X-ray Lβ215 emission spectrum of Ru in Ru(NH3)6Cl3

International Nuclear Information System (INIS)

Perera, R.C.C.; Barth, J.; LaVilla, R.E.; Nordling, C.

1984-07-01

One of the broader applications of synchrotron radiation has been to EXAFS studies for material structure determination, i.e., for an analysis of x-ray absorption over an extended energy region beyond a core ionization limit. Studies of the near edge structure (XANES) give a different type of information, characteristic of the local symmetry and electronic configuration of the absorbing atom. This type of information is reflected also in the x-ray emission spectra, in particular for transitions involving the valence levels. Examination of the near edge absorption or the emission spectrum does not require an instrument capable of scanning a wide energy range with high counting statistics, as does EXAFS; the needs are rather for good resolution and a reliable calibration of the energy scale. Some of the problems of near edge spectra were particularly evident in our investigation of Ru-Lβ 2 15 emission from Ru(NH 3 ) 6 Cl 3 . The Ru-Lβ 2 15 emission was measured with a laboratory Rowland circle x-ray spectrometer with a curved quartz (1010) crystal (radius = 22 inches) in a fixed position appropriate to the energy range, and a position sensitive detector which can be positioned along the Rowland circle. The Ru spectrum was excited mainly by Sn-L/sub α/ primary radiation from a Sn anode in a demountable x-ray tube operating at 13 kV and 120 mA. The resolution of the instrument in this region is 1.5 eV. An accurate calibration of the energy scale was conveniently obtained by measuring a reference x-ray emission line in the same instrumental configuration. In the present case the Pd-L/sub α/ emission line at 2838 eV was used to establish the energy scale. The energy dispersion of the instrument was determined from the Cl-K/sub β/ emission spectrum of CH 3 Cl between 2810 eV and 2830 eV and Pd-Lα 1 2 and extrapolated to the energy region of the recorded emission spectrum. 6 references, 1 figure

Vaporization of GaI3Py adduct

International Nuclear Information System (INIS)

Timoshkina, A.Yu.; Grigor'ev, A.A.; Suvorov, A.V.

1995-01-01

Processes of GaI 3 Py complex vaporization have been studied by mass-spectrometric, tensimetric and calorimetric methods. It is shown that adduct transformation into vapour is accompanied by its thermal dissociation. Thermodynamic characteristics of evaporation and dissociation of GaI 3 Py complex have been obtained. 14 refs., 2 figs., 6 tabs

Cu(OAc)2 catalyzed Sonogashira cross-coupling reaction in amines

Institute of Scientific and Technical Information of China (English)

Sheng Mei Guo; Chen Liang Deng; Jin Heng Li

2007-01-01

A simple Cu(OAc)2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu(OAc)2 as the catalyst and Et3N as the solvent.

Cyclopolymerization-derived block-copolymers of 4,4-bis(octyloxymethyl)-1,6-heptadiyne with 4,4- dipropargyl malonodinitrile for use in photovoltaics

DEFF Research Database (Denmark)

Sudheendran, Mavila; Horecha, Marta; Kiriy, Anton

2013-01-01

where polymerizations were triggered by [Ru(NCO)2(IMesH2)(]CH-2-(2-PrO)–C6H4] (I2) and [Ru(NCO)2(3-Br-Py)2(IMesH2)(CHPh)] (I3), (IMesH2 ¼ 1,3-dimesitylimidazolin-2-ylidene, 3-Br-Py ¼ 3-bromopyridine), the use of RuCl2(Py)2(IMesH2)(CHPh) (I1) in THF allowed for the synthesis of poly(M1) without any...... backbiting, though with a broad PDI. Block copolymers, i.e. poly(M1)-b-poly(M2), could be prepared in a living manner without any backbiting by the use of the Mo-based Schrock-type initiator Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)(OCH(CH3)2)2 (I4) and THF as solvent. Poly(M1)-b-poly(M2) was characterized by UV...

Band structure of metallic pyrochlore ruthenates Bi2Ru2O7 and Pb2Ru2O/sub 6.5/

International Nuclear Information System (INIS)

Hsu, W.Y.; Kasowski, R.V.; Miller, T.; Chiang, T.

1988-01-01

The band structure of Bi 2 Ru 2 O 7 and Pb 2 Ru 2 O/sub 6.5/ has been computed self-consistently from first principles for the first time by the pseudofunction method. We discover that the 6s bands of Bi and Pb are very deep and unlikely to contribute to the metallic behavior as previously believed. The unoccupied 6p bands, however, are only several eV above the Fermi energy and are mixed with the Ru 4d band at the Fermi surface via the framework O atoms, leading to band conduction and delocalized magnetic moments. The predicted location of the 6s bands and the location and width of the O 2p band are confirmed by synchrotron radiation and ultraviolet electron spectroscopy of single crystals

Unexpected Behavior of Enaminones: Interesting New Routes to 1,6-Naphthyridines, 2-Oxopyrrolidines and Pyrano[4,3,2-de][1,6]naphthyridines

Directory of Open Access Journals (Sweden)

Herbert Meier

2012-12-01

Full Text Available Reaction of enaminones 1a–d with 2-aminoprop-1-ene-1,1,3-tricarbonitrile (2 in the presence of AcOH/NH4OAc afforded 7-amino-5-oxo-5,6-dihydro-1,6-naphthyridine-8-carbonitrile derivatives 9a–d. On the other hand, 2-aminopyrano[4,3,2-de] [1,6]naphthyridine-3-carbonitriles 20a–c,e were the only obtained products from the reactions of 1a–d with 2 in the presence of AcOH/NaOAc, while 1d afforded [3,5-bis-(4-chloro-benzoyl-phenyl]-(4-chloro-phenyl-methanone 21 under the same condition. The reaction of 2 with diethyl acetylenedicarboxylate in the presence of AcOH/NH4OAc afforded (4-cyano-5-dicyanomethylene-2-oxo-2,5-dihydro-1H-pyrrol-3-yl-acetic acid ethyl ester 15B.

High temperature-induced phase transitions in Sr2GdRuO6 complex perovskite

International Nuclear Information System (INIS)

Triana, C.A.; Corredor, L.T.; Landínez Téllez, D.A.; Roa-Rojas, J.

2011-01-01

Highlights: ► Crystal structure, thermal expansion and phase transitions at high-temperature of Sr 2 GdRuO 6 perovskite has been investigated. ► X-ray diffraction pattern at 298 K of Sr 2 GdRuO 6 corresponds to monoclinic perovskite-type structure with P2 1 /n space group. ► Evolution of X-ray diffraction patterns at high-temperature shows that the Sr 2 GdRuO 6 perovskite suffers two-phase transitions. ► At 573 K the X-ray diffraction pattern of Sr 2 GdRuO 6 corresponds to monoclinic perovskite-type structure with I2/m space group. ► At 1273 K the Sr 2 GdRuO 6 perovskite suffers a complete phase-transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87). -- Abstract: The crystal structure behavior of the Sr 2 GdRuO 6 complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K ≤ T ≤ 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2 1 /n (no. 14) space group and 1:1 ordered arrangement of Ru 5+ and Gd 3+ cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Å, b =5.8234(1) Å, c =8.2193(9) Å, V = 278.11(2) Å 3 and angle β = 90.310(5)°. The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (no. 12) space group with lattice parameters a = 5.8275(6) Å, b = 5.8326(3) Å, c = 8.2449(2) Å, V = 280.31(3) Å 3 and angle β = 90.251(3)°. Close to 1273 K it undergoes a complete phase-transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87), with lattice parameters a = 5.8726(1) Å, c = 8.3051(4) Å, V = 286.39(8) Å 3 and angle β = 90.0°. The high-temperature phase transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87) is characterized

Chlorination of (PheboxIr(mesityl(OAc by Thionyl Chloride

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Meng Zhou

2015-06-01

Full Text Available Pincer (PheboxIr(mesityl(OAc (2 (Phebox = 3,5-dimethylphenyl-2,6-bis(oxazolinyl complex, formed by benzylic C-H activation of mesitylene (1,3,5-trimethylbenzene using (PheboxIr(OAc2OH2 (1, was treated with thionyl chloride to rapidly form 1-(chloromethyl-3,5-dimethylbenzene in 50% yield at 23 °C. A green species was obtained at the end of reaction, which decomposed during flash column chromatography to form (PheboxIrCl2OH2 in 87% yield.

Synthesis and crystal structure of a new homoleptic tetraarylruthenium(IV) complex Ru(2,4,5-Me{sub 3}C{sub 6}H{sub 2}){sub 4}

Energy Technology Data Exchange (ETDEWEB)

Wang, Chang-Jiu; Wu, Xiu-Li; Ma, Xiu-Fang; Jia, Ai-Quan; Zhang, Qian-Feng [Anhui Univ. of Technology, Anhui (China). Inst. of Molecular Engineering and Applied Chemistry and Anhui Province Key Lab. of Metallurgy Engineering and Resources Recycling

2017-08-01

Treatment of [Ru(acac){sub 3}] (acac-=acetylacetonate) with (2,4,5-Me{sub 3}C{sub 6}H{sub 2})MgBr, followed by column chromatography in air, afforded the homoleptic tetraaryl-ruthenium(IV) complex [Ru(2,4,5-Me{sub 3}C{sub 6}H{sub 2}){sub 4}] (1) in moderate yield. The product was characterized by proton NMR spectroscopy and microanalyses. Its crystal structure has also been established by X-ray crystallography.

Comparative study of the catalytic activity of the complexes Cp{sup *}RuCl(PAr{sub 3}){sub 2} [Ar = -C{sub 6H}5 and 4-CF{sub 3}-C{sub 6}H{sub 4}] in the ATRP of styrene

Energy Technology Data Exchange (ETDEWEB)

Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R., E-mail: rtorres@ciqa.mx [Departamento de Sintesis de Polimeros, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico); Saldivar-Guerra, Enrique [Departamento de Procesos de Polimerizacion, Centro de Investigacion en Quimica Aplicada, Coah. (Mexico)

2011-09-15

Styrene polymerization by ATRP was conducted independently using the complexes Cp{sup *}RuCl(PPh{sub 3}){sub 2}, and Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as catalysts, in order to evaluate the influence of the electronic properties of the phosphine ligands on the rate and control of the polymerization. The kinetic data for polymerizations carried out with Cp{sup *}RuCl(PPh{sub 3}){sub 2}, show that molecular weights increase linearly with conversion with an average initiation efficiency of 0.77. The molecular weights obtained in the kinetic study with Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} also increase with conversion but show a marked deviation below the theoretical molecular weights. This behavior was explained by the gradual, irreversible, oxidation of catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2} as confirmed by {sup 31}P-NMR spectroscopy. Catalyst Cp{sup *}RuCl(PPh{sub 3}){sub 2} promotes the polymerization with a rate of polymerization higher than that obtained using Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}; this is consistent with the better electron donating properties of PPh{sub 3} versus P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}. Preliminary studies of styrene polymerization by ATRP in supercritical CO{sub 2}, shows that only catalyst Cp{sup *}RuCl[P(4-CF{sub 3}-C{sub 6}H{sub 4}){sub 3}]{sub 2}, with fluorinated ligands, was active. (author)

Interaction between exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 and bromine

International Nuclear Information System (INIS)

Timofeev, S.V.; Lobanova, I.A.; Petrovskij, P.V.; Starikova, Z.A.; Bregadze, V.I.

2001-01-01

Interaction between exo-nido-ruthenacarborane [Cl(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 with bromine in CH 2 Cl 2 solutions at 0 deg C studied using the methods of elementary analysis, NMR, IR spectroscopy and X-ray diffraction analysis. It was ascertained that the reaction gives rise to bromine atom substitution for chlorine atom in octahedral surrounding of ruthenium atom with formation of complex [Br(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 . The complex is crystallized in monoclinic crystal system with the following unit cell parameters a = 12.592 (1), b = 20.687 (2), c = 16.628 (2) A, β = 94.372 (3) deg, sp. gr. P2 1 /n, Z = 4. Coordination octahedron of ruthenium atom is formed by three hydrogen atoms bound with boron atoms in one triangular face of carborane, two phosphorus atoms and one bromine atom [ru

1.3.3. Synthesis, characterization and crystal structure of a new ruthenium polypyridyl complex [Ru(phen2(4,4'-dicarboxy-2,2'- bipyridine]PF6

Directory of Open Access Journals (Sweden)

Jiaxi Chen, Jing Sun*, Jufang Kong, Wenxiu Chen and Hongqing Hao*

2015-03-01

Full Text Available Abstract: A new Ru(II polypyridyl complex, [Ru(phen2(4,4'-dicarboxy-2,2'-bipyridine]PF6·1.5H2O, was synthesized andcharacterized by single crystal X-ray diffraction, elementalanalyses, electrospray ionization mass spectrometry, infraredspectra, ultraviolet (UV spectra, and emission spectra. Thestructure of the cation [Ru(phen2(4,4'-(COO-,(COOH-2,2'-bpy]+ consists of a six-coordinated ruthenium atom chelated bytwo phen ligands and one 4,4'-dicarboxy-2,2'-bipyridine ligand.The absorption spectrum of the Ru(II complex is characterizedby two intense ligand-centered transitions in the UV region andone metal to ligand charge transfer in the visible region. Moreover,the complex can display luminescence in water at roomtemperature, with maximum emission at 623 nm.Supporting information: Cif file

Metal Dependence of Signal Transmission through MolecularQuantum-Dot Cellular Automata (QCA: A Theoretical Studyon Fe, Ru, and Os Mixed-Valence Complexes

Directory of Open Access Journals (Sweden)

Ken Tokunaga

2010-08-01

Full Text Available Dynamic behavior of signal transmission through metal complexes [L5M-BL-ML5]5+ (M=Fe, Ru, Os, BL=pyrazine (py, 4,4’-bipyridine (bpy, L=NH3, which are simplified models of the molecular quantum-dot cellular automata (molecular QCA, is discussed from the viewpoint of one-electron theory, density functional theory. It is found that for py complexes, the signal transmission time (tst is Fe(0.6 fs < Os(0.7 fs < Ru(1.1 fs and the signal amplitude (A is Fe(0.05 e < Os(0.06 e < Ru(0.10 e. For bpy complexes, tst and A are Fe(1.4 fs < Os(1.7 fs < Ru(2.5 fs and Os(0.11 e < Ru(0.12 e py complexes. Among all complexes, Fe complex with bpy BL shows the best result. These results are discussed from overlap integral and energy gap of molecular orbitals.

Enantioselective light switch effect of Δ- and Λ-[Ru(phenanthroline)2 dipyrido[3,2-a:2', 3'-c]phenazine]2+ bound to G-quadruplex DNA.

Science.gov (United States)

Park, Jin Ha; Lee, Hyun Suk; Jang, Myung Duk; Han, Sung Wook; Kim, Seog K; Lee, Young-Ae

2018-06-01

The interaction of Δ- and Λ-[Ru(phen) 2 DPPZ] 2+ (DPPZ = dipyrido[3,2-a:2', 3'-c]phenazine, phen = phenanthroline) with a G-quadruplex formed from 5'-G 2 T 2 G 2 TGTG 2 T 2 G 2-3 '(15-mer) was investigated. The well-known enhancement of luminescence intensity (the 'light-switch' effect) was observed for the [Ru(phen) 2 DPPZ] 2+ complexes upon formation of an adduct with the G-quadruplex. The emission intensity of the G-quadruplex-bound Λ-isomer was 3-fold larger than that of the Δ-isomer when bound to the G-quadruplex, which is opposite of the result observed in the case of double stranded DNA (dsDNA); the light switch effect is larger for the dsDNA-bound Δ-isomer. In the job plot of the G-quadruplex with Δ- and Λ-[Ru(phen) 2 DPPZ] 2+ , a major inflection point for the two isomers was observed at x ≈ .65, which suggests a binding stoichiometry of 2:1 for both enantiomers. When the G base at the 8th position was replaced with 6-methyl isoxanthopterin (6MI), a fluorescent guanine analog, the excited energy of 6-MI transferred to bound Δ- or Λ-[Ru(phen) 2 DPPZ] 2+ , which suggests that at least a part of both Ru(II) enantiomers is close to or in contact with the diagonal loop of the G-quadruplex. A luminescence quenching experiment using [Fe(CN) 6 ] 4- for the G-quadruplex-bound Ru(II) complex revealed downward bending curves for both enantiomers in the Stern-Volmer plot, which suggests the presence of Ru(II) complexes that are both accessible and inaccessible to the quencher and may be related to the 2:1 binding stoichiometry.

Synthesis process and structural characterization of the Sr{sub 2}EuRuO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales (GFNM), Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 5997 (Colombia)

2012-03-05

Highlights: Black-Right-Pointing-Pointer Crystal structure, surface morphology and composition of Sr{sub 2}EuRuO{sub 6} have been studied. Black-Right-Pointing-Pointer Sr{sub 2}EuRuO{sub 6} crystallize in a monoclinic perovskite-type structure in P2{sub 1}/n space group. Black-Right-Pointing-Pointer Ru{sup 5+} and Eu{sup 3+} ions are on the six coordinate M sites, Sr{sup 2+} is located in the A-site. Black-Right-Pointing-Pointer Scanning electron microscopy and Scherrer formula shows a particle size of D = 34.2 nm. Black-Right-Pointing-Pointer Activation energy Q through the Arrhenius plot for Sr{sub 2}EuRuO{sub 6} is close to 39.6 kJ/mol. - Abstract: The Sr{sub 2}EuRuO{sub 6} complex perovskite has been synthesized by the solid-state reaction method and the crystal structure, surface morphology and composition have been investigated. Results of powder X-ray diffraction measurements and Rietveld analysis show that this compound crystallizes in a monoclinic distorted perovskite-type structure, which belongs to the monoclinic P2{sub 1}/n (no. 14) space group, that corresponds to the (a{sup +}b{sup -}b{sup -}) tilt system on the Glazer notation. The structure presents an alternating distribution of the Ru{sup 5+} and Eu{sup 3+} ions on the six coordinate M sites, while the Sr{sup 2+} is located in the A-site of the Sr{sub 2}EuRuO{sub 6} complex perovskite, with lattice parameters a = 5.7996(5) Angstrom-Sign , b = 5.8960(7) Angstrom-Sign , c = 8.3234(6) Angstrom-Sign , angle {beta} = 90.234(7) Degree-Sign and V = 284.61(4) Angstrom-Sign {sup 3}. Morphological analysis of this material, performed by scanning electron microscopy (SEM), allows to establish the granular feature of compound with agglomerates from amongst Almost-Equal-To 1 to 3 {mu}m size, and by means of the Scherrer formula was calculated a particle size of D = 34.2 nm. Result suggests that crystal structure of the Sr{sub 2}EuRuO{sub 6} suffers grain size-induced polarization rotation, which produces a

Several novel Ru(II) and Ru(III) complexes formed by reduction of (RuO4bipy) and (RuO3phen)2O with hydroquinone and methanol

International Nuclear Information System (INIS)

Ishiyama, Toshio

1975-01-01

The geometrical isomers, cis-dichloro-trans-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II) and cis-dichloro-cis-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II), [RuCl 2 (MeOH)(QH 2 )bipy] (complex I and II), were synthesized by reduction and substitution reactions of [RuO 4 bipy] and [RuO 2 (OH) 2 bipy] with hydroquinone in hydrochloric acid solution, and methanol. cis-Chloro(hydroquinonato)bis(2,2'-bipyridine)ruthenium(II), cis-[RuCl(QH)(bipy) 2 ], was obtained from the substitution reaction of complex I or II with 2,2'-bipyridine in methanol, and cis-chloro(hydroquinone)bis(2,2'-bipyridine)ruthenium(II) chloride, cis-[RuCl(QH 2 )(bipy) 2 ]Cl, was also obtained from the substitution of cis-trans-[RuCl 2 (MeOH)(QH 2 )bipy] in methanol containing hydrochloric acid. cis-Dihydroxobis(2,2'-bipyridine)ruthenium(II), cis-[Ru(OH) 2 (bipy) 2 ], was obtained by heating an aqueous solution of cis-[RuCl(QH)(bipy) 2 ]. Trihydroxoaquo(1,10-phenanthroline)ruthenium(III), [Ru(OH) 3 (H 2 O)phen] was also synthesized from [RuO 3 phen] 2 O and [Ru(OH) 3 phen] 2 O by reduction reactions similar to those used for [RuCl 2 (MeOH)(QH 2 )bipy]. These complexes were characterized by the infrared, visible and ultraviolet absorption spectra, and also by polarographic and magnetic measurements. The structures are discussed. (auth.)

AuRu/meso-Mn2O3: A Highly Active and Stable Catalyst for Methane Combustion

Science.gov (United States)

Han, Z.; Fang, J. Y.; Xie, S. H.; Deng, J. G.; Liu, Y. X.; Dai, H. X.

2018-05-01

Three-dimensionally ordered mesoporous Mn2O3 (meso-Mn2O3) and its supported Au, Ru, and AuRu alloy (0.49 wt% Au/meso-Mn2O3, 0.48 wt% Ru/meso-Mn2O3, and 0.97 wt% AuRu/meso-Mn2O3 (Au/Ru molar ratio = 0.98)) nanocatalysts were prepared using the KIT-6-templating and polyvinyl alcohol-protected reduction methods, respectively. Physicochemical properties of the samples were characterized by means of numerous techniques, and their catalytic activities were evaluated for the combustion of methane. It is found that among all of the samples, 0.48 wt% Ru/meso-Mn 2O3 and 0.97 wt% AuRu/meso-Mn2O3 performed the best (the reaction temperature (T90% ) at 90% methane conversion was 530-540°C), but the latter showed a better thermal stability than the former. The partial deactivation of 0.97 wt% AuRu/meso-Mn2O3 due to H2O or CO2 introduction was reversible. It is concluded that the good catalytic activity and thermal stability of 0.97 wt% AuRu/meso-Mn2O3 was associated with the high dispersion of AuRu alloy NPs (2-5 nm) on the surface of meso-Mn2O3 and good low-temperature reducibility.

High temperature-induced phase transitions in Sr{sub 2}GdRuO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Corredor, L.T.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 14490 (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, Bogota D.C. A.A. 14490 (Colombia)

2011-12-15

Highlights: Black-Right-Pointing-Pointer Crystal structure, thermal expansion and phase transitions at high-temperature of Sr{sub 2}GdRuO{sub 6} perovskite has been investigated. Black-Right-Pointing-Pointer X-ray diffraction pattern at 298 K of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with P2{sub 1}/n space group. Black-Right-Pointing-Pointer Evolution of X-ray diffraction patterns at high-temperature shows that the Sr{sub 2}GdRuO{sub 6} perovskite suffers two-phase transitions. Black-Right-Pointing-Pointer At 573 K the X-ray diffraction pattern of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with I2/m space group. Black-Right-Pointing-Pointer At 1273 K the Sr{sub 2}GdRuO{sub 6} perovskite suffers a complete phase-transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87). -- Abstract: The crystal structure behavior of the Sr{sub 2}GdRuO{sub 6} complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K {<=} T {<=} 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2{sub 1}/n (no. 14) space group and 1:1 ordered arrangement of Ru{sup 5+} and Gd{sup 3+} cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Angstrom-Sign , b =5.8234(1) Angstrom-Sign , c =8.2193(9) Angstrom-Sign , V = 278.11(2) Angstrom-Sign {sup 3} and angle {beta} = 90.310(5) Degree-Sign . The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (no. 12) space group with lattice parameters a = 5.8275(6) Angstrom-Sign , b = 5.8326(3) Angstrom-Sign , c = 8.2449(2) Angstrom-Sign , V = 280.31(3) Angstrom-Sign {sup 3} and angle {beta} = 90.251(3) Degree-Sign . Close

PyKE3: data analysis tools for NASA's Kepler, K2, and TESS missions

Science.gov (United States)

Hedges, Christina L.; Cardoso, Jose Vinicius De Miranda; Barentsen, Geert; Gully-Santiago, Michael A.; Cody, Ann Marie; Barclay, Thomas; Still, Martin; BAY AREA ENVIRONMENTAL RESEARCH IN

2018-01-01

The PyKE package is a set of easy to use tools for working with Kepler/K2 data. This includes tools to correct light curves for cotrending basis vectors, turn the raw Target Pixel File data into motion corrected light curves, check for exoplanet false positives and run new PSF photometry. We are now releasing PyKE 3, which is compatible with Python 3, is pip installable and no longer depends on PyRAF. Tools are available both as Python routines and from the command line. New tutorials are available and under construction for users to learn about Kepler and K2 data and how to best use it for their science goals. PyKE is open source and welcomes contributions from the community. Routines and more information are available on the PyKE repository on GitHub.

Activity of carbon supported Pt3Ru2 nanocatalyst in CO oxidation

Directory of Open Access Journals (Sweden)

KSENIJA DJ. POPOVIĆ

2009-08-01

Full Text Available The electrocatalytic activity of Pt3Ru2/C nanocatalyst toward the electro-oxidation of bulk CO was examined in acid and alkaline solution at ambient temperature using the thin-film, rotating disk electrode (RDE method. The catalyst was characterized by XRD analysis. The XRD pattern revealed that the Pt3Ru2/C catalyst consisted of two structures, i.e., Pt–Ru-fcc and Ru-hcp (a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. Electrocatalytic activities were measured by applying potentiodynamic and steady state techniques. The oxidation of CO on the Pt3Ru2/C catalyst was influenced by pH and anions from the supporting electrolytes. The Pt3Ru2/C was more active in alkaline than in acid solution, as well as in perchloric than in sulfuric acid. Comparison of CO oxidation on Pt3Ru2/C and Pt/C revealed that the Pt3Ru2/C was more active than Pt/C in acid solution, while both catalysts had a similar activity in alkaline solution.

Standard enthalpies of formation of selected Ru{sub 2}YZ Heusler compounds

Energy Technology Data Exchange (ETDEWEB)

Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

2015-06-15

Highlights: • Standard enthalpies of formation of Ru{sub 2}YZ were measured using a drop calorimeter. • Result of L2{sub 1} structured compounds agrees with first principles data. • Lattice parameters and related phase relationships were consistent with literature data. • Ru{sub 2}HfSn, Ru{sub 2}TiSn, Ru{sub 2}VGa, Ru{sub 2}VSi, Ru{sub 2}VSn of L2{sub 1} structure were reported for the first time. - Abstract: The standard enthalpies of formation of selected ternary Ru-based Heusler compounds Ru{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V; Z = Al, Ga, In, Si, Ge, Sn) were measured using high temperature direct reaction calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Ru{sub 2}FeGe (−19.7 ± 3.3); Ru{sub 2}HfSn (−24.9 ± 3.6); Ru{sub 2}MnSi (−46.0 ± 2.6); Ru{sub 2}MnGe (−29.7 ± 1.0); Ru{sub 2}MnSn (−20.6 ± 2.4); Ru{sub 2}TiSi (−94.9 ± 4.0); Ru{sub 2}TiGe (−79.1 ± 3.2); Ru{sub 2}TiSn (−60.6 ± 1.8); Ru{sub 2}VSi (−55.9 ± 1.7);for the B2-structured compounds, Ru{sub 2}FeSi (−28.5 ± 0.8); Ru{sub 2}HfAl (−70.8 ± 1.9); Ru{sub 2}MnAl (−32.3 ± 1.9); Ru{sub 2}MnGa (−25.3 ± 3.0); Ru{sub 2}TiAl (−62.7 ± 3.5); Ru{sub 2}VAl (−30.9 ± 1.6); Ru{sub 2}ZrAl (−64.5 ± 1.5). Values were compared with those from published first principles calculations and the OQMD (Open Quantum Materials Database). Lattice parameters of these compounds were determined using X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and Energy Dispersive Spectroscopy (EDS)

Rare earth ruthenium gallides with the ideal composition Ln_2Ru_3Ga_5 (Ln = La-Nd, Sm) crystallizing with U_2Mn_3Si_5 (Sc_2Fe_3Si_5) type structure

International Nuclear Information System (INIS)

Jeitschko, Wolfgang; Schlueter, Martin

2010-01-01

The rare earth ruthenium gallides Ln_2Ru_3Ga_5 (Ln = La, Ce, Pr, Nd, Sm) were prepared by arc-melting of cold-pressed pellets of the elemental components. They crystallize with a tetragonal structure (P4/mnc, Z = 4) first reported for U_2Mn_3Si_5. The crystal structures of the cerium and samarium compounds were refined from single-crystal X-ray data, resulting in significant deviations from the ideal compositions: Ce_2Ru_2_._3_1_(_1_)Ga_5_._6_9_(_1_), a = 1135.10(8) pm, c = 580.58(6) pm, R_F = 0.022 for 742 structure factors; Sm_2Ru_2_._7_3_(_2_)Ga_5_._2_7_(_2_), a = 1132.95(9) pm, c = 562.71(6) pm, R_F = 0.026 for 566 structure factors and 32 variable parameters each. The deviations from the ideal compositions 2:3:5 are discussed. A mixed Ru/Ga occupancy occurs only for one atomic site. The displacement parameters are relatively large for atoms with mixed occupancy within their coordination shell and small for atoms with no neighboring sites of mixed occupancy. Chemical bonding is analyzed on the basis of interatomic distances. Ln-Ga bonding is stronger than Ln-Ru bonding. Ru-Ga bonding is strong and Ru-Ru bonding is weak. The Ga-Ga interactions are of similar strength as in elemental gallium. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Rotational and translational distortions of the crystal structure of the Sr2HrRuO6 (Hr = Ho, Dy, Gd, Eu) complex perovskites

International Nuclear Information System (INIS)

Triana, C.A.; Landínez Téllez, D.A.; Roa-Rojas, J.

2013-01-01

Sr 2 HrRuO 6 (Hr = Ho, Dy, Gd, Eu) complex perovskites were synthesized through the high-temperature solid-state reaction method, and their crystal structures were analyzed in detail as a function of the Hr-cation ionic radius. Results of powder XRD pattern measurement and Rietveld analysis of the experimental profiles show that the Sr 2 HrRuO 6 compounds crystallize in a monoclinic distorted perovskite-like structure, P2 1 /n (#14) space group, where the unit cell parameters are related to the primitive unit cell a p by a≈√(2)a p , b≈√(2)a p and c ≈ 2a p . The structures show an alternate distribution of the Ru 5+ (2d: 0.5, 0, 0) and Hr 3+ (2c: 0, 0.5, 0) making up RuO 6 and HrO 6 octahedra alternatively arranged in two interleaving fcc sublattices, where the O(1), O(2), and O(3) ions are localized at the corner of the octahedral, while the Sr 2+ is located at the A-site, occupying the cavities built by the corner-sharing octahedra with Wyckoff position 4e. Due to the existence of mismatched ionic sizes between the ionic radii of the Sr 2 HrRuO 6 compounds, the HrO 6 and RuO 6 octahedra are constrained to tilting around the [111] c , [001] c , and [110] c cubic directions so as to optimize the Sr–O inter-atomic bond lengths, tending to rotate the structure in order to fix the Ru 5+ and Hr 3+ ions on the M′ and M″ sites of the complex perovskites. The cell parameters a, b, and c, the inter-atomic bond angles, the inter-atomic bond lengths, and the tilting angles increase as the Hr-cation ionic radius increases. The mismatch that exists in the Sr 2 HrRuO 6 ionic radius produces a large distortion from the ideal cubic symmetry. The pure perovskite-like phase of Sr 2 HrRuO 6 is thermodynamically and kinetically stable at high temperatures above 1420 K, where it is entirely governed by the average size of the Hr 3+ and Ru 5+ cations. Highlights: ► Crystal structure of Sr 2 HrRuO 6 (Hr = Ho, Dy, Gd, Eu) as a function of Hr ionic radius. ► XRD

A new and general method for the preparation of novel II-heterocyclic derivatives of ruthenium [C5Me5Ru (η6-arene)]X (arene = benzene, thiophene, 3-methylthiophene, benzothiophene, pyridine, 2.6 and 3.5-lutidine, quinoline, acridine). X-ray crystal structure of [(C5Me5)2Ru2Cl2(pyridine)2] PF6

International Nuclear Information System (INIS)

Chaudret, B.; Jalon, F.; Perez-Manrique, M.; Lahoz, F.; Plou, F.J.

1990-01-01

Zinc reduction of (Cp*RuCl 2 ) n (Cp* = C 5 Me 5 ) in acetone or THF followed by addition of 1 equivalent of an arene or aromatic heterocycle leads to compounds of general formulation [Cp* Ru(arene)]X (X = Cl, BF 4 ). Coordination of benzene is rapid and competes successfully with any other arene. Thiophene and 3-methylthiophene give stable π adducts whereas benzothiophene is coordinated through the benzene not through the heterocyclic ring. 2.6 and 3.5-lutidine coordinate through the ring, thus demonstrating an electronic rather than steric stabilization. Again, quinoline and acridine coordinate through the benzene ring. Pyridine gives an unstable π adduct in THF. A paramagnetic mixed-valence species, byproduct of the reaction in THF, has been characterized by an X-ray crystal structure determination. Crystals are triclinic, space group P-1

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

Science.gov (United States)

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Ruthenium(II) 2,2'-bibenzimidazole complex as a second-sphere receptor for anions interaction and colorimeter.

Science.gov (United States)

Cui, Ying; Niu, Yan-Li; Cao, Man-Li; Wang, Ke; Mo, Hao-Jun; Zhong, Yong-Rui; Ye, Bao-Hui

2008-07-07

A ruthenium(II) complex [Ru(bpy) 2(H 2bbim)](PF 6) 2 ( 1) as anions receptor has been exploited, where Ru(II)-bpy moiety acts as a chromophore and the H 2bbim ligand as an anion binding site. A systematic study suggests that 1 interacts with the Cl (-), Br (-), I (-), NO 3 (-), HSO 4 (-), and H 2PO 4 (-) anions via the formation of hydrogen bonds. Whereas 1 undergoes a stepwise process with the addition of F (-) and OAc (-) anions: formation of the monodeprotonated complex [Ru(bpy) 2(Hbbim)] with a low anion concentration, followed by the double-deprotonated complex [Ru(bpy) 2(bbim)], in the presence of a high anion concentration. These stepwise processes concomitant with the changes of vivid colors from yellow to orange brown and then to violet can be used for probing the F (-) and OAc (-) anions by naked eye. The deprotonation processes are not only determined by the basicity of the anion but also related to the strength of hydrogen bonding, as well as the stability of the formed compounds. Moreover, a double-deprotonated complex [Ru(bpy) 2(bbim)].CH 3OH.H 2O ( 3) has been synthesized, and the structural changes induced by the deprotonation has also been investigated. In addition, complexes [Ru(bpy) 2(Hbbim)] 2(HOAc) 3Cl 2.12H 2O ( 2), [Ru(bpy) 2(Hbbim)](HCCl 3CO 2)(CCl 3CO 2).2H 2O ( 4), and [Ru(bpy) 2(H 2bbim)](CF 3CO 2) 2.4H 2O ( 5) have been synthesized to observe the second sphere coordination between the Ru(II)-H 2bbim moiety and carboxylate groups via hydrogen bonds in the solid state.

Supraconductivity of TR-Ru3Si2 compounds (TR = La, Ce)

International Nuclear Information System (INIS)

Godart, C.; Gupta, L.C.; Parks, R.D.; Rauschwalbe, U.; Alheim, U.; Gottwick, U.; Lieke, W.; Steglich, F.

1984-01-01

A new family of superconducting ternary silicides MRu 3 Si 2 with M = La (Tsub(s) approximately 7 K), Y and Th was discovered by Barz and Vandenberg. Same compounds with M from Nd to Tm are magnetic and not superconductors. We studied superconductivity in the solid solution Cesub(1-x)Lasub(x)Ru 3 Si 2 of hexagonal structure from x = 0 to 1. CeRu 3 Si 2 is type II superconductor (Tsub(s) approximately 1 K), like LaRu 3 Si 2 , and is mixed valent (M.V.). Spin fluctuations temperature (Tsub(sf) approximately 440 K) is between these of non superconducting M.V. like CeSn 3 (Tsub(sf) approximately 270) and these of superconducting M.V. like CeRu 2 (Tsub(sf) approximately 770 K). Cesub(1-x)Lasub(x)Ru 3 Si 2 is the first M.V. system of Ce which is superconductor from x = 0 to 1 [fr

Photocrystallographic structure determination of a new geometric isomer of [Ru(NH3)4(H2O)(eta1-OSO)][MeC6H4SO3]2.

Science.gov (United States)

Bowes, Katharine F; Cole, Jacqueline M; Husheer, Shamus L G; Raithby, Paul R; Savarese, Teresa L; Sparkes, Hazel A; Teat, Simon J; Warren, John E

2006-06-21

The structure of a new metastable geometric isomer of [Ru(NH3)4(H2O)(SO2)][MeC6H4SO3]2 in which the SO2 group is coordinated through a single oxygen in an eta1-OSO bonding mode has been determined at 13 K; the new isomer was obtained as a 36% component of the structure within a single crystal upon irradiation using a tungsten lamp.

Half-metallic and insulating natures in Ru-based ordered double perovskite oxides Ba{sub 2}X{sup III}Ru{sup V}O{sub 6} (X = V, Cr) induced by 3d-t{sub 2g}{sup n} orbital filling

Energy Technology Data Exchange (ETDEWEB)

Saad, H.-E.M. Musa, E-mail: musa.1964@gmail.com; Althoyaib, S.S.

2017-04-01

In this paper, we present results of a comprehensive systemic study of the crystal, electronic and magnetic structures on two members of Ru-based ordered double perovskite oxides Ba{sub 2}XRuO{sub 6} (X = V, Cr). For the corporate compound, the analysis of density of states (DOS) results suggests that the 3d-t{sub 2g} orbital filling plays a major role in governing the conduction mechanism in these systems. The DOS and magnetic results show that Ba{sub 2}XRuO{sub 6} exhibits half-metallic (HM) nature as X = V, where the electronic structure of Ba{sub 2}V{sup III}Ru{sup V}O{sub 6} with 3d-t{sub 2g}{sup 2} behaves like that of HM ferrimagnetic (FI), switches to compensate FI insulating behavior as X = Cr, with an extra electron filled 3d-t{sub 2g}{sup 3} in Ba{sub 2}Cr{sup III}Ru{sup V}O{sub 6}. We find, on consideration of electron correlation (LSDA+U) and spin-orbital coupling (SOC) effects that the electronic structure of Ba{sub 2}XRuO{sub 6} takes a HM nature, whereas it is completely transformed to insulating nature once an extra electron filled the 3d-t{sub 2g} orbitals in X = Cr case. Such tuning is accompanied by spin-state hopping of one electron from half-filled spin-state in Ru{sup V} (t{sub 2g}{sup 3} e{sub g}{sup 0}) to two and three occupied spin-state in V{sup III} (t{sub 2g}{sup 2} e{sub g}{sup 0}) and Cr{sup III} (t{sub 2g}{sup 3} e{sub g}{sup 0}), respectively. The charge distribution results show that this extra electron occupies chiefly the spin-down of conduction orbitals and plays a major role in determining the electronic and magnetic structures of Ba{sub 2}XRuO{sub 6} system. - Highlights: • Half-metallic and insulating natures are observed in Ba{sub 2}XRuO{sub 6} (X = V, Cr). • 3d-t{sub 2g}{sup n} orbitals filling plays a major role in governing the conduction mechanism. • LSDA+U method under density functional theory (DFT) is considered. • HM ferrimagnetic (FI) (X = V) switch to compensate FI insulating (X = Cr).

Polymerization of 1,3-butadiene catalyzed by pincer cobalt(II) complexes derived from 2-(1-arylimino)-6-(pyrazol-1-yl)pyridine ligands

KAUST Repository

Gong, Dirong; Jia, Weiguo; Chen, Tao; Huang, Kuo-Wei

2013-01-01

A new class of air stable and structurally well-defined cobalt complexes with unsymmetrical pincer type ligands ([2-(ArNCMe)-6-(Py)C5H 3N]CoCl2) (Ar = C6H5, Py = pyrazol-1-yl, 5a; Ar = 2,4,6-Me3C6H2, Py = pyrazol-1-yl, 5b; Ar = 2,6-iPr2C6H3, Py

Structural and electronic behavior of Sr2GdRuO6 complex perovskite

International Nuclear Information System (INIS)

Corredor, L.T.; Velasco Zarate, J.; Landinez Tellez, D.A.; Fajardo, F.; Arbey Rodriguez M, J.; Roa-Rojas, J.

2009-01-01

We report experimental and theoretical study of crystallographic lattice and electronic structure of Sr 2 GdRuO 6 complex perovskite, which is used as precursor in the fabrication process of superconducting ruthenocuprate RuSr 2 GdCu 2 O 8 . Samples were produced by the standard solid state reaction. Rietveld refinement of experimental X-ray diffraction patterns shows that material crystallizes in a monoclinic structure, which belongs to the P2 1 /n (no.14) space group, with lattice parameters a=5.8019(6)A, b=5.8296(5)A, c=8.2223(7)A, and tilt angle β=90.258 deg. Calculations of electronic structure were performed by the density functional theory. The exchange and correlation potentials were included through the LDA+U approximation. Density of states (DOS) study was carried out considering the two spin polarizations. Results show Gd are majority responsible for the magnetic character in this material, but Ru contribution is also relevant because d-orbital is closer to Fermi level. Theoretical results evidence that Sr 2 GdRuO 6 material behaves as a magnetic semiconductor, with 20μ B effective magnetic moment.

Relaxor behavior in spin glass perovskite Sr2CoRuO6

International Nuclear Information System (INIS)

Phatak, Rohan; Sali, S.K.; Mishra, S.K.; Das, A.

2014-01-01

Dielectric properties of Sr 2 CoRuO 6 perovskite have been investigated. The compound crystallizes in monoclinic I2/c space group, with random distribution of Co and Ru ion on B site. From our previous study, we showed this compound to be magnetic spin glass with transition at 95K, and was investigated using neutron diffraction and depolarization, ac magnetization and time dependent magnetization

The methylcobalt(III) complex of a tetrapodal pentadentate amine ligand, 2,6-bis(1′,3′-diamino-2′-methyl-prop-2′-yl)pyridine

DEFF Research Database (Denmark)

Grohmann, Andreas; Heinemann, Frank W; Kofod, Pauli

1999-01-01

The pentaamine methylcobalt(III) compound [Co(pyN4)(CH3)](NO3)2 (pyN4=2,6-bis(1′,3′-diamino-2′-methyl-prop-2′-yl)pyridine) has been synthesised from [Co(NH3)5(CH3)](NO3)2 and pyN4 by ligand exchange, and characterised by IR, 1H, 13C and 59Co NMR spectroscopy as well as elemental analysis. The str......The pentaamine methylcobalt(III) compound [Co(pyN4)(CH3)](NO3)2 (pyN4=2,6-bis(1′,3′-diamino-2′-methyl-prop-2′-yl)pyridine) has been synthesised from [Co(NH3)5(CH3)](NO3)2 and pyN4 by ligand exchange, and characterised by IR, 1H, 13C and 59Co NMR spectroscopy as well as elemental analysis...... nitrogen atom, while the four equivalent primary amino groups take the equatorial positions. The other axial position, trans to the pyridine ring, is occupied by the methyl group. The Co–Npy bond length of 2.018(2) Å is significantly elongated compared with other cobalt(III) complexes of the pyN4 ligand...

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

Science.gov (United States)

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

2011-09-07

This paper discusses the synthesis of two carbon-based pyridine ligands of fullerene pyrrolidine pyridine (C(60)-py) and multi-walled carbon nanotube pyrrolidine pyridine (MWCNT-py) via 1,3-dipolar cycloaddition. The two complexes, C(60)-Ru and MWCNT-Ru, were synthesized by ligand substitution in the presence of NH(4)PF(6), and Ru(II)(bpy)(2)Cl(2) was used as a reaction precursor. Both complexes were characterized by mass spectroscopy (MS), elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy (IR), ultraviolet/visible spectroscopy (UV-VIS) spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and cyclic voltammetry (CV). The results showed that the substitution way of C(60)-py is different from that of MWCNT-py. The C(60)-py and a NH(3) replaced a Cl(-) and a bipyridine in Ru(II)(bpy)(2)Cl(2) to produce a five-coordinate complex of [Ru(bpy)(NH(3))(C(60)-py)Cl]PF(6), whereas MWCNT-py replaced a Cl(-) to generate a six-coordinate complex of [Ru(bpy)(2)(MWCNT-py)Cl]PF(6). The cyclic voltammetry study showed that the electron-withdrawing ability was different for C(60) and MWCNT. The C(60) showed a relatively stronger electron-withdrawing effect with respect to MWCNT. This journal is © The Royal Society of Chemistry 2011

Formation of heavy d-electron quasiparticles in Sr3Ru2O7

International Nuclear Information System (INIS)

Allan, M P; Tamai, A; Rozbicki, E; King, P D C; Meevasana, W; Perry, R S; Mercure, J F; Mackenzie, A P; Fischer, M H; Wang, M A; Lee, Jinho; Kim, E-A; Lawler, M J; Shen, K M; Voss, J; Fennie, C J; Thirupathaiah, S; Rienks, E; Fink, J; Tennant, D A

2013-01-01

The phase diagram of Sr 3 Ru 2 O 7 shows hallmarks of strong electron correlations despite the modest Coulomb interaction in the Ru 4d shell. We use angle-resolved photoelectron spectroscopy measurements to provide microscopic insight into the formation of the strongly renormalized heavy d-electron liquid that controls the physics of Sr 3 Ru 2 O 7 . Our data reveal itinerant Ru 4d-states confined over large parts of the Brillouin zone to an energy range of <6 meV, nearly three orders of magnitude lower than the bare band width. We show that this energy scale agrees quantitatively with a characteristic thermodynamic energy scale associated with quantum criticality and illustrate how it arises from a combination of back-folding due to a structural distortion and the hybridization of light and strongly renormalized, heavy quasiparticle bands. The resulting heavy Fermi liquid has a marked k-dependence of the renormalization which we relate to orbital mixing along individual Fermi surface sheets. (paper)

An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4.

Science.gov (United States)

Nicolaou, K C; Adsool, Vikrant A; Hale, Christopher R H

2010-04-02

PhI(OAc)(2) in the presence of OsO(4) (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with alpha-hydroxy ketones as byproduct. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO(4) (cat.), 2,6-lutidine, and PhI(OAc)(2).

Polymerization of 1,3-butadiene catalyzed by pincer cobalt(II) complexes derived from 2-(1-arylimino)-6-(pyrazol-1-yl)pyridine ligands

KAUST Repository

Gong, Dirong

2013-08-01

A new class of air stable and structurally well-defined cobalt complexes with unsymmetrical pincer type ligands ([2-(ArNCMe)-6-(Py)C5H 3N]CoCl2) (Ar = C6H5, Py = pyrazol-1-yl, 5a; Ar = 2,4,6-Me3C6H2, Py = pyrazol-1-yl, 5b; Ar = 2,6-iPr2C6H3, Py = pyrazol-1-yl, 5c; Ar = C6H5, Py = 3,5-Me 2pyrazol-1-yl, 5d; Ar = 2,4,6-Me3C6H 2, Py = 3,5-Me2pyrazol-1-yl, 5e; Ar = 2,6- iPr2C6H3, Py = 3,5-Me 2pyrazol-1-yl, 5f; Ar = 2,6-iPr2C 6H3, Py = 3,5-iPr2pyrazol-1-yl, 5g and [2-(OCMe)-6-(3,5-diphenylpyrazol-1-yl)C5H3N]CoCl 2 5h) were prepared and the molecular structures of 5a, 5c and 5f were determined by single crystal X-ray crystallography. Upon activation by methylaluminoxane (MAO) in toluene at room temperature, all complexes initiate polymerization of 1,3-butadiene (polymer yields: 65-99%), affording polybutadiene with excellent cis-1,4 regularity (97.5-98.7%). The polymer yields and properties in terms of molecular weight and distribution are well controlled by the substituents on iminoaryl rings and pyrazole rings. Selectivity switch from cis-1,4 to syndio-1,2 was also achievable by adding phosphine as microstructure regulator. © 2013 Elsevier B.V. All rights reserved.

Synthesis, P-31 NMR data and X-ray analysis of a ruthenium(II) dimethylphenylphosphine complex with dimerized phenylacetylene: The structure of [(PhMe(2)P)(4)Ru(eta(3)-PhC(3)CHPh)](PF6)

CSIR Research Space (South Africa)

Liles, DC

1996-09-06

Full Text Available Treatment of [RuHL (5)] (+) (L = PMe (2) Ph) with phenylacetylene in ethanol yielded the dimerization of HC=CPh to (Z)-1, 4-diphenylbut-3-en-1-yne. The molecular structure of [Ru(eta(3)-PhC(3)CHPh)L(4)](PF6) (L = PMe(2)Ph) (2) shows a seven...

Mixed valent noble metal perovskites Ba/sub 3/B/sup 3 +/Pt/sub x/Ru/sub 2-x//sup 4. 5+/O/sub 9/

Energy Technology Data Exchange (ETDEWEB)

Moessner, B; Kemmler-Sack, S; Ehmann, A [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1982-04-01

In perovskites of type Ba/sub 3/B/sup 3 +/Pt/sub x/Ru/sub 2-x//sup 4.5+/O/sub 9/ the ruthenium can be substituted by platinum up to x = 1. The compounds crystallize in a 1:2 ordered hexagonal BaTiO/sub 3/ structure (sequence (hcc)/sub 2/) with face connected Pt/sub x/Ru/sub 2-x/O/sub 9/ double octahedra. Intensity calculations on powder data of Ba/sub 3/YPt/sub 1/2/Ru/sub 3/2/O/sub 9/ (space group P6/sub 3//mmc) gave a refined, intensity related R' value of 8.6%. The vibrational spectroscopic and catalytic properties are reported.

Pd(II)/PhI(OAc)2 promoted direct cross coupling of glucals with aromatic acids.

Science.gov (United States)

Begum, Zubeda; Shankar, G; Sirisha, K; Reddy, B V Subba

2018-05-22

A highly efficient oxidative C2-aroyloxylation of D-glucal with aromatic carboxylic acids has been achieved for the first time using 5 mol% Pd(OAc) 2 and 1 equiv of PhI(OAc) 2 to produce C2-aroyloxyglycals in good yields. The use of excess of PhI(OAc) 2 (2 equiv) provides C2-acyloxyglycal exclusively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Rotational and translational distortions of the crystal structure of the Sr{sub 2}HrRuO{sub 6} (Hr = Ho, Dy, Gd, Eu) complex perovskites

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A., E-mail: ctrianae@unal.edu.co [Grupo de Física de Nuevos Materiales, Departamento de Física, Universidad Nacional de Colombia, A.A. 5997, Bogotá D.C. (Colombia); Landínez Téllez, D.A. [Grupo de Física de Nuevos Materiales, Departamento de Física, Universidad Nacional de Colombia, A.A. 5997, Bogotá D.C. (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Física de Nuevos Materiales, Departamento de Física, Universidad Nacional de Colombia, A.A. 5997, Bogotá D.C. (Colombia)

2013-05-15

Sr{sub 2}HrRuO{sub 6} (Hr = Ho, Dy, Gd, Eu) complex perovskites were synthesized through the high-temperature solid-state reaction method, and their crystal structures were analyzed in detail as a function of the Hr-cation ionic radius. Results of powder XRD pattern measurement and Rietveld analysis of the experimental profiles show that the Sr{sub 2}HrRuO{sub 6} compounds crystallize in a monoclinic distorted perovskite-like structure, P2{sub 1}/n (#14) space group, where the unit cell parameters are related to the primitive unit cell a{sub p} by a≈√(2)a{sub p}, b≈√(2)a{sub p} and c ≈ 2a{sub p}. The structures show an alternate distribution of the Ru{sup 5+} (2d: 0.5, 0, 0) and Hr{sup 3+} (2c: 0, 0.5, 0) making up RuO{sub 6} and HrO{sub 6} octahedra alternatively arranged in two interleaving fcc sublattices, where the O(1), O(2), and O(3) ions are localized at the corner of the octahedral, while the Sr{sup 2+} is located at the A-site, occupying the cavities built by the corner-sharing octahedra with Wyckoff position 4e. Due to the existence of mismatched ionic sizes between the ionic radii of the Sr{sub 2}HrRuO{sub 6} compounds, the HrO{sub 6} and RuO{sub 6} octahedra are constrained to tilting around the [111]{sub c}, [001]{sub c}, and [110]{sub c} cubic directions so as to optimize the Sr–O inter-atomic bond lengths, tending to rotate the structure in order to fix the Ru{sup 5+} and Hr{sup 3+} ions on the M′ and M″ sites of the complex perovskites. The cell parameters a, b, and c, the inter-atomic bond angles, the inter-atomic bond lengths, and the tilting angles increase as the Hr-cation ionic radius increases. The mismatch that exists in the Sr{sub 2}HrRuO{sub 6} ionic radius produces a large distortion from the ideal cubic symmetry. The pure perovskite-like phase of Sr{sub 2}HrRuO{sub 6} is thermodynamically and kinetically stable at high temperatures above 1420 K, where it is entirely governed by the average size of the Hr{sup 3+} and Ru

Epitaxial YBa2Cu3O7-δ/Sr2RuO4 heterostructures

International Nuclear Information System (INIS)

Schlom, D.G.; Merritt, B.A.; Madhavan, S.

1997-01-01

The anisotropic oxide superconductors YBa 2 Cu 3 O 7-δ and Sr 2 RuO 4 have been epitaxially combined in various ways (c-axis on c-axis, c-axis on a-axis, and a-axis on a-axis) though the use of appropriate substrates. Phase-pure a-axis oriented or c-axis oriented epitaxial Sr 2 RuO 4 films were grown by pulsed laser deposition. YBa 2 Cu 3 O 7-δ films were then grown on both orientations of Sr 2 RuO 4 films and the resulting epitaxy was characterized

Simple formation of products of exo-nido→closo-regrouping during substitution of PPh3-ligands by bis(diphenyl phosphino)alkanes in three-bridging ruthena carborane 5,6,10-[RuCl(PPh3)2]-5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H8

International Nuclear Information System (INIS)

Cheredilin, D.N.; Balagurova, E.V.; Godovikov, I.A.; Solodovnikov, S.P.; Chizhevskij, I.T.

2005-01-01

It is established that the substitution of PPh 3 -ligands by diphosphines [Ph 2 P(CH 2 ) n PPh] (n=3, 4) in three-bridging exo-nido-ruthena carborane 5,6,10-[RuCl(PPh 3 ) 2 ]-5,6,10-(μ-H) 3 -10-H-exo-nido-7,8-C 2 B 9 H 8 (1) decreases temperature of exo-nido→closo-regrouping (22 Deg C). It is demonstrated that the exo-nido-ruthena carborane complex (1) is well suited and available as reagent for preparation of closo-ruthena carboranes with different chelate diphosphines. Formation of closo-products follows through the stage of exo-nido→closo-regrouping of diphosphine complexes with exo-nido-structure [ru

101Ru NQR study in superconducting CeRu2

International Nuclear Information System (INIS)

Matsuda, Kazuyuki; Kohori, Yoh; Kohara, Takao

1995-01-01

We present measurements of the NQR spectrum and the nuclear spin lattice relaxation rate, 1/T 1 , of 101 Ru in superconducting CeRu 2 from 1.9 K to 10 K. From the NQR spectrum, the electric quadrupole interaction parameters were determined to be ν Q =13.2 MHz and η=0.1/T 1 varies in proportion to temperature in the normal state, and has the Hebel-Slichter coherence peak just below the superconducting transition temperature, T C , of 6.2 K, and decreases exponentially at low temperatures with the energy gap of 2Δ=4.0k B T C . 101 Ru NQR study indicates that CeRu 2 is an s-wave and strong-coupling superconductor. (author)

Mixed valent perovskites Ba/sub 3/B/sup 3 +/Ru/sub 2/sup(4. 5+)O/sub 9/. Catalytic activity of perovskite oxides with noble metals

Energy Technology Data Exchange (ETDEWEB)

Treiber, U; Kemmler-Sack, S; Ehmann, A; Schaller, H U; Duerrschmidt, E; Thumm, I; Bader, H [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-10-01

The black compounds Ba/sub 3/B/sup 3 +/Ru/sub 2/O/sub 9/ crystallize with B/sup 3 +/ = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y in a hexagonal BaTiO/sub 3/ structure (6L, sequence (hcc)/sub 2/) with an ordered distribution (1:2 order) of B/sup 3 +/ and ruthenium (BO/sub 6/ single octahedra; Ru/sub 2/O/sub 9/ double groups). The mean oxidation state of ruthenium is about +4.5. The properties are compared with those of other isotypic stacking polytypes Ba/sub 3/B/sup 3 +/M/sub 2/sup(4.5)O/sub 9/ (M/sub 2/ = IrRu, Ir/sub 2/, PtRu) and Ba/sub 3/B/sup 2 +/M/sub 2//sup 5 +/O/sub 9/ (M = Ru, Ir). The results of activity tests concerning the efficiency of perovskite oxides with noble metals in respect of the oxidation of CO or CHsub(x) and the reduction of NOsub(x) are reported.

Formation of nitrogen complexes when [Ru(NH3)5H2O]2+ ion reaction with diazo-acetic ester and aromatic salts of diazonium

International Nuclear Information System (INIS)

Shur, V.B.; Tikhonova, I.A.; Vol'pin, M.E.

1978-01-01

A possibility of formation of nitrogen complexes during transition metal compound interaction with aliphatic and aromatic diazo compounds is studied. It is shown that at the interaction of [Ru(NH 3 ) 5 H 2 O] 2+ with diazo-acetic ester in water (pH7) at 20 deg, quick splitting of the CN-bond in the ester molecule takes place with the formation of [Ru(NH 3 ) 5 N 2 ] 2+ and [(NH 3 ) 5 RuN 2 Ru(NH 3 ) 5 ] 4+ (NRRN) nitrogen complexes. The sum yield of complexes comprises 86% taking into acount diazo-acetic ester. Aromatic salts of diazonium, n-O 3 SC 6 H 4 N 2 and p-quinone diazide react with the [Ru(NH 3 ) 5 H 2 O] 2+ excess forming NRRN (the yield equals 40-53%). The reaction mechanism is discussed

Solid-state electrochemiluminescence sensor through the electrodeposition of Ru(bpy){sub 3}{sup 2+}/AuNPs/chitosan composite film onto electrode

Energy Technology Data Exchange (ETDEWEB)

Yun Wen; Xu Ying; Dong Ping; Ma Xiongxiong [Department of Chemistry, East China Normal University, ZhongShan Road North 3663, Shanghai 20062 (China); He Pingang [Department of Chemistry, East China Normal University, ZhongShan Road North 3663, Shanghai 20062 (China)], E-mail: pghe@chem.ecnu.edu.cn; Fang Yuzhi [Department of Chemistry, East China Normal University, ZhongShan Road North 3663, Shanghai 20062 (China)], E-mail: yuzhi@online.sh.cn

2009-03-02

Tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy){sub 3}{sup 2+}) has been successfully immobilized onto electrode through the electrodeposition of Ru(bpy){sub 3}{sup 2+}/AuNPs/chitosan composite film. In the experiments, chitosan solution was first mixed with Au nanoparticles (AuNPs) and Ru(bpy){sub 3}{sup 2+}. Then, during chronopotentiometry experiments in this mixed solution, a porous 3D network structured film containing Ru(bpy){sub 3}{sup 2+}, AuNPs and chitosan has been electrodeposited onto cathode due to the deposition of chitosan when pH value is over its pK{sub a} (6.3). The applied current density is crucial to the film thickness and the amount of the entrapped Ru(bpy){sub 3}{sup 2+}. Additionally, these doping Ru(bpy){sub 3}{sup 2+} in the composite film maintained their intrinsic electrochemical and electrochemiluminescence activities. Consequently, this Ru(bpy){sub 3}{sup 2+}/AuNPs/chitosan modified electrode has been used in ECL to detect tripropylamine, and the detection limit was 5 x 10{sup -10} M.

The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

Science.gov (United States)

Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

2015-05-26

Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

Science.gov (United States)

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Soft template synthesis of mesoporous Co3O4/RuO2.xH2O composites for electrochemical capacitors

International Nuclear Information System (INIS)

Liu Yang; Zhao Weiwei; Zhang Xiaogang

2008-01-01

Co 3 O 4 /RuO 2 .xH 2 O composites with various Ru content (molar content of Ru = 5%, 10%, 20%, 50%) were synthesized by one-step co-precipitation method. The precursors were prepared via adjusting pH of the mixed aqueous solutions of Co(NO 3 ) 2 .6H 2 O and RuCl 3 .0.5H 2 O by using Pluronic123 as a soft template. For the composite with molar ratio of Co:Ru = 1:1 annealed at 200 deg. C, Brunauer-Emmet-Teller (BET) results indicated that the composite showed mesoporous structure, and the specific surface area of the composite was as high as 107 m 2 g -1 . The electrochemical performances of these composites were measured in 1 M KOH electrolyte. Compared with the composite prepared without template, the composite with P123 exhibited a higher specific capacitance. When the molar content of Ru was rising, the specific capacitance of the composites increased significantly. It was also observed that the crystalline structures as well as the electrochemical activities were strongly dependent on the annealing temperature. A capacitance of 642 F/g was obtained for the composite (Co:Ru = 1:1) annealed at 150 deg. C. Meanwhile, the composites also exhibited good cycle stability. Besides, the morphologies and textural characteristic of the samples were also investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM)

Solid-phase thermolysis of hexachlororuthenates (4) of onium type

Energy Technology Data Exchange (ETDEWEB)

Kukushkin, Yu N; Maslov, E I; Ryabkova, T P; Lobadyuk, V I [Leningradskij Tekhnologicheskij Inst. (USSR)

1982-10-01

Methods of thermogravimetry, infrared spectroscopy, electron absorption spectra and magnetic moment measurings were used to a study thermal solid-phase behaviour of onium hexachlororuthenates (4) of (AH)/sub 2/(RuCl/sub 6/) and (A'H/sub 2/)(RuCl/sub 6/) type, where A-benzimidazole (BAZ), pyridine (py), ammonia, A'-phenanthroline-ortho (o-phen), ethylenediamine (en). It was established that heating of solid (BAZH)/sub 2/(RuCl/sub 6/)x2H/sub 2/O and (o-phen H/sub 2/)(RuCl/sub 6/)xH/sub 2/O in 20-500 deg C range leads to separation of crystallization water and the following extraction of hydrogen chloride with formation of cis-(Ru(BAZ)/sub 2/Cl/sub 4/) and (Ru(o-phen)Cl/sub 4/). (pyH)/sub 2/(RuCl/sub 6/) heating causes initially the separation of two moles of hydrogen chloride with formation of cis-(Ru(py)/sub 2/Cl/sub 4/); further increase of temperature leads to reduction separation of chloride with formation of (Ru(py)/sub 2/Cl/sub 3/)/sub 2/ dimer. The mixture of ruthernium chlorides is prepared under conditions of isothermal heating of (NH/sub 4/)/sub 2/(RuCl/sub 6/) and (enH/sub 2/)(RuCl/sub 6/) compounds at temperatures close to the beginning of their decomposition. The separation of intermediate ruthenium compounds of diamine type with ammonia and ethylendiamine failed.

Endosomes: guardians against [Ru(Phen)3]2+ photo-action in endothelial cells during in vivo pO2 detection?

Science.gov (United States)

Huntosova, Veronika; Stroffekova, Katarina; Wagnieres, Georges; Novotova, Marta; Nichtova, Zuzana; Miskovsky, Pavol

2014-12-01

Phototoxicity is a side-effect of in vitro and in vivo oxygen partial pressure (pO2) detection by luminescence lifetime measurement methods. Dichlorotris(1,10-phenanthroline)-ruthenium(ii) hydrate ([Ru(Phen)3]2+) is a water soluble pO2 probe associated with low phototoxicity, which we investigated in vivo in the chick's chorioallantoic membrane (CAM) after intravenous or topical administration and in vitro in normal human coronary artery endothelial cells (HCAEC). In vivo, the level of intravenously injected [Ru(Phen)3]2+ decreases within several minutes, whereas the maximum of its biodistribution is observed during the first 2 h after topical application. Both routes are followed by convergence to almost identical "intra/extra-vascular" levels of [Ru(Phen)3]2+. In vitro, we observed that [Ru(Phen)3]2+ enters cells via endocytosis and is then redistributed. None of the studied conditions induced modification of lysosomal or mitochondrial membranes without illumination. No nuclear accumulation was observed. Without illumination [Ru(Phen)3]2+ induces changes in endoplasmic reticulum (ER)-to-Golgi transport. The phototoxic effect of [Ru(Phen)3]2+ leads to more marked ultrastructural changes than administration of [Ru(Phen)3]2+ only (in the dark). These could lead to disruption of Ca2+ homeostasis accompanied by mitochondrial changes or to changes in secretory pathways. In conclusion, we have demonstrated that the intravenous injection of [Ru(Phen)3]2+ into the CAM model mostly leads to extracellular localization of [Ru(Phen)3]2+, while its topical application induces intracellular localization. We have shown in vivo that [Ru(Phen)3]2+ induces minimal photo-damage after illumination with light doses larger by two orders of magnitude than those used for pO2 measurements. This low phototoxicity is due to the fact that [Ru(Phen)3]2+ enters endothelial cells via endocytosis and is then redistributed towards peroxisomes and other endosomal and secretory vesicles before it

[μ2-Bis(diphenylphosphanylhexane]bis[undecacarbonyl-triangulo-triruthenium(3 Ru—Ru] hexane monosolvate: crystal structure and Hirshfeld surface analysis

Directory of Open Access Journals (Sweden)

Omar bin Shawkataly

2017-11-01

Full Text Available In the title cluster complex hexane solvate, [Ru6(C30H32P2(CO22]·C6H14, two Ru3(CO11 fragments are linked by a Ph2P(CH26PPh2 bridge with the P atoms equatorially disposed with respect to the Ru3 triangle in each case; the hexane solvent molecule is statistically disordered. The Ru...Ru distances span a relatively narrow range, i.e. 2.8378 (4 to 2.8644 (4 Å. The hexyl chain within the bridge has an all-trans conformation. In the molecular packing, C—H...O interactions between cluster molecules, and between cluster and hexane solvent molecules lead to a three-dimensional architecture. In addition, there are a large number of C[triple-bond]O...π(arene interactions in the crystal. The importance of the carbonyl groups in establishing the packing is emphasized by the contribution of 53.4% to the Hirshfeld surface by O...H/H...O contacts.

Synthesis of [Ru3(μ3-NPh)(Br)(CO)9]- on self-assembled monolayers of di(3-aminopropyl)viologen/ITO surfaces and its application to photoelectrochemical cells

International Nuclear Information System (INIS)

Lee, Deok Yeon; Lee, Mi-Sun; Lim, Iseul; Kang, Soon Hyung; Nah, Yoon-Chae; Lee, Wonjoo; Han, Sung-Hwan

2011-01-01

Triruthenium carbonyl clusters {[Ru 3 (Br)(CO) 11 ] - (denoted as Ru-1), [Ru 3 (μ 2 -Br)(CO) 10 ] - (denoted as Ru-2), and [Ru 3 (μ 3 -NPh)(Br)(CO) 9 ] - (denoted as Ru-3)} were synthesized on di(3-aminopropyl)viologen (DAPV)/indium tin oxide (ITO) using a surface reaction in a ruthenium (III) carbonyl [Ru 3 (CO) 12 ] solution, and were applied to photoelectrochemical cells (PECs) at the molecular level. The formation of DAPV on ITO was realized in the form of self-assembled monolayers. Ru 3 (CO) 12 then easily reacted with the Br - of DAPV, and a mixture of Ru-1 and Ru-2 was formed on DAPV/ITO. Furthermore, Ru-3 was successfully anchored on DAPV/ITO by adding nitrosobenzene in order to react with Ru-2 on DAPV/ITO. The photocurrents of (Ru-1 and Ru-2)/DAPV/ITO and Ru-3/DAPV/ITO in PECs at the molecular level were 6.3 nA cm -2 and 8.6 nA cm -2 , respectively. The quantum yield of Ru-3/DAPV/ITO was ∼0.8%. Time-resolved photoluminescence spectroscopy and emission spectroscopy were recorded to bring out the photoinduced charge transfer process from ruthenium clusters to DAPV.

Ruthenium perovskites of type Ba/sub 2/BRuO/sub 6/ and Ba/sub 3/BRu/sub 2/O/sub 9/ with B = indium, rhodium

Energy Technology Data Exchange (ETDEWEB)

Schaller, H U; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1981-02-01

The black perovskites Ba/sub 2/InRu/sup 5 +/O/sub 6/ and Ba/sub 3/InRu/sub 2/O/sub 9/ (mean oxydation state of ruthenium: +4.5) adopt the hexagonal BaTiO/sub 3/ structure and form a continuous series of mixed crystals. According to the intensity calculations and analysis of the vibrational spectroscopic data an ordered distribution between indium and ruthenium is present: 1:1 order in Ba/sub 2/RuO/sub 6/ (space group P-3m1 respective Dsub(3d)/sup 3/; R' = 5.3%); 1:2 order in Ba/sub 3/InRu/sub 2/O/sub 9/ (space group P6/sub 3//mmc respective Dsub(6h)/sup 4/; R' = 4.6%). The corresponding black Rh compounds, Ba/sub 2/RhRuO/sub 6/ and Ba/sub 3/RhRu/sub 2/O/sub 9/, crystallize in the rhombohedral 9 L type of BaRuO/sub 3/ (author).

Synthesis, spectroscopic, structural and optical studies of Ru2S3 nanoparticles prepared from single-source molecular precursors

Science.gov (United States)

Mbese, Johannes Z.; Ajibade, Peter A.

2017-09-01

Homonuclear tris-dithiocarbamato ruthenium(III) complexes, [Ru(S2CNR2)3] were prepared and characterized by spectroscopic techniques and thermogravimetric analyses. The thermogravimetric analyses (TGA) of the ruthenium complexes showed that the complexes decompose to ruthenium(III) sulfide nanoparticles. The ruthenium(III) complexes were dispersed in oleic acid and thermolysed in hexadecylamine to prepared oleic acid/hexadecylamine capped Ru2S3 nanoparticles. FTIR revealed that Ru2S3 nanoparticles are capped through the interaction of the -NH2 group of hexadecylamine HDA adsorbed on the surfaces of nanoparticles and it also showed that oleic acid (OA) is acting as both coordinating stabilizing surfactant and capping agent. EDS spectra revealed that the prepared nanoparticles are mainly composed of Ru and S, confirming the formation of Ru2S3 nanoparticles. Powder XRD confirms that the nanoparticles are in cubic phase. The inner morphology of nanoparticles obtained from transmission electron microscopy (TEM) showed nanoparticles with narrow particle size distributions characterized by an average diameter of 8.45 nm with a standard deviation of 1.6 nm. The optical band gap (Eg) determined from Tauc plot are in the range 3.44-4.18 eV.

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.

Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

International Nuclear Information System (INIS)

Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

1994-01-01

Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

Pd(OAc)2/DPPF-catalysed microwave-assisted cyanides-free ...

Indian Academy of Sciences (India)

Pd(OAc)2/DPPF-catalysed microwave-assisted cyanides-free synthesis of aryl nitriles. DINESH N. SAWANT and BHALCHANDRA M. BHANAGE*. Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga,. Mumbai 400019 India. e-mail bm.bhanage@ictmumbai.edu.in. INDEX ...

Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides.

Science.gov (United States)

You, Qing; Wang, Fei; Wu, Chaoting; Shi, Tianchao; Min, Dewen; Chen, Huajun; Zhang, Wu

2015-06-28

Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.

Electrochemiluminescence immunosensor for ultrasensitive detection of biomarker using Ru(bpy)(3)(2+)-encapsulated silica nanosphere labels.

Science.gov (United States)

Qian, Jing; Zhou, Zhenxian; Cao, Xiaodong; Liu, Songqin

2010-04-14

Here, we describe a new approach for electrochemiluminescence (ECL) assay with Ru(bpy)(3)(2+)-encapsulated silica nanoparticle (SiO(2)@Ru) as labels. A water-in-oil (W/O) microemulsion method was employed for one-pot synthesis of SiO(2)@Ru nanoparticles. The as-synthesized SiO(2)@Ru nanoparticles have a narrow size distribution, which allows reproducible loading of Ru(bpy)(3)(2+) inside the silica shell and of alpha-fetoprotein antibody (anti-AFP), a model antibody, on the silica surface with glutaraldehyde as linkage. The silica shell effectively prevents leakage of Ru(bpy)(3)(2+) into the aqueous solution due to strong electrostatic interaction between the positively charged Ru(bpy)(3)(2+) and the negatively charged surface of silica. The porous structure of silica shell allowed the ion to move easily through the pore to exchange energy/electrons with the entrapped Ru(bpy)(3)(2+). The as-synthesized SiO(2)@Ru can be used as a label for ultrasensitive detection of biomarkers through a sandwiched immunoassay process. The calibration range of AFP concentration was 0.05-30 ng mL(-1) with linear relation from 0.05 to 20 ng mL(-1) and a detection limit of 0.035 ng mL(-1) at 3sigma. The resulting immunosensors possess high sensitivity and good analytical performance. Copyright 2010 Elsevier B.V. All rights reserved.

Mononuclear Amido and Binuclear Imido Zirconium Complexes Supported by Dibenzotetraaza[14]annulene Ligands. X-ray Structure of [(Me(4)taa)Zr(&mgr;-NR)(2)Zr(NHR)(2)] (R = Bu(t) or 2,6-C(6)H(3)Me(2)).

Science.gov (United States)

Nikonov, Georgii I.; Blake, Alexander J.; Mountford, Philip

1997-03-12

Reaction of 2 equiv of Li[NH-2,6-C(6)H(3)R(2)] with [(Me(4)taa)ZrCl(2)] (Me(4)taaH(2) = tetramethyldibenzotetraaza[14]annulene) gives the bis(amido) derivatives [(Me(4)taa)Zr(NH-2,6-C(6)H(3)R(2))(2)] [R = Pr(i) (1) and Me (2)]. Addition of Me(4)taaH(2) to [Zr(N-2,6-C(6)H(3)Pr(i)(2))(NH-2,6-C(6)H(3)Pr(i)(2))(2)(py)(2)] also affords 1. The reaction of 2 equiv of aryl or alkyl amines H(2)NR with the bis(alkyl) complex [(Me(4)taa)Zr(CH(2)SiMe(3))(2)] is the most versatile method for preparing [(Me(4)taa)Zr(NHR)(2)] (R = 2,6-C(6)H(3)Pr(i)(2), 2,6-C(6)H(3)Me(2), Ph, or Bu(t)). Reaction of 1 equiv of Me(4)taaH(2) with the binuclear complexes [(Bu(t)NH)(2)Zr(&mgr;-NBu(t))(2)Zr(NHBu(t))(2)] or [(py)(HN-2,6-C(6)H(3)Me(2))(2)Zr(&mgr;-N-2,6-C(6)H(3)Me(2))(2)Zr(NH-2,6-C(6)H(3)Me(2))(2)(py)] gives the asymmetrically substituted derivatives [(Me(4)taa)Zr(&mgr;-NR)(2)Zr(NHR)(2)] [R = Bu(t) (6) or 2,6-C(6)H(3)Me(2) (8)], which have been crystallographically characterized.

Construction of three metal-organic frameworks based on multifunctional T-shaped tripodal ligands, H3PyImDC

KAUST Repository

Jing, Xuemin

2010-08-04

Three novel metal-organic frameworks (MOFs), |(C3H 7NO)2(H2O)|[Zn3(C10H 5N3O4)3(C3H 7NO)2] (1), |(H2O)5(H 3O)(NO3)|[Nd2(C10H5N 3O4)3(H2O)4] (2), and |(H2O)2|[Nd3(C10H5N 3O4)3(C10H4N 3O4)] (3), based on the T-shaped tripodal ligands 2-(pyridine-4-yl)-1H-4,5-imidazoledicarboxylic acid and 2-(pyridine-3-yl)-1H-4, 5-imidazoledicarboxylic acid (H3PyImDC), have been constructed under solvo-/hydrothermal conditions. The diverse coordination modes of H 3PyImDC ligands have afforded the assembly of three novel compounds. In compound 1, two oxygen atoms and three nitrogen atoms of the H 3PyImDC ligand, a T-shaped linker, coordinate to two zinc centers to form a novel bbm net with two distinct channels along the [100] and [001] directions. In compound 2, H3PyImDC ligands coordinate to neodymium centers to form a ladder-like chain which then interacts with a water molecules chain via hydrogen-bondings to construct a 3D supermolecular structure. In compound 3, H3PyImDC ligands, a T-shaped linker, coordinate to neodymium centers to form a (3,6)-connected net with an ant topology. In compounds 1-3, the two H3PyImDC ligands exhibit different coordination modes with zinc and neodymium centers, which afforded the expected structural diversity. Additionally, all three compounds exhibit strong fluorescence emissions in the solid state at room temperature. © 2010 American Chemical Society.

Nearest-neighbor Kitaev exchange blocked by charge order in electron-doped α -RuCl3

Science.gov (United States)

Koitzsch, A.; Habenicht, C.; Müller, E.; Knupfer, M.; Büchner, B.; Kretschmer, S.; Richter, M.; van den Brink, J.; Börrnert, F.; Nowak, D.; Isaeva, A.; Doert, Th.

2017-10-01

A quantum spin liquid might be realized in α -RuCl3 , a honeycomb-lattice magnetic material with substantial spin-orbit coupling. Moreover, α -RuCl3 is a Mott insulator, which implies the possibility that novel exotic phases occur upon doping. Here, we study the electronic structure of this material when intercalated with potassium by photoemission spectroscopy, electron energy loss spectroscopy, and density functional theory calculations. We obtain a stable stoichiometry at K0.5RuCl3 . This gives rise to a peculiar charge disproportionation into formally Ru2 + (4 d6 ) and Ru3 + (4 d5 ). Every Ru 4 d5 site with one hole in the t2 g shell is surrounded by nearest neighbors of 4 d6 character, where the t2 g level is full and magnetically inert. Thus, each type of Ru site forms a triangular lattice, and nearest-neighbor interactions of the original honeycomb are blocked.

Cu(OAc)2/TFA-promoted formal [3 + 3] cycloaddition/oxidation of enamines and enones for synthesis of multisubstituted aromatic amines.

Science.gov (United States)

Li, Liang; Zhao, Mi-Na; Ren, Zhi-Hui; Li, Jian-Li; Guan, Zheng-Hui

2012-07-06

New strategies for the oxidative cycloaddition of enones with enamines are developed. These cycloaddition reactions directly afford substituted aromatic amines, which are important in organic chemistry, in moderate to good yield. Cu(OAc)(2)/TFA is shown to be essential to achieve high reaction efficiency.

Metal-metal bonding and aromaticity in [M2(NHCHNH)3]2 (μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh).

Science.gov (United States)

Yan, Xiuli; Meng, Lingpeng; Sun, Zheng; Li, Xiaoyan

2016-02-01

The nature of M-M bonding and aromaticity of [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh), the Nb-Nb, Ru-Ru, and Rh-Rh bonds belong to "metallic" bonds, whereas Mo-Mo and Tc-Tc drifted toward the "dative" side; all these bonds are partially covalent in character. The Nb-Nb, Mo-Mo, and Tc-Tc bonds are stronger than Ru-Ru and Rh-Rh bonds. The M-M bonds in [M2(NHCHNH)3]2(μ-S)2 are stronger than those in [M2(NHCHNH)3]2(μ-O)2 for M = Nb, Mo, Tc, and Ru. The NICS(1)ZZ values show that all of the studied molecules, except [Ru2(NHCHNH)3]2(μ-O)2, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds. Graphical Abstract Left Molecular graph, and right electron localization function (ELF) isosurface of [M2(NHCHNH)3]2(μ-E)2(E = O, S; M = Nb, Mo, Tc, Ru, Rh).

Effect of B-site cation stoichiometry on electrical fatigue of RuO2//Pb(ZrxTi1-x)O3//RuO2 capacitors

International Nuclear Information System (INIS)

Al-Shareef, H.N.; Tuttle, B.A.; Warren, W.L.; Headley, T.J.; Dimos, D.; Voigt, J.A.; Nasby, R.D.

1996-01-01

There have been numerous reports that Pb(Zr x Ti 1-x )O 3 (PZT) thin-film capacitors with RuO 2 electrodes and compositions near the morphotropic phase boundary exhibit minimal decrease in switched polarization with electric-field cycling. We show that the fatigue performance of RuO 2 //PZT//RuO 2 capacitors strongly depends on PZT film composition. Specifically, we demonstrate that the rate of polarization fatigue increases with increasing Ti content for PZT thin films of tetragonal crystal symmetry deposited on RuO 2 electrodes. As the Ti content of the PZT films increased, the film gain morphology changed from columnar to granular and the volume percent of a fluorite-type second phase decreased. These microstructural trends and the possibility that the electrode material acts as a sink for oxygen vacancies are discussed to explain the fatigue dependence on B-site cation ratio for PZT films with RuO 2 electrodes. copyright 1996 American Institute of Physics

Structure and microstructure of hexagonal Ba3Ti2RuO9 by electron diffraction and microscopy

International Nuclear Information System (INIS)

Maunders, C.; Etheridge, J.; Whitfield, H.J.

2005-01-01

We have used electron microscopy and diffraction to refine the structure and investigate the microstructure of Ba 3 Ti 2 RuO 9 . The parent compound is hexagonal BaTiO 3 with the space group P6 3 /mmc. Using convergent-beam electron diffraction (CBED) combined with electron-sensitive image plates we have found that the space group of Ba 3 Ti 2 RuO 9 is the non-centrosymmetric group P6 3 mc. at room temperature and at ∝ 110 K. This is consistent with the Ru and Ti atoms occupying alternate face-sharing octahedral sites in the h0001i direction. This maintains the c-glide, but breaks the mirror normal to the c axis and consequently removes the centre of symmetry. Using powder X-ray diffraction, we have measured the lattice parameters from polycrystalline samples to be a = 5.7056 ± 0.0005, c = 14.0093 ± 0.0015 Aa at room temperature. Using high-resolution electron microscopy (HREM) we observed highly coherent, low-strain {10 anti 10} grain boundaries intersecting at 60 and 120 . From CBED we deduce that adjacent grains are identical but for the relative phase of the Ti and Ru atom ordering along the c axis. HREM also revealed occasional stacking faults, normal to the c-axis

Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH3)5N2]Br2 and [Os(NH3)5N2]Cl2.

Science.gov (United States)

Schaniel, Dominik; Woike, Theo; Delley, Bernard; Boskovic, Colette; Güdel, Hans-Ueli

2008-09-28

Photogeneration of side-on N2 linkage isomers in [Ru(NH3)5N2]2+ and [Os(NH3)5N2]2+ is achieved by irradiation with lambda = 325 nm of powder samples at T = 80 K and detected by the downshift of the nu(N-N) vibration and by the heat release at elevated temperature due to the back switching of the side-on configuration to the ground state. The concentration of the transferred molecules is evaluated by the decrease of the area of the nu(N-N) or 2nu(N-N) vibrational bands. All characteristic changes between the linear Ru-N-N and side-on configuration are predicted by DFT calculations: the structure of the anion, shifts of the vibrations, electronic excitation energy, energetic position and sequence of the electronic orbitals, the potentials of the ground and relaxed metastable state with the activation energy, saddle points and energetic position of the minimum.

Synthesis and Crystal Structure of a New Ruthenium Silicophosphate: RuP 3SiO 11

Science.gov (United States)

Fukuoka, Hiroshi; Imoto, Hideo; Saito, Taro

1996-01-01

A new ruthenium silicophosphate RuP3SiO11was obtained and the structure was determined by single-crystal X-ray diffraction. It crystallizes in the trigonal space groupR3cwitha= 8.253(3)Å,c= 39.317(4)Å,V= 2319(2)Å3,Z= 12,R= 0.029, andRW= 0.026. The structure is composed of RuO6, Si2O7, and P2O7units. The Si2O7unit shares the six oxygen atoms with six P2O7units, while the P2O7unit shares the six oxygen atoms with two Si2O7units and four RuO6octahedra. The anionic part forms an infinite three-dimensional network of silicophosphate. RuP3SiO11is isotypic with MoP3SiO11.

Amino Acids Sequence Based in Silico Analysis of RuBisCO (Ribulose-1,5 Bisphosphate Carboxylase Oxygenase Proteins in Some Carthamus L. ssp.

Directory of Open Access Journals (Sweden)

Emre SEVİNDİK

2017-06-01

Full Text Available RuBisCO is an important enzyme for plants to photosynthesize and balance carbon dioxide in the atmosphere. This study aimed to perform sequence, physicochemical, phylogenetic and 3D (three-dimensional comparative analyses of RuBisCO proteins in the Carthamus ssp. using various bioinformatics tools. The sequence lengths of the RuBisCO proteins were between 166 and 477 amino acids, with an average length of 411.8 amino acids. Their molecular weights (Mw ranged from 18711.47 to 52843.09 Da; the most acidic and basic protein sequences were detected in C. tinctorius (pI = 5.99 and in C. tenuis (pI = 6.92, respectively. The extinction coefficients of RuBisCO proteins at 280 nm ranged from 17,670 to 69,830 M-1 cm-1, the instability index (II values for RuBisCO proteins ranged from 33.31 to 39.39, while the GRAVY values of RuBisCO proteins ranged from -0.313 to -0.250. The most abundant amino acid in the RuBisCO protein was Gly (9.7%, while the least amino acid ratio was Trp (1.6 %. The putative phosphorylation sites of RuBisCO proteins were determined by NetPhos 2.0. Phylogenetic analysis revealed that RuBisCO proteins formed two main clades. A RAMPAGE analysis revealed that 96.3%-97.6% of residues were located in the favoured region of RuBisCO proteins. To predict the three dimensional (3D structure of the RuBisCO proteins PyMOL was used. The results of the current study provide insights into fundamental characteristic of RuBisCO proteins in Carthamus ssp.

Kinetic study of methanol oxidation on Pt2Ru3/C catalyst in the alkaline media

Directory of Open Access Journals (Sweden)

A. V. TRIPKOVIC

2007-11-01

Full Text Available The interaction of acridine orange (AO with double-stranded (ds The electrochemical oxidation of methanol in NaOH solution was examined on a thin film Pt2Ru3/C electrode. The XRD pattern revealed that the Pt2Ru3 alloy consisted of a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. It was shown that in alkaline solution, the difference in activity between Pt/C and Pt2Ru3/C is significantly smaller than in acid solution. It is proposed that the reaction follows a quasi bifunctional mechanism. The kinetic parameters indicated that the chemical reaction between adsorbed COad and OHad species could be the rate limiting step.

Development of antifouling of electrochemical solid-state dissolved oxygen sensors based on nanostructured Cu0.4Ru3.4O7 + RuO2 sensing electrodes

International Nuclear Information System (INIS)

Zhuiykov, Serge; Kalantar-zadeh, Kourosh

2012-01-01

Tailoring nanostructured sensing electrode materials to high antifouling resistance has been one of the main priorities of the development of water quality sensors in the 21st century. Nanostructured Cu 0.4 Ru 3.4 O 7 + RuO 2 -SEs have been developed to address the bio-fouling problem. The change in Cu 0.4 Ru 3.4 O 7 + RuO 2 structural development being promoted by advances in nano- and micro-scale pattering. Nanostructured Cu 0.4 Ru 3.4 O 7 + RuO 2 -SEs with different mol% of Cu 2 O were screen-printed on alumina sensor substrates and were consequently subjected to a 3-month field trial at the Water Treatment Plant. Their structural and electrochemical properties before and after the experiment were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical cyclic voltammerty (CV) techniques. The relationship between dissolved oxygen (DO) and the sensor's potential difference was found to be relatively linear, with the maximum sensitivity of −46 mV per decade being achieved at 20 mol% Cu 2 O at 7.27 pH. Moreover, a 3-month field trial in the sewerage environment has shown that Cu 0.4 Ru 3.4 O 7 + RuO 2 -SE with 20 mol% of Cu 2 O possesses much higher defences against bio-fouling than the same SE with only 10 mol% of Cu 2 O. The super-hydrophobic property of the developed Cu 0.4 Ru 3.4 O 7 + RuO 2 complex oxide has been considered as one of the essential pre-requisites for high antifouling resistance. Multiple antifouling defence strategies from biomimetic to bio-inspired must be incorporated in further development of nanostructured oxide SE to solve problems of bio-fouling on the sensor's SE.

Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework

Energy Technology Data Exchange (ETDEWEB)

Larsen, Randy W., E-mail: rwlarsen@usf.edu; Wojtas, Lukasz

2017-03-15

The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2′-bipyridine){sub 3}]{sup 2+}([Ru(bpy){sub 3}]{sup 2+}) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation of Uio-66 in the presence of [Ru(bpy){sub 3}]{sup 2+}. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy){sub 3}]{sup 2+} complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy){sub 3}]{sup 2+} into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclear but may involve interactions of the [Ru(bpy){sub 3}]{sup 2+} encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy){sub 3}]{sup 2+} complexes. - Graphical abstract: One-pot synthesis of Ru(II)tris(2,2-bipyridine)@Uio-66 (left) and the effects of encapsulation on the excited state energy levels and decay pathways of the Ru(II)tris(2,2-bipyridine) complex (right).

Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface.

Science.gov (United States)

Muratsugu, Satoshi; Kityakarn, Sutasinee; Wang, Fei; Ishiguro, Nozomu; Kamachi, Takashi; Yoshizawa, Kazunari; Sekizawa, Oki; Uruga, Tomoya; Tada, Mizuki

2015-10-14

Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, with an average diameter of less than 2 nm, were formed on the support and acted as efficient catalysts for nitrile hydrogenation at 343 K under hydrogen at atmospheric pressure. The structure and catalytic performance of Ru catalysts depended strongly on the type of oxide support, and the K-doped Al2O3 support acted as a good oxide for the selective nitrile hydrogenation without basic additives like ammonia. The activation of nitriles on the modelled Ru catalyst was also investigated by DFT calculations, and the adsorption structure of a nitrene-like intermediate, which was favourable for high primary amine selectivity, was the most stable structure on Ru compared with other intermediate structures.

The Metalloporphyrin Antioxidant, MnTE-2-PyP, Inhibits Th2 Cell Immune Responses in an Asthma Model

Directory of Open Access Journals (Sweden)

Paiboon Jungsuwadee

2012-08-01

Full Text Available MnTE-2-PyP, a superoxide dismutase mimetic, inhibited OVA-induced airway inflammation in mice suggesting an effect on Th2 responsiveness. Thus, we hypothesized that MnTE-2-PyP may alter dendritic cell-Th2 interactions. Bone marrow derived dendritic cells (DC and OVA_323-339-specific Th2 cells were cultured separately in the presence or absence of MnTE-2-PyP for 3 days prior to the co-culturing of the two cell types in the presence of an OVA_323-339 peptide and in some cases stimulated with CD3/CD28. MnTE-2-PyP-pretreated DC inhibited IL-4, IL-5 and IFNγ production and inhibited Th2 cell proliferation in the DC-Th2 co-culturing system in the presence of the OVA_323-339 peptide. Similar results were obtained using the CD3/CD28 cell-activation system; the addition of MnTE-2-PyP inhibited Th2 cell proliferation. MnTE-2-PyP suppressed CD25 expression on OVA-specific Th2 cells, which implied that MnTE-2-PyP can inhibit the activation of Th2 cells. MnTE-2-PyP also down-regulated co-stimulatory molecules: CD40, CD80 and CD86 on immature DC. Our studies suggest that the major mechanism by which MnTE-2-PyP inhibits airway inflammation is by acting on the DC and suppressing Th2 cell proliferation and activation.

High electrochemical performance of RuO_2–Fe_2O_3 nanoparticles embedded ordered mesoporous carbon as a supercapacitor electrode material

International Nuclear Information System (INIS)

Xiang, Dong; Yin, Longwei; Wang, Chenxiang; Zhang, Luyuan

2016-01-01

The electrode materials RuO_2 or RuO_2–Fe_2O_3 nanoparticle embedded OMC (ordered mesoporous carbon) are prepared by the method of impregnation and heating in situ. The mesoporous structure optimized the electron and proton conducting pathways, leading to the enhanced capacitive performances of the composite materials. The average nanoparticle size of RuO_2 and RuO_2–Fe_2O_3 is 2.54 and 1.96 nm, respectively. The fine RuO_2–Fe_2O_3 nanoparticles are dispersed evenly in the pore channel wall of the two-dimensional mesoporous carbon without blocking the mesoporous channel, and they have a higher specific surface area, a larger pore volume, a proper pore size and a small charge transfer impedance value. The special electrochemical capacitance of RuO_2–Fe_2O_3/OMC tested in acid electrolyte (H_2SO_4) is measured to be as high as 1668 F g"−"1, which is higher than that of RuO_2/OMC. Meanwhile, the supercapacitor properties of the RuO_2–Fe_2O_3/OMC composites show a good cycling performance of 93% capacitance retention (3000 cycles), a better reversibility, a higher energy density (134 Wh kg"−"1) and power density (4000 W kg"−"1). The composite electrode of RuO_2–Fe_2O_3/OMC, which combines a double layer capacitance with pseudo-capacitance, is proved to be suitable for ideal high performance electrode material of a hybrid supercapacitor application. - Highlights: • The nanocomposites of RuO_2–Fe_2O_3/OMC are prepared by impregnation and heating in situ. • The fine RuO_2–Fe_2O_3 nanoparticles distribute in the pore channel wall of OMC. • We discuss a reversible redox reaction mechanism of RuO_2–Fe_2O_3/OMC in acid solutions. • RuO_2–Fe_2O_3 nanoparticles embedded OMC shows a higher supercapacitive performance.

Assessment for the role of rare earth oxide in the R2O3 - RuO2 - Pt composite electrode

International Nuclear Information System (INIS)

Do Ngoc Lien; Nguyen Van Sinh

2004-01-01

Our work has showed several results related to assessment for the role of rare earth oxide in the R 2 O 3 - RuO 2 - Pt composite electrode. The precursor method was used for preparing composite electrode in the following forms: a- RuO 2 - Pt electrode b- La 2 O 3 (55%) - RuO 2 (45%) - Pt electrode c- CeO 2 (60%) - RuO 2 (40%) - Pt electrode By measurements of anodic polarization and cyclic potential for the types of a, b, c electrodes we can see that the La 2 O 3 (55%) - 45% RuO 2 - Pt electrode will be the best anodic electrode. It means that the partial replacement of ruthenium oxide by lanthanum oxide in composite oxide electrode will be an effective one. (author)

web2py Application Development Cookbook

CERN Document Server

Mulone, Pablo Martin; Gordon, Richard

2012-01-01

This is a cookbook and you may read the chapters in any order. The recipes need not be read sequentially. There are a good amount of code examples and relevant screenshots to ease learning pains. The target audience are Python developers with basic knowledge of web2py who want to gain further knowledge of web2py

Enhanced photocurrent in RuL2(NCS)2/di-(3-aminopropyl)-viologen/SnO2/ITO system

International Nuclear Information System (INIS)

Lee, Wonjoo; Kwak, Chang Gon; Mane, R.S.; Min, Sun Ki; Cai, Gangri; Ganesh, T.; Koo, Gumae; Chang, Jinho; Cho, Byung Won; Kim, Sei-Ki; Han, Sung-Hwan

2008-01-01

A Ru(2,2'-bipyridine-4,4'-dicarboxylic acid) 2 (NCS) 2 [RuL 2 (NCS) 2 ]/di-(3-aminopropyl)-viologen (DAPV)/tin oxide (SnO 2 ) system was prepared and applied to extensive photocurrent generation with its maximum surface area. The SnO 2 thin films on tin-doped indium oxide (ITO) were prepared using the chemical bath deposition method. Then, RuL 2 (NCS) 2 /DAPV on SnO 2 /ITO was easily prepared using self-assembled monolayers (SAMs). The photocurrent measurement of the system showed an excellent photocurrent of 20 nA cm -2 under the air mass 1.5 conditions (100 mW cm -2 ), which was increased by a factor of four compared to ones without SnO 2 layers

Anthocyanin biosynthesis in pears is regulated by a R2R3-MYB transcription factor PyMYB10.

Science.gov (United States)

Feng, Shouqian; Wang, Yanling; Yang, Song; Xu, Yuting; Chen, Xuesen

2010-06-01

Skin color is an important factor in pear breeding programs. The degree of red coloration is determined by the content and composition of anthocyanins. In plants, many MYB transcriptional factors are involved in regulating anthocyanin biosynthesis. In this study, a R2R3-MYB transcription factor gene, PyMYB10, was isolated from Asian pear (Pyrus pyrifolia) cv. 'Aoguan'. Sequence analysis suggested that the PyMYB10 gene was an ortholog of MdMYB10 gene, which regulates anthocyanin biosynthesis in red fleshed apple (Malus x domestica) cv. 'Red Field'. PyMYB10 was identified at the genomic level and had three exons, with its upstream sequence containing core sequences of cis-acting regulatory elements involved in light responsiveness. Fruit bagging showed that light could induce expression of PyMYB10 and anthocyanin biosynthesis. Quantitative real-time PCR revealed that PyMYB10 was predominantly expressed in pear skins, buds, and young leaves, and the level of transcription in buds was higher than in skin and young leaves. In ripening fruits, the transcription of PyMYB10 in the skin was positively correlated with genes in the anthocyanin pathway and with anthocyanin biosynthesis. In addition, the transcription of PyMYB10 and genes of anthocyanin biosynthesis were more abundant in red-skinned pear cultivars compared to blushed cultivars. Transgenic Arabidopsis plants overexpressing PyMYB10 exhibited ectopic pigmentation in immature seeds. The study suggested that PyMYB10 plays a role in regulating anthocyanin biosynthesis and the overexpression of PyMYB10 was sufficient to induce anthocyanin accumulation.

Electron correlation in CaRuO3 and SrRuO3

International Nuclear Information System (INIS)

Singh, Ravi Shankar; Maiti, Kalobaran

2005-01-01

We investigate the role of electron correlation in the electronic structure of 4d transition-metal oxides CaRuO 3 and SrRuO 3 . The photoemission spectra collected at different surface sensitivities reveal qualitatively different surface and bulk electronic structures in these systems. Extracted bulk spectra could be simulated using first principle approaches consistently with their thermodynamic parameters within the same model. The estimated electron correlation strength (U/W ∼ 0.2) is significantly weak as expected in 4d systems and resolves the long-standing issue that arose due to the prediction of large U/W similar to 3d systems. (author)

Synthesis, characterization and spectroscopic studies of the dihydrobis(1,2,3-benzotriazolylborate anion and its complexes with MCl2·py2

Directory of Open Access Journals (Sweden)

KHWAJA S. SIDDIQI

2006-11-01

Full Text Available The preparation of sodium dihydrobis(1,2,3-benzotriazolylborate was realised by refluxing one mole of sodium borohydride with two moles of 1,2,3-benzotriazole in toluene over a period of 12 h. Its complexes with MCl2·py2 [whereM=Mn(II, Fe(II, Co(II, Ni(II, Cu(II and py=pyridine] were characterized by elemental analysis as well as magnetic, spectroscopic and conductivity measurements. On the basis of these studies, it is proposed that the geometry of all the complexes is octahedral. The ligand field parameters 10 Dq, B and b show extensive overlap between the M–L orbital. The molar conductance of 10-3 M solutions of the complexes in DMSO suggest them to be non-ionic in nature.

Reaction of H{sub 2}S with MoRu(CO){sub 6}(dppm){sub 2} to give H{sub 2} and a bridged-sulfide product via hydrido-sulfhydryl intermediates (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2})

Energy Technology Data Exchange (ETDEWEB)

Khorasani-Motlagh, M. [Sistan and Baluchestan Univ., Zahedan (Iran, Islamic Republic of). Dept. of Chemistry; Safari, N. [Shahid Beheshti Univ., Tehran (Iran, Islamic Republic of). Dept. of Chemistry; Pamplin, C.B.; Patrick, B.O.; James, B.R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemistry

2006-02-15

The reactivity of hydrogen sulphide toward transition metal complexes was studied with particular focus on the reactions of hydrogen sulphide (H{sub 2}S) with solutions of bimetallic-dppm complexes. The complex MoRu(CO){sub 6}({mu}-dppm){sub 2} (1) (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2}) reaction toward hydrogen sulphide was examined because of the fact that Ru is the second-row analogue of Fe and because of the key role of sulphur ligands in the Mo-Fe enzyme systems. This paper reported on the interaction of the Mo-Ru complex with hydrogen sulphide to form the bridged sulphide complex Mo(CO){sub 2}({mu}-CO)({mu}-S)(dppm){sub 2}Ru(CO) which can be synthesized with elemental sulphur. Oxidative addition of H{sub 2}S to MoRu(CO){sub 6}({mu}-dppm){sub 2} (1) at 20 degrees C in toluene yields an isolable complex formulated as Mo(CO){sub 3}({mu}-SH)({mu}-CO)({mu}-dppm){sub 2}RuH(CO) (2) via the possible intermediate Mo(CO){sub 3}({mu}-H)({mu}-CO)({mu}-dppm){sub 2}Ru(SH)(CO) (4) (dppm equals Ph{sub 2}PCH{sub 2}PPh{sub 2}) that is detectable at lower temperatures. Over 2 days, species 2 in toluene lost H{sub 2} (and CO) to yield the bridged-sulfide product, Mo(CO){sub 2}({mu}-CO)({mu}-S)({mu}-dppm){sub 2}Ru(CO) (5) that is also formed directly from the reaction of 1 with elemental sulfur. The solid-state molecular structure of 5 was determined by X-ray crystallography. A further hydrido-sulfhydryl species was found to be in equilibrium with 2 at ambient temperature. It was concluded that it is not impossible that hydrogen sulphide can react in a concerted manner with dimetallic precursors, without prior formation of an adduct. 24 refs., 2 tabs., 3 figs.

Electrochemiluminescence immunosensor for ultrasensitive detection of biomarker using Ru(bpy){sub 3}{sup 2+}-encapsulated silica nanosphere labels

Energy Technology Data Exchange (ETDEWEB)

Qian Jing [School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189 (China); Zhou Zhenxian [Nanjing Second Hospital, Nanjing, 210003 (China); Cao Xiaodong [School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189 (China); Liu Songqin, E-mail: liusq@seu.edu.cn [School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189 (China)

2010-04-14

Here, we describe a new approach for electrochemiluminescence (ECL) assay with Ru(bpy){sub 3}{sup 2+}-encapsulated silica nanoparticle (SiO{sub 2}-Ru) as labels. A water-in-oil (W/O) microemulsion method was employed for one-pot synthesis of SiO{sub 2}-Ru nanoparticles. The as-synthesized SiO{sub 2}-Ru nanoparticles have a narrow size distribution, which allows reproducible loading of Ru(bpy){sub 3}{sup 2+} inside the silica shell and of {alpha}-fetoprotein antibody (anti-AFP), a model antibody, on the silica surface with glutaraldehyde as linkage. The silica shell effectively prevents leakage of Ru(bpy){sub 3}{sup 2+} into the aqueous solution due to strong electrostatic interaction between the positively charged Ru(bpy){sub 3}{sup 2+} and the negatively charged surface of silica. The porous structure of silica shell allowed the ion to move easily through the pore to exchange energy/electrons with the entrapped Ru(bpy){sub 3}{sup 2+}. The as-synthesized SiO{sub 2}-Ru can be used as a label for ultrasensitive detection of biomarkers through a sandwiched immunoassay process. The calibration range of AFP concentration was 0.05-30 ng mL{sup -1} with linear relation from 0.05 to 20 ng mL{sup -1} and a detection limit of 0.035 ng mL{sup -1} at 3{sigma}. The resulting immunosensors possess high sensitivity and good analytical performance.

Magnetic properties and structural characterization of Sr2RuHoO6 complex perovskite

International Nuclear Information System (INIS)

Corredor, L.T.; Landínez Téllez, D.A.; Martínez Buitrago, D.; Albino Aguiar, J.; Roa-Rojas, J.

2012-01-01

We report an experimental study of the crystallographic lattice, morphologic characteristics and magnetic feature of Sr 2 RuHoO 6 complex perovskite, which is used as a precursor in the fabrication process of the superconducting ruthenocuprate RuSr 2 HoCu 2 O 8 . The samples were produced through the standard solid state reaction. A Rietveld refinement of experimental X-ray diffraction patterns shows that the material crystallizes in a monoclinic structure, which belongs to the P21/n (no.14) space group, with lattice parameters a=5.7719(6) Å, b=5.8784(5) Å, c=8.1651(9) Å, and tilt angle β=90.200°. Magnetic susceptibility measurements reveal the occurrence of an antiferromagnetic ordering for a Néel temperature T N =10.1 K. From the Curie-Weiss fitting of the paramagnetic regime we obtain an effective magnetic moment of 11.31 μ B .

Neutron investigation of Ru-doped Nd1/2Ca1/2MnO3. Comparison with Cr-doped Nd1/2Ca1/2MnO3

International Nuclear Information System (INIS)

Moritomo, Yutaka; Nonobe, Toshihiko; Machida, Akihiko; Ohoyama, Kenji

2002-01-01

Lattice and magnetic properties are investigated for 3% Ru- and Cr-doped Nd 1/2 Ca 1/2 MnO 3 . The parent Nd 1/2 Ca 1/2 MnO 3 is a charge-ordered insulator (T CO =250K). With decreasing temperature below ≅210K, these compounds are separated into two perovskite phases, that is, the long-c and short-c phases. The long-c region shows a ferromagnetic transition at T C ≅210K for the Ru-doped compound and ≅130K for the Cr-doped compound, while the short-c region shows antiferromagnetic transition at T N ≅150K for Ru and ≅110K for Cr. We discuss the origin of the enhanced T C for the Ru-doped compound in terms of the effective one-electron bandwidth W of the e g -band. (author)

Ir-Ru/Al2O3 catalysts used in satellite propulsion

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T.G. Soares Neto

2003-09-01

Full Text Available Ir/Al2O3, Ir-Ru/Al2O3 and Ru/Al2O3, catalysts with total metal contents of 30% were prepared using the methods of incipient wetness and incipient coimpregnation wetness and were tested in a 2N microthruster. Their performances were then compared with that of the Shell 405 commercial catalyst (30% Ir/Al2O3. Tests were performed in continuous and pulsed regimes, where there are steep temperature and pressure gradients, from ambient values up to 650 ºC and 14 bar. Performance stability, thrust produced, temperature and stagnation pressure in the chamber and losses of mass were analyzed and compared to the corresponding parameters in Shell 405 tests. It was observed that the performance of all the above-mentioned catalysts was comparable to that of the commercial one, except for in loss of mass, where the values was higher, which was attributed to the lower mechanical resistance of the support.

Perovskites with noble metals of type Ba/sub 3/BM/sub 2/O/sub 9/; B = Mg, Fe, Co, Ni, Zn, Cd; M = Ru, Ir

Energy Technology Data Exchange (ETDEWEB)

Treiber, U; Kemmler-Sack, S; Ehmann, A [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

1982-04-01

The perovskites Ba/sub 3/BM/sub 2/O/sub 9/ crystallize in a hexagonal BaTiO/sub 3/ structure and could be prepared for M = Ru; B = Mg, Fe, Co, Ni, Zn, Cd and M = Ir; B = Co, Ni. According to intensity calculations on powder data of Ba/sub 3/MgRu/sub 2/O/sub 9/ and Ba/sub 3/NiIr/sub 2/O/sub 9/ (refined intensity related R' value 6.7% (Ba/sub 3/MgRu/sub 2/O/sub 9/) and 6.9% (Ba/sub 3/NiIr/sub 2/O/sub 9/)) an 1:2 order is present and both lattices contain face connected M/sub 2/O/sub 9/ double octahedra linked by another via common corners through BO/sub 6/ single octahedra. The occurrence of this typ of cationic order results for B = Mg, Co, Ni, Zn, Cd from the analysis of the vibrational spectra. For B = Mg, Zn, Cd and presumable with B = Ni the charge distribution is B/sup 2 +// 2 M/sup 5 +/; for B = Co deviation can not be excluded. On the opposite in Ba/sub 3/FeRu/sub 2/O/sub 9/ an electron delocalisation is present.

Characterization of arene di-oxygenases involved in polycyclic aromatic hydrocarbons biodegradation in Mycobacterium sp. 6PY1; Caracterisation d'arene dioxygenases impliquees dans la biodegradation des hydrocarbures aromatiques polycycliques chez Mycobacterium sp. 6PY1

Energy Technology Data Exchange (ETDEWEB)

Kuony, S.

2005-06-15

This thesis deals with the bacterial biodegradation of pollutants called polycyclic aromatic hydrocarbons (PAHs). The bacterium Mycobacterium sp. 6PY1 was isolated from a polluted soil for its ability to use pyrene, a 4-ring PAH, as sole source of carbon and energy. To learn about the pyrene metabolic pathway, the identification of the enzymes involved in this process has been undertaken using a proteomic approach. This approach revealed the occurrence of two ring-hydroxylating di-oxygenases in strain 6PY1, which could catalyze the initial attack of pyrene. The goal of this study was to clone the genes encoding the di-oxygenases identified in Mycobacterium sp. 6PY1, over-express these genes in an heterologous system in order to facilitate the purification of the corresponding enzymes, and determine the biochemical and catalytic properties of these enzymes. The pdoA1B1 genes encoding the terminal component of a di-oxygenase were cloned and over-expressed in Escherichia coli. The catalytic properties of this enzyme, called Pdo1, were determined in vivo by measuring the oxidation products of 2- to 4-ring PAHs by gas chromatography coupled to mass spectrometry (GC-MS). Analysis of the selectivity of the enzyme, as determined using GC-MS, showed that Pdo1 preferentially oxidized 3- or 4-ring PAHs, including phenanthrene and pyrene, but was inactive on di-aromatic compounds such as naphthalene and biphenyl. Pdo1 was unstable and was therefore purified in inactive form. The genes encoding a second di-oxygenase component were found in a locus containing two other catabolic genes. The pdoA2B2 genes encoded an enzyme called Pdo2 showing a narrow specificity towards 2- to 3-ring PAHs, and a high preference for phenanthrene. Pdo2 is an a3{beta}3 hexamer, containing [2Fe-2S] Rieske clusters which confer it a characteristic absorbance spectrum. A third set of genes possibly encoding another di-oxygenase was discovered in the genome of Mycobacterium sp. 6PY1. This set is closely

On the solubility of yttrium in RuO2

International Nuclear Information System (INIS)

Music, Denis; Zumdick, Naemi A.; Hallstedt, Bengt; Schneider, Jochen M.

2011-01-01

We have investigated the solubility of Y in rutile RuO 2 using experimental and theoretical methods. Nanostructured Ru-Y-O thin films were synthesized via combinatorial reactive sputtering with an O/metal ratio of 2.6 and a Y content of 0.3 to 12.6 at. %. A solubility limit of 1.7 at. % was identified using x-ray photoelectron spectroscopy and x-ray diffraction. Based on ab initio and thermodynamic modeling, the solubility of Y can be understood. Smaller Y amounts are incorporated into the lattice, forming a metastable film, with local structural deformations due to size effects. As the Y content is increased, extensive local structural deformations are observed, but phase separation does not occur due to kinetic limitations. Nanostructured RuO 2 alloyed with Y might lead to enhanced phonon scattering and quantum confinement effects, which in turn improve the thermoelectric efficiency.

Magnetic properties of Heusler alloy Mn2RuGe and Mn2RuGa ribbons

International Nuclear Information System (INIS)

Yang, Ling; Liu, Bohua; Meng, Fanbin; Liu, Heyan; Luo, Hongzhi; Liu, Enke; Wang, Wenhong; Wu, Guangheng

2015-01-01

Heusler alloys Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning method successfully. Theoretical and experimental studies reveal a ferrimagnetic ground state in the two alloys. The Curie temperatures are 303 K for Mn 2 RuGe and 272 K for Mn 2 RuGa. The calculated total spin moments of Mn 2 RuGe and Mn 2 RuGa are integral values of 2.00 μ B and 1.03 μ B , respectively. And the theoretical spin polarization ratio is also quite high. However, due to the atomic disorder in the ribbons, the saturation moments of them measured at 5 K are smaller than the calculated values, especially that of Mn 2 RuGa. This coincides with the disappearance of the superlattice reflection (111) and (200) peaks in the XRD pattern of Mn 2 RuGa. Annealing Mn 2 RuGa ribbon at 773 K can enhance the atomic ordering. Both saturation magnetic moment and Curie temperature increase obviously after the heat treatment. - Highlights: • Mn 2 RuGe and Mn 2 RuGa have been prepared by melt-spinning successfully. • Ferrimagnetic ground state has been confirmed in Mn 2 RuGe and Mn 2 RuGa. • High spin polarization has been predicted in Mn 2 RuGe. • Melt-spinning can be a possible way to adjust the atomic order of Heusler alloys

Synthesis and characterisation of 5-acyl-6,7-dihydrothieno[3,2-c]pyridine inhibitors of Hedgehog acyltransferase

Directory of Open Access Journals (Sweden)

Thomas Lanyon-Hogg

2016-06-01

Full Text Available In this data article we describe synthetic and characterisation data for four members of the 5-acyl-6,7-dihydrothieno[3,2-c]pyridine (termed “RU-SKI” class of inhibitors of Hedgehog acyltransferase, including associated NMR spectra for final compounds. RU-SKI compounds were selected for synthesis based on their published high potencies against the enzyme target. RU-SKI 41 (9a, RU-SKI 43 (9b, RU-SKI 101 (9c, and RU-SKI 201 (9d were profiled for activity in the related article “Click chemistry armed enzyme linked immunosorbent assay to measure palmitoylation by Hedgehog acyltransferase” (Lanyon-Hogg et al., 2015 [1]. 1H NMR spectral data indicate different amide conformational ratios between the RU-SKI inhibitors, as has been observed in other 5-acyl-6,7-dihydrothieno[3,2-c]pyridines. The synthetic and characterisation data supplied in the current article provide validated access to the class of RU-SKI inhibitors.

Facile synthesis of RuII Schiff base complexes: spectral characterization and antimicrobial applications

International Nuclear Information System (INIS)

Arunachalam, S.; Padma Priya, N.; Shahul Meeran, H.

2014-01-01

Diamagnetic ruthenium (II) complexes of the type (RuCl (CO) (pyridine) (L)) (where L = monobasic tridentate Schiff base ligands) were synthesized by the reactions of Schiff bases derived from the reactions of o-aminobenzoic acid and Knovenegal condensate of β - ketoesters and appropriate ruthenium metal precursor (RuHCl (CO) (PPh 3 ) 2 (py)). Elemental analyses and spectral (FT-IR, UV-Vi s and 1 H, 31 P NMR) studies of all the new synthesized complexes suggest the presence of an octahedral environment around the Ru II ion. Cyclic voltammograms of all the complexes display oxidation and reduction potentials. Superoxide dismutase activity (SOD) of these complexes has also been examined. These complexes were also subjected to study their biocidal activity against Staphylococcus epidermidis, Escherichia coli, Botrytis cinerea and Aspergillus niger. (author)

Expeditious Entry to Novel 2-Methylene-2,3-dihydrofuro[3,2-c] chromen-2-ones from 6-Chloro-4-hydroxychromen-2-one and Propargylic Alcohols

Directory of Open Access Journals (Sweden)

Josefina Díez

2011-08-01

Full Text Available A catalytic system consisting of the ruthenium(II complex [Ru(η3-2-C3H4Me(CO(dppf][SbF6] (dppf = 1,1’-bis(diphenylphosphinoferrocene and trifluoroacetic acid has been used to promote the coupling of secondary propargylic alcohols with 6-chloro-4-hydroxychromen-2-one. The reactions afforded unusual 2-methylene-2,3-dihydrofuro[3,2-c]chromen-2-ones in good yields.

Characterization of RuO sub 2 electrodes for ferroelectric thin films prepared by metal-organic chemical-vapor deposition using Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3

CERN Document Server

Lee, J M; Shin, J C; Hwang, C S; Kim, H J; Suk, C G

1999-01-01

Pure and conducting RuO sub 2 thin films were deposited on Si substrates at 250 approx 450 .deg. C using Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3 as a precursor by low-pressure metal-organic chemical-vapor deposition (LP-MOCVD). At a lower deposition temperature,smoother and denser RuO sub 2 thin films were deposited. The RuO sub 2 thin films, which were crack free, adhered well onto the substrates and showed very low resistivities around 45 approx 60 mu OMEGA cm. RuO sub 2 thin films on (Ba, Sr)/TiO sub 3 /Pt/SiO sub 2 /Si showed good properties, indicating that MOCVD RuO sub 2 thin films from Ru(C sub 1 sub 1 H sub 1 sub 9 O sub 2) sub 3 can be applied as electrodes of high-dielectric thin films for capacitors in ultra-large-scale DRAMs.

Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations.

Science.gov (United States)

Aarnts, Maxim P.; Wilms, Maikel P.; Peelen, Karin; Fraanje, Jan; Goubitz, Kees; Hartl, Frantisek; Stufkens, Derk J.; Baerends, Evert Jan; Vlcek, Antonín

1996-09-11

Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.

Synthesis and characterization of RuO(2)/poly(3,4-ethylenedioxythiophene) composite nanotubes for supercapacitors.

Science.gov (United States)

Liu, Ran; Duay, Jonathon; Lane, Timothy; Bok Lee, Sang

2010-05-07

We report the synthesis of composite RuO(2)/poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes with high specific capacitance and fast charging/discharging capability as well as their potential application as electrode materials for a high-energy and high-power supercapacitor. RuO(2)/PEDOT nanotubes were synthesized in a porous alumina membrane by a step-wise electrochemical deposition method, and their structures were characterized using electron microscopy. Cyclic voltammetry was used to qualitatively characterize the capacitive properties of the composite RuO(2)/PEDOT nanotubes. Their specific capacitance, energy density and power density were evaluated by galvanostatic charge/discharge cycles at various current densities. The pseudocapacitance behavior of these composite nanotubes originates from ion diffusion during the simultaneous and parallel redox processes of RuO(2) and PEDOT. We show that the energy density (specific capacitance) of PEDOT nanotubes can be remarkably enhanced by electrodepositing RuO(2) into their porous walls and onto their rough internal surfaces. The flexible PEDOT prevents the RuO(2) from breaking and detaching from the current collector while the rigid RuO(2) keeps the PEDOT nanotubes from collapsing and aggregating. The composite RuO(2)/PEDOT nanotube can reach a high power density of 20 kW kg(-1) while maintaining 80% energy density (28 Wh kg(-1)) of its maximum value. This high power capability is attributed to the fast charge/discharge of nanotubular structures: hollow nanotubes allow counter-ions to readily penetrate into the composite material and access their internal surfaces, while a thin wall provides a short diffusion distance to facilitate ion transport. The high energy density originates from the RuO(2), which can store high electrical/electrochemical energy intrinsically. The high specific capacitance (1217 F g(-1)) which is contributed by the RuO(2) in the composite RuO(2)/PEDOT nanotube is realized because of the high

Deuteration of acetanilides and other substituted aromatics using [Ir(COD)(Cy3P)(Py)]PF6 as catalyst

International Nuclear Information System (INIS)

Hesk, D.; Das, P.R.; Evans, B.

1995-01-01

Deuterium exchange labelling using [Ir(COD)(Cy 3 P)(Py)]PF 6 as catalyst and deuterium gas was studied on a number of substituted acetanilides. In most cases products containing deuterium ortho to the anilide group were obtained with a high degree of enrichment. With one exception no evidence for meta, para or anilide methyl labelling was seen. The catalyst was also effective in the ortho deuteration of acetophenone, benzophenone and the β-lactam containing compound Sch 48461. (Author)

Polyelectrolyte-based electrochemiluminescence enhancement for Ru(bpy){sub 3}{sup 2+} loaded by SiO{sub 2} nanoparticle carrier and its high sensitive immunoassay

Energy Technology Data Exchange (ETDEWEB)

Ge, Zhi-Li; Song, Tian-Mei; Chen, Zhe [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); Guo, Wu-Run [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002 (China); Xie, Hong-Ping, E-mail: hpxie@suda.edu.cn [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China); Xie, Lian, E-mail: xielian@suda.edu.cn [College of Pharmaceutical Science, Soochow University, Suzhou 215123 (China)

2015-03-03

Highlights: • Preparation of strong ECL nanoparticles PAA–Ru@SiO{sub 2}/[PAA⋯Ru&Nafion⋯Ru]. • Ion-pair macromolecule PAA–Ru formed to greatly increase the doping amount. • PAA&Nafion membrane increased the amount of ion-exchanged Ru(bpy){sub 3}{sup 2+}. • PAA&Nafion membrane enhanced the ability of electron transfer. • Realized antibody labeling and established a high-sensitive immunoassay. - Abstract: In this paper the strong electrochemiluminescence (ECL) nanoparticles have been prepared based on the anionic polyelectrolyte sodium polyacrylate (PAA)-ECL enhancement for Ru(bpy){sub 3}{sup 2+}, which were loaded by the carrier of SiO{sub 2} nanoparticle. There were two kinds of Ru(bpy){sub 3}{sup 2+} for the as-prepared nanoparticles, the doped one and the exchanged one. The former was loaded inside the ECL nanoparticles by doping, in a form of ion-pair macromolecules PAA–Ru(bpy){sub 3}{sup 2+}. The corresponding ECL was enhanced about 2 times owing to the doping increase of Ru(bpy){sub 3}{sup 2+}. The latter was loaded on the PAA-doped Nafion membrane by ion exchange. The corresponding ECL was enhanced about 3 times owing to the ion-exchanging increase of Ru(bpy){sub 3}{sup 2+}. At the same time, ECL intensity of the doped-inside Ru(bpy){sub 3}{sup 2+} was further enhanced 13 times because polyelectrolyte PAA in the doped membrane could obviously enhance electron transfer between the doped Ru(bpy){sub 3}{sup 2+} and the working electrode. Furthermore, based on hydrophobic regions of the doped membrane antibody labeling could be easily realized by the as-prepared nanoparticles and then a high sensitive ECL immunoassay for HBsAg was developed. The linear range was between 1.0 and 100 pg mL{sup −1} (R{sup 2} = 0.9912). The detection limit could be as low as 0.11 pg mL{sup −1} (signal-to-noise ratio = 3)

Structural phase transitions at high-temperature in double perovskite Sr{sub 2}GdRuO{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Triana, C.A.; Corredor, L.T.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, A.A. 14490, Bogota D.C (Colombia); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, A.A. 14490, Bogota D.C (Colombia)

2012-08-15

The crystal structure evolution of the Sr{sub 2}GdRuO{sub 6} complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K{<=}T{<=}1273 K. Powder X-ray diffraction measurements at room temperature and Rietveld analysis show that this compounds crystallizes in a monoclinic perovskite-type structure with P2{sub 1}/n (no. 14) space group and the 1:1 ordered arrangement of Ru{sup 5+} and Gd{sup 3+} cations over the six-coordinate M sites, with lattice parameters a=5.81032(8) A, b=5.82341(4) A, c=8.21939(7) A, V=278.11(6) A{sup 3} and angle {beta}=90.311(2){sup o}. The high-temperature analysis shows that this material suffers two-phase transitions. At 373 K it adopts a monoclinic perovskite structure with I2/m space group, and lattice parameters a=5.81383(2) A, b=5.82526(4) A, c=8.22486(1) A, V=278.56(2) A{sup 3} and angle {beta}=90.28(2){sup o}. Above of 773 K, it suffers a phase transition from monoclinic I2/m to tetragonal I4/m, with lattice parameters a=5.84779(1) A, c=8.27261(1) A, V=282.89(5) A{sup 3} and angle {beta}=90.02(9){sup o}. The high-temperature phase transition from monoclinic I2/m to tetragonal I4/m is characterized by strongly anisotropic displacements of the anions.

Crystal structures of bromo- and iododerivatives of ruthenium nitroso complexes K2[RuNOX5

International Nuclear Information System (INIS)

Mikhajlov, Yu.N.; Kanishcheva, A.S.; Svetlov, A.A.

1989-01-01

Method of X-ray diffraction analysis was used to interpret crystal structure of ruthenium pentahalogenonitroso complexes: K 2 [RuNOBr 5 ] (1) and K 2 [RuOI 5 ] (2). Crystals belong to rhombic syngony, sp.gr. Pcmn. Lattice parameters: (1) - a 7.236(2), b = 10.791(2), c = 13.949(3) A, V = 1089.14(1) A 3 , Z = 4; (2) - a = 7.755(1), b = 11.506(6), c = 14.951(5) A, V 133.97(8) A 3 , Z = 4. It was revealed that lengths of Ru-Br equatorial bonds in (1) exceeded the axial ones, and in the compound (2) the reverse relation was observed. The obtained results were correlated with the structural data for K 2 [RuNOF 5 ]H 2 O and K 2 [RuNOCl 5 ] complexes and similar osmium compounds

Hypotensive effect and vascular relaxation in different arteries induced by the nitric oxide donor RuBPY.

Science.gov (United States)

Pereira, Amanda de Carvalho; Araújo, Alice Valença; Paulo, Michele; Andrade, Fernanda Aparecida de; Silva, Bruno Rodrigues; Vercesi, Juliana Aparecida; da Silva, Roberto Santana; Bendhack, Lusiane Maria

2017-01-30

NO donors are compounds that release NO that can be used when the endogenous NO bioavailability is impaired. The compound cis-[Ru(bpy) 2 (py)(NO 2 )](PF 6 ) (RuBPY) is a nitrite-ruthenium, since it has a NO 2 in its molecule. The aim of the present study was to evaluate the effect of RuBPY on arterial pressure, as well as on the vascular relaxation of different vascular arteries in renal hypertensive (2K-1C) and normotensive (2K) rats. We have evaluated the arterial pressure and heart rate changes as well as the RuBPY and SNP-induced relaxation (thoracic aorta, mesenteric resistance, coronary and basilar arteries). The administration of RuBPY in awake rats evoked a smaller but long lasting hypotensive effect when compared to SNP, with no increase in heart rate. The relaxation induced by RuBPY was similar between 2K-1C and 2K rats in thoracic aorta, mesenteric resistance and coronary arteries. However, the relaxation induced by RuBPY was smaller in basilar arteries from 2K-1C than in 2K. Taken together, our results show that RuBPY presents several advantages over SNP, since it does not induce hypotensive effect in normotensive animals, the hypotensive effect is slower, with no reflex tachycardia, and it is long lasting. In addition, RuBPY induces coronary artery relaxation (useful for angina) and presented only a small effect on basilar artery (may not induce headache). Copyright © 2016 Elsevier Inc. All rights reserved.

Electronic and Crystalline Structure, Magnetic Response, and Optical Characterization of Rare-Earth Ruthenate Sr2HoRuO6

Science.gov (United States)

Velásquez Moya, X. A.; Cardona, R.; Villa Hernández, J. I.; Landínez Téllez, D. A.; Roa-Rojas, J.

2018-03-01

Sr2HoRuO6 ceramic has been synthesized and its structural, morphological, magnetic, optical, and electronic properties studied. Rietveld refinement of x-ray diffraction patterns revealed that this oxide material crystallizes in monoclinic perovskite structure in space group P2 1 /n (no. 14). Scanning electron microscopy revealed polycrystalline surface morphology. x-Ray dispersive spectroscopy suggested that Sr2HoRuO6 was obtained with expected stoichiometry. Magnetic susceptibility curves as a function of temperature revealed ferrimagnetic feature of this material below the Néel temperature T N of 14 K. Evidence of magnetic disorder was provided by the irreversibility observed in the zero-field-cooled and field-cooled responses of the susceptibility below T irr = 169 K. Analysis of the diffuse reflectance spectrum suggested that this material behaves as a semiconductor with energy gap E g of 1.38 eV. Results of band structure and density-of-states calculations are in agreement with the interpretation of Sr2HoRuO6 as a semiconductor. The ferrimagnetic behavior is interpreted as due to exchange mechanisms of d-f (Ru-O-Ho) electrons. The effective magnetic moment calculated from density functional theory was 93.5% of the experimental value obtained from Curie-Weiss fitting of the susceptibility curve.

Synthesis, characterization, and magnetic properties of the new boride solid solutions M{sub 0.5}Ru{sub 6.5}B{sub 3} (M = Cr, Mn, Co, Ni)

Energy Technology Data Exchange (ETDEWEB)

Misse, Patrick R.N.; Fokwa, Boniface P.T. [Institute of Inorganic Chemistry, RWTH Aachen University (Germany)

2010-05-15

Powder samples and single crystals of the borides M{sub 0.5}Ru{sub 6.5}B{sub 3} (M = Cr, Mn, Co, Ni) were synthesized by arc-melting the elements in a water-cooled copper crucible under argon. The new phases were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX-Analyses. They crystallize in the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z = 2) and a pronounced site preferential M/Ru substitution is observed. Magnetic properties of the compounds were investigated and Pauli paramagnetism was observed in all cases. However, a strong temperature dependency is subsequently observed in Mn{sub 0.5}Ru{sub 6.5}B{sub 3} below 250 K, but no hint of magnetic ordering was found. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Pressure effects on the magnetic and transport properties of the Kondo lattice system Ce3RuSn6

Science.gov (United States)

Wakiya, Kazuhei; Tomaki, Takeru; Kimura, Minami; Uehara, Masatomo; Gouchi, Jun; Uwatoko, Yoshiya; Umehara, Izuru

2018-05-01

The magnetization and electrical resistivity of Ce3RuSn6 have been measured in the temperature range from 2 to 300 K and in the pressure range up to 1 GPa. At ambient pressure, the magnetization shows a ferromagnetic-like steep rise below 4 K. The electrical resistivity drops at TC = 3.3 K due to the magnetic transition. We found that TC is slightly enhanced by applying pressure, suggesting that this compound sits on the left side of the peak in the Doniach phase diagram.

On the solubility of yttrium in RuO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Music, Denis; Zumdick, Naemi A.; Hallstedt, Bengt; Schneider, Jochen M. [Materials Chemistry, RWTH Aachen University, D-52056 Aachen (Germany)

2011-09-01

We have investigated the solubility of Y in rutile RuO{sub 2} using experimental and theoretical methods. Nanostructured Ru-Y-O thin films were synthesized via combinatorial reactive sputtering with an O/metal ratio of 2.6 and a Y content of 0.3 to 12.6 at. %. A solubility limit of 1.7 at. % was identified using x-ray photoelectron spectroscopy and x-ray diffraction. Based on ab initio and thermodynamic modeling, the solubility of Y can be understood. Smaller Y amounts are incorporated into the lattice, forming a metastable film, with local structural deformations due to size effects. As the Y content is increased, extensive local structural deformations are observed, but phase separation does not occur due to kinetic limitations. Nanostructured RuO{sub 2} alloyed with Y might lead to enhanced phonon scattering and quantum confinement effects, which in turn improve the thermoelectric efficiency.

Modulation of transport properties of RuO2 with 3d transition metals

International Nuclear Information System (INIS)

Music, Denis; Chen, Yen-Ting; Geyer, Richard W; Bliem, Pascal; Schneider, Jochen M

2014-01-01

Using density functional theory, we have demonstrated that alloying of RuO 2 (P4 2 /mnm) with 3d transition metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) gives rise to a substantial increase in the Seebeck coefficient probably due to quantum confinement. As Fe yields the largest enhancement, it was selected for experimental verification. We synthesized combinatorial Ru–Fe–O thin films and subsequently measured their transport properties at elevated temperatures. The Fe-alloyed samples increase the Seebeck coefficient threefold with respect to the unalloyed RuO 2 specimen thereby verifying the theoretical prediction. The here obtained power factor of 274 μW K −2 m −1 is not only the largest reported value for RuO 2 based compounds but it also occurs at ∼600 °C thus increasing the Carnot efficiency significantly. (paper)

Magnetic field effects in UNi.sub.1/3./sub.Ru.sub.2/3./sub.Al

Czech Academy of Sciences Publication Activity Database

Alsmadi, A. M.; El-Khatib, S.; de Chatel, P.F.; Nakotte, H.; Lacerda, A. H.; Jung, M. H.; Andreev, Alexander V.; Honda, F.; Sechovský, V.

2005-01-01

Roč. 97, - (2005), 10A919/1-10A919/3 ISSN 0021-8979 R&D Projects: GA ČR(CZ) GA202/02/0739 Keywords : UNi 1/3 Ru 2/3 Al * magnetic field effects Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.498, year: 2005

Flotation-spectrophotometric determination of ruthenium in the Ru(IV)-chloride-rhodamine 6G-toluene system

International Nuclear Information System (INIS)

Balcerzak, M.

1985-01-01

The reduction of RuO 4 in hydrochloric acid has been examined. A sensitive flotation-spectrophotometric method of the determination of ruthenium based on the ion associate formed by the anionic chlorid complex of ruthenium RuCl 2- 6 with the basic dye Rhodamine 6G (R6G) has been developed. The solution of the ion associate obeys Beer's law up to the concentration of 0.25 μg Ru/ml. The ion associate precipitates when the aqueous solution is shaken with toluene. The separated compound is dissolved in acetone. The molar absorptivity (epsilon) at 530 nm is 5.1 x 10 5 l x mole -1 x cm -1 . The relative standard deviation is 3-7%. The mole ratio of Ru:R6G in the complex is 1:5. Osmium reacts similarly. The determination of ruthenium can be selective after the preliminary separation of osmium as OsO 4 . The method was applied to the determination of microgram amounts of ruthenium in crucible platinum. (Author)

Hydrostatic Pressure Study on 3-K Phase Superconductivity in Sr2RuO4-Ru Eutectic Crystals by AC Magnetic Susceptibility Measurements

International Nuclear Information System (INIS)

Yaguchi, Hiroshi; Watanabe, Hiromichi; Sakaue, Akira

2012-01-01

We have investigated the effect of hydrostatic pressure on 3-K phase superconductivity in Sr 2 RuO 4 -Ru eutectic crystals by means of AC magnetic susceptibility measurements. We have found that the application of hydrostatic pressure suppresses the superconducting transition temperature T c of the 3-K phase with a pressure coefficient of dT c /dP ≈ −0.2 K/GPa, similar to the case of the 1.5-K phase. We have also observed that the effect of hydrostatic pressure on the 3-K phase seems to be elastic whilst that of uniaxial pressure is plastic.

Anion-selective interaction and colorimeter by an optical metalloreceptor based on ruthenium(II) 2,2'-biimidazole: hydrogen bonding and proton transfer.

Science.gov (United States)

Cui, Ying; Mo, Hao-Jun; Chen, Jin-Can; Niu, Yan-Li; Zhong, Yong-Rui; Zheng, Kang-Cheng; Ye, Bao-Hui

2007-08-06

A new anion sensor [Ru(bpy)2(H2biim)](PF6)2 (1) (bpy = 2,2'-bipyridine and H2biim = 2,2'-biimidazole) has been developed, in which the Ru(II)-bpy moiety acts as a chromophore and the H2biim ligand as an anion receptor via hydrogen bonding. A systematic investigation shows that 1 is an eligible sensor for various anions. It donates protons for hydrogen bonding to Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, and OAc- anions and further actualizes monoproton transfer to the OAc- anion, changing color from yellow to orange brown. The fluoride ion has a high affinity toward the N-H group of the H2biim ligand for proton transfer, rather than hydrogen bonding, because of the formation of the highly stable HF2- anion, resulting in stepwise deprotonation of the two N-H fragments. These processes are signaled by vivid color changes from yellow to orange brown and then to violet because of second-sphere donor-acceptor interactions between Ru(II)-H2biim and the anions. The significant color changes can be distinguished visually. The processes are not only determined by the basicity of anion but also by the strength of hydrogen bonding and the stability of the anion-receptor complexes. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of anion sensors.

Determination of itopride hydrochloride by high-performance liquid chromatography with Ru(bpy)3(2+) electrogenerated chemiluminescence detection.

Science.gov (United States)

Sun, Yonghua; Zhang, Zhujun; Xi, Zhijun; Shi, Zuolong; Tian, Wei

2009-08-26

In this work, a stable electrogenerated chemiluminescence (ECL) detector was developed. The detector was prepared by packing cation-exchanged resin particles in a glass tube, followed by inserting Pt wires (working electrode) in this tube and sealing. The leakage of Ru(bpy)(3)(2+) can be compensated by adding a small amount of Ru(bpy)(3)(2+) into solution phase. Coupled with high-performance liquid chromatography separation, the detector has been used for determination of itopride hydrochloride in human serum. Under the optimal conditions, the ECL intensity has a linear relationship with the concentration of itopride hydrochloride in the range of 1.0 x 10(-8) g mL(-1) to 1.0 x 10(-6) g mL(-1) and the detection limit was 3 x 10(-9) g mL(-1) (S/N=3). The as-prepared ECL detector displayed good sensitivity and stability.

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.

Thermodynamic assessment of the Al-Ru system

CSIR Research Space (South Africa)

Prins, SN

2003-03-01

Full Text Available describes the order disorder transformation with one Gibbs energy function. The RuAl6 phase was described as a stoichiometric phase and the remaining intermetallic phases (Ru4Al13, RuAl2 and Ru2Al3) were modelled with the sublattice model. The solubility...

Pd(OAc)2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.

Science.gov (United States)

Kellner, Dominik; Weger, Maximilian; Gini, Andrea; Mancheño, Olga García

2017-01-01

The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc) 2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero)-Diels-Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

Selective Hydrogenation of m-Dinitrobenzene to m-Nitroaniline over Ru-SnOx/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Haiyang Cheng

2014-07-01

Full Text Available Series catalysts of Ru-SnOx/Al2O3 with varying SnOx loading of 0–3 wt% were prepared, and their catalytic activity and selectivity have been discussed and compared for the selective hydrogenation of m-dinitrobenzene (m-DNB to m-nitroaniline (m-NAN. The Ru-SnOx/Al2O3 catalysts were characterized by X-ray powder diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and hydrogen temperature-programmed reduction (H2-TPR and desorption (H2-TPD. Under the modification of SnOx, the reaction activity increased obviously, and the best selectivity to m-NAN reached above 97% at the complete conversion of m-DNB. With the increasing of the SnOx loading, the amount of active hydrogen adsorption on the surface of the catalyst increased according to the H2-TPD analysis, and the electron transferred from Ru to SnOx species, as determined by XPS, inducing an electron-deficient Ru, which is a benefit for the absorption of the nitro group. Therefore, the reaction rate and product selectivity were greatly enhanced. Moreover, the Ru-SnOx/Al2O3 catalyst presented high stability: it could be recycled four times without any loss in activity and selectivity.

Effects of countercations on the structures and redox and spectroscopic properties of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

Science.gov (United States)

Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

2005-05-30

The molecular structures and physicochemical properties of diruthenium complexes with ligand-unsupported Ru-Ru bonds, generally formulated as [A2{Ru2(DTBCat)4}] (DTB = 3,5- or 3,6-di-tert-butyl; Cat(2-) = catecholate), were studied in detail by changing the countercations. First, the binding structures of the cations in a family of [{A(DME)n}2{Ru2(3,5-DTBCat)4}] (n = 2 for A+ = Li+ and Na+ and n = 1 for A+ = K+ and Rb+) were systematically examined to reveal the effects of the cations on the molecular structures and electrochemical properties. Second, the complex (n-Bu4N)2[Ru2(3,6-DTBCat)4] with a cation-free structure was synthesized using tetra-n-butylammonium cations. The complex clearly demonstrates first that the ligand-unsupported Ru-Ru bonds are essentially stabilized by the dianionic nature of the catecholate derivatives without any other bridging or supporting species. In contrast, the redox potentials and absorption spectra of the complexes can sensitively respond to the countercations depending upon the polarity of the solvents.

Magnetic Excitations in α-RuCl3

Science.gov (United States)

Nagler, Stephen; Banerjee, Arnab; Bridges, Craig; Yan, Jiaqiang; Mandrus, David; Stone, Matthew; Aczel, Adam; Li, Ling; Yiu, Yuen; Lumsden, Mark; Knolle, Johannes; Moessner, Roderich; Tennant, Alan

2015-03-01

The layered material α-RuCl3 is composed of stacks of weakly coupled honeycomb lattices of octahedrally coordinated Ru3+ ions. The Ru ion ground state has 5 d electrons in the low spin state, with spin-orbit coupling very strong compared to other terms in the single ion Hamiltonian. The material is therefore an excellent candidate for investigating possible Heisenberg-Kitaev physics. In addition, this compound is very amenable to investigation by neutron scattering to explore the magnetic ground state and excitations in detail. Here we discuss new time-of-flight inelastic neutron scattering data on α-RuCl3. A high energy excitation near 200 meV is identified as a transition from the single ion J=1/2 ground state to the J=3/2 excited state, yielding a direct measurement of the spin orbit coupling energy. Higher resolution measurements reveal two collective modes at much lower energy scales. The results are compared with the theoretical expectations for excitations in the Heisenberg - Kitaev model on a honeycomb lattice, and show that Kitaev interactions are important. Research at SNS supported by the DOE BES Scientific User Facilities Division.

DFT calculations of the structures and vibrational spectra of the [Fe(bpy)3]2+ and [Ru(bpy)3]2+ complexes

International Nuclear Information System (INIS)

Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

2008-01-01

Structures of the [M(bpy) 3 ] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3 ] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1 E MLCT excited state

DFT calculations of the structures and vibrational spectra of the [Fe(bpy) 3] 2+ and [Ru(bpy) 3] 2+ complexes

Science.gov (United States)

Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

2008-09-01

Structures of the [M(bpy) 3] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1E MLCT excited state.

Electrochemical oxidation of cyanide on 3D Ti-RuO2 anode using a filter-press electrolyzer.

Science.gov (United States)

Pérez, Tzayam; López, Rosa L; Nava, José L; Lázaro, Isabel; Velasco, Guillermo; Cruz, Roel; Rodríguez, Israel

2017-06-01

The novelty of this communication lies in the use of a Ti-RuO 2 anode which has not been tested for the oxidation of free cyanide in alkaline media at concentrations similar to those found in wastewater from the Merrill Crowe process (100 mg L -1 KCN and pH 11), which is typically used for the recovery of gold and silver. The anode was prepared by the Pechini method and characterized by SEM. Linear sweep voltammetries on a Ti-RuO 2 rotating disk electrode (RDE) confirmed that cyanide is oxidized at 0.45 cyanide was investigated on Ti-RuO 2 meshes fitted into a filter-press electrolyzer. Bulk electrolyzes were performed at constant potentials of 0.85 V and 0.95 V and at different mean linear flow rates ranging between 1.2 and 4.9 cm s -1 . The bulk anodic oxidation of cyanide at 0.85 V and 3.7 cm s -1 achieved a degradation of 94%, with current efficiencies of 38% and an energy consumption of 24.6 kWh m -3 . Moreover, the degradation sequence of cyanide was also examined by HPLC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical, spectroscopic, and photophysical properties of structurally diverse polyazine-bridged Ru(II),Pt(II) and Os(II),Ru(II),Pt(II) supramolecular motifs.

Science.gov (United States)

Knoll, Jessica D; Arachchige, Shamindri M; Wang, Guangbin; Rangan, Krishnan; Miao, Ran; Higgins, Samantha L H; Okyere, Benjamin; Zhao, Meihua; Croasdale, Paul; Magruder, Katherine; Sinclair, Brian; Wall, Candace; Brewer, Karen J

2011-09-19

Five new tetrametallic supramolecules of the motif [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) and three new trimetallic light absorbers [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) (TL = bpy = 2,2'-bipyridine or phen = 1,10-phenanthroline; M = Ru(II) or Os(II); BL = dpp = 2,3-bis(2-pyridyl)pyrazine, dpq = 2,3-bis(2-pyridyl)quinoxaline, or bpm = 2,2'-bipyrimidine) were synthesized and their redox, spectroscopic, and photophysical properties investigated. The tetrametallic complexes couple a Pt(II)-based reactive metal center to Ru and/or Os light absorbers through two different polyazine BL to provide structural diversity and interesting resultant properties. The redox potential of the M(II/III) couple is modulated by M variation, with the terminal Ru(II/III) occurring at 1.58-1.61 V and terminal Os(II/III) couples at 1.07-1.18 V versus Ag/AgCl. [{(TL)(2)M(dpp)}(2)Ru(BL)](PF(6))(6) display terminal M(dπ)-based highest occupied molecular orbitals (HOMOs) with the dpp(π*)-based lowest unoccupied molecular orbital (LUMO) energy relatively unaffected by the nature of BL. The coupling of Pt to the BL results in orbital inversion with localization of the LUMO on the remote BL in the tetrametallic complexes, providing a lowest energy charge separated (CS) state with an oxidized terminal Ru or Os and spatially separated reduced BL. The complexes [{(TL)(2)M(dpp)}(2)Ru(BL)](6+) and [{(TL)(2)M(dpp)}(2)Ru(BL)PtCl(2)](6+) efficiently absorb light throughout the UV and visible regions with intense metal-to-ligand charge transfer (MLCT) transitions in the visible at about 540 nm (M = Ru) and 560 nm (M = Os) (ε ≈ 33,000-42,000 M(-1) cm(-1)) and direct excitation to the spin-forbidden (3)MLCT excited state in the Os complexes about 720 nm. All the trimetallic and tetrametallic Ru-based supramolecular systems emit from the terminal Ru(dπ)→dpp(π*) (3)MLCT state, λ(max)(em) ≈ 750 nm. The tetrametallic systems display complex excited state dynamics with quenching of the (3)MLCT emission at

Structural and magnetic properties of UCo1/3T2/3Al solid solutions (T = Ru, Pt, Rh)

International Nuclear Information System (INIS)

Andreev, A. V.; Bordallo, H. N.; Chang, S.; Nakotte, H.; Schultz, A. J.; Sechovsky, V.; Torikachvili, M. S.

1999-01-01

We report on neutron diffraction studies of UCo 1/3 T 2/3 Al (T = Ru, Pt, Rh). All three solid solutions form in the hexagonal ZrNiAl structure. The Ru-containing compound is found to be chemically ordered, while the Pt-containing compound is nearly disordered and the Rh-containing compound is purely disordered. All three compounds exhibit long-range magnetic order with rather small U moments

Half-metallic and insulating natures in Ru-based ordered double perovskite oxides Ba_2X"I"I"IRu"VO_6 (X = V, Cr) induced by 3d-t_2_g"n orbital filling

International Nuclear Information System (INIS)

Saad, H.-E.M. Musa; Althoyaib, S.S.

2017-01-01

In this paper, we present results of a comprehensive systemic study of the crystal, electronic and magnetic structures on two members of Ru-based ordered double perovskite oxides Ba_2XRuO_6 (X = V, Cr). For the corporate compound, the analysis of density of states (DOS) results suggests that the 3d-t_2_g orbital filling plays a major role in governing the conduction mechanism in these systems. The DOS and magnetic results show that Ba_2XRuO_6 exhibits half-metallic (HM) nature as X = V, where the electronic structure of Ba_2V"I"I"IRu"VO_6 with 3d-t_2_g"2 behaves like that of HM ferrimagnetic (FI), switches to compensate FI insulating behavior as X = Cr, with an extra electron filled 3d-t_2_g"3 in Ba_2Cr"I"I"IRu"VO_6. We find, on consideration of electron correlation (LSDA+U) and spin-orbital coupling (SOC) effects that the electronic structure of Ba_2XRuO_6 takes a HM nature, whereas it is completely transformed to insulating nature once an extra electron filled the 3d-t_2_g orbitals in X = Cr case. Such tuning is accompanied by spin-state hopping of one electron from half-filled spin-state in Ru"V (t_2_g"3 e_g"0) to two and three occupied spin-state in V"I"I"I (t_2_g"2 e_g"0) and Cr"I"I"I (t_2_g"3 e_g"0), respectively. The charge distribution results show that this extra electron occupies chiefly the spin-down of conduction orbitals and plays a major role in determining the electronic and magnetic structures of Ba_2XRuO_6 system. - Highlights: • Half-metallic and insulating natures are observed in Ba_2XRuO_6 (X = V, Cr). • 3d-t_2_g"n orbitals filling plays a major role in governing the conduction mechanism. • LSDA+U method under density functional theory (DFT) is considered. • HM ferrimagnetic (FI) (X = V) switch to compensate FI insulating (X = Cr).

2,2/-Dipyridylketone (dpk) as Ancillary Acceptor and Reporter Ligand in Complexes [(dpk)(Cl)Ru(.mu.-tppz)Ru(Cl)(dpk)]n+ where tppz = 2,3,5,6-Tetrakis(2-pyridyl)pyrazine

Czech Academy of Sciences Publication Activity Database

Ghumaan, S.; Sarkar, B.; Chanda, N.; Sieger, M.; Fiedler, Jan; Kaim, W.; Lahiri, G. K.

2006-01-01

Roč. 45, č. 19 (2006), s. 7955-7961 ISSN 0020-1669 R&D Projects: GA MŠk OC 139; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear Ru complexes * Creutz-Taube ion * mixed -valence system Subject RIV: CG - Electrochemistry Impact factor: 3.911, year: 2006

Relativistic effects in iron-, ruthenium-, and osmium porphyrins

International Nuclear Information System (INIS)

Liao Mengsheng; Scheiner, Steve

2002-01-01

Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py) 2 and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a 3 A 2g ground state, while this state is nearly degenerate with 3 E g for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be 3 E g . For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d z 2 -orbital, thereby making the M II ion diamagnetic. The calculated redox properties of MP(py) 2 and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects

Synthesis, structure, and electronic properties of a dimer of Ru(bpy)2 doubly bridged by methoxide and pyrazolate.

Science.gov (United States)

Jude, Hershel; Rein, Francisca N; White, Peter S; Dattelbaum, Dana M; Rocha, Reginaldo C

2008-09-01

The heterobridged dinuclear complex cis,cis-[(bpy) 2Ru(mu-OCH 3)(mu-pyz)Ru(bpy) 2] (2+) ( 1; bpy = 2,2'-bipyridine; pyz = pyrazolate) was synthesized and isolated as a hexafluorophosphate salt. Its molecular structure was fully characterized by X-ray crystallography, (1)H NMR spectroscopy, and ESI mass spectrometry. The compound 1.(PF 6) 2 (C 44H 38F 12N 10OP 2Ru 2) crystallizes in the monoclinic space group P2 1/ c with a = 13.3312(4) A, b = 22.5379(6) A, c = 17.2818(4) A, beta = 99.497(2) degrees , V = 5121.3(2) A (3), and Z = 4. The meso diastereoisomeric form was exclusively found in the crystal structure, although the NMR spectra clearly demonstrated the presence of two stereoisomers in solution (rac and meso forms at approximately 1:1 ratio). The electronic properties of the complex in acetonitrile were investigated by cyclic voltammetry and UV-vis and NIR-IR spectroelectrochemistries. The stepwise oxidation of the Ru (II)-Ru (II) complex into the mixed-valent Ru (II)-Ru (III) and fully oxidized Ru (III)-Ru (III) states is fully reversible on the time scale of the in situ (spectro)electrochemical measurements. The mixed-valent species displays strong electronic coupling, as evidenced by the large splitting between the redox potentials for the Ru(III)/Ru(II) couples (Delta E 1/2 = 0.62 V; K c = 3 x 10 (10)) and the appearance of an intervalence transfer (IT) band at 1490 nm that is intense, narrow, and independent of solvent. Whereas this salient band in the NIR region originates primarily from highest-energy of the three IT transitions predicted for Ru(II)-Ru(III) systems, a weaker absorption band corresponding to the lowest-energy IT transition was clearly evidenced in the IR region ( approximately 3200 cm (-1)). The observation of totally coalesced vibrational peaks in the 1400-1650 cm (-1) range for a set of five bpy spectator vibrations in Ru (II)-Ru (III) relative to Ru (II)-Ru (II) and Ru (III)-Ru (III) provided evidence for rapid electron transfer and

Pd(OAc2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

Directory of Open Access Journals (Sweden)

Dominik Kellner

2017-08-01

Full Text Available The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero-Diels–Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

Magnetic properties and structural characterization of Sr{sub 2}RuHoO{sub 6} complex perovskite

Energy Technology Data Exchange (ETDEWEB)

Corredor, L.T.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, AA 5997, Bogota DC (Colombia); Martinez Buitrago, D. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, AA 5997, Bogota DC (Colombia); Grupo Fisica de Materiales, Escuela de Fisica, Universidad Pedagogica y Tecnologica de Colombia, Tunja (Colombia); Albino Aguiar, J. [Departamento de Fisica, Universidade Federal de Pernambuco, 50670-901, Recife PE (Brazil); Roa-Rojas, J., E-mail: jroar@unal.edu.co [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, AA 5997, Bogota DC (Colombia)

2012-08-15

We report an experimental study of the crystallographic lattice, morphologic characteristics and magnetic feature of Sr{sub 2}RuHoO{sub 6} complex perovskite, which is used as a precursor in the fabrication process of the superconducting ruthenocuprate RuSr{sub 2}HoCu{sub 2}O{sub 8}. The samples were produced through the standard solid state reaction. A Rietveld refinement of experimental X-ray diffraction patterns shows that the material crystallizes in a monoclinic structure, which belongs to the P21/n (no.14) space group, with lattice parameters a=5.7719(6) A, b=5.8784(5) A, c=8.1651(9) A, and tilt angle {beta}=90.200 Degree-Sign . Magnetic susceptibility measurements reveal the occurrence of an antiferromagnetic ordering for a Neel temperature T{sub N}=10.1 K. From the Curie-Weiss fitting of the paramagnetic regime we obtain an effective magnetic moment of 11.31 {mu}{sub B}.

Investigation on the structure of thiocyanatoruthenate (3) complex by isotopic exchange method in the system [Ru(SCN)6]-3-S14CN-

International Nuclear Information System (INIS)

Wajda, S.; Rachlewicz, K.

1973-01-01

Because of the discrepancy in the literature data and the difficulties in the synthesis of Ru(3) thiocyanate complexes, an attempt was made to obtain them under different conditions than usual. Our attempts turned out to be successful. This allowed to examine the radioisotopic exchange in the system [Ru(SCN) 6 ] -3 -S 14 CN - . The experimental data indicated that the thiocyanate groups in the complex are nonequivalent and exchange with various rate. The two groups in the axial plane exchange with a rate by two orders higher than the remaining four groups in the equatorial plane. On this ground the electronic structure of the examined complex was discussed and its symmetry was determined. (author)

Anomalous perovskite PbRuO3 stabilized under high pressure

Science.gov (United States)

Cheng, J.-G.; Kweon, K. E.; Zhou, J.-S.; Alonso, J. A.; Kong, P.-P.; Liu, Y.; Jin, Changqing; Wu, Junjie; Lin, Jung-Fu; Larregola, S. A.; Yang, Wenge; Shen, Guoyin; MacDonald, A. H.; Manthiram, Arumugam; Hwang, G. S.; Goodenough, John B.

2013-01-01

Perovskite oxides ABO3 are important materials used as components in electronic devices. The highly compact crystal structure consists of a framework of corner-shared BO6 octahedra enclosing the A-site cations. Because of these structural features, forming a strong bond between A and B cations is highly unlikely and has not been reported in the literature. Here we report a pressure-induced first-order transition in PbRuO3 from a common orthorhombic phase (Pbnm) to an orthorhombic phase (Pbn21) at 32 GPa by using synchrotron X-ray diffraction. This transition has been further verified with resistivity measurements and Raman spectra under high pressure. In contrast to most well-studied perovskites under high pressure, the Pbn21 phase of PbRuO3 stabilized at high pressure is a polar perovskite. More interestingly, the Pbn21 phase has the most distorted octahedra and a shortest Pb—Ru bond length relative to the average Pb—Ru bond length that has ever been reported in a perovskite structure. We have also simulated the behavior of the PbRuO3 perovskite under high pressure by first principles calculations. The calculated critical pressure for the phase transition and evolution of lattice parameters under pressure match the experimental results quantitatively. Our calculations also reveal that the hybridization between a Ru:t2g orbital and an sp hybrid on Pb increases dramatically in the Pbnm phase under pressure. This pressure-induced change destabilizes the Pbnm phase to give a phase transition to the Pbn21 phase where electrons in the overlapping orbitals form bonding and antibonding states along the shortest Ru—Pb direction at P > Pc. PMID:24277807

Inner-shell photodetachment from Ru-

International Nuclear Information System (INIS)

Dumitriu, I.; Gorczyca, T. W.; Berrah, N.; Bilodeau, R. C.; Pesic, Z. D.; Rolles, D.; Walter, C. W.; Gibson, N. D.

2010-01-01

Inner-shell photodetachment from Ru - was studied near and above the 4p excitation region, 29-to-91-eV photon energy range, using a merged ion-photon-beam technique. The absolute photodetachment cross sections of Ru - ([Kr]4d 7 5s 2 ) leading to Ru + , Ru 2+ , and Ru 3+ ion production were measured. In the near-threshold region, a Wigner s-wave law, including estimated postcollision interaction effects, locates the 4p 3/2 detachment threshold between 40.10 and 40.27 eV. Additionally, the Ru 2+ product spectrum provides evidence for simultaneous two-electron photodetachment (likely to the Ru + 4p 5 4d 6 5s 2 state) located near 49 eV. Resonance effects are observed due to interference between transitions of the 4p electrons to the quasibound 4p 5 4d 8 5s 2 states and the 4d→εf continuum. Despite the large number of possible terms resulting from the Ru - 4d open shell, the cross section obtained from a 51-state LS-coupled R-matrix calculation agrees qualitatively well with the experimental data.

Competing magnetic fluctuations in Sr3Ru2O7 probed by Ti doping

DEFF Research Database (Denmark)

Hooper, J.; Fang, M.H.; Zhou, M.

2007-01-01

We report the effect of nonmagnetic Ti4+ impurities on the electronic and magnetic properties of Sr3Ru2O7. Small amounts of Ti suppress the characteristic peak in magnetic susceptibility near 16 K and result in a sharp upturn in specific heat. The metamagnetic quantum phase transition and related...... anomalous features are quickly smeared out by small amounts of Ti. These results provide strong evidence for the existence of competing magnetic fluctuations in the ground state of Sr3Ru2O7. Ti doping suppresses the low-temperature antiferromagnetic interactions that arise from Fermi surface nesting...

Synthesis, characterisation and antibacterial activity of [(p-cym)RuX(L)](+/2+) (X = Cl, H2O; L = bpmo, bpms) complexes.

Science.gov (United States)

Tripathy, Suman Kumar; Taviti, Ashoka Chary; Dehury, Niranjan; Sahoo, Anupam; Pal, Satyanaryan; Beuria, Tushar Kant; Patra, Srikanta

2015-03-21

Mononuclear half-sandwiched complexes [(p-cym)RuCl(bpmo)](ClO4) {[1](ClO4)} and [(p-cym)RuCl(bpms)](PF6) {[2](PF6)} have been prepared by reacting heteroscorpionate ligands bpmo = 2-methoxyphenyl-bis(3,5-dimethylpyrazol-1-yl)methane and bpms = 2-methylthiophenyl-bis(3,5-dimethylpyrazol-1-yl)methane, respectively, with a dimeric precursor complex [(p-cym)RuCl(μ-Cl)]2 (p-cym = 1-isopropyl-4-methylbenzene) in methanol. The corresponding aqua derivatives [(p-cym)Ru(H2O)(bpmo)](ClO4)2 {[3](ClO4)2} and [(p-cym)Ru(H2O)(bpms)](PF6)2 {[4](PF6)2} are obtained from {[1](ClO4)} and {[2](PF6)}, respectively, via Cl(-)/H2O exchange process in the presence of appropriate equivalents of AgClO4/AgNO3 + KPF6 in a methanol-water mixture. The molecular structures of the complexes {[1]Cl, [3](ClO4)2 and [4](PF6)(NO3)} are authenticated by their single crystal X-ray structures. The complexes show the expected piano-stool geometry with p-cym in the η(6) binding mode. The aqua complexes [3](ClO4)2 and [4](PF6)2 show significantly good antibacterial activity towards E. coli (gram negative) and B. subtilis (gram positive) strains, while chloro derivatives ({[1](ClO4)} and {[2](PF6)} are found to be virtually inactive. The order of antibacterial activity of the complexes according to their MIC values is [1](ClO4) (both 1000 μg mL(-1)) < [2](PF6) (580 μg mL(-1) and 750 μg mL(-1)) < [3](ClO4)2 (both 100 μg mL(-1)) < [4](PF6)2 (30 μg mL(-1) and 60 μg mL(-1)) for E. coli and B. subtilis strains, respectively. Further, the aqua complexes [3](ClO4)2 and [4](PF6)2 show clear zones of inhibition against kanamycin, ampicillin and chloramphenicol resistant E. coli strains. The detailed mechanistic aspects of the aforesaid active aqua complexes [3](ClO4)2 and [4](PF6)2 have been explored, and it reveals that both the complexes inhibit the number of nucleoids per cell in vivo and bind to DNA in vitro. The results indeed demonstrate that both [3](ClO4)2 and [4](PF6)2 facilitate the inhibition of

Zn(II) coordination polymer of an in situ generated 4-pyridyl (4Py) attached bis(amido)phosphate ligand, [PO2(NH4Py)2]- showing preferential water uptake over aliphatic alcohols.

Science.gov (United States)

Gupta, Arvind K; Nagarkar, Sanjog S; Boomishankar, Ramamoorthy

2013-08-14

Two polymorphic 2D-coordination polymers of composition [ZnL(HCO2)]∞ were synthesized from an in situ generated ligand [PO2(NH(4)Py)2](-) (L(-)). The ligand L(-) was generated by a facile metal-assisted P-N bond hydrolysis reaction from the corresponding phosphonium salt 1, [P(NH(4)Py)4]Cl, or from the neutral phosphoric triamide 2, [PO(NH(4)Py)3]. The de-solvated sample of the polymer [ZnL(HCO2)]∞ features polar micropores and shows a type I isotherm for CO2 sorption whereas a type II behaviour was observed for N2. The vapour sorption isotherm of the de-solvated sample of [ZnL(HCO2)]∞ shows preferential adsorption of water vapour over aliphatic alcohols.

Proximate Kitaev quantum spin liquid behavior in α-RuCl{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Nagler, Stephen [Quantum Condensed Matter Division, Oak Ridge National Laboratory (United States)

2016-07-01

The magnetic semiconductor α-RuCl{sub 3} is composed of very weakly coupled honeycomb layers of edge-sharing RuCl{sub 6} octahedra. The Ru{sup 3+} ion has 5d electrons in a low spin state, and the system is expected to have an effective J = 1/2 single ion ground state with an interacting spin Hamiltonian containing Kitaev-like terms. Inelastic neutron scattering on powders and single crystals has been used to determine the energy scale of the magnetic interactions and the overall form of the magnetic fluctuations. The results indicate that the Kitaev term is significant. Moreover, detailed measurements of the response show evidence for the fractionalized excitations that are characteristic of the Kitaev Quantum Spin-liquid.

Thermal properties of GdSr{sub 2}RuCu{sub 2}O{sub 8-{delta}} based mixtures in the GdSr{sub 2}RuO{sub 6}-CuO pseudo-binary system

Energy Technology Data Exchange (ETDEWEB)

Gombos, Marcello [Laboratorio Regionale Supermat CNR-INFM Via Salvador Allende, I-84081 Baronissi (Italy); Dipartimento di Fisica ' E.R.Caianiello' , Universita di Salerno, Via Salvador Allende, I-84081 Baronissi (Italy)], E-mail: gombos@sa.infn.it; Ciancio, Regina; Vecchione, Antonio; Pace, Sandro [Laboratorio Regionale Supermat CNR-INFM Via Salvador Allende, I-84081 Baronissi (Italy); Dipartimento di Fisica ' E.R.Caianiello' , Universita di Salerno, Via Salvador Allende, I-84081 Baronissi (Italy)

2007-09-01

GdSr{sub 2}RuCu{sub 2}O{sub 8-{delta}} (Gd1212) rutheno-cuprate compound is widely studied because it shows the coexistence of superconductivity and highly anisotropic magnetic ordering in the same cell. Anyway the nature of the magnetic ordering is still debated and the fabrication of macroscopic samples oriented along a crystallographic axis, that could help to clarify its details, appears to be quite difficult. For this reason, accurate investigation on Gd1212 incongruent melting reaction, producing liquid copper oxide and the solid GdSr{sub 2}RuO{sub 6} (Gd1210), appears to be necessary to improve the fabrication of crystallographically oriented bulk superconducting samples. Thermo-gravimetric and differential thermal measurements were performed to analyse the thermal behaviour up to 1200 deg. C and the melting temperatures of different mixtures of Gd1212 with Gd1210 or CuO, in view to perform a scan of the whole CuO-Gd1212-Gd1210 coexistence line of the Gd-Sr-Ru-Cu-O phase diagram. Dependence on the atmosphere and the formation of different spurious phases was also studied.

Peierls-distorted Ru-chains and boron dumbbells in Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} from first-principles calculations and experiments

Energy Technology Data Exchange (ETDEWEB)

Touzani, Rachid S.; Mbarki, Mohammed; Chen, Ximeng [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Fokwa, Boniface P.T. [Institute of Inorganic Chemistry, RWTH Aachen University (Germany); Department of Chemistry, University of California Riverside (UCR), Riverside, CA (United States)

2016-09-15

Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases were recently predicted by GGA-VASP structure optimization to crystallize in the Nb{sub 2}OsB{sub 2}-type structure. Although the Fe-based (Mo{sub 2}FeB{sub 2} type) and Os-based (Nb{sub 2}OsB{sub 2} type, superstructure variant of Mo{sub 2}FeB{sub 2} type) analogues have been synthesized and characterized successfully, the Ru-based phases remained unknown. Crystal structure prediction of Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} phases, using an evolutionary algorithm, led to the AlMn{sub 2}B{sub 2}-type structure in contrast to the aforementioned optimization; however, phonon calculations showed that the Nb{sub 2}OsB{sub 2}-type phases are dynamically more stable than the AlMn{sub 2}B{sub 2}-type phases. A slightly modified synthetic strategy finally led to the successful preparation of the predicted phases. The extremely quick arc-melting procedure, under argon atmosphere, not only led to a quantitative amount of the phases but also to single crystals suitable for structure determination. Powder and single-crystal X-ray diffraction as well as EDX analysis of the metal ratio have confirmed the GGA-VASP structure optimization: Nb{sub 2}RuB{sub 2} and Ta{sub 2}RuB{sub 2} compounds indeed crystallize isotypically with Nb{sub 2}OsB{sub 2} structure, a superstructure variant of Mo{sub 2}FeB{sub 2} type, in which B-dumbbells and Peierls-distorted Ru-chains are found. Susceptibility measurements on a Ta{sub 2}RuB{sub 2} single crystal reveal no superconducting transition down to 2 K, even though some features in the band structures of both phases, similar to those reported in superconducting NbRuB, hinted at possible superconductivity. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Room temperature photoinduced magnetism in [py.H]{sub 3}[FeCl{sub 4}]{sub 2}Cl

Energy Technology Data Exchange (ETDEWEB)

Baniasadi, F. [Physics Department, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Tehranchi, M.M., E-mail: teranchi@sbu.ac.ir [Physics Department, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Fathi, M.B. [Physics Department, Kharazmi University, Tehran (Iran, Islamic Republic of); Hamidi, S.M. [Laser and Plasma Research Institute, Shahid Beheshti University, Tehran (Iran, Islamic Republic of); Safari, N.; Amani, V. [Faculty of Chemistry, Shahid Beheshti University, Tehran (Iran, Islamic Republic of)

2015-11-15

Photoinduced magnetism in a homogeneous solution of [py.H]{sub 3}[FeCl{sub 4}]{sub 2}Cl is measured by Faraday rotation in visible light (λ∼450–750 nm) at room temperature. The physics of this phenomenon may be attributed to electronic transitions caused by absorption of light. X-ray diffraction and Debye function analysis are therefore applied to find the abundant unit of molecules dissolved in the solution which are being further utilized to investigate the electronic structure and molecular orbitals by means of hybrid density function theory (B3LYP). Faraday rotation is observed at certain wavelengths consistent with energy differences of HOMO-LUMO energy levels. Thus this work puts forward a new material with certain photomagnetic properties which may be used in fabrication of room temperature magneto-optical switches. - Highlights: • Photoinduced magnetism in (FeCl{sub 4}){sub 2}(py.H){sub 3}Cl is illustrated via Faraday rotation. • The abundant unit of molecule is characterized by Debye function analysis of XRD. • PIM in the molecule is attributed to the charge transfer between HOMO-LUMO.

Spectra and relaxation dynamics of the pseudohalide (PS) vibrational bands for Ru(bpy)2(PS)2 complexes, PS = CN, NCS and N3

International Nuclear Information System (INIS)

Compton, Ryan; Gerardi, Helen K.; Weidinger, Daniel; Brown, Douglas J.; Dressick, Walter J.; Heilweil, Edwin J.; Owrutsky, Jeffrey C.

2013-01-01

Highlights: ► Static and transient infrared spectroscopy of pseudohalide bipyridine ruthenium complexes. ► Vibrational energy relaxes faster for the azide than the thiocyanate and cyanide analogs. ► Intramolecular vibrational relaxation is prevalent in cis-Ru(bpy) 2 (N 3 ) 2 . - Abstract: Static and transient infrared spectroscopy were used to investigate cis-Ru(bpy) 2 (N 3 ) 2 (bpy = 2,2′-bipyridine), cis-Ru(bpy) 2 (NCS) 2 , and cis-Ru(bpy) 2 (CN) 2 in solution. The NC stretching IR band for cis-Ru(bpy) 2 (NCS) 2 appears at higher frequency (∼2106 cm −1 in DMSO) than for the free NCS − anion while the IR bands for the azide and cyanide complexes are closer to those of the respective free anions. The vibrational energy relaxation (VER) lifetime for the azide complex is found to be much shorter (∼5 ps) than for either the NCS or CN species (both ∼70 ps in DMSO) and the lifetimes resemble those for each corresponding free anion in solution. However, for cis-Ru(bpy) 2 (N 3 ) 2 , it is determined that the transition frequency depends more on the solvent than the VER lifetime implying that intramolecular vibrational relaxation is predominant over solvent energy-extracting interactions. These results are compared to the behavior of other related metal complexes in solution

Space Charge Modules for PyHEADTAIL

CERN Multimedia

Oeftiger, Adrian

2016-01-01

PyHEADTAIL is a 6D tracking tool developed at CERN to simulate collective effects. We present recent developments of the direct space charge (SC) suite, which is available for both the CPU and GPU. A new 3D particle-in-cell solver with open boundary conditions has been implemented. For the transverse plane, there is a semi-analytical Bassetti-Erskine model as well as 2D self-consistent particle-in-cell solvers with both open and closed boundary conditions. For the longitudinal plane, PyHEADTAIL offers line density derivative models. Simulations with these models are benchmarked with experiments at the injection plateau of CERN’s SPS.

Interface Control of Ferroelectricity in an SrRuO3 /BaTiO3 /SrRuO3 Capacitor and its Critical Thickness.

Science.gov (United States)

Shin, Yeong Jae; Kim, Yoonkoo; Kang, Sung-Jin; Nahm, Ho-Hyun; Murugavel, Pattukkannu; Kim, Jeong Rae; Cho, Myung Rae; Wang, Lingfei; Yang, Sang Mo; Yoon, Jong-Gul; Chung, Jin-Seok; Kim, Miyoung; Zhou, Hua; Chang, Seo Hyoung; Noh, Tae Won

2017-05-01

The atomic-scale synthesis of artificial oxide heterostructures offers new opportunities to create novel states that do not occur in nature. The main challenge related to synthesizing these structures is obtaining atomically sharp interfaces with designed termination sequences. In this study, it is demonstrated that the oxygen pressure (PO2) during growth plays an important role in controlling the interfacial terminations of SrRuO 3 /BaTiO 3 /SrRuO 3 (SRO/BTO/SRO) ferroelectric (FE) capacitors. The SRO/BTO/SRO heterostructures are grown by a pulsed laser deposition method. The top SRO/BTO interface, grown at high PO2 (around 150 mTorr), usually exhibits a mixture of RuO 2 -BaO and SrO-TiO 2 terminations. By reducing PO2, the authors obtain atomically sharp SRO/BTO top interfaces with uniform SrO-TiO 2 termination. Using capacitor devices with symmetric and uniform interfacial termination, it is demonstrated for the first time that the FE critical thickness can reach the theoretical limit of 3.5 unit cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

μ3-Carbonato-κ3 O:O′:O′′-tris­{(η6-ben­zene)[(R)-1-(1-amino­ethyl)naphthyl-κ2 C 2,N]ruthenium(II)} hexa­fluorido­phosphate dichloro­methane solvate

Science.gov (United States)

Sortais, Jean-Baptiste; Brelot, Lydia; Pfeffer, Michel; Barloy, Laurent

2008-01-01

The title compound, [Ru3(C12H12N)3(CO3)(C6H6)3]PF6·CH2Cl2, was obtained unintentionally as the product of an attempted deprotonation of the monomeric parent ruthenium complex [Ru(C12H12N)(C6H6)(C2H3N)]PF6. The carbonate ligand bridges three half-sandwich cyclo­ruthenated fragments, each of them exhibiting a pseudo-tetra­hedral geometry. The configuration of the Ru atoms is S. The naphthyl groups of the enanti­opure cyclo­ruthenated benzylic amine ligands point in the same direction, adopting a propeller shape. PMID:21201869

A Renewable and Ultrasensitive Electrochemiluminescence Immunosenor Based on Magnetic RuL@SiO2-Au~RuL-Ab2 Sandwich-Type Nano-Immunocomplexes

Directory of Open Access Journals (Sweden)

Ning Gan

2011-08-01

Full Text Available An ultrasensitive and renewable electrochemiluminescence (ECL immunosensor was developed for the detection of tumor markers by combining a newly designed trace tag and streptavidin-coated magnetic particles (SCMPs. The trace tag (RuL@SiO2-Au~RuL-Ab2 was prepared by loading Ru(bpy32+(RuL-conjuged secondary antibodies (RuL-Ab2 on RuL@SiO2 (RuL-doped SiO2 doped Au (RuL@SiO2-Au. To fabricate the immunosensor, SCMPs were mixed with biotinylated AFP primary antibody (Biotin-Ab1, AFP, and RuL@SiO2-Au~RuL-Ab2 complexes, then the resulting SCMP/Biotin-Ab1/AFP/RuL@SiO2-Au~RuL-Ab2 (SBAR sandwich-type immunocomplexes were absorbed on screen printed carbon electrode (SPCE for detection. The immunocomplexes can be easily washed away from the surface of the SPCE when the magnetic field was removed, which made the immunosensor reusable. The present immunosensor showed a wide linear range of 0.05–100 ng mL–1 for detecting AFP, with a low detection limit of 0.02 ng mL–1 (defined as S/N = 3. The method takes advantage of three properties of the immunosensor: firstly, the RuL@SiO2-Au~RuL-Ab2 composite exhibited dual amplification since SiO2 could load large amount of reporter molecules (RuL for signal amplification. Gold particles could provide a large active surface to load more reporter molecules (RuL-Ab2. Accordingly, through the ECL response of RuL and tripropylamine (TPA, a strong ECL signal was obtained and an amplification analysis of protein interaction was achieved. Secondly, the sensor is renewable because the sandwich-type immunocomplexes can be readily absorbed or removed on the SPCE’s surface in a magnetic field. Thirdly, the SCMP modified probes can perform the rapid separation and purification of signal antibodies in a magnetic field. Thus, the present immunosensor can simultaneously realize separation, enrichment and determination. It showed potential application for the detection of AFP in human sera.

Synthesis and DNA binding properties of 1-(3-aminopropyl)-imidazole-containing triamide f-Im*PyIm: a novel diamino polyamide designed to target 5'-ACGCGT-3'.

Science.gov (United States)

Satam, Vijay; Babu, Balaji; Porte, Alexander; Savagian, Mia; Lee, Megan; Smeltzer, Thomas; Liu, Yang; Ramos, Joseph; Wilson, W David; Lin, Shicai; Kiakos, Kostantinos; Hartley, John A; Lee, Moses

2012-09-15

A novel diamino/dicationic polyamide f-Im(*)PyIm (5) that contains an orthogonally positioned aminopropyl chain on an imidazole (Im(*)) moiety was designed to target 5'-ACGCGT-3'. The DNA binding properties of the diamino polyamide 5, determined by CD, ΔT(M), DNase I footprinting, SPR, and ITC studies, were compared with those of its monoamino/monocationic counterpart f-ImPyIm (1) and its diamino/dicationic isomer f-ImPy(*)Im (2), which has the aminopropyl group attached to the central pyrrole unit (Py(*)). The results gave evidence for the minor groove binding and selectivity of polyamide 5 for the cognate sequence 5'-ACGCGT-3', and with strong affinity (K(eq)=2.3×10(7) M(-1)). However, the binding affinities varied according to the order: f-ImPy(*)Im (2)>f-ImPyIm (1)≥f-Im(*)PyIm (5) confirming that the second amino group can improve affinity, but its position within the polyamide can affect affinity. Copyright © 2012 Elsevier Ltd. All rights reserved.

A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(ii)(2,2'-bipyridine)3]2+: synthesis and photophysics of RWLC-5.

Science.gov (United States)

Larsen, Randy W; Mayers, Jacob M; Wojtas, Lukasz

2017-09-26

The development of photoactive porous materials is of significant importance for applications ranging from sustainable energy to pharmaceutical development and catalysis. A particularly attractive class of photo-active materials is the metal-organic framework (MOF)-based platform in which the photo-active elements are components of the framework itself or photo-active guests encapsulated within the MOF cavities. It has now been demonstrated that the photo-active [Ru(2,2'-bipyridine) 3 ] 2+ (RuBpy) complex can template the formation of MOFs with varying three dimensional structures. Here we report the synthesis and structural and photo-physical characterization of a new RuBpy-templated MOF composed of Cd 2+ ions with 1,4-benzenedicarboxylate ligands (RWLC-5) that contains crystallographically resolved RuBpy complexes. The new material displays a biphasic emission decay (130 ns and 1180 ns, T = 20 °C) and a bathochromically shifted emission maximum, relative to RuBpy in solution (603 nm for RuBpy in ethanol vs. 630 nm for RWLC-5). The emission lifetimes also do not display temperature-dependent decays which are characteristic of RuBpy type complexes as well as other RuBpy templated MOFs. The lack of temperature dependence is consistent with the complete deactivation of the 3 LF state of the encapsulated RuBpy complex due to a constrained environment. The fast phase decay is attributed to a water molecule hydrogen bonded to a bipyridine ligand associated with ∼38% of the encapsulated RuBpy complexes resulting in the nonradiative deactivation of the 3 MLCT state.

Effects of annealing on the properties of atomic layer deposited Ru thin films deposited by NH{sub 3} and H{sub 2} as reactants

Energy Technology Data Exchange (ETDEWEB)

Lee, Seung-Joon; Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr

2016-08-01

Atomic layer deposition (ALD) of Ru using a non-oxidizing reactant is indispensable considering its application as a seed layer for Cu electroplating and a bottom electrode for dynamic random access memory capacitors. In this study, ALD-Ru films were deposited using a sequential supply of dicarbonyl-bis(5-methyl-2,4-hexanediketonato) Ru(II) (C{sub 16}H{sub 22}O{sub 6}Ru) and potential non-oxidizing reducing agents, NH{sub 3} or H{sub 2}, as the reactants at a substrate temperature of 250 °C, and the effects of post-annealing in a H{sub 2} ambient on the film properties were investigated. The highly conformal deposition of Ru films was possible using the present reaction scheme but its resistivity was as high as ~ 750 μΩ-cm due to carbon incorporation into the film and the formation of an amorphous structure. Low temperature annealing at 300 °C at H{sub 2} ambient after deposition was found to improve the properties significantly in terms of the resistivity, impurities contents and crystallinity. For example, the film resistivity was decreased drastically to ~ 40 μΩ-cm with both the release of C in the film and crystallization after annealing based on secondary ion mass spectrometry and transmission electron microscopy, whereas perfect step coverage at a very small-sized dual trench (aspect ratio: ~ 3, the top opening size of 45 nm and bottom size of 20 nm) was maintained after annealing. - Highlights: • Ru thin films were deposited by atomic layer deposition (ALD) using NH{sub 3} and H{sub 2} molecules. • Effects of low temperature (300 °C) post-annealing on the film properties were investigated. • Post annealing improved the properties of ALD-Ru films. • Perfect step coverage of ALD-Ru was confirmed at trench structure (top opening width: 45 nm).

Development of Al2O3 carrier-Ru composite catalyst for hydrogen generation from alkaline NaBH4 hydrolysis

International Nuclear Information System (INIS)

Huang, Yao-Hui; Su, Chia-Chi; Wang, Shu-Ling; Lu, Ming-Chun

2012-01-01

A recyclable and reusable Ru/Al 2 O 3 catalyst is prepared for hydrogen generation from the hydrolysis process of alkaline sodium borohydride (NaBH 4 ) solution. The hydrogen generation rate by the hydrolysis and methanolysis of alkaline NaBH 4 was explored as a function of NaOH concentration. Meantime, the byproducts derived from the spent alkaline NaBH 4 solution were characterized by X-ray diffraction (XRD), scanning electro microscope/energy dispersive spectrometer (SEM/EDS) and NMR (Nuclear Magnetic Resonance). The effect of NaOH concentration on the hydrogen generation from the hydrolysis of NaBH 4 significantly depends on the type of catalysts. With increasing NaOH concentration, the hydrogen generation rates decrease when using ruthenium (Ru) composite as a catalyst. The hydrogen generation rate of the methanolysis of NaBH 4 is significantly inhibited in the presence of NaOH as compared with the hydrolysis of NaBH 4 . The durability test of the Ru/Al 2 O 3 catalyst shows that the hydrogen generation rate decreases with recycling and reuse. The XRD and NMR analysis results show that the borate hydrate (NaBO 2 H 2 O) was derived from the hydrolysis of 20 wt% and 30 wt% NaBH 4 . -- Highlights: ► A recyclable Ru/Al 2 O 3 catalyst was synthesized for hydrogen generation. ► Ru/Al 2 O 3 significantly promotes the hydrogen generation rate from alkaline NaBH 4 solution. ► The prepared Ru/Al 2 O 3 catalyst can easily collect from the spent alkaline NaBH 4 solution.

Strain Induced Magnetism in SrRuO3 Epitaxial Thin Films

Energy Technology Data Exchange (ETDEWEB)

Grutter, A.; Wong, F.; Arenholz, E.; Liberati, M.; Suzuki, Y.

2010-01-10

Epitaxial SrRuO{sub 3} thin films were grown on SrTiO{sub 3}, (LaAlO{sub 3}){sub 0.3}(SrAlO{sub 3}){sub 0.7} and LaAlO{sub 3} substrates inducing different biaxial compressive strains. Coherently strained SrRuO{sub 3} films exhibit enhanced magnetization compared to previously reported bulk and thin film values of 1.1-1.6 {micro}{sub B} per formula unit. A comparison of (001) and (110) SrRuO{sub 3} films on each substrate indicates that films on (110) oriented have consistently higher saturated moments than corresponding (001) films. These observations indicate the importance of lattice distortions in controlling the magnetic ground state in this transitional metal oxide.

O-O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis.

Science.gov (United States)

Xie, Yan; Shaffer, David W; Concepcion, Javier J

2018-04-30

A deeper mechanistic understanding of the key O-O bond formation step of water oxidation by the [Ru(bda)(L) 2 ] (bdaH 2 = 2,2'-bipyridine-6,6'-dicarboxylic acid; L is a pyridine or isoquinoline derivative) family of catalysts is reached through harmonious experimental and computational studies of two series of modified catalysts with systematic variations in the axial ligands. The introduction of halogen and electron-donating substituents in [Ru(bda)(4-X-py) 2 ] and [Ru(bda)(6-X-isq) 2 ] (X is H, Cl, Br, and I for the pyridine series and H, F, Cl, Br, and OMe for the isoquinoline series) enhances the noncovalent interactions between the axial ligands in the transition state for the bimolecular O-O coupling, resulting in a lower activation barrier and faster catalysis. From detailed transition state calculations in combination with experimental kinetic studies, we find that the main contributor to the free energy of activation is entropy due to the highly organized transition states, which is contrary to other reports. Previous work has considered only the electronic influence of the substituents, suggesting electron-withdrawing groups accelerate catalysis, but we show that a balance between polarizability and favorable π-π interactions is the key, leading to rationally devised improvements. Our calculations predict the catalysts with the lowest Δ G ⧧ for the O-O coupling step to be [Ru(bda)(4-I-py) 2 ] and [Ru(bda)(6,7-(OMe) 2 -isq) 2 ] for the pyridine and isoquinoline families, respectively. Our experimental results corroborate these predictions: the turnover frequency for [Ru(bda)(4-I-py) 2 ] (330 s -1 ) is a 10-fold enhancement with respect to that of [Ru(bda)(py) 2 ], and the turnover frequency for [Ru(bda)(6-OMe-isq) 2 ] reaches 1270 s -1 , two times faster than [Ru(bda)(isq) 2 ].

Direct evidence for double-exchange coupling in Ru- substituted La0.7Pb0.3Mn 1 - x Ru x O3, 0.0 <= x <= 0.4

Science.gov (United States)

Sundar Manoharan, S.; Sahu, R. K.; Rao, M. L.; Elefant, D.; Schneider, C. M.

2002-08-01

The La0.7Pb0.3Mn 1 - x Ru x O3 (0.0 innate relationship between Mn and Ru ions by a unique double-exchange mediated transport behavior. This is exonerated by the coexistence of Tp and Tc (range 330 K 245 K for 0.0 30%, the hole carrier mass influences the transport property. X-ray absorption spectra suggest that the Tc-Tp match is due to the transport mediated by the Mn3+/Mn4+ leftrightarrow Ru4+/Ru5+ redox pair and also due to the broad low-spin Ru:4d conduction band. For x > 0.2, T < 0.5Tc obeys a modified variable-range hopping model, where kT0 propto (M/Ms)2, suggesting a random magnetic potential which localizes the charge carriers.

The electrocatalytic application of RuO2 in direct borohydride fuel cells

International Nuclear Information System (INIS)

Yang, Xiaodong; Wei, Xiaozhu; Liu, Ce; Liu, Yongning

2014-01-01

A high electrocatalytic activity of RuO 2 has been found for oxygen reduction reaction (ORR) in the cathode of direct borohydride fuel cells (DBFCs). The electron transfer number n during the ORR changes from 3.58 to 3.86 and the percentage of the intermediate product H 2 O 2 decreases from 20.8% to 7.2% correspondingly when the disk potential scans negatively from −0.39 V to −0.8 V versus Hg/HgO. Peak power densities of 425 mW cm −2 has been obtained at 60 °C, when RuO 2 has been used as a cathodic catalyst in DBFCs. RuO 2 displays low sensitivity to the BH 4 − oxidation in DBFCs. Moreover, RuO 2 , as a cathodic catalyst, demonstrates a superb stability during a 200-h durability test. The identical X-ray diffraction (XRD) patterns of the RuO 2 before and after the durability test also prove its stability. - Highlights: • RuO 2 exhibits oxygen reduction reaction (ORR) activity in an alkaline solution. • RuO 2 provides 3.58–3.86 electron transfer number during the ORR. • Direct borohydride fuel cell (DBFC) with RuO 2 cathode displays a peak power density of 425 mW cm −2 at 60 °C. • DBFC with RuO 2 cathode exhibits a superb stability during a 200-h durability test

Interaction of cis-[Ru(DMSO)4Cl2] with acetate-ion in solutions

International Nuclear Information System (INIS)

Buslaeva, T.M.; Rudnitskaya, O.V.; Kabanova, A.G.; Fedorova, G.A.

2000-01-01

Solutions of cis-[Ru(DMSO) 4 Cl 2 ] in water and alcohols in the presence of CH 3 COONa in dependence on concentration and relation of reagents are studied. It is shown that introduction of acetate-ion in solution of cis-[Ru(DMSO) 4 Cl 2 ] in methanol directs to formation of fac-[Ru(DMSO) 3 Cl 3 ] - which can be separated as sodium salt insoluble in methanol. It is necessary to mention that spectrum of solution of cis-[Ru(DMSO) 4 Cl 2 ] in methanol varies in time but these changes are insignificant in comparison with changes taking place in the presence of CH 3 COONa. Compound Na[Ru(DMSO) 3 (CH 3 COO) 2 Cl] is prepared and characterized spectrally for the first time [ru

Progress in doping of ruthenium silicide (Ru2Si3)

International Nuclear Information System (INIS)

Vining, C.B.; Allevato, C.E.

1992-01-01

This paper reports that ruthenium silicide (Ru 2 Si 3 ) is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels

Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole-Based Tripodal Tetraphosphine Ligand

NARCIS (Netherlands)

van de Watering, F.F.; van der Vlugt, J.I.; Dzik, W.I.; de Bruin, B.; Reek, J.N.H.

2017-01-01

The tripodal, tetradentate tris(1-(diphenylphosphanyl)-3-methyl-1H-indol-2-yl)phosphane PP3-ligand 1 stabilizes Ru in the RuII, RuI, and Ru0 oxidation states. The octahedral [(PP3)RuII(Cl)2] ( 2 ), distorted trigonal bipyramidal [(PP3)RuI(Cl)] ( 3 ), and trigonal bipyramidal [(PP3)Ru0(N2)] ( 4 )

Nonacarbonyl-1κ3C,2κ3C,3κ3C-μ-bis(diphenylarsinomethane-1:2κ2As:As'-[tris(2-chloroethyl phosphite-3κP]-triangulo-triruthenium(0

Directory of Open Access Journals (Sweden)

Omar bin Shawkataly

2010-08-01

Full Text Available In the title triangulo-triruthenium(0 compound, [Ru3(C25H22As2(C6H12Cl3O3P(CO9], the bis(diphenylarsinomethane ligand bridges an Ru—Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. In the crystal packing, the molecules are linked by intermolecular C—H...O hydrogen bonds into a three-dimensional framework. Weak intermolecular C—H...π interactions further stabilize the crystal structure.

Development of metal complexes which has a novel type of dhotocatalysis activity; Shinki hikari shokubai tokusei wo yusuru kinzoku sakutai no sousei

Energy Technology Data Exchange (ETDEWEB)

Ishitani, Osamu [Saitama University, Saitama (Japan). Graduate School of Sceince and Engineering

1999-12-16

Purpose of this research are (1) development of photocatalysts which selectively drive hydride transfer and (2) their application to the enantioselective reduction of an unsaturated substrate. photocatalysis of [Ru(bpy){sub 2}(py){sub 2}]{sup 2+} (1) and [Ru(tpy)(bpy)(py)]{sup 2+} (2) (bpy=2,2'-bipyridine, tpy=2,2' : 6',2' '-terpyridine, py=pyridine) for reduction of unsaturated compounds was investigated using triethylamine as a reductant. Formation of the hydrogenated compounds was observed but the corresponding one electron reduced compounds were not detected at all. The complex 1 photocatalysed the reduction of trifluoroacetophenone (5) and gave the alcohol in a 67% yield but 2 gave only a 27% yield. The reaction proceeds via the photosubstitution of a py ligand of the ruthenium complex, followed by photochemical formation of the hydride complex. The ruthenium hydride complex reacts with 5 to give [Ru(tpy)(bpy)(OCHPhCF{sub 3})]{sup +} (4). Dissociation of 4 to the alcohol was not efficient and the yield was 10%. (author)

Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf.

Science.gov (United States)

Aprile, Antonino; Iversen, Kalon J; Wilson, David J D; Dutton, Jason L

2015-05-18

We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2](2+). Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.

Magnetic, electrical and structural properties of the Re-doped ruthenocuprate Ru1−xRexSr2GdCu2Oy

International Nuclear Information System (INIS)

Corredor, L.T.; Albino Aguiar, J.; Landínez Téllez, D.A.; Pureur, P.; Mesquita, F.; Roa-Rojas, J.

2015-01-01

Highlights: • We investigated the effect of the dilution of magnetic Ru sub-lattice of RuSr 2 GdCu 2 O 8 . • We synthesized the doped compound Rui x Re x Sr 2 GdCu 2 O y , for 3%, 6%, 9% and 12% Re. • Re would affect the electron coupling: just 3 and 6% samples were superconductor. • Superconductivity emergence strongly affects magnetic properties of 3 and 6% samples. • A weak ferromagnetic component is consistent with a globally antiferromagnetic system. - Abstract: Despite the discovery of new superconductors classes, high-Tc oxides continue to be a current topic, because of their complex phase diagrams and doping-dependant effects (allowing one to investigate the interaction between orbitals), as well as structural properties such as lattice distortion and charge ordering, among many others. Ruthenocuprates are magnetic superconductors in which the magnetic transition temperature is much higher than the critical superconducting temperature, making them unique compounds. With the aim of investigating the dilution of the magnetic Ru sub-lattice, we proposed the synthesis of the Ru 1−x Re x Sr 2 GdCu 2 O y ruthenocuprate-type family, adapting the known two-step process (double perovskite + CuO) by directly doping the double perovskite, thus obtaining the perovskite compound Sr 2 GdRu 1−x Re x O y , which represents a new synthesis process to the best of our knowledge. Our samples were structurally characterized through X-ray diffraction, and the patterns were analysed via Rietveld refinement. A complete magnetic characterization as a function of temperature and applied field, as well as transport measurements were carried out. We discuss our results in the light of the two-lattice model for ruthenocuprates, and a relation between RuO 2 (magnetic) and CuO 2 (superconductor) sub-lattices can clearly be observed

Synthesis of Ru/PDMS nano-composites via supercritial deposition

Energy Technology Data Exchange (ETDEWEB)

Ge, Minglan [Dept. of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617 (China); Bozbag, Selmi E. [Dept. of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul (Turkey); Ayala, Christian J.; Aindow, Mark [Department of Materials Science and Engineering, Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States); Erkey, Can, E-mail: cerkey@ku.edu.tr [Dept. of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul (Turkey); Koç University TÜPRAŞ Energy Center (KUTEM), Koç University, 34450 Sariyer, Istanbul (Turkey)

2016-09-01

Nanomaterials consisting of Ru nanoparticles dispersed in polydimethylsiloxane films were synthesized by supercritical deposition. The films were impregnated with the organometallic precursor bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene) ruthenium (II) under thermodynamic control in the presence of supercritical carbon dioxide (scCO{sub 2}) at 40 °C and 10.34 MPa. The precursor molecules were then converted to metallic Ru by thermal treatment in flowing N{sub 2} at ambient pressure, resulting in well-dispersed nanoparticles with diameters of ≈2 nm. - Highlights: • PDMS-Ru nanoparticle composites were prepared using supercritical deposition. • PDMS-Ru nanoparticle composites were prepared without using an immobilization agent. • PDMS films were impregnated with Ru(cod)(tmhd){sub 2} in supercritical CO{sub 2}. • The impregnated Ru(cod)(tmhd){sub 2} was then reduced to metallic Ru in flowing N{sub 2}. • The resulting Ru nanoparticles were well-dispersed and had diameters of ≈2 nm.

Crystals structure of Na3Li(TiF6)2

International Nuclear Information System (INIS)

Popov, D.Yu.; Antokhina, T.F.; Gerasimenko, A.V.; Kajdalova, T.A.; Sergienko, V.I.

2004-01-01

Crystals of Na 3 Li(TiF 6 ) 2 (1) were synthesized in aqueous solution and characterized by the elementary and X-ray phase analysis methods. According to X-ray diffraction analysis data compound 1 is crystallized in a tetragonal crystal system with the following parameters: a=5.130(1), c=18.046(4) A, Z=2, space group P4-bar2 1 c. Alternating layers on the basis of dimers made up by octahedrons of TiF 6 and Na(1)F 6 constitute the frame of compound 1 crystal structure. The dimer layers are joined in a continuous frame by Na(2) and Li cations. Coordination polyhedron of Li atom is tetrahedron (Li-F 1.898(3) A) [ru

Synthesis and Characterization of RuO₂/poly (3,4-ethylenedioxythiophene) (PEDOT) Composite Nanotubes for Supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Liu, Ran [Univ. of Maryland, College Park, MD (United States); Duay, Jonathon [Univ. of Maryland, College Park, MD (United States); Lane, Timothy [Univ. of Maryland, College Park, MD (United States); Lee, Sang Bok [Univ. of Maryland, College Park, MD (United States); Korea Advance Inst. of Science and Technology, Daejeon (Korea)

2010-01-18

We report the synthesis of composite RuO₂/poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes with high specific capacitance and fast charging/discharging capability as well as their potential application as electrode materials for a high-energy and high-power supercapacitor. RuO₂/PEDOT nanotubes were synthesized in a porous alumina membrane by a step-wise electrochemical deposition method, and their structures were characterized using electron microscopy. Cyclic voltammetry was used to qualitatively characterize the capacitive properties of the composite RuO₂/PEDOT nanotubes. Their specific capacitance, energy density and power density were evaluated by galvanostatic charge/discharge cycles at various current densities. The pseudocapacitance behavior of these composite nanotubes originates from ion diffusion during the simultaneous and parallel redox processes of RuO₂ and PEDOT. We show that the energy density (specific capacitance) of PEDOT nanotubes can be remarkably enhanced by electrodepositing RuO₂ into their porous walls and onto their rough internal surfaces. The flexible PEDOT prevents the RuO₂ from breaking and detaching from the current collector while the rigid RuO₂ keeps the PEDOT nanotubes from collapsing and aggregating. The composite RuO₂/PEDOT nanotube can reach a high power density of 20 kW kg^-1 while maintaining 80% energy density (28 Wh kg^-1) of its maximum value. This high power capability is attributed to the fast charge/discharge of nanotubular structures: hollow nanotubes allow counter-ions to readily penetrate into the composite material and access their internal surfaces, while a thin wall provides a short diffusion distance to facilitate ion transport. The high energy density originates from the RuO₂, which can store high electrical/electrochemical energy intrinsically. The high specific capacitance (1217 Fg^-1

Switching properties of SrRuO3/Pb(Zr0.4Ti0.6)O3/SrRuO3 capacitor grown on Cu-coated Si substrate measured at various temperatures

Science.gov (United States)

Chen, J. H.; Liu, B. T.; Li, C. R.; Li, X. H.; Dai, X. H.; Guo, J. X.; Zhou, Y.; Wang, Y. L.; Zhao, Q. X.; Ma, L. X.

2014-09-01

SrRuO3(SRO)/Ni-Al/Cu/Ni-Al/SiO2/Si heterostructures annealed at various temperatures are found to remain intact after 750 \\circ\\text{C} annealing. Moreover, a SRO/Pb(Zr0.4Ti0.6)O3 (PZT)/SRO capacitor is grown on a Ni-Al/Cu/Ni-Al/SiO2/Si heterostructure, which is tested up to 100 \\circ\\text{C} to investigate the reliability of the memory capacitor. It is found that besides the good fatigue resistance and retention characteristic, the capacitor, measured at 5 V and room temperature, possesses a large remnant polarization of 25.0 μ \\text{C/cm}2 and a small coercive voltage of 0.83 V, respectively. Its dominant leakage current behavior satisfies the space-charge-limited conduction at various temperatures. Very clear interfaces can be observed from the cross-sectional images of transmission electron microscopy, indicating that the Ni-Al film can be used as a diffusion barrier layer for copper metallization as well as a conducting barrier layer between copper and oxide layer.

Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6- arene)(en)Cl]+ complexes: Density functional theory computational study

Science.gov (United States)

Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V.

2011-01-01

The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl2 (from the RAPTA family) and [Ru(arene)(en)Cl]+ (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP/6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt/Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal/mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

Ti atoms in Ru0.3Ti0.7O2 mixed oxides form active and selective sites for electrochemical chlorine evolution

DEFF Research Database (Denmark)

Karlsson, Rasmus K. B.; Hansen, Heine Anton; Bligaard, Thomas

2014-01-01

affected by the presence of small amounts of Ru dopant, whereas oxygen adsorption is relatively unaffected by Ti dopants in RuO2. The calculations also indicate that coordinatively unsaturated Ti sites on Ru-doped TiO2 and on Ru0.3Ti0.7O2 could form active and selective sites for Cl2 evolution....... These results suggest a reason for why DSA shows a higher chlorine selectivity than RuO2 and propose an experimental test of the hypothesis....

Fast hydrogen elimination from the [Ru(PH3)3(CO)(H)2] and [Ru(PH3)4(H)2] complexes in the first singlet excited states: A diabatic quantum dynamics study

International Nuclear Information System (INIS)

Vendrell, Oriol; Moreno, Miquel; Lluch, Jose M.

2004-01-01

The photodissociation dynamics of [Ru(PH 3 ) 3 (CO)(H) 2 ] and cis-[Ru(PH 3 ) 4 (H) 2 ] is theoretically analyzed in the lowest two excited singlet states. Energies obtained through electronic density functional theory calculations that use the time-dependent formalism are fitted to analytical reduced two-dimensional potential energy surfaces (2D-PES). The metal-H 2 (R) and H-H (r) distances are the variables of these 2D-PES, the rest of the parameters being kept frozen at the values of the minimum energy structure in the ground electronic state. The time evolution in these 2D-PES is exactly followed by means of a fast Fourier transform algorithm applied to solve the time-dependent Schroedinger equation. A simple diabatization scheme is devised to take into account the probability of transitions between both excited states. The quantum dynamics results point out that photoelimination is almost inexistent if the H 2 fragment is to be expelled without further rearrangement of the rest of the complex. Conversely, when the geometries of the complex are optimized by keeping r and R frozen at the hydrogen elimination barrier coordinates, the new 2D-PES so obtained are highly dissociative, the H 2 fragment being expelled in less than 100 fs. Finally the picture of the whole reaction that emerges from our theoretical results is described and the main differences between both complexes are examined

RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

Science.gov (United States)

In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

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.

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: brandalise@usp.br, E-mail: mmtusi@usp.br, E-mail: rmpiasen@ipen.br, E-mail: ovcorrea@ipen.br, E-mail: mlinardi@ipen.br, E-mail: espinace@ipen.br, E-mail: aolivei@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2009-07-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H{sub 2}PtCl{sub 6.6}H{sub 2}O, RuCl{sub 3.x}H{sub 2}O and Bi(NO{sub 3}){sub 3.5}H{sub 2}O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

International Nuclear Information System (INIS)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir

2009-01-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H 2 PtCl 6.6 H 2 O, RuCl 3.x H 2 O and Bi(NO 3 ) 3.5 H 2 O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

Probabilistic programming in Python using PyMC3

Directory of Open Access Journals (Sweden)

John Salvatier

2016-04-01

Full Text Available Probabilistic programming allows for automatic Bayesian inference on user-defined probabilistic models. Recent advances in Markov chain Monte Carlo (MCMC sampling allow inference on increasingly complex models. This class of MCMC, known as Hamiltonian Monte Carlo, requires gradient information which is often not readily available. PyMC3 is a new open source probabilistic programming framework written in Python that uses Theano to compute gradients via automatic differentiation as well as compile probabilistic programs on-the-fly to C for increased speed. Contrary to other probabilistic programming languages, PyMC3 allows model specification directly in Python code. The lack of a domain specific language allows for great flexibility and direct interaction with the model. This paper is a tutorial-style introduction to this software package.

New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes.

Science.gov (United States)

Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M

2012-03-05

The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF-CH=CH-Py) radical cation salts containing poly(beta-diketonate) rare earth complexes: synthesis, crystal structure, photoluminescent and magnetic properties.

Science.gov (United States)

Pointillart, Fabrice; Maury, Olivier; Le Gal, Yann; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

2009-08-03

The reactions between the redox-active 4-(2-tetrathiafulvalenyl-ethenyl)pyridine ligand (TTF-CH=CH-Py) and the tris(1,1,1,5,5,5-hexafluoroacetylacetonate)Ln(III) (Ln = La and Nd) lead to the formation of compounds with the formulas {[La(hfac)(5)][(TTF-CH=CH-Py(*+))](2)} (1), {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2) (2), and {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2)(H(2)O)(C(6)H(14))(0.5) (3) (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion). These compounds have been characterized by single-crystal X-ray diffraction, optical, and magnetic measurements. Compounds 1, 2, and 3 crystallize in the monoclinic C2/c, triclinic P1, and monoclinic P2(1)/c space groups, respectively. La(III) adopts a tetradecahedral geometry, while Nd(III) stands in a distorted capped square antiprism one. In 1, the inorganic network is formed by the [La(hfac)(5)](2-) dianionic complexes, while it is formed by a pseudo-dimeric dianionic unit of formula {[Nd(hfac)(4)(H(2)O)](2)}(2-) in 2 and 3. In all crystal structures, the organic network is constituted by the TTF-CH=CH-Py(*+) radical cations. The inorganic and organic networks interact through intermolecular contacts between the pyridine moieties of the TTF-CH=CH-Py(*+) radical cations and the Ln(III) ions. The luminescence properties of the Nd(III) ions (9400 cm(-1)) and fluorescence band of the TTF-CH=CH-Py(*+) radical cations (10200 cm(-1)) have been observed and studied for compound 2. Complexes 2 and 3 are paramagnetic because of Nd(III) ions. Compound 2 is a paramagnetic luminescent TTF-radical-cation-based material. Resistivity measurements have also been performed on these materials.

Preparation of PtRu/Carbon hybrid materials by hydrothermal carbonization: A study of the Pt:Ru atomic ratio

International Nuclear Information System (INIS)

Tusi, Marcelo Marques; Brandalise, Michele; Correa, Olandir Vercino; Oliveira Neto, Almir; Linardi, Marcelo; Spinace, Estevam Vitorio; Villalba, Juan Carlo

2009-01-01

PtRu/Carbon materials with different Pt:Ru atomic ratios (30:70, 50:50, 60:40, 80:20 and 90:10) and 5 wt% of nominal metal load were prepared by hydrothermal carbonization using H 2 PtCl 6.6 H 2 O and RuCl 3. xH 2 O as metals sources and catalysts of the carbonization process and starch as carbon source and reducing agent. The obtained materials were treated at 900 deg C under argon and characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of methanol was studied by cyclic voltammetry and chronoamperometry using thin porous coating technique. The PtRu/Carbon materials showed Pt:Ru atomic ratios obtained by EDX similar to the nominal ones. XRD analysis showed that Pt face-cubic centered (FCC) and Ru hexagonal close-packed (HCP) phases coexist in the obtained materials. The average crystallite sizes of the Pt (FCC) phase were in the range of 8-12 nm. The material prepared with Pt:Ru atomic ratio of 50:50 showed the best performance for methanol electro-oxidation. (author)

Fuel management simulation for CANFLEX-RU in CANDU 6

Energy Technology Data Exchange (ETDEWEB)

Jeong, Chang Joon; Suk, Ho Chun [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1998-12-31

Fuel management simulations have been performed for CANFLEX-09% RU fuel in the CANDU 6 reactor. In this study, the bi-directional 4-bundle shift fuelling scheme was assumed. The lattice cell and time-average calculation were carried out. The refuelling simulation calculations were performed for 600 full power days. Time-averaged results show good axial power profile with the CANFLEX-RU fuel. During the simulation period, the maximum channel and bundle power were maintained below the licensing limit of CANDU 6 reactor. 7 refs., 4 figs. (Author)

Fuel management simulation for CANFLEX-RU in CANDU 6

Energy Technology Data Exchange (ETDEWEB)

Jeong, Chang Joon; Suk, Ho Chun [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1997-12-31

Fuel management simulations have been performed for CANFLEX-09% RU fuel in the CANDU 6 reactor. In this study, the bi-directional 4-bundle shift fuelling scheme was assumed. The lattice cell and time-average calculation were carried out. The refuelling simulation calculations were performed for 600 full power days. Time-averaged results show good axial power profile with the CANFLEX-RU fuel. During the simulation period, the maximum channel and bundle power were maintained below the licensing limit of CANDU 6 reactor. 7 refs., 4 figs. (Author)

Structural, optical and magnetic characterization of Ru doped ZnO nanorods

International Nuclear Information System (INIS)

Kumar, Sanjeev; Kaur, Palvinder; Chen, C.L.; Thangavel, R.; Dong, C.L.; Ho, Y.K.; Lee, J.F.; Chan, T.S.; Chen, T.K.; Mok, B.H.; Rao, S.M.; Wu, M.K.

2014-01-01

Graphical abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice distortion. Highlights: • Ru doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). • PL and Raman studies show the formation of singly ionized oxygen vacancies in 2% Ru doped ZnO. • XAS reveals that Ru replace the Zn atoms in the host lattice with slightly lattice distortion. • Doping of Ru in ZnO nanostructures gives rise to RTFM ordering. -- Abstract: Ruthenium (Ru = 0%, 1% and 2%) doped nano-crystalline zinc oxide (ZnO) nanorods were synthesized by using well-known sol–gel technique. X-ray diffraction (XRD) results show that Ru (0%, 1% and 2%) doped ZnO nanorods crystallized in the wurtzite structure having space group C 3v (P6 3 mc). Williamson and Hall plot reveal that in the nanoscale dimensions, incorporation of Ru induced the tensile strain in ZnO host matrix. Photoluminescence (PL) and Raman studies of Ru doped ZnO nanorods show the formation of singly ionized oxygen vacancies which may account for the observed room temperature ferromagnetism (RTFM) in 2% Ru doped ZnO. X-ray absorption spectroscopy (XAS) reveals that Ru replace the Zn atoms in the host lattice and maintain the crystal symmetry with slightly lattice

Local structure distortion induced by Ti dopants boosting the pseudocapacitance of RuO2-based supercapacitors

Science.gov (United States)

Chen, I.-Li; Wei, Yu-Chen; Lu, Kueih-Tzu; Chen, Tsan-Yao; Hu, Chi-Chang; Chen, Jin-Ming

2015-09-01

Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated using H2O2-oxidative precipitation with the assistance of a cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment at 200 °C. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of the RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among the three binary oxides studied, (Ru70-Ti30)O2 exhibits a capacitance improvement of about 1.4-fold relative to the CTAB-modified RuO2, mainly due to the enhanced crystallinity of the distorted RuO6 structure rather than the surface area effect. Upon increasing the extent of Ti doping, the deteriorated supercapacitive performance of (Ru50-Ti50)O2 results from the formation of localized nano-clusters of TiO2 crystallites. These results provide insight into the important role of Ti doping in RuO2 that boosts the pseudocapacitive performance for RuO2-based supercapacitors. The present result is crucial for the design of new binary oxides for supercapacitor applications with extraordinary performance.Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated using H2O2-oxidative precipitation with the assistance of a cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment at 200 °C. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of the RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among the three binary

Synthesis, characterization, structure and properties of heterobimetallic complexes [CuNi(μ-OAc) (μ-OH) (μ-OH2) (bpy)2] (BF4)2 and [CuNi(bz)3(bpy)2] ClO4 from 2,2‧ bipyridine

Science.gov (United States)

Kurbah, Sunshine D.; Kumar, A.; Syiemlieh, I.; Dey, A. K.; Lal, R. A.

2018-02-01

Heterobimetallic complexes of the composition [CuNi(bpy)2 (μ-OAc) (μ-OH) (μ-OH2)](BF4)2 (1) and [CuNi(bz)3 (bpy)2]ClO4 (2) were synthesized in moderate yield through solid state reaction and have been characterized by elemental analyses, molar conductance, mass spectra, magnetic moment, EPR, UV-Vis, IR spectroscopies and cyclic voltammetry. The ground state in complex (1) is doublet while that in complex (2), the ground state is a mixture of doublet and quartet, respectively. The structure of the complexes has been established by X-ray crystallography. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry.

Preparation of supported heterogeneous catalysts by pulse impregnation: Application to Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst

Energy Technology Data Exchange (ETDEWEB)

Haukka, M.; Pakkanen, T.A. (Univ. of Joensuu (Finland))

1994-07-01

In this paper, the authors introduce pulse impregnation, a method for preparing supported heterogeneous catalysts by successive impregnation cycles. Pulse impregnation is a method for preparing supported heterogeneous catalysts from the liquid phase. In the pulse-impregnation technique the catalyst surface is grown gradually in consecutive cycles, with each cycle consisting of separate deposition and activation steps. During the deposition step, the catalyst precursor or precursors are deposited onto the support from a suitable solvent. The actual chemically bonded catalyst phase is formed during the activation step (e.g., thermal activation). Pulse impregnation was tested in the separate deposition of 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12] onto a silica support, and in the preparation of Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, in a column-type reactor system. Macroscopically uniform deposition was achieved with both 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12]. Various solvent systems were used to control the amount of solute adsorbed during deposition. In the preparation of the Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, the ruthenium content increased nearly linearly with the number of preparation cycles. The effects of the preparation method on the catalyst activity was also tested in 1-hexane hydroformylation. 31 refs., 7 figs., 1 tab.

The effects of rare earths on activity and surface properties of Ru/γ-Al2O3 catalyst for water gas shift reaction

Directory of Open Access Journals (Sweden)

Laitao Luo

2007-04-01

Full Text Available A series of Ru-RE/γ- Al2O3 (RE = Ce, Pr, La, Sm, Tb or Gd and Ru/γ- Al2O3 catalysts were prepared by impregnation method. The influence of rare earths on the catalytic performance of Ru/γ- Al2O3 catalyst for the water gas shift reaction was studied. The catalysts were characterized by X-ray diffraction (XRD, temperature programmed reduction (TPR, temperature programmed desorption (TPD, and CO chemisorption. The results show that the addition of rare earths increases the catalytic activity of Ru based catalyst. Among these cerium is the most remarkably. The addition of cerium increases the active surface area, improves the dispersion of ruthenium, and weakens the interaction between ruthenium and the support. Cerium also affects the adsorption and reduction properties of Ru/γ-Al2O3 catalyst.

Atomic layer deposition of Ru thin film using N{sub 2}/H{sub 2} plasma as a reactant

Energy Technology Data Exchange (ETDEWEB)

Hong, Tae Eun [Busan Center, Korea Basic Science Institute, 1275 Jisadong, Gangseogu, Busan, 618-230 (Korea, Republic of); Mun, Ki-Yeung; Choi, Sang-Kyung; Park, Ji-Yoon [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Kim, Soo-Hyun, E-mail: soohyun@ynu.ac.kr [School of Materials Science and Engineering Yeungnam University 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Cheon, Taehoon [Center for Core Research Facilities, Daegu Gyeongbuk Institute of Science and Technology, Sang-ri, Hyeonpung-myeon, Dalseong-gun, Daegu (Korea, Republic of); Kim, Woo Kyoung [School of Chemical Engineering, Yeungnam University, 214-1, Dae-dong, Gyeongsan-si, Gyeongsangbuk-do, 712-749 (Korea, Republic of); Lim, Byoung-Yong; Kim, Sunjung [School of Materials Science and Engineering, University of Ulsan, Mugeo-dong, Nam-go, Ulsan, 680-749 (Korea, Republic of)

2012-07-31

Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [({eta}6-1-Isopropyl-4-MethylBenzene)({eta}4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N{sub 2}/H{sub 2}) plasma as a reactant, at the substrate temperature of 270 Degree-Sign C. In the wide range of the ratios of N{sub 2} and total gas flow rates (fN{sub 2}/N{sub 2} + H{sub 2}) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from {approx} 20 to {approx} 30 {mu} Ohm-Sign cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO{sub 2} was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film ({approx} 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of {approx} 340 {mu} Ohm-Sign cm. - Highlights: Black-Right-Pointing-Pointer Atomic layer deposition (ALD) of Ru and N-incorporated Ru film using N{sub 2}/H{sub 2} plasma. Black-Right-Pointing-Pointer The growth rate of 0.057 nm/cycle and negligible incubation cycle. Black-Right-Pointing-Pointer A low resistivity of Ru ({approx} 16.5 {mu} Ohm-Sign cm) at the deposition temperature of 270 Degree-Sign C. Black-Right-Pointing-Pointer Electroplating of Cu on a 10-nm-thick ALD-Ru film.

Functional properties of electrospun NiO/RuO{sub 2} composite carbon nanofibers

Energy Technology Data Exchange (ETDEWEB)

Wu Yongzhi [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Physics Department, National University of Singapore, Singapore 117542 (Singapore); NUS Graduate School for Integrated Science and Engineering, 10 Kent Ridge Crescent, National University of Singapore, Singapore 119260 (Singapore); Balakrishna, Rajiv [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Physics Department, National University of Singapore, Singapore 117542 (Singapore); Reddy, M.V., E-mail: phymvv@nus.edu.sg [Physics Department, National University of Singapore, Singapore 117542 (Singapore); Nair, A. Sreekumaran, E-mail: nniansn@nus.edu.sg [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Chowdari, B.V.R. [Physics Department, National University of Singapore, Singapore 117542 (Singapore); Ramakrishna, S. [Healthcare and Energy Materials Laboratory, Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore 117576 (Singapore); Kind Saud University, Riyadh 11451 (Saudi Arabia)

2012-03-15

Highlights: Black-Right-Pointing-Pointer Fabrication of carbon nanofibers with nickel-ruthenium composites by electrospinning. Black-Right-Pointing-Pointer An interesting observation of increase in capacitance with increase in the number of cycles for supercapacitor applications. Black-Right-Pointing-Pointer Li ion battery testing showed a stable capacity ranging from 350 mAh g{sup -1} to 400 mAh g{sup -1}. Black-Right-Pointing-Pointer Lower impedance with the incorporation of 15 wt% Ru precursor than those without Ru. - Abstract: One-dimensional (1D) nickel oxide/ruthenium oxide (NiO/RuO{sub 2})-carbon composite nanofibers (NiRu-C-NFs) were fabricated via electrospinning of a homogenous mixture of polyacrylonitrile (PAN) and Ni/Ru salt precursors at different ratios followed by heat treatments. The 1D nanostructures of the composite material were characterized by field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (XRD), Rietveld refinement and Brunauer-Emmett-Teller (BET) surface area measurements. Li-cycling properties were evaluated using cyclic voltammetry and galvanostatic properties. The asymmetric hybrid supercapacitor studies were carried out with activated carbon as a cathode and NiRu-C-NFs composites as anodes in the cycling range, 0.005-3.0 V using 1 M LiPF{sub 6} (EC;DMC) electrolyte. NiRu-C-NFs fabricated from 5 wt% nickel (II) and 15 wt% ruthenium (III) precursors showed a capacitance up to {approx}60 F g{sup -1} after 30 cycles. Anodic Li-cycling studies of NiRu-C-NF-0 and NiRu-C-NF-2 composite samples showed a reversible capacity of 230 and 350 m Ahg{sup -1} at current rate of 72 mA g{sup -1} at the end of 40th cycle in the voltage range of 0.005-3.0 V. Electrochemical impedance studies (EIS) on NiRu-C-NFs showed lower impedance value for 15 wt% Ru than the bare sample.

MnTE-2-PyP modulates thiol oxidation in a hydrogen peroxide-mediated manner in a human prostate cancer cell.

Science.gov (United States)

Tong, Qiang; Zhu, Yuxiang; Galaske, Joseph W; Kosmacek, Elizabeth A; Chatterjee, Arpita; Dickinson, Bryan C; Oberley-Deegan, Rebecca E

2016-12-01

To improve the treatment of advanced prostate cancer, the development of effective and innovative antitumor agents is needed. Our previous work demonstrated that the ROS (reactive oxygen species) scavenger, MnTE-2-PyP, inhibited human prostate cancer growth and also inhibited prostate cancer migration and invasion. We showed that MnTE-2-PyP treatment altered the affinity of the histone acetyltransferase enzyme, p300, to bind to DNA. We speculate that this may be one mechanism by which MnTE-2-PyP inhibits prostate cancer progression. Specifically, MnTE-2-PyP decreased p300/HIF-1/CREB complex (p300/hypoxia-inducible factor-1/cAMP response element-binding protein) binding to a specific hypoxia-response element (HRE) motif within the plasminogen activator inhibitor-1 (PAI-1) gene promoter region, and consequently, repressed PAI-1 expression. However, it remains unclear how MnTE-2-PyP reduces p300 complex binding affinity to the promoter region of specific genes. In this study, we found that overexpression of Cu/ZnSOD (superoxide dismutase 1, SOD1) significantly suppressed PAI-1 gene expression and p300 complex binding to the promoter region of PAI-1 gene, just as was observed in cells treated with MnTE-2-PyP. Furthermore, catalase (CAT) overexpression rescued the inhibition of PAI-1 expression and p300 binding by MnTE-2-PyP. Taken together, the above findings suggest that hydrogen peroxide (H 2 O 2 ) is likely the mediator through which MnTE-2-PyP inhibits the PAI-1 expression and p300 complex binding in PC3 cells. To confirm this, we measured the production of H 2 O 2 following overexpression of SOD1 or catalase with MnTE-2-PyP treatment in the presence or absence of radiation. We found that MnTE-2-PyP increased the intracellular steady-state levels of H 2 O 2 and increased nuclear H 2 O 2 levels. As expected, catalase overexpression significantly decreased the levels of intracellular H 2 O 2 induced by MnTE-2-PyP. We then determined if this increased H 2 O 2

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

Science.gov (United States)

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectra and relaxation dynamics of the pseudohalide (PS) vibrational bands for Ru(bpy){sub 2}(PS){sub 2} complexes, PS = CN, NCS and N{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Compton, Ryan; Gerardi, Helen K. [Chemistry Division, Naval Research Laboratory, Washington, DC 20375 (United States); Weidinger, Daniel [SRA International, 4300 Fair Lakes Court, Fairfax, VA 22033 (United States); Brown, Douglas J. [Chemistry Department, US Naval Academy, Annapolis, MD 21402 (United States); Dressick, Walter J. [Center for Bio/Molecular Science and Engineering, Naval Research Laboratory, Washington, DC 20375 (United States); Heilweil, Edwin J. [Radiation and Biomolecular Physics Division, Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Owrutsky, Jeffrey C., E-mail: Jeff.Owrutsky@nrl.navy.mil [Chemistry Division, Naval Research Laboratory, Washington, DC 20375 (United States)

2013-08-30

Highlights: ► Static and transient infrared spectroscopy of pseudohalide bipyridine ruthenium complexes. ► Vibrational energy relaxes faster for the azide than the thiocyanate and cyanide analogs. ► Intramolecular vibrational relaxation is prevalent in cis-Ru(bpy){sub 2}(N{sub 3}){sub 2}. - Abstract: Static and transient infrared spectroscopy were used to investigate cis-Ru(bpy){sub 2}(N{sub 3}){sub 2} (bpy = 2,2′-bipyridine), cis-Ru(bpy){sub 2}(NCS){sub 2}, and cis-Ru(bpy){sub 2}(CN){sub 2} in solution. The NC stretching IR band for cis-Ru(bpy){sub 2}(NCS){sub 2} appears at higher frequency (∼2106 cm{sup −1} in DMSO) than for the free NCS{sup −} anion while the IR bands for the azide and cyanide complexes are closer to those of the respective free anions. The vibrational energy relaxation (VER) lifetime for the azide complex is found to be much shorter (∼5 ps) than for either the NCS or CN species (both ∼70 ps in DMSO) and the lifetimes resemble those for each corresponding free anion in solution. However, for cis-Ru(bpy){sub 2}(N{sub 3}){sub 2}, it is determined that the transition frequency depends more on the solvent than the VER lifetime implying that intramolecular vibrational relaxation is predominant over solvent energy-extracting interactions. These results are compared to the behavior of other related metal complexes in solution.

Direction of Intercalation of a bis-Ru(II) Complex to DNA Probed by a Minor Groove Binding Molecule 4',6-Diamidino-2-phenylindole

Energy Technology Data Exchange (ETDEWEB)

Jang, Yoon Jung; Kim, Raeyeong; Chitrapriya, Nataraj; Kim, Seog K.; Bae, Inho [Yeungnam Univ., Gyeongsan (Korea, Republic of)

2013-10-15

Direction of intercalation to DNA of the planar dipyrido[3,2-a:2',3'-c]phenazine ligands (dppz) of a bis-Ru(II) complex namely, [Ru(1,10-phenanthroline){sub 2}dipyrido[3,2-a:2',3'-c]phenazine]{sup 2+} linkered by a 1,3-bis(4-pyridyl)propane, was investigated by probing the behavior of 4',6-diamidino-2-phenylindole (DAPI) that bound deep in the minor groove. Bis-intercalation of DPPZ resulted in a little blue shift and hyperchromism in DAPI absorption band, and a large decrease in DAPI fluorescence intensity which accompanied by an increase in the dppz emission intensity. Diminishing the intensity of the positive induced circular dichroism (CD) and linear dichroism (LD) were also observed. These spectral changes indicated that insertion of dppz ligand caused the change of the binding mode of DAPI, which probably moved to the exterior of DNA from the minor groove and interacted with the phospghate groups of DNA by electrostatic interaction. At the surface of DNA, DAPI binds at the phosphate groups of DNA by electrostatic attraction. Consequently, this observation indicated that the dppz ligand intercalated from the minor groove.

A Novel Ruthenium-Decorating Polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O: An Active Heterogeneous Oxidation Catalyst for Alcohols

Directory of Open Access Journals (Sweden)

Rong Wan

2018-01-01

Full Text Available The first example of wholly inorganic ruthenium-containing polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O (1 was isolated and systematically characterized by element analysis, infrared spectroscopy (IR, thermogravimetric analyses (TGA, X-ray photoelectron spectroscopy (XPS, energy dispersive X-ray spectroscopy (EDX and single-crystal X-ray diffraction. Compound 1 is composed of an unprecedented {Mo14}-type isopolymolybdate with a di-ruthenium core precisely encapsulated in its center, exhibiting a three-tiered ladder-like structure. The title compound can act as an efficient heterogeneous catalyst in the transformation of 1-phenylethanol to acetophenone. This catalyst is also capable of being recycled and reused for at least ten cycles with its activity being retained under the optimal conditions.

DFT calculations of the structures and vibrational spectra of the [Fe(bpy){sub 3}]{sup 2+} and [Ru(bpy){sub 3}]{sup 2+} complexes

Energy Technology Data Exchange (ETDEWEB)

Alexander, Bruce D. [School of Science, University of Greenwich at Medway, Central Avenue, Chatham Maritime, Kent ME4 4TB (United Kingdom); Dines, Trevor J. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)], E-mail: t.j.dines@dundee.ac.uk; Longhurst, Rayne W. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)

2008-09-03

Structures of the [M(bpy){sub 3}]{sup 2+} complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy){sub 3}]{sup 2+} which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the {sup 1}E MLCT excited state.

Microstructure and dielectric parameters of epitaxial SrRuO3/BaTiO3/SrRuO3 heterostructures

Science.gov (United States)

Boikov, Yu. A.; Claeson, T.

2001-05-01

Epitaxial films of ferroelectric barium titanate are desirable in a number of applications but their properties are inferior to those of bulk material. Relations between microstructure and dielectric properties may give better understanding of limitations. Trilayer heterostructures SrRuO3/BaTiO3/SrRuO3 were grown by laser ablation on (100)LaAlO3 and (100)MgO substrates. The BaTiO3 layer was granular in structure. When grown on (100)SrRuO3/(100)LaAlO3, it was preferentially a-axis oriented due to tensile mechanical stress. Using (100)MgO as a substrate, on the other hand, produced a mixture of about equal value of a-axis and c-axis oriented grains of BaTiO3. The dielectric permittivity, ɛ, of the BaTiO3 layer was almost twice as large, at T>200 K and f=100 kHz, for the LaAlO3 substrate as compared to the MgO one. Its maximum value (ɛ/ɛ0≈6200) depended on temperature of growth, grain size, and electric field and compares well with optimal values commonly used for ceramic material. The maximum in the ɛ(T) shifted from about 370 to 320 K when the grain size in the BaTiO3 film decreased from 100 to 40 nm. At T300 K, hysteresis loops in polarization versus electric field were roughly symmetric. The BaTiO3 films grown on (100)SrRuO3/(100)MgO exhibit the largest remnant polarizations and coercive fields in the temperature range 100-380 K.

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

Science.gov (United States)

Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

2016-06-30

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

RuO2-TiO2 mixed oxides prepared from the hydrolysis of the metal alkoxides

International Nuclear Information System (INIS)

Osman, Julian R.; Crayston, Joe A.; Pratt, Allin; Richens, David T.

2008-01-01

The hydrolysis of ruthenium alkoxide/titanium tetraethoxide mixtures to gels and powders containing 30-40 mol% Ru was investigated. Basic or neutral conditions led to powders consisting of 2-10 nm diameter crystalline RuO 2 nanoparticles embedded in a matrix of crystalline (anatase) and amorphous TiO 2 . Acid hydrolysis conditions gave gels containing smaller, amorphous RuO 2 nanoparticles (1-3 nm). In all samples the RuO 2 nanoparticles tended to clump into aggregates up to 0.5 μm across. Acid or neutral hydrolysis of ruthenium ethoxide gave samples which displayed lower surface Ru:Ti ratios as measured by XPS compared to the bulk (XRF), and also contained more low-valent Ru (as measured by XRF), probably due to incomplete hydrolysis of the precursors. These samples also contained more Ru metal after calcination (XRD). Calcination (450 deg. C) was accompanied by Ru-promoted combustion of organic material and led to crystalline (anatase) TiO 2 and Ti x Ru 1-x O 2 solid solution (rutile phase)

Synthesis and crystal structure of Na6[(UO2)3O(OH)3(SeO4)2]2·10H2O

International Nuclear Information System (INIS)

Baeva, E.Eh.; Serezhkina, L.B.; Virovets, A.V.; Peresypkina, E.V.

2006-01-01

The complex Na 6 [(UO 2 ) 3 O(OH) 3 (SeO 4 ) 2 ] 2 ·10H 2 O (I) is synthesized and studied by monocrystal X-ray diffraction. The compound crystallizes in the orthorhombic crystal system with the unit cell parameters: a=14.2225(7) A, b=18.3601(7) A, c=16.5406(6) A, V=4319.2(3) A 3, Z=4, space group Cmcm, R 1 =0.0406. Compound I is found to be a representative of the crystal-chemical group A 3 M 3 M 3 2 T 2 3 (A=UO 2 2+ , M 3 =O 2- , M 2 =OH - , T 3 =SeO 4 2- ) of the uranyl complexes; it contains layer uranium-containing groups [(UO 2 ) 3 O(OH) 3 (SeO 4 ) 2 ] 3- . These layers are linked to form a three-dimensional cage through bonds formed by the sodium atoms with the oxygen atoms of the uranyl ions and SeO 4 groups that belong to different layers [ru

Theoretical study on the antitumor properties of Ru(II) complexes containing 2-pyridyl, 2-pyridine-4-carboxylic acid ligands

Science.gov (United States)

Erkan kariper, Sultan; Sayin, Koray; Karakaş, Duran

2017-12-01

[Ru(bipy)2(CppH)]2+(1), [Ru(bipy)2(Cpp-NH-Hex-COOH)]2+(2), [Ru(dppz)2(CppH)]2+(3) and [Ru(dppz)2(Cpp-NH-Hex-COOH)]2+(4) were calculated by Hartree-Fock (HF), Density Functional Theory (DFT) hybrid B3LYP and Moller-Plesset Perturbation (MPn n = 2,3) theory method and CEP-4G, CEP-31G, CEP-121G, LANL2DZ, LANL2MB, SDD basic sets and a mixed basic set with the keyword GEN in gas phase and water. Structure parameters obtained from optimized structures were compared with experimental parameters. M062X/(6-31G(d))(CEP-4G) level was taken into account for the most appropriate calculation level. IR, UV-VIS and NMR spectrums were examined for structural characterization. The optimal structure was identified via structure parameters, IR, UV-VIS and NMR spectrums. For the most compatible structure, the highest molecular orbital energy (EHOMO) which one of the most effective chemical determiners on the antitumor activity of the complexes, the lowest molecular orbital energy (ELUMO), LUMO-HOMO energy gap, hardness (η), softness (σ), electronegativity (χ), chemical potential (μ), electrophilicity index (ω), molar volume (V), dipole moment (DM), total negative charge (TNC), enthalpy (H), entropy (S) and total energy (E) were calculated. The causes of anticancer activity of the complexes have been studied.

Fragment-based Quantum Mechanical/Molecular Mechanical Simulations of Thermodynamic and Kinetic Process of the Ru2+-Ru3+ Self-Exchange Electron Transfer.

Science.gov (United States)

Zeng, Xiancheng; Hu, Xiangqian; Yang, Weitao

2012-12-11

A fragment-based fractional number of electron (FNE) approach, is developed to study entire electron transfer (ET) processes from the electron donor region to the acceptor region in condensed phase. Both regions are described by the density-fragment interaction (DFI) method while FNE as an efficient ET order parameter is applied to simulate the electron transfer process. In association with the QM/MM energy expression, the DFI-FNE method is demonstrated to describe ET processes robustly with the Ru 2+ -Ru 3+ self-exchange ET as a proof-of-concept example. This method allows for systematic calculations of redox free energies, reorganization energies, and electronic couplings, and the absolute ET rate constants within the Marcus regime.

Synthesis and characterization of Ru(II) complexes with polyfunctional quinazoline-(3H)-4-ones

International Nuclear Information System (INIS)

Prabhakar, B.; Lingaiah, P.; Laxma Reddy, K.

1991-01-01

Few Ru(II) complexes of the type Ru(O-N-O) 2 with tridentate O-N-O donors and of the type RuCl 2 (O-N) 2 with bidentate O-O and O-N donors have been synthesized and characterized on the basis of analytical, conductivity, thermal, magnetic, IR, electronic and PMR spectral data. The IR and PMR spectral data of the metal complexes indicate that the lignads like 2-methyl/phenyl-3-(2'-hydroxybenzalamino) quinazoline-(3H)-4-one(MHBQ/PHBQ) act as uninegative tridentate, 2-methyl/phenyl-3-(carboxymethyl) quinazoline(3H)-4-one (MCMQ/PCMQ) as uninegative bidentate and 2-methyl/phenyl-3-(furfuralamino) quinazoline-(3H)-4-one (MFQ/PFQ), 2-methyl/phenyl-3-(acetamino) quinazoline-(3H)-4-one (MAQ/PAQ), 2-methyl/phenyl3-(uramino)quinazoline-(3H)-4-one (MUQ/PUQ) and 2-methyl/phenyl-3-thiouramino)quinazoline-(3H)-4-one-(MTUQ/PTUQ) as neutral bidentate ligands. The electronic spectral data of the complexes indicate that the arrangement around Ru(II) is octahedral. (author). 25 refs., 2 tabs

Addition of IrO2 to RuO2+TiO2 coated anodes and its effect on electrochemical performance of anodes in acid media

Directory of Open Access Journals (Sweden)

Farhad Moradi

2014-04-01

Full Text Available Ternary mixed metal oxide coatings with the nominal composition IrxRu(0.6−xTi0.4O2 (x=0, 0.1, 0.2, 0.3 on the titanium substrate were prepared by thermal decomposition of a chloride precursor mixture. Surface morphology and microstructure of the coatings were investigated by Scanning electron microscopy (SEM, Field emission scanning electron microscopy (FE-SEM and X-ray diffraction (XRD analysis. Systematic study of electrochemical properties of these coatings was performed by cyclic voltammetry (CV and polarization measurements. The corrosion behavior of the coatings was evaluated under accelerated conditions (j=2 A cm−2 in acidic electrolyte. The role of iridium oxide admixture in the change of electrocatalytic activity and stability of Ru0.6Ti0.4O2 coating was discussed. Small addition of IrO2 can improve the stability of the RuO2+TiO2 mixed oxide, while the electrocatalytic activity for oxygen evolution reaction (OER is decreased. The shift of redox potentials for Ru0.6Ti0.4O2 electrode that is slightly activated with IrO2 and improvement in the stability can be attributed to the synergetic effect of mixed oxide formation.

PyGirl: Generating Whole-System VMs from High-Level Prototypes Using PyPy

Science.gov (United States)

Bruni, Camillo; Verwaest, Toon

Virtual machines (VMs) emulating hardware devices are generally implemented in low-level languages for performance reasons. This results in unmaintainable systems that are difficult to understand. In this paper we report on our experience using the PyPy toolchain to improve the portability and reduce the complexity of whole-system VM implementations. As a case study we implement a VM prototype for a Nintendo Game Boy, called PyGirl, in which the high-level model is separated from low-level VM implementation issues. We shed light on the process of refactoring from a low-level VM implementation in Java to a high-level model in RPython. We show that our whole-system VM written with PyPy is significantly less complex than standard implementations, without substantial loss in performance.

SpiceyPy, a Python Wrapper for SPICE

Science.gov (United States)

Annex, A.

2017-06-01

SpiceyPy is an open source Python wrapper for the NAIF SPICE toolkit. It is available for macOS, Linux, and Windows platforms and for Python versions 2.7.x and 3.x as well as Anaconda. SpiceyPy can be installed by running: “pip install spiceypy.”

New Ru(II)N'NN'-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO_2 or bicarbonates to formate salts

International Nuclear Information System (INIS)

Zengjin Dai; Qi Luo; Hengjiang Cong; Jing Zhang; Tianyou Peng

2017-01-01

[RuCl(L1)(MeCN)_2]Cl (1) and [RuCl(L2)(MeCN)_2]Cl (2) complexes were prepared through the reaction of [RuCl2(p-cymene)]_2 with 2,6-bis(benzimidazole-2-yl)-4-hydroxy-pyridine (L1) or 2,6-bis(benzimidazole- 2-yl) pyridine (L2) in acetonitrile, respectively. The treatment of [Ru(OTf)(L2)(MeCN)_2]OTf (3) with 1 equivalent of PPh_3 in ethanol resulted in the formation of [Ru(L2"-"1)(MeCN)(PPh_3)_2]OTf (4), in which one of the N-H moieties of L2 is deprotonated to give an anionic ligand (L2"-"1). It was found that complex 1 can catalyze the hydrogenation of CO_2 to formate salts, producing sodium formate in 34.0% yield with a turnover number (TON) of 407 under the optimized conditions. Further investigations revealed that complexes 1-4 can efficiently catalyze the hydrogenation of sodium bicarbonate to sodium formate, and the catalytic activity follows the order 4 ≥ 1 ≥ 2 ≅ 3. In particular, sodium formate was obtained in good yield (77%) with a high TON (1530) when complex 4 was used as the catalyst. The present results illustrate a new example of Ru(II) complexes bearing a rigid N'NN' framework for the efficient hydrogenation of CO_2 to formate salts in a homogeneous system. (authors)

Lactococcus lactis KR-050L inhibit IL-6/STAT3 activation.

Science.gov (United States)

Hwang, J T; Jang, H-J; Kim, J H; Park, C S; Kim, Y; Lim, C-H; Lee, S W; Rho, M-C

2017-05-01

The purpose of this study was to investigate IL-6/STAT3 inhibitory activity using lactic acid bacteria (LABs) isolated from Gajuknamu kimchi. Six LABs were isolated from Gajuknamu kimchi and identified through 16S rRNA sequencing. Among them, the culture broth of Lactococcus lactis KR-050L inhibited IL-6-induced STAT3 luciferase activity. Fifteen compounds were isolated from the EtOAc extract of culture broth though column chromatography and preparative high-performance liquid chromatography, and they were identified as 2,5-diketopipperazine structures by spectroscopic analyses (MS, 1 H- and 13 C-NMR). They also showed inhibitory activities on IL-6-induced STAT3 activation, and showed the different in activity according to the presence of a phenylalanine residue, hydroxyl groups and isometric structure. The six new LABs isolated from Gajuknamu kimchi, and Lc. lactis KR-050L was selected as candidate IL-6/STAT3 inhibitors. The activity levels of 15 2,5-DKPs isolated from Lc. lactis KR-050L were verified. This study constitutes the first attempt to isolate various LABs from Gajuknamu kimchi and to discover IL-6/STAT3 inhibitors in the EtOAc extract of Lc. lactis KR-050L culture broth. Moreover, our data provide useful biochemical information regarding the commercialization of Lc. lactis isolated from Gajuknamu kimchi as an approach to use functional foods for the treatment of various diseases via IL-6/STAT3 activation. © 2017 The Society for Applied Microbiology.

Enhanced electrogenerated chemiluminescence of Ru(bpy){sub 3}{sup 2+}/TPrA (bpy=2,2'-bipyridine; TPrA=tri-n-propylamine) via oxygen quenching using melatonin

Energy Technology Data Exchange (ETDEWEB)

Witt, Maria D.; Roughton, Sarah; Isakson, Timothy J.; Richter, Mark M., E-mail: markrichter@missouristate.edu

2016-03-15

The effect on the electrogenerated chemiluminescence (ECL) of the Ru(bpy){sub 3}{sup 2+}/TPrA (bpy=2,2'-bipyridine; TPra=tri-n-propylamine) system when melatonin (N-acetyl-5-methoxytryptamine; MLT) and structurally related compounds (e.g., D- and L-Tryptophan (TRY), 7-Azatryptophan (7-AZA) and Serotonin (SER)) are present in aqueous buffered solution is reported. MLT, D- and L-TRY, SER and 7-AZA display weak intrinsic ECL when TPrA is used as an oxidative–reductive coreactant. However, micromolar concentrations of melatonin result in up to 2.5-fold enhancement of Ru(bpy){sub 3}{sup 2+}/TPrA ECL while the other analytes attenuate ECL between 2- and 1000-fold. Photoluminescence (PL) emission efficiencies do not change in the presence of melatonin unless the melatonin solution has undergone electrochemical bulk oxidation, at which point PL and ECL are nearly indistinguishable. Spectroscopic, electrochemical and spectroelectrochemical studies indicate that the mechanism involves oxygen scavenging by melatonin oxidation products. This scavenging prevents the quenching of the {sup *}Ru(bpy){sub 3}{sup 2+} excited states by dissolved oxygen in solution. Melatonin can be coupled with 30% by volume 2,2,2-trifluorethanol (TFE) or with the nonionic surfactant Triton X-100 (polyethylene glycol tert-octylphenyl ether) for even greater enhancement of Ru(bpy){sub 3}{sup 2+}/TPrA ECL.

Thiolato-bridged RuIIAgIRuII trinuclear complex composed of bis(bipyridine)ruthenium(II) units with chelating 2-aminoethanethiolate: conversion to a disulfide-bridged RuIIRuII dinuclear complex.

Science.gov (United States)

Tamura, Motoshi; Matsuura, Noriyuki; Kawamoto, Tatsuya; Konno, Takumi

2007-08-20

The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2'-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged RuIIAgIRuII trinuclear complex, [Ag{Ru(aet)(bpy)2}2]3+, in which two [RuII(aet)(bpy)2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged RuIIRuII dinuclear complex, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [Ru2(cysta)(bpy)4]4+ is reverted back to [Ag{Ru(aet)(bpy)2}2]3+ by treatment with Ag+ assisted by Zn reduction.

Enhanced rate performance of mesoporous Co3O4 nanosheet supercapacitor electrodes by hydrous RuO2 nanoparticle decoration

KAUST Repository

Baby, Rakhi Raghavan

2014-03-26

Mesoporous cobalt oxide (Co3O4) nanosheet electrode arrays are directly grown over flexible carbon paper substrates using an economical and scalable two-step process for supercapacitor applications. The interconnected nanosheet arrays form a three-dimensional network with exceptional supercapacitor performance in standard two electrode configuration. Dramatic improvement in the rate capacity of the Co3O4 nanosheets is achieved by electrodeposition of nanocrystalline, hydrous RuO 2 nanoparticles dispersed on the Co3O4 nanosheets. An optimum RuO2 electrodeposition time is found to result in the best supercapacitor performance, where the controlled morphology of the electrode provides a balance between good conductivity and efficient electrolyte access to the RuO2 nanoparticles. An excellent specific capacitance of 905 F/g at 1 A/g is obtained, and a nearly constant rate performance of 78% is achieved at current density ranging from 1 to 40 A/g. The sample could retain more than 96% of its maximum capacitance even after 5000 continuous charge-discharge cycles at a constant high current density of 10 A/g. Thicker RuO2 coating, while maintaining good conductivity, results in agglomeration, decreasing electrolyte access to active material and hence the capacitive performance. © 2014 American Chemical Society.

Electronic and elastic properties of new semiconducting oP12-type RuB2 and OsB2

International Nuclear Information System (INIS)

Hao Xianfeng; Xu Yuanhui; Gao Faming

2011-01-01

Using first-principles total energy calculations we investigate the structural, elastic and electronic properties of new hypothetical oP 12 -type phase RuB 2 and OsB 2 . The calculations indicate that the oP 12 -type phase RuB 2 and OsB 2 are thermodynamically and mechanically stable. Remarkably, the new phases RuB 2 and OsB 2 are predicted to be semiconductors, and the appearance of band gaps is ascribed to the enhanced B-B covalent hybridization. Compared to metallic oP 6 -type RuB 2 and OsB 2 phases, the new phases possess similar mechanical properties and hardness. The combination of the probability of tunable electronic properties, strong stiffness and high hardness make RuB 2 and OsB 2 attractive and interesting for advanced applications.

Effect of anisotropic strain on the quantum critical phase of Sr{sub 3}Ru{sub 2}O{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Brodsky, Daniel; Barber, Mark; Mackenzie, Andrew [MPI-Chemische Physik fester Stoffe, Dresden (Germany); Scottish Universities Physics Alliance (SUPA), School of Physics and Astronomy, University of St Andrews, St Andrews (United Kingdom); Hicks, Clifford [MPI-Chemische Physik fester Stoffe, Dresden (Germany); Perry, Robin [SUPA, School of Physics, University of Edinburgh, Edinburgh (United Kingdom)

2015-07-01

We have developed a novel piezoelectric-based device for applying both compressive and tensile strains to single crystals. One particularly appealing target for such studies is Sr{sub 3}Ru{sub 2}O{sub 7}. Sr{sub 3}Ru{sub 2}O{sub 7} has a novel quantum critical phase around a metamagnetic transition at 8 T, which shows very strong transport anisotropy in the presence of weak symmetry-breaking fields. We discuss the response of this phase to applied anisotropic lattice strain.

Hydrogenation of naphthalene on NiMo- Ni- and Ru/Al{sub 2}O{sub 3} catalysts. Langmuir-Hinshelwood kinetic modelling

Energy Technology Data Exchange (ETDEWEB)

Monteiro-Gezork, Ana Cristina Alves; Winterbottom, John Mike [Department of Chemical Engineering, School of Engineering, The University of Birmingham, Birmingham B15 2TT (United Kingdom); Natividad, Reyna [Department of Chemical Engineering, Faculty of Chemistry, Universidad Autonoma del Estado de Mexico, Paseo Colon Esq. Tollocan, Toluca, Edo. de Mexico, Mexico CP 50120 (Mexico)

2008-01-30

The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al{sub 2}O{sub 3}) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir-Hinshelwood (L-H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al{sub 2}O{sub 3} catalysts) on the initial reaction rate. The L-H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al{sub 2}O{sub 3} catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al{sub 2}O{sub 3} or the presulphided NiMo/Al{sub 2}O{sub 3} catalyst. (author)

Surface chemistry of PH 3, PF 3 and PCl 3 on Ru(0001)

Science.gov (United States)

Tao, H.-S.; Diebold, U.; Shinn, N. D.; Madey, T. E.

1994-06-01

The adsorption, desorption and decomposition of PH 3, PF 3 and PCl 3 on Ru(0001) have been studied by soft X-ray photoelectron spectroscopy (SXPS) using synchrotron radiation. Due to large chemical shifts in the P 2p core levels, different phosphorus containing surface species can be identified. We find that PF 3 adsorbs molecularly on Ru(0001) at 80 and 300 K. At 80 K, PH 3 saturates the surface with one layer of atomic hydrogen, elemental phosphorus, subhydride (i.e., PHx (0 PH 3, with a total phosphorus coverage of 0.4 ML. At 300 K, PH 3 decomposes into atomic hydrogen and elemental phosphorus with a phosphorus coverage of 0.8 ML. At 80 K, PCl 3 adsorbs dissociatively into atomic chlorine, elemental phosphorus, PCl and possibly PCl 2 and PCl 3 in the first monolayer. Formation of multilayers of PCl 3 is observed at 80 K. At 300 K, PCl 3 adsorbs dissociatively as atomic chlorine and elemental phosphorus with a saturation phosphorus coverage of 0.1 ML. The variation in total phosphorus uptake at 300 K from PX3 ( X = H, FandCl) adsorption is a result of competition between site blocking by dissociation fragments and displacement reactions. Annealing surfaces with adsorbed phosphorus to 1000 K results in formation of RuzP ( z = 1 or 2), which is manifested by the chemical shifts in the P2p core level, as well as the P LVV Auger transition. The recombination of adsorbed phosphorus and adsorbed X ( = H, FandCl) from decomposition is also observed, but is a minor reaction channel on the surface. Thermochemical data are used to analyze the different stabilities of PX 3 at 300 K, namely, PF 3 adsorbs molecularly and PH 3 and PCl 3 dissociate completely. First, we compare the heat of molecular adsorption and the heat of dissociative adsorption of PX 3 on Ru(0001), using an enthalpy approach, and find results consistent with experimental observations. Second, we compare the total bond energy difference between molecular adsorption and complete dissociation of PX 3 on Ru

Electronic and elastic properties of new semiconducting oP(12)-type RuB(2) and OsB(2).

Science.gov (United States)

Hao, Xianfeng; Xu, Yuanhui; Gao, Faming

2011-03-30

Using first-principles total energy calculations we investigate the structural, elastic and electronic properties of new hypothetical oP(12)-type phase RuB(2) and OsB(2). The calculations indicate that the oP(12)-type phase RuB(2) and OsB(2) are thermodynamically and mechanically stable. Remarkably, the new phases RuB(2) and OsB(2) are predicted to be semiconductors, and the appearance of band gaps is ascribed to the enhanced B-B covalent hybridization. Compared to metallic oP(6)-type RuB(2) and OsB(2) phases, the new phases possess similar mechanical properties and hardness. The combination of the probability of tunable electronic properties, strong stiffness and high hardness make RuB(2) and OsB(2) attractive and interesting for advanced applications. © 2011 IOP Publishing Ltd

Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

Science.gov (United States)

Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

2017-04-01

Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

Raman and electronic transport characterization of few- and single-layer-thick α-RuCl3

Science.gov (United States)

Zhou, Boyi; Henriksen, Erik

The layered magnetic semiconductor α-RuCl3, having a honeycomb lattice of spin-1/2 moments, has been identified as a potential candidate material to realize the Kitaev quantum spin liquid. In particular, bulk RuCl3 crystals have been studied and found to be on the cusp of manifesting QSL behavior. As the QSL is primarily a two-dimensional phenomenon, and since the layers of RuCl3 are weakly coupled, we propose to create and study a 2D spin-1/2 honeycomb system by isolating single sheets. Here we report the exfoliation of RuCl3 down to few- and single-layer-thick samples, which we characterize by Raman spectroscopy and atomic force microscopy at room temperature. We will also report our progress on measurements of basic electronic transport properties in the 2D RuCl3 system by controlling the chemical potential via gating in a field-effect configuration.

Visible-Light-Driven Oxidation of Organic Substrates with Dioxygen Mediated by a [Ru(bpy)3 ](2+) /Laccase System.

Science.gov (United States)

Schneider, Ludovic; Mekmouche, Yasmina; Rousselot-Pailley, Pierre; Simaan, A Jalila; Robert, Viviane; Réglier, Marius; Aukauloo, Ally; Tron, Thierry

2015-09-21

Oxidation reactions are highly important chemical transformations that still require harsh reaction conditions and stoichiometric amounts of chemical oxidants that are often toxic. To circumvent these issues, olefins oxidation is achieved in mild conditions upon irradiation of an aqueous solution of the complex [Ru(bpy)3 ](2+) and the enzyme laccase. Epoxide formation is coupled to the light-driven reduction of O2 by [Ru(bpy)3 ](2+) /laccase system. The reactivity can be explained by dioxygen acting both as an oxidative agent and as renewable electron acceptor, avoiding the use of a sacrificial electron acceptor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of new mixed ligand complexes of ruthenium(II) containing triphenylphosphine and 2'-hydroxychalcones

International Nuclear Information System (INIS)

Dharmaraj, N.; Natarajan, K.

1994-01-01

A few hexacoordinated ruthenium(II) complexes of the type [RuCl(CO) (HLL')(PPh 3 ) 2 ] and [RuCl(CO)(HLL')(B) (PPh 3 )] (where HLL' 2'-hydroxychalcone, 2'-hydroxy-4-methoxychalcone, 2'-hydroxy-3,4-dimethoxychalcone and B=pyridine(Py), piperidine(Pip), morpholine (Morph)) have been synthesised and characterized on the basis of their analytical and spectral data (IR, electronic and 1 H NMR). In all these complexes, the 2'-hydroxychalcones behave as a uninegative bidentate (OO - ) chelating ligand. (author). 17 refs., 1 tab

Bioaccumulation study of acrylate monomers in algae (Chlorella Kessleri) by PY-GC and PY-GC/MS

International Nuclear Information System (INIS)

Halas, L.; Orinak, A.; Adamova, M.; Ladomersky, J.

2004-01-01

Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the paralytic cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2 -, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied. (authors)

[Ru(bpy){sub 3}]{sup 2+}-mediated photoelectrochemical detection of bisphenol A on a molecularly imprinted polypyrrole modified SnO{sub 2} electrode

Energy Technology Data Exchange (ETDEWEB)

Zhang, Bintian [State Key Laboratory of Structures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 (China); Lu, Lili; Huang, Feng [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 (China); Lin, Zhang, E-mail: zlin@fjirsm.ac.cn [State Key Laboratory of Structures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002 (China)

2015-08-05

A ruthenium-mediated photoelectrochemical sensor was developed for the detection of BPA, using molecularly imprinted polymers (MIPs) as the recognition element, a tin oxide (SnO{sub 2}) nanoparticle-modified ITO as the electrode, and a blue 473-nm LED as the excitation light source. Photoelectrochemical oxidation of BPA on SnO{sub 2} electrode was achieved by [Ru(bpy){sub 3}]{sup 2+} under the irradiation of light. It was found that BPA was oxidized by Ru{sup 3+} species produced in the photoelectrochemical reaction, resulting in the regeneration of Ru{sup 2+} and the concomitant photocurrent enhancement. MIPs film was prepared by electropolymerization of pyrrole on SnO{sub 2} electrode using BPA as the template. Surface morphology and properties of the as-prepared electrode were characterized by SEM, electrochemical impedance spectroscopy, and photocurrent measurement. In the presence of BPA, an enhanced photocurrent was observed, which was dependent on the amount of BPA captured on the electrode. A detection limit of 1.2 nM was obtained under the optimized conditions, with a linear range of 2–500 nM. Selectivity of the sensor was demonstrated by measuring five BPA analogs. To verify its practicality, this sensor was applied to analyze BPA spiked tap water and river water. With advantages of high sensitivity and selectivity, low-cost instrument, and facile sensor preparation procedure, this sensor is potentially suitable for the rapid monitoring of BPA in real environmental samples. Moreover, the configuration of this sensor is universal and can be extended to organic molecules that can be photoelectrochemically oxidized by Ru{sup 3+}. - Highlights: • [Ru(bpy){sub 3}]{sup 2+}-mediated photoelectrochemical sensor was developed for BPA detection. • Molecularly imprinted polypyrrole was modified on a SnO{sub 2} electrode as the recognition element. • The measurement was realized using a visible light source. • This sensor was highly sensitive and

Continuous degradation of trichloroethylene by Xanthobacter sp. strain Py2 during growth on propene.

OpenAIRE

Reij, M W; Kieboom, J; de Bont, J A; Hartmans, S

1995-01-01

Propene-grown Xanthobacter sp. strain Py2 cells can degrade trichloroethylene (TCE), but the transformation capacity of such cells was limited and depended on both the TCE concentration and the biomass concentration. Toxic metabolites presumably accumulated extracellularly, because the fermentation of glucose by yeast cells was inhibited by TCE degradation products formed by strain Py2. The affinity of the propene monooxygenase for TCE was low, and this allowed strain Py2 to grow on propene i...

Fermi surfaces of YRu2Si2 and LaRu2Si2

International Nuclear Information System (INIS)

Settai, R.; Ikezawa, H.; Toshima, H.; Takashita, M.; Ebihara, T.; Sugawara, H.; Kimura, T.; Motoki, K.; Onuki, Y.

1995-01-01

We have measured the de Haas-van Alphen effect of YRu 2 Si 2 and LaRu 2 Si 2 to clarify the Fermi surfaces and cyclotron masses. Main hole-Fermi surfaces of both compounds with a distorted ellipsoid shape are similar, occupying about half of the Brillouin zone. The small hole-Fermi surfaces with the shape of a rugby ball are three in number for LaRu 2 Si 2 , and one for YRu 2 Si 2 . An electron-Fermi surface consists of a doughnut like shape for LaRu 2 Si 2 , while a cylinder along the [001] direction and a multiply-connected shape exist for YRu 2 Si 2 . The cyclotron masses of YRu 2 Si 2 are a little larger than those of LaRu 2 Si 2 . ((orig.))

The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

Science.gov (United States)

Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

2018-06-13

The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absence of magnetic long range order in Ba3ZnRu2O9. A spin-liquid candidate in the S = 3/2 dimer lattice

International Nuclear Information System (INIS)

Terasaki, Ichiro; Igarashi, Taichi; Nagai, Takayuki

2017-01-01

We have discovered a novel candidate for a spin liquid state in a ruthenium oxide composed of dimers of S = 3/2 spins of Ru 5+ , Ba 3 ZnRu 2 O 9 . This compound lacks a long range order down to 37 mK, which is a temperature 5000-times lower than the magnetic interaction scale of around 200 K. Partial substitution for Zn can continuously vary the magnetic ground state from an antiferromagnetic order to a spin-gapped state through the liquid state. This indicates that the spin-liquid state emerges from a delicate balance of inter- and intra-dimer interactions, and the spin state of the dimer plays a vital role. This unique feature should realize a new type of quantum magnetism. (author)

NMR study of ligand exchange and electron self-exchange between oxo-centered trinuclear clusters [Fe3(μ3-O)(μ-O2CR)6(4-R'py)3](+/0).

Science.gov (United States)

Novitchi, Ghenadie; Helm, Lothar; Anson, Christopher; Powell, Annie K; Merbach, André E

2011-10-17

The syntheses, single crystal X-ray structures, and magnetic properties of the homometallic μ₃-oxo trinuclear clusters [Fe₃(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃](ClO₄) (1) and [Fe₃(μ₃-O)(μ-O₂CAd)₆(4-Mepy)₃](NO₃) (2) are reported (Ad = adamantane). The persistence of the trinuclear structure within 1 and 2 in CD₂Cl₂ and C₂D₂Cl₄ solutions in the temperature range 190-390 K is demonstrated by ¹H NMR. An equilibrium between the mixed pyridine clusters [Fe₃(μ₃-O)(μ-O₂CAd)₆(4-Mepy)(3-x)(4-Phpy)(x)](NO₃) (x = 0, 1, 2, 3) with a close to statistical distribution of these species is observed in CD₂Cl₂ solutions. Variable-temperature NMR line-broadening made it possible to quantify the coordinated/free 4-Rpy exchanges at the iron centers of 1 and 2: k(ex)²⁹⁸ = 6.5 ± 1.3 × 10⁻¹ s⁻¹, ΔH(‡) = 89.47 ± 2 kJ mol⁻¹, and ΔS(‡) = +51.8 ± 6 J K⁻¹ mol⁻¹ for 1 and k(ex)²⁹⁸ = 3.4 ± 0.5 × 10⁻¹ s⁻¹, ΔH(‡) = 91.13 ± 2 kJ mol⁻¹, and ΔS(‡) = +51.9 ± 5 J K⁻¹ mol⁻¹ for 2. A limiting D mechanism is assigned for these ligand exchange reactions on the basis of first-order rate laws and positive and large entropies of activation. The exchange rates are 4 orders of magnitude slower than those observed for the ligand exchange on the reduced heterovalent cluster [Fe(III)₂Fe(II)(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃] (3). In 3, the intramolecular Fe(III)/Fe(II) electron exchange is too fast to be observed. At low temperatures, the 1/3 intermolecular second-order electron self-exchange reaction is faster than the 4-Phpy ligand exchange reactions on these two clusters, suggesting an outer-sphere mechanism: k₂²⁹⁸ = 72.4 ± 1.0 × 103 M⁻¹ s⁻¹, ΔH(‡) = 18.18 ± 0.3 kJ mol⁻¹, and ΔS(‡) = -90.88 ± 1.0 J K⁻¹ mol⁻¹. The [Fe₃(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃](+/0) electron self-exchange reaction is compared with the more than 3 orders of magnitude faster [Ru₃(μ₃-O)(μ-O₂CCH₃)₆(py