely absent, and the height of the peak ionization in the F2 region is decreased. It is suggested that these effects are caused by a narrow band of current flowing westward in the E region of the ionosphere and within the latitude region of the normal equatorial electrojet, due to the reversal of the east-west electrostatic field at low latitudes.

  20. A study of evolution/suppression parameters of equatorial postsunset plasma instability

    Directory of Open Access Journals (Sweden)

    O. S. Oyekola

    2009-01-01

    Full Text Available Evening equatorial pre-reversal vertical ion E×B drift (VZP and the peak of the ionospheric F2 maximum altitude (hmF2P of the postsunset equatorial F-layer, which are the essential parameters requisite for the generation or inhibition of postsunset bottomside equatorial irregularities were deduced from ionosonde observations made in the Africa region (Ouagadougou: ~3° N dip latitude between January 1987 and December 1990 for solar activity minimum, medium, and maxima (F10.7=85, 141, 214, and 190, respectively for quiet geomagnetic conditions. We investigate variations of evening equatorial pre-reversal drift and the corresponding altitude at four levels of solar activity. Our observations show strong variations with solar variability. Correlation analysis between these parameters indicates that the correlation coefficient value between hmF2P versus VZP decreases considerably with increasing solar flux value. There seems to be no significant link between these parameters under high solar activity, especially for solar intensity F10.7>200 units. We conclude that meridional neutral wind in the F-region contributes substantially to the variations of the pre-reversal vertical plasma drifts enhancement and the peak hmF2, particularly the electrodynamics during twilight high solar flux conditions.

  1. The heat and moisture budgets of the atmosphere over central equatorial Indian Ocean during summer monsoon

    Digital Repository Service at National Institute of Oceanography (India)

    Sadhuram, Y.; Gopalakrishna, V.V.; RameshBabu, V.; Sastry, J.S.

    The heat and moisture budgets of the atmosphere (surface to 100 mb) over the central equatorial Indian Ocean (2 degrees N to 2 degrees S; 76 degrees E to 80 degrees E) have been investigated utilising the surface and upper air data collected...

  2. Post sunset equatorial spread-F at Kwajalein and interplanetary magnetic field

    Science.gov (United States)

    Rastogi, R. G.; Chandra, H.; Janardhan, P.; Reinisch, B. W.; Bisoi, Susanta Kumar

    2017-10-01

    We connect the time sequence of changes in the IMF-Bz to the development of spread-F at an equatorial station Kwajalein on three different nights in November 2004, one during a geomagnetic quiet period and other two during geomagnetic disturbed periods. The chosen days show clear and smooth variations of IMF-Bz without any large fluctuations thereby enabling one to correlate changes in equatorial spread-F with corresponding changes in IMF-Bz. It is shown that a slow and continuous increase in the IMF-Bz over a duration of few hours has a similar effect on the equatorial ionosphere as of a sudden northward turning of the IMF-Bz in causing an electric field through the polar region and then to the equator. We conclude that the Spread-F at equatorial and low latitudes are due to echoes from ionization irregularities that arise due to the plasma instabilities generated by an eastward electric field on the large plasma density gradient in or below the base of the F-layer during any period of the night time along with the gravity driven Rayleigh-Taylor instability.

  3. Nonlinear theory of the collisional Rayleigh-Taylor instability in equatorial spread F

    International Nuclear Information System (INIS)

    Chaturvedi, P.K.; Ossakow, S.L.

    1977-01-01

    The nonlinear behavior of the collisional Rayleigh-Taylor instability is studied in equatorial Spread F by including a dominant two-dimensional nonlinearity. It is found that on account of this nonlinearity the instability saturates by generating damped higher spatial harmonics. The saturated power spectrum for the density fluctuations is discussed. A comparison between experimental observations and theory is presented

  4. Targeting Aurora B to the equatorial cortex by MKlp2 is required for cytokinesis.

    Directory of Open Access Journals (Sweden)

    Mayumi Kitagawa

    Full Text Available Although Aurora B is important in cleavage furrow ingression and completion during cytokinesis, the mechanism by which kinase activity is targeted to the cleavage furrow and the molecule(s responsible for this process have remained elusive. Here, we demonstrate that an essential mitotic kinesin MKlp2 requires myosin-II for its localization to the equatorial cortex, and this event is required to recruit Aurora B to the equatorial cortex in mammalian cells. This recruitment event is also required to promote the highly focused accumulation of active RhoA at the equatorial cortex and stable ingression of the cleavage furrow in bipolar cytokinesis. Specifically, in drug-induced monopolar cytokinesis, targeting Aurora B to the cell cortex by MKlp2 is essential for cell polarization and furrow formation. Once the furrow has formed, MKlp2 further recruits Aurora B to the growing furrow. This process together with continuous Aurora B kinase activity at the growing furrow is essential for stable furrow propagation and completion. In contrast, a MKlp2 mutant defective in binding myosin-II does not recruit Aurora B to the cell cortex and does not promote furrow formation during monopolar cytokinesis. This mutant is also defective in maintaining the ingressing furrow during bipolar cytokinesis. Together, these findings reveal that targeting Aurora B to the cell cortex (or the equatorial cortex by MKlp2 is essential for the maintenance of the ingressing furrow for successful cytokinesis.

  5. Intensities and spatiotemporal variability of equatorial noise emissions observed by the Cluster spacecraft

    Czech Academy of Sciences Publication Activity Database

    Němec, F.; Santolík, Ondřej; Hrbáčková, Zuzana; Cornilleau-Wehrlin, N.

    2015-01-01

    Roč. 120, č. 3 (2015), s. 1620-1632 ISSN 2169-9380 R&D Projects: GA MŠk(CZ) LH11122 Institutional support: RVO:68378289 Keywords : equatorial noise * magnetosonic waves Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.318, year: 2015 http://onlinelibrary.wiley.com/doi/10.1002/2014JA020814/full

  6. Estimation of eddy diffusivity coefficient of heat in the upper layers of equatorial Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Zavialov, P.O.; Murty, V.S.N.

    in the Central Equatorial Arabian Sea (CEAS). A comparison of the model computed K sub(h) values with those estimated from the heat balance of the upper layer (50 m) of the sea shows good agreement in the region of weak winds (CEAS) or low turbulent mixing regime...

  7. Effective potential for equatorial motion in the Tomimatsu-Sato space-times

    Energy Technology Data Exchange (ETDEWEB)

    Calvani, M [Padua Univ. (Italy). Ist. di Astronomia

    1978-01-28

    We give general rules to draw the effective potential curves for equatorial motion in the T-S space-times either with am. Some general properties of the potentials are pointed out and few examples shown.

  8. Variability in foF2 at an equatorial station and the influence of magnetic activity

    International Nuclear Information System (INIS)

    Adeniyi, J.O.; Radicella, S.M.

    2003-01-01

    Variability in foF2 is investigated for an equatorial station in the African region. Variability during the day time at high solar activity varies between 10 and 30 percent. It varies between 10 and 20 percent at high solar activity. Magnetic storms increase the variability at both solar activity periods. (author)

  9. An Enduring Rapidly Moving Storm as a Guide to Saturn's Equatorial Jet's Complex Structure

    Science.gov (United States)

    Sanchez-Lavega, A.; Garcia-Melendo, E.; Perez-Hoyos, S.; Hueso, R.; Wong, M. H.; Simon, A.; Sanz-Requena, J. F.; Antunano, A.; Barrado-Izagirre, N.; Garate-Lopez, I.; hide

    2016-01-01

    Saturn has an intense and broad eastward equatorial jet with a complex three-dimensional structure mixed with time variability. The equatorial region experiences strong seasonal insolation variations enhanced by ring shadowing, and three of the six known giant planetary-scale storms have developed in it. These factors make Saturn's equator a natural laboratory to test models of jets in giant planets. Here we report on a bright equatorial atmospheric feature imaged in 2015 that moved steadily at a high speed of 450/ms not measured since 1980-1981 with other equatorial clouds moving within an ample range of velocities. Radiative transfer models show that these motions occur at three altitude levels within the upper haze and clouds. We find that the peak of the jet (latitudes 10degN to 10degS) suffers intense vertical shears reaching + 2.5/ms/km, two orders of magnitude higher than meridional shears, and temporal variability above 1 bar altitude level.

  10. Effect of solar flare on the equatorial electrojet in eastern Brazil region

    Indian Academy of Sciences (India)

    The effect of solar flare, sudden commencement of magnetic storm and of the disturbances ring current on the equatorial electrojet in the Eastern Brazil region, where the ground magnetic declination is as large as 20∘W is studied based on geomagnetic data with one minute resolution from Bacabal during ...

  11. Separation of Trace Amount Zn (II Using Additional Carbonyl and Carboxyl Groups Functionalized-Nano Graphene

    Directory of Open Access Journals (Sweden)

    A. Moghimi

    2013-01-01

    Full Text Available A novel and selective method for the fast determination of trace amounts of Zn(IIions in water samples has been developed.  The first additional carbonyl and carboxyl functionalized-nano graphene (SPFNano graphene. The presence of additional carbonyl and carboxyl groups located at the edge of the sheets makes GO sheets strongly hydrophilic, allowing them to readily swell and disperse in water. Based on these oxygen functionalities, different model structures of GO were used as absorbent for extraction of Zn (II   ions by solid phase extraction method. The complexes were eluted with HNO3 (2M10% V.V-1 methanol in acetone and determined the analyte by flame atomic absorption spectrometry.  The procedure is based on the selective formation of Zn (II at optimum pH by elution with organic eluents and determination by flame atomic absorption spectrometry. The method is based on complex formation on the surface of the ENVI-18 DISKTM disks modified carbonyl and carboxyl functionalized-nano graphene oxide molecules covalently bonded together followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution is efficient and quantitative. The effect of potential interfering ions, pH, SPFNano graphene, amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to about 1000mL providing a preconcentration factor of 500. The maximum capacity of the disks was found to be 456± 3 µg for Zn2+.The limit of detection of the proposed method is 5ng per 1000mL.The method was applied to the extraction and recovery of Zn in different water samples.

  12. Hydrothermal synthesis of carbonyl iron-carbon nanocomposite: Characterization and electromagnetic performance

    Directory of Open Access Journals (Sweden)

    Hakimeh Pourabdollahi

    Full Text Available In this research, the electromagnetic absorption properties of the carbonyl iron-carbon (CI/C nanocomposite prepared via hydrothermal reaction using glucose as carbon precursor was studied in the range of 8.2–12.4 GHz. In hydrothermal reaction, glucose solution containing CI particles, placed in autoclave for 4 h under 453 K. Using surface coating technology is a method that prevents Cl oxidation and improves CI electromagnetic absorption. The structure, morphology and magnetic performances of the prepared nanocomposites were characterized by X-ray diffraction (XRD, energy dispersive spectrometry (EDS, transmission electron microscopy (TEM and vibrating sample magnetometer (VSM. The electromagnetic properties including complex permittivity (εr, the permeability (µr, dielectric loss, magnetic loss, reflection loss, and attenuation constant were investigated using a vector network analyzer. For The CI/C nanocomposite, the bandwidth of −10 dB and −20 dB were obtained in the frequency range of 9.8–12.4 and 11.0–11.8 GHz, respectively. As well as, the reflection loss was −46.69 dB at the matching frequency of 11.5 GHz, when the matching thickness was 1.3 mm. While for CI particles the reflection loss for 4.4 mm thickness was −16.86 dB at the matching frequency of 12.3 GHz. The results indicate that the existence layer of carbon on carbonyl iron enhance the electromagnetic absorbing properties. Therefore, this nanocomposite can be suitable for in the radar absorbing coatings. Keywords: Hydrothermal synthesis, Carbonyl iron-carbon nanocomposite, Microwave absorption, Reflection loss

  13. The Drosophila carbonyl reductase sniffer is an efficient 4-oxonon-2-enal (4ONE) reductase.

    Science.gov (United States)

    Martin, Hans-Jörg; Ziemba, Marta; Kisiela, Michael; Botella, José A; Schneuwly, Stephan; Maser, Edmund

    2011-05-30

    Studies with the fruit-fly Drosophila melanogaster demonstrated that the enzyme sniffer prevented oxidative stress-induced neurodegeneration. Mutant flies overexpressing sniffer had significantly extended life spans in a 99.5% oxygen atmosphere compared to wild-type flies. However, the molecular mechanism of this protection remained unclear. Sequence analysis and database searches identified sniffer as a member of the short-chain dehydrogenase/reductase superfamily with a 27.4% identity to the human enzyme carbonyl reductase type I (CBR1). As CBR1 catalyzes the reduction of the lipid peroxidation products 4HNE and 4ONE, we tested whether sniffer is able to metabolize these lipid derived aldehydes by carbonyl reduction. To produce recombinant enzyme, the coding sequence of sniffer was amplified from a cDNA-library, cloned into a bacterial expression vector and the His-tagged protein was purified by Ni-chelate chromatography. We found that sniffer catalyzed the NADPH-dependent carbonyl reduction of 4ONE (K(m)=24±2 μM, k(cat)=500±10 min(-1), k(cat)/K(m)=350 s(-1) mM(-1)) but not that of 4HNE. The reaction product of 4ONE reduction by sniffer was mainly 4HNE as shown by HPLC- and GC/MS analysis. Since 4HNE, though still a potent electrophile, is less neurotoxic and protein reactive than 4ONE, one mechanism by which sniffer exerts its neuroprotective effects in Drosophila after oxidative stress may be enzymatic reduction of 4ONE. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  14. Carbonyl Stress and Microinflammation-Related Molecules as Potential Biomarkers in Schizophrenia

    Directory of Open Access Journals (Sweden)

    Tohru Ohnuma

    2018-03-01

    Full Text Available This literature review primarily aims to summarize our research, comprising both cross-sectional and longitudinal studies, and discuss the possibility of using microinflammation-related biomarkers as peripheral biomarkers in the diagnosis and monitoring of patients with schizophrenia. To date, several studies have been conducted on peripheral biomarkers to recognize the potential markers for the diagnosis of schizophrenia and to determine the state and effects of therapy in patients with schizophrenia. Research has established a correlation between carbonyl stress, an environmental factor, and the pathophysiology of neuropsychiatric diseases, including schizophrenia. In addition, studies on biomarkers related to these stresses have achieved results that are either replicable or exhibit consistent increases or decreases in patients with schizophrenia. For instance, pentosidine, an advanced glycation end product (AGE, is considerably elevated in patients with schizophrenia; however, low levels of vitamin B6 [a detoxifier of reactive carbonyl compounds (RCOs] have also been reported in some patients with schizophrenia. Another study on peripheral markers of carbonyl stress in patients with schizophrenia revealed a correlation of higher levels of glyceraldehyde-derived AGEs with higher neurotoxicity and lower levels of soluble receptors capable of diminishing the effects of AGEs. Furthermore, studies on evoked microinflammation-related biomarkers (e.g., soluble tumor necrosis factor receptor 1 have reported relatively consistent results, suggesting the involvement of microinflammation in the pathophysiology of schizophrenia. We believe that our cross-sectional and longitudinal studies as well as various previous inflammation marker studies that could be interpreted from several perspectives, such as mild localized encephalitis and microvascular disturbance, highlighted the importance of early intervention as prevention and distinguished the possible

  15. A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

    OpenAIRE

    Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

    2013-01-01

    The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst...

  16. A green synthesis of α,β-unsaturated carbonyl compounds from glyceraldehyde acetonide

    Directory of Open Access Journals (Sweden)

    Cláudia O. Veloso

    2011-01-01

    Full Text Available The catalytic behavior of Cs-exchanged and Cs-impregnated zeolites (X and Y was studied using the Knoevenagel condensation between glyceraldehyde acetonide and ethyl acetoacetate in order to produce the corresponding α,β-unsaturated carbonyl compound that is an important intermediate for fine chemicals. The influence of reaction temperature, type of zeolite, and basicity of the sites on the catalytic behavior of the samples was evaluated. All zeolites were active for the studied reaction. The formation of the main condensation product was favored at lower reaction temperatures. Products of further condensations were also observed especially for samples that were only dried before catalytic test.

  17. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Rosilio, Charles; Ruaudel-Teixier, Annie.

    1976-01-01

    Evidence is given for chemical reactions of hydrazine (NH 2 -NH 2 ) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers [fr

  18. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol

    DEFF Research Database (Denmark)

    Mang, Stephen A.; Henricksen, Dana K.; Bateman, Adam P.

    2008-01-01

    of freshly prepared SOA was estimated to be on the order of' 15 L mol(-1) cm(-1) at 300 rim, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result......The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored...

  19. Determination of carbonyl compounds in air by HPLC; Determinacion de compuestos carbonilicos en aire por HPLC

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, S; Perez, R M; Campos, A; Gonzalez, D

    1995-07-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs.

  20. 13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

    International Nuclear Information System (INIS)

    Ben Taarit, Y.

    1979-01-01

    13 C NMR spectroscopy was used to investigate the nature of carbon monoxide adsorbed on transition metal ions hosted in a synthetic faujastite type zeolite. The adsorbed CO species was characterised by a highly shielded carbon nucleus. Using the Pople approximation for the paramagnetic shielding term, the observed chemical shift was rationalised assuming the formation of a cationic carbonyl species with an appreciable electronic transfer from the carbon lone pair to the transition metal ion and negligible π back-bonding if at all. (Auth.)