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Sample records for cluster compound au55pph312cl6

  1. Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

    Science.gov (United States)

    Rubinstein, Leon I.; Pignolet, Louis H.

    1996-11-06

    The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2

  2. Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

    Science.gov (United States)

    Adrowski, Michael J.; Mason, W. Roy

    1997-03-26

    Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

  3. Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups.

    Science.gov (United States)

    Kenzler, Sebastian; Schrenk, Claudio; Frojd, Andrew R; Häkkinen, Hannu; Clayborne, Andre Z; Schnepf, Andreas

    2018-01-02

    Reducing (Ph 3 P)AuSC(SiMe 3 ) 3 with l-Selectride® gives the medium-sized metalloid gold cluster Au 70 S 20 (PPh 3 ) 12 . Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of Au 70 S 20 (PPh 3 ) 12 , but also behave as electron acceptors leading to auride-like gold atoms on the exterior.

  4. Preparation, Spectroscopic Characterization, and Frontier MO Study of the Heteronuclear Luminescent [Pt(2)Au(2)(dmb)(2)(PPh(3))(4)](PF(6))(2) Cluster (dmb = 1,8-Diisocyano-p-menthane). A Cluster with a Formal Au(0)-Au(0) Bond Encapsulated inside a "Pt(2)(dmb)(2)(2+) " Fragment.

    Science.gov (United States)

    Zhang, Tianle; Drouin, Marc; Harvey, Pierre D.

    1999-11-01

    The title compound is prepared from the direct reaction of Pt(2)(dba)(3) (dba = dibenzylideneacetone) and [Au(PPh(3))(2)](PF(6)) in the presence of 1,8-diisocyano-p-methane (dmb), with Pt(2)(dmb)(2)Cl(2), [Pt(4)(dmb)(4)(PPh(3))(2)](PF(6))(2), and (PPh(3))AuCl being formed as parallel products. X-ray crystallography reveals the presence of a quasi-linear PPh(3)Au-AuPPh(3) fragment encapsulated inside a "Pt(2)(dmb)(2)(2+)" ring which is axially coordinated with two PPh(3) ligands. The d(AuAu) is 2.5977(6) Å and is indicative of a strong Au-Au single bond. The IR nu(CN) data reveal that the Pt oxidation state is I, which places the Au oxidation state at 0. The PtAu distances are 2.8422(5) and 2.8082(5) Å. The Raman-active nu(Au(2)), nu(PtAu) (b(2g) + a(g)), nu(PtP), nu(AuP), and nu(PtC) are found at 121.2, approximately 100, 85.5, 162.1, 183.1, and 457.2, and 440.9 cm(-)(1), respectively. The PtAu (0.67 mdyn Å(-)(1)) and Au(2) (1.21 mdyn Å(-)(1)) force constants (F) confirm the presence of medium PtAu and strong Au(2) bonding interactions. The absorption spectra are characterized by strong bands at lambda(max) (epsilon, M(-1) cm(-1)) at 316 (32 300), 366 (37 800), and 418 nm (21 500) and lower intensity features at 516 (2860) and 655 nm (834). The cluster is luminescent at low temperatures (solid and frozen glasses), and in the solid state at room temperature, and exhibits an emission band at approximately 875 nm, and an emission lifetime, tau(e), of 4.4 +/- 0.4 ns (solvent = butyronitrile, T = 77 K).

  5. Fabrication and characterization of thin films of covalently interconnected Au{sub 55} clusters; Herstellung und Charakterisierung duenner Filme aus kovalent vernetzten Au{sub 55}-Clustern

    Energy Technology Data Exchange (ETDEWEB)

    Pollmeier, K.

    2006-07-01

    The aim of the present thesis was the synthesis of novel ligands for the Au{sub 55} for the production of interconnected arrangements. First an approach could be optimized, where Au{sub 55}(PPh{sub 3}){sub 12}Cl{sub 6} on PVP was arranged on the phase boundary of water and dichloromethane, whereby the system was further chemically stabilized by addition of a phosphate containing buffer solution and the change of the polymer connected with this. The obtained cluster layers exhibited extensions of several mm{sup 2}, whereby however the layers were not completely closed. Additionally on the layers stabilized with PVP aging problems and the formation of nanocrystals resulting from this could be observed. Next it was tried to connect the gold clusters covalently together. Furthermore the preparation of octavinyldisilanolsilsesquioxane-stabilized Au{sub 55} clusters was shown. In the first performed polymerization attempts by this cluster layers of many cm{sup 2} could be produced. In a further reaction the polymerization of the gold cluster by means of vinyl-substituated triphylene phosphate was successfully performed.

  6. Chemically induced magnetism in atomically precise gold clusters.

    Science.gov (United States)

    Krishna, Katla Sai; Tarakeshwar, Pilarisetty; Mujica, Vladimiro; Kumar, Challa S S R

    2014-03-12

    Comparative theoretical and experimental investigations are reported into chemically induced magnetism in atomically-precise, ligand-stabilized gold clusters Au25 , Au38 and Au55 . The results indicate that [Au25 (PPh3 )10 (SC12 H25 )5 Cl2 ](2+) and Au38 (SC12 H25 )24 are diamagnetic, Au25 (SC2 H4 Ph)18 is paramagnetic, and Au55 (PPh3 )12 Cl6 , is ferromagnetic at room temperature. Understanding the magnetic properties resulting from quantum size effects in such atomically precise gold clusters could lead to new fundamental discoveries and applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

    Science.gov (United States)

    Ren, Xiuqing; Fu, Junhong; Lin, Xinzhang; Fu, Xuemei; Yan, Jinghui; Wu, Ren'an; Liu, Chao; Huang, Jiahui

    2018-05-22

    We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.

  8. Water-soluble phosphine-protected Au9 clusters: Electronic structures and nuclearity conversion via phase transfer

    Science.gov (United States)

    Yao, Hiroshi; Tsubota, Shuhei

    2017-08-01

    In this article, isolation, exploration of electronic structures, and nuclearity conversion of water-soluble triphenylphosphine monosulfonate (TPPS)-protected nonagold (Au9) clusters are outlined. The Au9 clusters are obtained by the reduction of solutions containing TPPS and HAuCl4 and subsequent electrophoretic fractionation. Mass spectrometry and elemental analysis reveal the formation of [Au9(TPPS)8]5- nonagold cluster. UV-vis absorption and magnetic circular dichroism (MCD) spectra of aqueous [Au9(TPPS)8]5- are quite similar to those of [Au9(PPh3)8]3+ in organic solvent, so the solution-phase structures are likely similar for both systems. Simultaneous deconvolution analysis of absorption and MCD spectra demonstrates the presence of some weak electronic transitions that are essentially unresolved in the UV-vis absorption. Quantum chemical calculations for a model compound [Au9(pH3)8]3+ show that the possible (solution-phase) skeletal structure of the nonagold cluster has D2h core symmetry rather than C4-symmetrical centered crown conformation, which is known as the crystal form of the Au9 compound. Moreover, we find a new nuclearity conversion route from Au9 to Au8; that is, phase transfer of aqueous [Au9(TPPS)8]5- into chloroform using tetraoctylammonium bromide yields [Au8(TPPS)8]6- clusters in the absence of excess phosphine.

  9. Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

    International Nuclear Information System (INIS)

    Quinten, M.; Sander, I.; Steiner, P.; Kreibig, U.; Fauth, K.; Schmid, G.

    1991-01-01

    We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters. (orig.)

  10. Cs_7Sm_1_1[TeO_3]_1_2Cl_1_6 and Rb_7Nd_1_1[TeO_3]_1_2Br_1_6, the new tellurite halides of the tetragonal Rb_6LiNd_1_1[SeO_3]_1_2Cl_1_6 structure type

    International Nuclear Information System (INIS)

    Charkin, Dmitri O.; Black, Cameron; Downie, Lewis J.; Sklovsky, Dmitry E.; Berdonosov, Peter S.; Olenev, Andrei V.; Zhou, Wuzong; Lightfoot, Philip; Dolgikh, Valery A.

    2015-01-01

    Two new rare-earth – alkali – tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffraction. The structures of the new compounds Cs_7Sm_1_1[TeO_3]_1_2Cl_1_6 (I) and Rb_7Nd_1_1[TeO_3]_1_2Br_1_6 (II) (both tetragonal, space group I4/mcm) correspond to the sequence of [MLn_1_1(TeO_3)_1_2] and [M_6X_1_6] layers and bear very strong similarities to those of known selenite analogs. We discuss the trends in similarities and differences in compositions and structural details between the Se and Te compounds; more members of the family are predicted. - Graphical abstract: Two new rare-earth – alkali – tellurium oxide halides were predicted and synthesized. - Highlights: • Two new rare-earth – alkali – tellurium oxide halides were synthesized. • They adopt slab structure of rare earth-tellurium-oxygen and CsCl-like slabs. • The Br-based CsCl-like slabs have been observed first in this layered family.

  11. Selective coupling reaction between 2,6-diiodoanisoles and terminal alkynes catalyzed by Pd(PPh32Cl2 and CuI

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    Allan F. C. Rossini

    2012-06-01

    Full Text Available The cross-coupling reaction between aryl halides and terminal alkynes, catalyzed by palladium complexes and copper (I salts, consists in an efficient synthetic tool for the formation of C-C bonds, resulting in disubstituted acetylenic compounds. Accordingly, in this work we present our preliminary results involving the selective cross-coupling reaction between 2,6-diiodoanisoles and terminal alkynes, catalyzed by Pd(PPh32Cl2 and CuI, in the formation of 2-iodo-alkynylanisoles (scheme 1.

  12. Cs7Sm11[TeO3]12Cl16 and Rb7Nd11[TeO3]12Br16, the new tellurite halides of the tetragonal Rb6LiNd11[SeO3]12Cl16 structure type

    Science.gov (United States)

    Charkin, Dmitri O.; Black, Cameron; Downie, Lewis J.; Sklovsky, Dmitry E.; Berdonosov, Peter S.; Olenev, Andrei V.; Zhou, Wuzong; Lightfoot, Philip; Dolgikh, Valery A.

    2015-12-01

    Two new rare-earth - alkali - tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffraction. The structures of the new compounds Cs7Sm11[TeO3]12Cl16 (I) and Rb7Nd11[TeO3]12Br16 (II) (both tetragonal, space group I4/mcm) correspond to the sequence of [MLn11(TeO3)12] and [M6X16] layers and bear very strong similarities to those of known selenite analogs. We discuss the trends in similarities and differences in compositions and structural details between the Se and Te compounds; more members of the family are predicted.

  13. Estudo de alguns compostos organolantanídeos: [LnCp2Cl.PPh3

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    Gatti Paula M.

    2000-01-01

    Full Text Available In this work we present the synthesis and characterization of some organolanthanide compounds [LnCp2Cl.PPh3], Ln = La, Nd, Eu, Yb and Lu. The catalytic activity of these compounds has been verified in cyclohexene hydrogenation. Cyclohexane was identified by¹H NMR analysis in the reaction products.

  14. Oxidative Addition Reactions of I2 with [HIr4(CO10-n(PPh3 n(m-PPh2] (n = 1 and 2 and Crystal and Molecular Structure of [HIr4(m-I2(CO7 (PPh3(m-PPh2

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    Braga Dario

    2002-01-01

    Full Text Available The reactions of the cluster compounds [HIr4(CO10-n(PPh3 n(mu-PPh2] [n = 0, (1; 1, (2 and 2, (3] with I2 have been investigated. Compound 1 does not react, however, the presence of PPh3 in place of CO ligand(s activates the cluster. Both compounds 2 and 3 react with I2 under mild conditions to give [HIr4(mu-I2(CO7(PPh3(mu-PPh 2] (4, as the result of oxidative addition of I2 and dissociation of two CO ligands, or one CO and one PPh3 ligands, respectively. The molecular structure of 4, determined by an X-ray diffraction study, exhibits a butterfly arrangement of iridium atoms with the wings spanned by a mu-PPh2 ligand, the hinge bridged by a mu-H ligand, two hinge to wing tip edges bridged by iodine atoms and all metal atoms bearing two CO ligands, with the exception of one of the hinge atoms that contains a CO and a PPh3 ligands. This cluster exhibits the shortest average Irfraction three-quartersIr bond length [2.698(2 Å] observed so far for a derivative of 1 and this is in accord with the relatively high average oxidation state of its metal atoms (+1 for a carbonyl cluster compound.

  15. Gold(I) Complexes with N-Donor Ligands. 2.(1) Reactions of Ammonium Salts with [Au(acac-kappaC(2))(PR(3))] To Give [Au(NH(3))L](+), [(AuL)(2)(&mgr;(2)-NH(2))](+), [(AuL)(4)(&mgr;(4)-N)](+), or [(AuL)(3)(&mgr;(3)-O)](+). A New and Facile Synthesis of [Au(NH(3))(2)](+) Salts. Crystal Structure of [{AuP(C(6)H(4)OMe-4)(3)}(3)(&mgr;(3)-O)]CF(3)SO(3).

    Science.gov (United States)

    Vicente, José; Chicote, María-Teresa; Guerrero, Rita; Jones, Peter G.; Ramírez De Arellano, M. Carmen

    1997-09-24

    The complexes [Au(acac-kappaC(2))(PR(3))] (acac = acetylacetonate, R = Ph, C(6)H(4)OMe-4) react with (NH(4))ClO(4) to give amminegold(I), [Au(NH(3))(PR(3))]ClO(4), amidogold(I), [(AuPR(3))(2)(&mgr;(2)-NH(2))]ClO(4), or nitridogold(I), [(AuPR(3))(4)(&mgr;(4)-N)]ClO(4), complexes, depending on the reaction conditions. Similarly, [Au(acac-kappaC(2))(PPh(3))] reacts with (NH(3)R')OTf (OTf = CF(3)SO(3)) (1:1) or with [H(3)N(CH(2))(2)NH(2)]OTf (1:1) to give (amine)gold(I) complexes [Au(NH(2)R')(PPh(3))]OTf (R' = Me, C(6)H(4)NO(2)-4) or [(AuPPh(3))(2){&mgr;(2)-H(2)N(CH(2))(2)NH(2)}](OTf)(2), respectively. The ammonium salts (NH(2)R'(2))OTf (R' = Et, Ph) react with [Au(acac-kappaC(2))(PR(3))] (R = Ph, C(6)H(4)OMe-4) (1:2) to give, after hydrolysis, the oxonium salts [(AuPR(3))(3)(&mgr;(3)-O)]OTf (R = Ph, C(6)H(4)OMe-4). When NH(3) is bubbled through a solution of [AuCl(tht)] (tht = tetrahydrothiophene), the complex [Au(NH(3))(2)]Cl precipitates. Addition of [Au(NH(3))(2)]Cl to a solution of AgClO(4) or TlOTf leads to the isolation of [Au(NH(3))(2)]ClO(4) or [Au(NH(3))(2)]OTf, respectively. The crystal structure of [(AuPR(3))(3)(&mgr;(3)-O)]OTf.Me(2)CO (R = C(6)H(4)OMe-4) has been determined: triclinic, space group P&onemacr;, a = 14.884(3) Å, b = 15.828(3) Å, c = 16.061(3) Å, alpha = 83.39(3) degrees, beta = 86.28(3) degrees, gamma = 65.54(3) degrees, R1 (wR2) = 0.0370 (0.0788). The [(AuPR(3))(3)(&mgr;(3)-O)](+) cation shows an essentially trigonal pyramidal array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175 degrees and Au.Au contacts in the range 2.9585(7)-3.0505(14) Å. These cations are linked into centrosymmetric dimers through two short Au.Au [2.9585(7), 3.0919(9) Å] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.

  16. Synthesis, structure and electronic configuration of [Rh{sub 6}Te{sub 8}(PPh{sub 3}){sub 6}].4C{sub 6}H{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, Guenther; Balmer, Markus [Marburg Univ. (Germany). Fachbereich Chemie; Dehnen, Stefanie [Marburg Univ. (Germany). Fachbereich Chemie and Wissenschaftliches Zentrum fuer Materialwissenschaften

    2016-08-01

    [Rh{sub 6}Te{sub 8}(PPh{sub 3}){sub 6}].4C{sub 6}H{sub 6}, the first compound with a molecular Chevrel-type [Rh{sub 6}Te{sub 8}] cluster core has been synthesized and structurally characterized. By means of quantum chemical calculation, the close relationship of its electronic configuration to that of the lighter homologue has been demonstrated. The different crystal solvent content prevents an isostructural crystallization.

  17. Au55, a stable glassy cluster: results of ab initio calculations

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    Dieter Vollath

    2017-10-01

    Full Text Available Structure and properties of small nanoparticles are still under discussion. Moreover, some thermodynamic properties and the structural behavior still remain partially unknown. One of the best investigated nanoparticles is the Au55 cluster, which has been analyzed experimentally and theoretically. However, up to now, the results of these studies are still inconsistent. Consequently, we have carried out the present ab initio study of the Au55 cluster, using up-to-date computational concepts, in order to clarify these issues. Our calculations have confirmed the experimental result that the thermodynamically most stable structure is not crystalline, but it is glassy. The non-crystalline structure of this cluster was validated by comparison of the coordination numbers with those of a crystalline cluster. It was found that, in contrast to bulk materials, glass formation is connected to an energy release that is close to the melting enthalpy of bulk gold. Additionally, the surface energy of this cluster was calculated using two different theoretical approaches resulting in values close to the surface energy for bulk gold. It shall be emphasized that it is now possible to give a confidence interval for the value of the surface energy.

  18. Gold chloride clusters with Au(III) and Au(I) probed by FT-ICR mass spectrometry and MP2 theory.

    Science.gov (United States)

    Lemke, Kono H

    2014-05-07

    Microsolvated clusters of gold chloride are probed by electrospray ionization mass spectrometry (ESI-MS) and scalar relativistic electronic structure calculations. Electrospray ionization of aqueous AuCl3 leads to mononuclear clusters of types [AuCl2](+)(H2O)n (n = 0-4), [AuOHCl](+)(H2O)n (n = 0-1) and [AuCl2](+)(HCl)2(H2O)n (n = 0-4). In addition, strong ion signals due to dinuclear [Au2Cl5-xOHx](+)(H2O)n (x = 0-1) are present in ESI mass spectra of aqueous AuCl3, with the abundance of individual dinuclear species controlled by the concentration-dependent variation of the precursor complexes [AuCl2-xOHx](+)(H2O)n and AuCl3. Equilibrium structures, energies and thermodynamic properties of mono- and dinuclear gold clusters have been predicted using MP2 and CCSD(T) theory, and these data have been applied to examine the influence of microsolvation on cluster stability. Specifically, results from CCSD(T) calculations indicate that non-covalently bound ion-neutral complexes Au(+)(Cl2)(H2O)n, with formal Au(I), are the dominant forms of mononuclear gold with n = 0-2, while higher hydrates (n > 2) are covalently bound [AuCl2](+)(H2O)n complexes in which gold exists as Au(III). MP2 calculations show that the lowest energy structure of dinuclear gold is an ion-molecule cluster [Au2Cl(Cl2)2](+) consisting of a single-bridged digold-chloronium ion bound end-on to two dichlorine ligands, with two higher energy isomers, single-bridged [Au2Cl3(Cl2)](+) and double-bridged [Au2Cl5](+) clusters. Finally, AuAu interactions in the singly-bridged clusters [Au2Cl(Cl2)2](+)(H2O)n and [Au2Cl3(Cl2)](+)(H2O)n are examined employing a wide range of computational tools, including natural bond order (NBO) analysis and localized orbital locator (LOL) profiles.

  19. Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Kozlov, Sergey M.; Cao, Zhen; Harb, Moussab; Maity, Niladri; Shkurenko, Aleksander; Parida, Manas R.; Hedhili, Mohamed N.; Eddaoudi, Mohamed; Mohammed, Omar F.; Bakr, Osman; Cavallo, Luigi; Basset, Jean-Marie

    2017-01-01

    Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

  20. Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2017-01-09

    Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

  1. 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

  2. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  3. The synthesis and structural characterization of the technetium nitrosyl complexes [TcCl(NO)(SC5H4N)(PPh3)2] and [Tc(NO)(SC5H4N)2(PPh3)

    Science.gov (United States)

    Nicholson, Terrence L.; Mahmood, Ashfaq; Muller, Peter; Davison, Alan; Storm-Blanchard, Shannon; Jones, Alun G.

    2011-01-01

    The reaction of the Tc(I) complex [Tc(NO)Cl2(HOMe)(PPh3)2] with stoichiometric amounts of 2-mercatopyridine and a proton scavenger yields [Tc(NO)Cl(Spy)(PPh3)2] or [Tc(NO)(Spy)2(PPh3)], depending upon quantities of ligands employed. These two complexes have been structurally characterized. The small bite angles of the bidentate mercaptopyridine ligands cause significant deviation from octahedral coordination geometry. PMID:23750048

  4. Influence of ligand polarizability on the reversible binding of O2 by trans-[Rh(X)(XNC)(PPh3)2] (X = Cl, Br, SC6F5, C2Ph; XNC = xylyl isocyanide). Structures and a kinetic study.

    Science.gov (United States)

    Carlton, Laurence; Mokoena, Lebohang V; Fernandes, Manuel A

    2008-10-06

    The complexes trans-[Rh(X)(XNC)(PPh 3) 2] (X = Cl, 1; Br, 2; SC 6F 5, 3; C 2Ph, 4; XNC = xylyl isocyanide) combine reversibly with molecular oxygen to give [Rh(X)(O 2)(XNC)(PPh 3) 2] of which [Rh(SC 6F 5)(O 2)(XNC)(PPh 3) 2] ( 7) and [Rh(C 2Ph)(O 2)(XNC)(PPh 3) 2] ( 8) are sufficiently stable to be isolated in crystalline form. Complexes 2, 3, 4, and 7 have been structurally characterized. Kinetic data for the dissociation of O 2 from the dioxygen adducts of 1- 4 were obtained using (31)P NMR to monitor changes in the concentration of [Rh(X)(O 2)(XNC)(PPh 3) 2] (X = Cl, Br, SC 6F 5, C 2Ph) resulting from the bubbling of argon through the respective warmed solutions (solvent chlorobenzene). From data recorded at temperatures in the range 30-70 degrees C, activation parameters were obtained as follows: Delta H (++) (kJ mol (-1)): 31.7 +/- 1.6 (X = Cl), 52.1 +/- 4.3 (X = Br), 66.0 +/- 5.8 (X = SC 6F 5), 101.3 +/- 1.8 (X = C 2Ph); Delta S (++) (J K (-1) mol (-1)): -170.3 +/- 5.0 (X = Cl), -120 +/- 13.6 (X = Br), -89 +/- 18.2 (X = SC 6F 5), -6.4 +/- 5.4 (X = C 2Ph). The values of Delta H (++) and Delta S (++) are closely correlated (R (2) = 0.9997), consistent with a common dissociation pathway along which the rate-determining step occurs at a different position for each X. Relative magnitudes of Delta H (++) are interpreted in terms of differing polarizabilities of ligands X.

  5. Preparation of compounds AWCl6 from WCl6 in Cl--containing solvents

    International Nuclear Information System (INIS)

    Seifert, H.J.; Kiewisch, B.; Wuesteneck, A.

    1977-01-01

    In Glyme, ACN or CH 2 Cl 2 WCl 6 is reduced by Cl - to WCl 6 - . From those solutions compounds AWCl 6 can be isolated with A = Cs (Glyme, ACN), A = Rb, K, NH 4 (ACN) and A = N(C 2 H 5 ) 4 (CH 2 Cl 2 ). By concentrating of glyme-solutions a precipitate of A 2 WCl 6 is formed by disproportionation. In methanol/HCl also solvolysis to oxo-compounds of W 6+ takes place as function of the H + -concentration. With N(C 2 H 5 ) 4 Cl not only chlorotungstates but also methoxy- and oxo-spezies of W 5+ can be isolated. (author)

  6. [Mo5VMo7VIO30(BPO4)2(O3P-Ph)6]5-: a phenyl-substituted molybdenum(V/VI) boro-phosphate polyoxometalate.

    Science.gov (United States)

    Sassoye, Capucine; Norton, Kieran; Sevov, Slavi C

    2003-03-10

    The title polyanion is the first hybrid borophosphate-phenylphosphonate polyoxometalate. It was structurally characterized as its imidazolium salt, (C(3)N(2)H(5))(5)[Mo(12)O(30)(BPO(4))(2)(O(3)P-Ph)(6)].H(2)O (monoclinic, P2(1)/c, a = 22.120(3) A, b = 13.042(2) A, and c = 32.632(4) A, beta = 101.293(3) degrees ), which was synthesized hydrothermally from imidazole, molybdenum oxide and metal, and boric, phosphoric, and phenylphosphonic acids. The anion is the second example of a new class of polyoxometalates that resemble Dawson anions but where the two pole caps of three edge-sharing MoO(6) octahedra in the latter are replaced by other units, in this case tetrahedral borate sharing corners with three phenylphosphonic groups, [(OB)(O(3)P-Ph)(3)]. The 12 molybdenum atoms forming the two equatorial belts of the cluster are of mixed-valence, five are Mo(V) and seven are Mo(VI), and the resulting five electrons are delocalized. Four of these electrons are paired according to the temperature dependence of the magnetic susceptibility. The new compound is soluble in a mixture of water and pyridine (in equal volumes) as well as in nitromethane, and the anions are intact in these solutions.

  7. The quiescent state of the neutron-star X-ray transient GRS 1747-312 in the globular cluster Terzan 6

    Science.gov (United States)

    Vats, Smriti; Wijnands, Rudy; Parikh, Aastha S.; Ootes, Laura; Degenaar, Nathalie; Page, Dany

    2018-04-01

    We studied the transient neutron-star low-mass X-ray binary GRS 1747-312, located in the globular cluster Terzan 6, in its quiescent state after its outburst in August 2004, using an archival XMM-Newton observation. A source was detected in this cluster and its X-ray spectrum can be fitted with the combination of a soft, neutron-star atmosphere model and a hard, power-law model. Both contributed roughly equally to the observed 0.5-10 keV luminosity (˜4.8 × 1033 erg s-1). This type of X-ray spectrum is typically observed for quiescent neutron-star X-ray transients that are perhaps accreting in quiescence at very low rates. Therefore, if this X-ray source is the quiescent counterpart of GRS 1747-312, then this source is also accreting at low levels in-between outbursts. Since source confusion a likely problem in globular clusters, it is quite possible that part, if not all, of the emission we observed is not related to GRS 1747-312, and is instead associated with another source or conglomeration of sources in the cluster. Currently, it is not possible to determine exactly which part of the emission truly originates from GRS1747-312, and a Chandra observation (when no source is in outburst in Terzan 6) is needed to be conclusive. Assuming that the detected emission is due to GRS 1747-312, we discuss the observed results in the context of what is known about other quiescent systems. We also investigated the thermal evolution of the neutron-star in GRS 1747-312, and inferred that GRS 1747-312 can be considered a typical quiescent system under our assumptions.

  8. The quiescent state of the neutron-star X-ray transient GRS 1747-312 in the globular cluster Terzan 6

    Science.gov (United States)

    Vats, Smriti; Wijnands, Rudy; Parikh, Aastha S.; Ootes, Laura; Degenaar, Nathalie; Page, Dany

    2018-06-01

    We studied the transient neutron-star low-mass X-ray binary GRS 1747-312, located in the globular cluster Terzan 6, in its quiescent state after its outburst in August 2004, using an archival XMM-Newton observation. A source was detected in this cluster and its X-ray spectrum can be fitted with the combination of a soft, neutron-star atmosphere model and a hard, power-law model. Both contributed roughly equally to the observed 0.5-10 keV luminosity (˜4.8 × 1033 erg s-1). This type of X-ray spectrum is typically observed for quiescent neutron-star X-ray transients that are perhaps accreting in quiescence at very low rates. Therefore, if this X-ray source is the quiescent counterpart of GRS 1747-312, then this source is also accreting at low levels in-between outbursts. Since source confusion is a likely problem in globular clusters, it is quite possible that part, if not all, of the emission we observed is not related to GRS 1747-312, and is instead associated with another source or conglomeration of sources in the cluster. Currently, it is not possible to determine exactly which part of the emission truly originates from GRS 1747-312, and a Chandra observation (when no source is in outburst in Terzan 6) is needed to be conclusive. Assuming that the detected emission is due to GRS 1747-312, we discuss the observed results in the context of what is known about other quiescent systems. We also investigated the thermal evolution of the neutron star in GRS 1747-312, and inferred that GRS 1747-312 can be considered a typical quiescent system under our assumptions.

  9. Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters

    Science.gov (United States)

    Guedes-Sobrinho, Diego; Chaves, Anderson S.; Piotrowski, Maurício J.; Da Silva, Juarez L. F.

    2017-04-01

    (PPh3) molecules on Au55, in which the relative stability between ICO and DRC is the same as for PH3 and SH2. However, for Pt55, we found an inversion of stability due to the PPh3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

  10. Homogeneous catalytic hydrogenation of bio-oil and related model aldehydes with RuCl{sub 2}(PPh{sub 3}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Huang, F.; Li, W.; Lu, Q.; Zhu, X. [Anhui Province Key Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei (China)

    2010-12-15

    A homogeneous RuCl{sub 2}(PPh{sub 3}){sub 3} catalyst was prepared for the hydrogenation of bio-oil to improve its stability and fuel quality. Experiments were first performed on three model aldehydes of acetaldehyde, furfural and vanillin selected to represent the linear aldehydes, oxygen heterocyclic aldehydes and aromatic aldehydes in bio-oil. The results demonstrated the high hydrogenation capability of this homogeneous catalyst under mild conditions (55-90 C, 1.3-3.3 MPa). The highest conversion of the three model aldehydes was over 90 %. Furfural and acetaldehyde were singly converted to furfuryl alcohol and ethanol after hydrogenation, while vanillin was mainly converted to vanillin alcohol, together with a small amount of 2-methoxy-4-methylphenol and 2-methoxyphenol. Further experiments were conducted on a bio-oil fraction extracted by ethyl acetate and on the whole bio-oil at 70 C and 3.3 MPa. Most of the aldehydes were transformed to the corresponding alcohols, and some ketones and compounds with C-C double bond were converted to more stable compounds. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

    2017-01-01

    Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

  12. Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters.

    Science.gov (United States)

    Guedes-Sobrinho, Diego; Chaves, Anderson S; Piotrowski, Maurício J; Da Silva, Juarez L F

    2017-04-28

    triphenylphosphine (PPh 3 ) molecules on Au 55 , in which the relative stability between ICO and DRC is the same as for PH 3 and SH 2 . However, for Pt 55 , we found an inversion of stability due to the PPh 3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

  13. NMR in metal cluster compounds compared to glasses

    International Nuclear Information System (INIS)

    Staveren, M.P.J. van; Brom, H.B.; Jongh, L.J. de; Schmid, G.

    1991-01-01

    The field and temperature dependence of the 31 P nuclear spin lattice relaxation rate in the metal cluster compound Ru 55 (P(t-Bu) 3 ) 12 Cl 20 follows a power law: 1/T 1 ∝ T n B -m , with n = 1.5 ± 0.1 at 3.25 T and n = 1.3 ± 0.1 at 6.45 T; m ≅ 1.4. Such dependences have so far only been observed in inorganic glasses and been attributed to two level systems. The correspondence suggests that the relaxation rate is due to interaction of the P-nuclear moment with electronic spins of stochastically moving charge carriers, which are thought to be responsible for the electrical conductivity through hopping between neigboring cluster molecules. (orig.)

  14. [Hyp-Au-Sn9(Hyp)3-Au-Sn9(Hyp)3-Au-Hyp]-: the longest intermetalloid chain compound of tin.

    Science.gov (United States)

    Binder, Mareike; Schrenk, Claudio; Block, Theresa; Pöttgen, Rainer; Schnepf, Andreas

    2017-10-12

    The reaction of the metalloid tin cluster [Sn 10 (Hyp) 4 ] 2- with (Ph 3 P)Au-SHyp (Hyp = Si(SiMe 3 ) 3 ) gave an intermetalloid cluster [Au 3 Sn 18 (Hyp) 8 ] - 1, which is the longest intermetalloid chain compound of tin to date. 1 shows a structural resemblance to binary AuSn phases, which is expected for intermetalloid clusters.

  15. Synthesis and Characterization of Atomically Precise Copper Nanoclusters

    Science.gov (United States)

    Nguyen, Thuy-Ai Dang

    The reactivity of MCl3(eta1-TEMPO) (M = Fe, Al; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of lignin models, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol and 1,2-diphenyl-2-methoxyethanol is investigated. FeCl3(TEMPO) is effective in cleanly converting these substrates to the corresponding aldehyde or ketone. AlCl3(eta1-TEMPO) is also able to oxidize these substrates, however in a few instances the products of over-oxidation are also observed. In contrast, 2-phenoxyethanol is not oxidized by MCl 3(eta1-TEMPO); instead it likely coordinates to the metal center, forming a 2-phenoxyethoxide complex. Oxidation of activated alkanes by MCl3(eta1-TEMPO) suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et 2O results in oxidation of the solvent. The copper hydride clusters [Cu14H12(phen) 6(PPh3)4][X]2 (X = Cl, OTf) are obtained in good yields by reaction of [(Ph3P)CuH]6 with 1,10-phenanthroline, in the presence of a halide or pseudohalide source. [Cu14H 12(phen)6(PPh3)4][Cl]2 reacts with CO2 in CH2Cl2, in the presence of excess Ph3P, to form the formate complex, [(Ph3P)2Cu(kappa 2-O2CH)], along with [(phen)(Ph3P)CuCl]. [Cu25H22(PPh3)12]Cl and [Cu 18H17(PPh3)10]Cl, are isolated from the reaction of Cu(OAc) and CuCl with Ph2SiH2, in the presence of PPh3. [Cu25H22(PPh3) 12]Cl formally features partial Cu(0) character. Subsequent reaction with Ph2phen resulted in the isolation of [Cu29Cl 4H22(Ph2phen)12]Cl (Ph2phen = 4,7-diphenyl-1,10-phenanthroline), in good yields. A time-resolved kinetic evaluation of the formation of [Cu29Cl4H22(Ph 2phen)12]Cl reveals that the mechanism of cluster growth is initiated by rapid ligand exchange, followed by slower extrusion of CuCl monomer, transport, and subsequent capture by intact clusters. Two Cu26 nanoclusters, tentatively formulated as [Cu 26H17(PPh3)9(OAc)3] and [Cu26H22(PPh3)10(OAc)2], are

  16. The anti-tumour properties and biodistribution (as determined by the radiolabeled equivalent) of Au-compounds intended as potential chemotherapeutics

    Energy Technology Data Exchange (ETDEWEB)

    Nell, M.J. [Department of Pharmacology, University of Pretoria, P.O. Box 2034, Pretoria 0001 (South Africa); Wagener, J.M. [Radiochemistry, NECSA (South African Nuclear Energy Corporation Ltd.), P.O. Box 582, Pretoria 0001 (South Africa)], E-mail: jwagener@necsa.co.za; Zeevaart, J.R. [CARST, North West University, Mafikeng Campus, P. Bag X2046, Mmabatho 2735 (South Africa); Kilian, E. [Department of Pharmacology, Onderstepoort, University of Pretoria, P.O. Box 2034, Pretoria 0001 (South Africa); Mamo, M.A.; Layh, M. [Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, Wits, 2050 Johannesburg (South Africa); Coyanis, M. [Project AuTEK, Mintek, Private Bag X3015, Randburg 2125 (South Africa); Rensburg, C.E.J. van [Department of Pharmacology, University of Pretoria, P.O. Box 2034, Pretoria 0001 (South Africa)

    2009-07-15

    The anti-tumour activity of the Au (I) phosphine complex [Au(dppe{sub 2}]Cl was first discovered in the mid 1980s although promising results were obtained it did not pass clinical studies because of its toxicity to organs such as the liver and heart. The aim of this study was to determine whether the two novel gold compounds (MM5 and MM6), selected for this study, have higher selectivity for cancer cells with less toxicity towards normal cells than [Au(dppe){sub 2}]Cl, and also to determine whether they have improved bio distribution compared to [Au(dppe){sub 2}]Cl. The Au-compounds as potential chemotherapeutic drugs were evaluated by using radioactive tracers in the in vitro and in vivo studies. Results obtained from these experiments showed that the uptake of these experimental compounds was dependent on their octanol/water partition coefficient. However; the inhibition of cell growth did not correlate with the uptake of these compounds by the cells that were tested. In terms of the total uptake it was found that the compounds that were less lipophilic (MM5, MM6) were taken up less efficiently in cells than those that are more lipophilic. Therefore hydrophilic drugs are expected to have a limited biodistribution compared to lipophilic drugs. This might imply a more selective tumour uptake.

  17. Chalcogenhalide cluster rhenium- and molybdenum complexes

    International Nuclear Information System (INIS)

    Fedin, V.P.; Gubin, S.P.; Mishchenko, A.V.; Fedorov, V.E.

    1984-01-01

    The interaction of rhenium- and molybdenum chalcogenhalides with n-donor ligands (L) is studied. At heating Re 3 X 2 Hal 5 complexes up to 100 deg in DMSO in the L presence obtained are the complexes of the 1-6 composition Re 3 X 2 Hal 5 -x Lx DMSO (X=Se, Hal=Cl, L=Et 3 N(1); X=Se, Hal=Cl, L=Bipy(2); X=Se, Hal=Br, L=Et 3 N(3); X=Se, Hal=Br, L=Bipy(4); X=Te, Hal=Br, L=Et 3 N(5); X=Te, Hal=Br, L=(Me 2 NCH 2 ) 2 (6). In the course of boiling of Mo 3 S 7 Hal 4 with PPh 3 in MeCN the Mo 3 S 7 Hal 4 2PPh 3 complexes (Hal=Cl(7); Br(8)) are obtained. For 1 through 8 complexes the chemical analysis data and IR spectra are given. For 4 and 8 complexes the molecular mass is measured. A possible method of obtaining molecular trinuclear clusters from polymer clusters is discussed

  18. Comparative study of the catalytic activity of the complexes Cp*RuCl(PAr3)2 [Ar = -C6H5 and 4-CF3-C6H4] in the ATRP of styrene

    International Nuclear Information System (INIS)

    Villa-Hernandez, Alejandro M.; Rosales-Velazquez, Claudia P.; Torres-Lubian, Jose R.; Saldivar-Guerra, Enrique

    2011-01-01

    Styrene polymerization by ATRP was conducted independently using the complexes Cp * RuCl(PPh 3 ) 2 , and Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 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 * RuCl(PPh 3 ) 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 * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 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 * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 as confirmed by 31 P-NMR spectroscopy. Catalyst Cp * RuCl(PPh 3 ) 2 promotes the polymerization with a rate of polymerization higher than that obtained using Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 ; this is consistent with the better electron donating properties of PPh 3 versus P(4-CF 3 -C 6 H 4 ) 3 . Preliminary studies of styrene polymerization by ATRP in supercritical CO 2 , shows that only catalyst Cp * RuCl[P(4-CF 3 -C 6 H 4 ) 3 ] 2 , with fluorinated ligands, was active. (author)

  19. Structure determination of two structural analogs, named 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16F2N4S) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16ClFN4S) by synchrotron X-ray powder diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Gündoğdu, Gülsüm; Aytaç, Sevim Peri; Müller, Melanie; Tozkoparan, Birsen; Kaynak, Filiz Betül

    2017-12-01

    Two novel compounds, 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16F2N4S) (1) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16ClFN4S) (2), have been designed and synthesized as cytotoxic agents. The compounds were characterized by infrared, proton nuclear magnetic resonance, mass spectral data, elemental analysis and X-ray powder diffraction. The present study comprises spectral data and crystal structures of these novel compounds determined from synchrotron X-ray powder diffraction data. The structure solutions were obtained by simulated annealing. The final structures were achieved by Rietveld refinement using soft restraints for all bond lengths, bond angles, and planar groups. Both compounds crystallize in space group$P\\bar 1$,Z= 2, with the unit-cell parametersa= 6.37433(9),b= 11.3641(2),c= 14.09115(19) Å,α= 80.1740(8)°,β= 85.1164(8)°,γ= 80.9831(10)°,V= 991.55(3) Å3of compound (1) anda= 6.53736(6),b= 11.55725(15),c= 14.01373(13) Å,α= 80.3323(7)°,β= 84.8939(6)°,γ= 79.3954(8)°,V= 1024.08(2) Å3of compound (2). Structural analyses reveal that the title compounds are isostructural.

  20. Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

    Science.gov (United States)

    Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

    2001-11-05

    A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo

  1. The crystal structure of TeCl3+AuCl4-

    International Nuclear Information System (INIS)

    Jones, P.G.; Jentsch, D.; Schwarzmann, E.

    1986-01-01

    TeCl 3 + AuCl 4 - crystallizes in the triclinic space group Panti 1 with a=7.564(2), b=7.720(3), c=8.964(3) A, α=78.26(3), β=88.84(3), γ=89.35(3) 0 , Z=2. The structure was refined to R 0.041 for 1380 reflections. The cation polyhedron, including secondary Te...Cl interactions, is a square pyramid with mean Te-Cl 2.294, Te...Cl 3.028 A. The secondary interactions link the ions to form centrosymmetric (TeCl 3 .AuCl 4 ) 2 dimers. (orig.)

  2. Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

    2017-01-01

    Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

  3. Regulation of cortical contractility and spindle positioning by the protein phosphatase 6 PPH-6 in one-cell stage C. elegans embryos

    Science.gov (United States)

    Afshar, Katayoun; Werner, Michael E.; Tse, Yu Chung; Glotzer, Michael; Gönczy, Pierre

    2010-01-01

    Modulation of the microtubule and the actin cytoskeleton is crucial for proper cell division. Protein phosphorylation is known to be an important regulatory mechanism modulating these cytoskeletal networks. By contrast, there is a relative paucity of information regarding how protein phosphatases contribute to such modulation. Here, we characterize the requirements for protein phosphatase PPH-6 and its associated subunit SAPS-1 in one-cell stage C. elegans embryos. We establish that the complex of PPH-6 and SAPS-1 (PPH-6/SAPS-1) is required for contractility of the actomyosin network and proper spindle positioning. Our analysis demonstrates that PPH-6/SAPS-1 regulates the organization of cortical non-muscle myosin II (NMY-2). Accordingly, we uncover that PPH-6/SAPS-1 contributes to cytokinesis by stimulating actomyosin contractility. Furthermore, we demonstrate that PPH-6/SAPS-1 is required for the proper generation of pulling forces on spindle poles during anaphase. Our results indicate that this requirement is distinct from the role in organizing the cortical actomyosin network. Instead, we uncover that PPH-6/SAPS-1 contributes to the cortical localization of two positive regulators of pulling forces, GPR-1/2 and LIN-5. Our findings provide the first insights into the role of a member of the PP6 family of phosphatases in metazoan development. PMID:20040490

  4. Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

    Science.gov (United States)

    Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

    2017-06-05

    The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

  5. The solubility of Pd and Au in hydrous intermediate silicate melts: The effect of oxygen fugacity and the addition of Cl and S

    Science.gov (United States)

    Sullivan, Neal A.; Zajacz, Zoltan; Brenan, James M.

    2018-06-01

    The solubilities of Pd and Au in a hydrous trachyandesitic melt were experimentally determined at 1000 °C and 200 MPa at oxygen fugacity (ƒO2) from 0.45 log units below to 6.55 log units above the Ni-NiO buffer (NNO). The effect of adding metal-binding ligands (i.e. Cl and S) to the silicate melt was also studied. The solubility of Au increases from 0.15 ± 0.1 to 3.85 ± 1.48 ppm in Cl- and S-free melts with ƒO2 increasing from NNO-0.45 to NNO+6.55 with a slope that suggests that it is present in 1+ oxidation state over the entire studied ƒO2 range. On the other hand, Pd solubility, shows a more moderate increase with ƒO2, especially in the lower half of the studied range, increasing from 2.66 ± 0.25 ppm at NNO-0.45 to only 3.62 ± 0.38 ppm at NNO+1.72 in Cl- and S-free melts. Overall, the variation in Pd solubility as a function of ƒO2 indicates Pd being dissolved in the silicate melt in both zero and 1+ oxidation state, with the former being dominant below NNO+4.5. At NNO-0.45 to +3.48, the addition of 3170-4060 ppm Cl to the silicate melt increased the solubility of Au by an average factor of 1.5, in comparison to Cl-free melts. However, at NNO+6.55, Au solubility increased by a factor of 2.5. The addition of Cl had a negligible effect on the solubility of Pd except for a large increase (factor of 2.4) at NNO+6.55. At reducing conditions (NNO-0.45), the addition of 170 ppm S to the silicate melt increased the solubility of Au by a factor of ∼4 but did not change the solubility of Pd in comparison to S-free melts. The observation that Pd is dominantly present as Pd0 at NNO one may expect similar behavior in fluids degassing from magmas at depth, the lack of oxidized Pd species could be an important factor behind the scarcity of economically viable Pd-rich magmatic-hydrothermal deposits observed in nature.

  6. A redox-switchable Au8-cluster sensor.

    Science.gov (United States)

    Wu, Te-Haw; Hsu, Yu-Yen; Lin, Shu-Yi

    2012-07-09

    The proof of concept of a simple sensing platform based on the fluorescence of a gold cluster consisting of eight atoms, which is easily manipulated by reduction and oxidation of a specific molecule in the absence of chemical linkers, is demonstrated. Without using any coupling reagents to arrange the distance of the donor-acceptor pair, the fluorescence of the Au(8) -cluster is immediately switched off in the presence of 2-pyridinethiol (2-PyT) quencher. Through an upward-curving Stern-Volmer plot, the system shows complex fluorescence quenching with a combination of static and dynamic quenching processes. To analyze the static quenching constant (V) by a "sphere of action" model, the collisional encounter between the Au(8) -cluster and 2-PyT presents a quenching radius (r) ≈5.8 nm, which is larger than the sum of the radii of the Au(8) -cluster and 2-PyT. This implies that fluorescence quenching can occur even though the Au(8) -cluster and 2-PyT are not very close to each other. The quenching pathway may be derived from a photoinduced electron-transfer process of the encounter pair between the Au(8) -cluster (as an electron donor) and 2-PyT (as an electron acceptor) to allow efficient fluorescence quenching in the absence of coupling reagents. Interestingly, the fluorescence is restored by oxidation of 2-PyT to form the corresponding disulfide compound and then quenched again after the reduction of the disulfide. This redox-switchable fluorescent Au(8) -cluster platform is a novel discovery, and its utility as a promising sensor for detecting H(2) O(2) -generating enzymatic transformations is demonstrated. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of the first dimetallacarborane ruthenium-iridium cluster

    International Nuclear Information System (INIS)

    Lobanova, I.A.; Chizhevskij, I.T.; Petrovskij, P.V.; Bregadze, V.I.

    1996-01-01

    New electron-deficient dimetallic cluster (η 4 -C 8 H 12 )IrRu(μ-H)(PPh 3 ) 2 (η 5 -C 2 B 9 H 11 ) (1), has been prepared by the reaction of exo-nido-5,6,10-[Cl(PPh 3 ) 2 Ru]-5,6.10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 with dimeric or acetylacetonate complexes of Ir in the presence of KOH in ethanol at 22 deg C. 1 H, 13 C, 31 P, 11 B NMR and IR spectral data for 1 are presented. 8 refs., 1 scheme

  8. Deformation of Ag clusters deposited on Au(111) - Experiment and molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Miroslawski, Natalie; Groenhagen, Niklas; Hoevel, Heinz [TU Dortmund, Experimentelle Physik I (Germany); Issendorff, Bernd von [Universitaet Freiburg, Fakultaet Physik (Germany); Jaervi, Tommi [Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Moseler, Michael [Universitaet Freiburg, Fakultaet Physik (Germany); Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Freiburger Materialforschungszentrum (Germany)

    2011-07-01

    Mass selected clusters from Ag{sup +}{sub 55} to Ag{sup +}{sub 147{+-}}{sub 2} were deposited with different deposition energies at 77 K on Au(111) and imaged with STM at 77 K. We observed a deformation of the cluster shape due to the strong metallic interaction between the cluster and the substrate. The clusters became epitaxial and developed a structure composed of several Ag monolayers. The number of these monolayers depends on the number of atoms in the cluster and the deposition energy. The larger the cluster mass the more monolayers the cluster develops on Au(111) and the larger the deposition energy the fewer monolayers occur. These results were verified by molecular dynamic simulations. Additionally the behaviour of Ag{sub N} clusters on Au(111) after different annealing steps was investigated.

  9. Solid energy calibration standards for P K-edge XANES: electronic structure analysis of PPh4Br.

    Science.gov (United States)

    Blake, Anastasia V; Wei, Haochuan; Donahue, Courtney M; Lee, Kyounghoon; Keith, Jason M; Daly, Scott R

    2018-03-01

    P K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs 2 CuCl 4 ) and S (Na 2 S 2 O 3 ·5H 2 O), but not neighboring P. This paper presents a review of common P K-edge XANES energy calibration standards and analysis of PPh 4 Br as a potential alternative. The P K-edge XANES region of commercially available PPh 4 Br revealed a single, highly resolved pre-edge feature with a maximum at 2146.96 eV. PPh 4 Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh 3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh 3 and PPh 4 + revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time-dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre-edge feature in the P K-edge XANES spectrum of PPh 4 Br was assigned to P 1s → P-C π* transitions, whereas those at higher energy were P 1s → P-C σ*. Overall, the analysis suggests that PPh 4 Br is an excellent alternative to other solid energy calibration standards commonly used in P K-edge XANES experiments.

  10. Reactions at the Metal Vertex of a Monometal Metallocarborane Cluster. The Chemistry of (closo-3,3-(PPh3)2-3-(HSO4)-3,1,2-RhC2B9H11) and (closo-3-(PPh3)-3,3-(NO3)-3,1,2RhC2B9H11).

    Science.gov (United States)

    1982-03-09

    4) produced by dissociation of PPh 3 from (2) or through an ionic species such as [closo-3,3- (PPh 3)2 -3,1,2-RhC 289 H ] [HSO4 (4a). Secondly, the...acetylene molecule and subsequent insertion into a metal-carbon bond has been observed in the linear oligomerization of acetylere catalyzed by [Ni(CO...monoxide were obtained from Liquid Carbonic and used without further treatment. Phenylacetylene (Aldrich) was distilled under vacuum before use and n

  11. Facile one-pot synthesis of 1-amido alkyl-2-naphthols by RuCl2(PPh3)3-catalyzed multi-component reactions

    International Nuclear Information System (INIS)

    Zhu, Xiaoyan; Lee, Yong Rok; Kim, Sung Hong

    2012-01-01

    We have developed an efficient and general synthesis of 1-amidoalkyl-2-naphthols by RuCl 2 (PPh 3 ) 3 -catalyzed one-pot multi-component reaction of 2-naphthol with aromatic aldehydes and amides. The advantages of these methodologies are easy handling, mild reaction conditions, and use of an effective and non-toxic catalyst. Molecules bearing 1,3-amino oxygenated functional groups have been reported to exhibit a variety of biological and pharmacological activities including nucleoside antibiotics and HIV protease inhibitors such as ritonavir and lipinavir. Importantly, 1-amidoalkyl-2-naphthols can be easily converted to biologically active 1-aminomethyl-2-naphthols by amide hydrolysis. These compounds also exhibit potent antihypertensive, adrenoceptor-blocking, and Ca +2 channel-blocking activities. Because of the importance of these compounds, numerous methods for the synthesis of 1-amidoalkyl-2-naphthols have been described. The reported methods mainly include one-pot three-component reactions of 2-naphthol, aromatic aldehydes, and amides

  12. Measurement of {sup 197}Au(n,γ){sup 198g}Au reaction cross-section at the neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Vansola, Vibha [M.S. Univ., Baroda (India). Dept. of Physics; Ghosh, Reetuparna; Badwar, Sylvia [North Eastern Hill Univ., Meghalaya (India). Dept. of Physics; and others

    2015-07-01

    The {sup 197}Au(n,γ){sup 198}Au reaction cross-sections at the neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV were determined by using activation and off-line γ-ray spectrometric technique. The mono-energetic neutron energies of 1.12-4.12 MeV were generated from the {sup 7}Li(p,n) reaction by using the proton energies of 3 and 4 MeV from the folded tandem ion beam accelerator (FOTIA) at BARC as well as 5 and 6 MeV from the Pelletron facility at TIFR, Mumbai. The {sup 115}In(n,γ){sup 116m}In reaction cross-section was used as the neutron flux monitor. The {sup 197}Au(n,γ){sup 198}Au reaction cross-section at the neutron energies of 3.12 and 4.12 MeV are reported for the first time. The {sup 197}Au(n,γ){sup 198}Au reaction cross-sections at 1.12 and 2.12 MeV are close to the literature data of in between neutron energies. The {sup 197}Au(n,γ){sup 198}Au cross-section was also calculated theoretically by using the computer code TALYS 1.6 and found to be higher than the experimental data of present work and literature data within the neutron energies of 0.8 to 4 MeV.

  13. 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)

  14. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    dppe)CN] (2), [(Cp)Ru(PPh3)2CN] (3), with the corresponding chloro complexes [(Ind)Ru(PPh3)2Cl] (4), [(Ind)Ru(dppe)Cl] (5), [(Cp)Ru(PPh3)2Cl] (6), in the presence of NH4PF6 salt give homometallic cyano-bridged compounds of the type ...

  15. Label-free sensitive luminescence biosensor for immunoglobulin G based on Ag6Au6 ethisterone cluster-estrogen receptor α aggregation and graphene.

    Science.gov (United States)

    Chen, Nannan; Guo, Wenjing; Lin, Zhixiang; Wei, Qiaohua; Chen, Guonan

    2018-08-01

    A specific and label-free "on-off-on" luminescence biosensor based on a novel heterometallic cluster [Ag 6 Au 6 (ethisterone) 12 ]-estrogen receptor α (Ag 6 Au 6 Eth-ERα) aggregation utilizing graphene oxide (GO) as a quencher to lead a small background signal was firstly constructed to detect immunoglobulin G (IgG) with a simple process and high selectivity. The efficient photoluminescent (PL) Ag 6 Au 6 Eth-ERα aggregation is strongly quenched by GO. In the presence of IgG, the PL of this system will be restored, and perceivable by human eyes under UV lamp excitation (365 nm). The quenching mechanism of GO on Ag 6 Au 6 Eth-ERα and enhancement mechanism of IgG on Ag 6 Au 6 Eth-ERα-GO were investigated in detail. Under the optimum conditions, the biosensor for high sensitive IgG detection expressed a wider linear range of 0.0078-10 ng/mL and a lower detection limit of 0.65 pg/mL with good stability and repeatability, which provided a new approach for label-free IgG detection. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Direct synthesis of acetylketene N,S-acetals with benzoylcyanamide

    International Nuclear Information System (INIS)

    Kolomnikova, G.D.; Sorokin, P.V.; Chizhevskij, I.T.; Petrovskij, P.V.; Bregadze, V.I.; Dolgushin, F.M.; Yanovskij, A.I.

    1997-01-01

    The reaction of the OsCl 2 (PPh 3 ) 3 with K + -salts of the [nido-7,8-R 2 -7,8-C 2 B 9 H 10 ] - afforded novel exo-nido-osmacarborane complexes, exo-nido-5,6,10-[Cl(PPh 3 ) 2 Os]-5,6,1-μ-(H) 3 -10-H-7,8-R 2 C 2 B 9 H 6 (2, R = H; 3, R = Me) in 78 and 85% yields, respectively. Complex 2 is transformed quantitatively in to know closo-3-Cl-3-H-3,3-(PPh 3 ) 2 -3,1,2-OsC 2 B 9 H 11 upon heating in benzene. The structure of exo-nido-osmacarboranes have been confirmed by 1 H and 31 P NMR spectral data and by single crystal X-ray diffraction study of 3

  17. Detached dust shell around Wolf-Rayet star WR60-6 in the young stellar cluster VVV CL036

    Energy Technology Data Exchange (ETDEWEB)

    Borissova, J.; Amigo, P.; Kurtev, R. [Departamento de Física y Astronomía, Universidad de Valparaíso, Av. Gran Bretaña 1111, Playa Ancha, Casilla 5030 (Chile); Kumar, M. S. N. [Centro de Astrofísica da Universidade do Porto, Rua das Estrelas, 4150-762 Porto (Portugal); Chené, A.-N. [Gemini Observatory, Northern Operations Center, 670 North A' ohoku Place Hilo, HI 96720 (United States); Minniti, D., E-mail: jura.borissova@uv.cl [Pontificia Universidad Católica de Chile, Facultad de Física, Departamento de Astronomía y Astrofísica, Av. Vicuña Mackenna 4860, 782-0436 Macul, Santiago (Chile)

    2014-01-01

    The discovery of a detached dust shell around the Wolf-Rayet (WR) star WR60-6 in the young stellar cluster VVV CL036 is reported. This shell is uncovered through the Spitzer-MIPS 24 μm image, where it appears brightest, and it is invisible at shorter wavelengths. Using new APEX observations and other data available from the literature, we have estimated some of the shell parameters: the inner and outer radii of 0.15 and 0.90 pc, respectively; the overall systemic velocity of the molecular {sup 12}CO(3 → 2) emission of –45.7 ± 2.3 km s{sup –1}; an expansion velocity of the gas of 16.3 ± 1 km s{sup –1}; the dust temperature and opacity of 122 ± 12 K and 1.04, respectively; and an age of 2.8 × 10{sup 4} yr. The WR star displays some cyclic variability. The mass computed for the WR60-6 nebula indicates that the material was probably ejected during its previous stages of evolution. In addition, we have identified a bright spot very close to the shell, which can be associated with the Midcourse Space Experiment source G312.13+00.20.

  18. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

    2012-01-01

    is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster......Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

  19. Stabilizing ultrasmall Au clusters for enhanced photoredox catalysis.

    Science.gov (United States)

    Weng, Bo; Lu, Kang-Qiang; Tang, Zichao; Chen, Hao Ming; Xu, Yi-Jun

    2018-04-18

    Recently, loading ligand-protected gold (Au) clusters as visible light photosensitizers onto various supports for photoredox catalysis has attracted considerable attention. However, the efficient control of long-term photostability of Au clusters on the metal-support interface remains challenging. Herein, we report a simple and efficient method for enhancing the photostability of glutathione-protected Au clusters (Au GSH clusters) loaded on the surface of SiO 2 sphere by utilizing multifunctional branched poly-ethylenimine (BPEI) as a surface charge modifying, reducing and stabilizing agent. The sequential coating of thickness controlled TiO 2 shells can further significantly improve the photocatalytic efficiency, while such structurally designed core-shell SiO 2 -Au GSH clusters-BPEI@TiO 2 composites maintain high photostability during longtime light illumination conditions. This joint strategy via interfacial modification and composition engineering provides a facile guideline for stabilizing ultrasmall Au clusters and rational design of Au clusters-based composites with improved activity toward targeting applications in photoredox catalysis.

  20. Contact-based ligand-clustering approach for the identification of active compounds in virtual screening

    Directory of Open Access Journals (Sweden)

    Mantsyzov AB

    2012-09-01

    Full Text Available Alexey B Mantsyzov,1 Guillaume Bouvier,2 Nathalie Evrard-Todeschi,1 Gildas Bertho11Université Paris Descartes, Sorbonne, Paris, France; 2Institut Pasteur, Paris, FranceAbstract: Evaluation of docking results is one of the most important problems for virtual screening and in silico drug design. Modern approaches for the identification of active compounds in a large data set of docked molecules use energy scoring functions. One of the general and most significant limitations of these methods relates to inaccurate binding energy estimation, which results in false scoring of docked compounds. Automatic analysis of poses using self-organizing maps (AuPosSOM represents an alternative approach for the evaluation of docking results based on the clustering of compounds by the similarity of their contacts with the receptor. A scoring function was developed for the identification of the active compounds in the AuPosSOM clustered dataset. In addition, the AuPosSOM efficiency for the clustering of compounds and the identification of key contacts considered as important for its activity, were also improved. Benchmark tests for several targets revealed that together with the developed scoring function, AuPosSOM represents a good alternative to the energy-based scoring functions for the evaluation of docking results.Keywords: scoring, docking, virtual screening, CAR, AuPosSOM

  1. Corrosion mitigation of J55 steel in 3.5% NaCl solution by a macrocyclic inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Ambrish [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Southwest Petroleum University), Chengdu, Sichuan 610500 (China); Department of Chemistry, LFTS, Lovely Professional University, Phagwara, Punjab 144402 (India); Lin, Yuanhua, E-mail: yhlin28@163.com [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Southwest Petroleum University), Chengdu, Sichuan 610500 (China); Obot, I.B. [Centre of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Ebenso, Eno E. [Department of Chemistry, School of Mathematical & Physical Sciences, North-West University (Mafikeng Campus), Private Bag X2046, Mmabatho 2735 (South Africa); Material Science Innovation & Modelling (MaSIM) Focus Area, Faculty of Agriculture, Science and Technology, North-West University (Mafikeng Campus), Private Bag X2046, Mmabatho 2735 (South Africa); Ansari, K.R.; Quraishi, M.A. [Department of Applied Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221005, Uttar Pradesh (India)

    2015-11-30

    Graphical abstract: SECM studies revealed decrease of steady current in the presence of inhibitor while it increased for 3.5% NaCl solution that acted as the conductor. - Highlights: • J55 steel protection in 3.5% NaCl solution saturated with CO{sub 2} by HPT. • Potentiodynamic polarization curves reveal that the actions of HPT are mixed type. • The adsorption of HPT obeys the Langmuir adsorption isotherm. • Scanning electrochemical microscopy is used to discuss the insulated and conductive surface. - Abstract: 1,2,4,7,9,10-Hexaazacyclo-pentadeca-10,15-dien-3,5,6,8-tetraone (HPT) a macrocyclic compound has been studied using electrochemical methods and scanning electrochemical microscopy (SECM) techniques. The R{sub ct} values increased and C{sub dl} values decreased with the increase in concentration of the inhibitor. The corrosion inhibition of J55 steel in 3.5 wt.% NaCl solution saturated with CO{sub 2} by polarization studies revealed that HPT acted as a mixed type inhibitor. The adsorption of HPT on the J55 steel surface obeyed the Langmuir adsorption isotherm. The thermodynamic parameters (K{sub ads}, ΔG°{sub ads}) were also computed and discussed.

  2. Corrosion mitigation of J55 steel in 3.5% NaCl solution by a macrocyclic inhibitor

    International Nuclear Information System (INIS)

    Singh, Ambrish; Lin, Yuanhua; Obot, I.B.; Ebenso, Eno E.; Ansari, K.R.; Quraishi, M.A.

    2015-01-01

    Graphical abstract: SECM studies revealed decrease of steady current in the presence of inhibitor while it increased for 3.5% NaCl solution that acted as the conductor. - Highlights: • J55 steel protection in 3.5% NaCl solution saturated with CO 2 by HPT. • Potentiodynamic polarization curves reveal that the actions of HPT are mixed type. • The adsorption of HPT obeys the Langmuir adsorption isotherm. • Scanning electrochemical microscopy is used to discuss the insulated and conductive surface. - Abstract: 1,2,4,7,9,10-Hexaazacyclo-pentadeca-10,15-dien-3,5,6,8-tetraone (HPT) a macrocyclic compound has been studied using electrochemical methods and scanning electrochemical microscopy (SECM) techniques. The R ct values increased and C dl values decreased with the increase in concentration of the inhibitor. The corrosion inhibition of J55 steel in 3.5 wt.% NaCl solution saturated with CO 2 by polarization studies revealed that HPT acted as a mixed type inhibitor. The adsorption of HPT on the J55 steel surface obeyed the Langmuir adsorption isotherm. The thermodynamic parameters (K ads , ΔG° ads ) were also computed and discussed.

  3. Studies on the experimental variables effects on rhodium catalyzed hydroformylation of unsaturated fatty esters and comparison of [RhH(CO)(PPh3)3] and [RhCl3.3H2O] as starting catalytic precursors

    International Nuclear Information System (INIS)

    Mendes, Ana N.F.; Gregorio, Jose R.; Rosa, Ricardo G. da

    2005-01-01

    Hydroformylation experiments were performed with technical-grade methyl oleate (MO) and soybean oil (SO) using [RhH(CO)(PPh 3 ) 3 ] and [RhCl 3 .3H 2 O] (double bond/Rh = 745) as catalyst precursors modified or not by triphenylphosphine. [RhH(CO)(PPh 3 ) 3 ] shows 100% conversion and 80-91% selectivity to aldehydes in only 4h for both substrates under mild conditions (100 deg C, 40 bar, CO/H 2 = 2:1, ligand/Rh = 10:1). Despite the rapid isomerization of the soybean oil, producing trans isomers and conjugated dienes, no effects were observed on its further conversion to aldehydes. The reaction of soybean oil conducted with pure [RhCl 3 .3H 2 O] produced only conjugated dienes, and when this precursor was modified with triphenylphosphine (ligand/Rh = 10:1) no reaction was observed at all. Curiously, yellow crystals corresponding to the complex [Rh(Cl)(CO)(PPh 3 ) 2 ] were quantitatively isolated at the end of the reaction. (author)

  4. Electronic structure and optical properties of the thiolate-protected Au28(SMe)20 cluster.

    Science.gov (United States)

    Knoppe, Stefan; Malola, Sami; Lehtovaara, Lauri; Bürgi, Thomas; Häkkinen, Hannu

    2013-10-10

    The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: p-tert-butylbenzenethiolate) is analyzed with (time-dependent) density functional theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au14(6+) core and the ligand-protected cluster were analyzed, and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and circular dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.

  5. Effect on postpartum hemorrhage of prophylactic oxytocin (10 IU by injection by community health officers in Ghana: a community-based, cluster-randomized trial.

    Directory of Open Access Journals (Sweden)

    Cynthia K Stanton

    2013-10-01

    Full Text Available BACKGROUND: Oxytocin (10 IU is the drug of choice for prevention of postpartum hemorrhage (PPH. Its use has generally been restricted to medically trained staff in health facilities. We assessed the effectiveness, safety, and feasibility of PPH prevention using oxytocin injected by peripheral health care providers without midwifery skills at home births. METHODS AND FINDINGS: This community-based, cluster-randomized trial was conducted in four rural districts in Ghana. We randomly allocated 54 community health officers (stratified on district and catchment area distance to a health facility: ≥10 km versus <10 km to intervention (one injection of oxytocin [10 IU] one minute after birth and control (no provision of prophylactic oxytocin arms. Births attended by a community health officer constituted a cluster. Our primary outcome was PPH, using multiple definitions; (PPH-1 blood loss ≥500 mL; (PPH-2 PPH-1 plus women who received early treatment for PPH; and (PPH-3 PPH-2 plus any other women referred to hospital for postpartum bleeding. Unsafe practice is defined as oxytocin use before delivery of the baby. We enrolled 689 and 897 women, respectively, into oxytocin and control arms of the trial from April 2011 to November 2012. In oxytocin and control arms, respectively, PPH-1 rates were 2.6% versus 5.5% (RR: 0.49; 95% CI: 0.27-0.88; PPH-2 rates were 3.8% versus 10.8% (RR: 0.35; 95% CI: 0.18-0.63, and PPH-3 rates were similar to those of PPH-2. Compared to women in control clusters, those in the intervention clusters lost 45.1 mL (17.7-72.6 less blood. There were no cases of oxytocin use before delivery of the baby and no major adverse events requiring notification of the institutional review boards. Limitations include an unblinded trial and imbalanced numbers of participants, favoring controls. CONCLUSION: Maternal health care planners can consider adapting this model to extend the use of oxytocin into peripheral settings including, in some

  6. DFT study on stability and H2 adsorption activity of bimetallic Au79−nPdn (n = 1–55) clusters

    International Nuclear Information System (INIS)

    Liu, Xuejing; Tian, Dongxu; Meng, Changgong

    2013-01-01

    Highlights: ► Stability of Pd substitution type is face > mid-edge > corner > edge. ► H 2 adsorption activity is in contrast with the stability of Pd substitution type. ► Non-activated dissociation of H 2 occurs in Au 36 Pd 43−3 with high thermal stability. ► ε d agrees with that Pd at edge and corner are more active than face and mid-edge. - Abstract: The stability and H 2 adsorption activity of bimetallic Au 79−n Pd n (n = 1–55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H 2 adsorption activity is corner ≈ edge > mid-edge > face. The Au 36 Pd 43 (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H 2 non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ε d and the adsorption energies, the ε d order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites

  7. Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

    Directory of Open Access Journals (Sweden)

    Cristina Tubaro

    2013-02-01

    Full Text Available Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3. Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

  8. Synthesis and Structural Characterisation of [Ir4(CO8(CH3(m4-h3-Ph2PCCPh(m-PPh2] and of the Carbonylation Product [Ir4(CO8{C(OCH3}(m4-h3-Ph2PCCPh(m-PPh2]; First Evidence for the Formation of a CO Cluster Adduct before CO Insertion

    Directory of Open Access Journals (Sweden)

    Braga Dario

    1999-01-01

    Full Text Available Deprotonation of [(mu-HIr4(CO10(mu-PPh2], 1, gives [Ir4(CO10(mu-PPh2]- that reacts with Ph2PCCPh and CH3I to afford [Ir4(CO8(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2], 2 (34%, besides [Ir4(CO9(mu3-eta³-Ph2PC(HCPh(mu-PPh2] and [(mu-HIr4(CO9(Ph2PCºCPh(mu-PPh2]. Compound 2 was characterised by a single crystal X-ray diffraction analysis and exhibits a flat butterfly of metal atoms, with the Ph2PCCPh ligand interacting with all four Ir atoms and the methyl group bonded terminally to a wingtip Ir atom. Carbonylation of 2 yields initially (25 °C, 20 min a CO addition product that, according to VT 31P{¹H} and 13C{¹H} studies, exists in solution in the form of two isomers 4A and 4B (8:1, and then (40 °C, 7 h, the CO insertion product [Ir4(CO8{C(OCH3}(mu4-eta³-Ph2PCCPh(mu-PPh2], 5. The molecular structure of 5, established by an X-ray analysis, is similar to that of 2, except for the acyl group that remains bound to the same Ir atom. The process is reversible at both stages. Treatment of 2 with PPh3 and P(OMe3 affords the CO substitution products [Ir4(CO7L(CH3(mu4-eta³-Ph2PCCPh(mu-PPh2] (L = PPh3, 6 and P(OMe3, 7, instead of the expected CO inserted products. According to the ¹H and 31P{¹H} NMR studies, the PPh3 derivative 6 exists in the form of two isomers (1:1 that differ with respect to the position of this ligand.

  9. Substitution and Redox Chemistry of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)].

    Science.gov (United States)

    Prokopuk, Nicholas; Kennedy, Vance O.; Stern, Charlotte L.; Shriver, Duward F.

    1998-09-21

    Two sequential electrochemical reductions occur for the cluster anion [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) at 0.89 and 0.29 V vs Ag/AgCl, with the generation [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) and [Ta(6)Cl(12)(OSO(2)CF(3))(6)](4)(-). Chemical reduction of [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) by ferrocene produces [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) with the concomitant shift of the nu(SO(2)) stretch from 1002 to 1018 cm(-)(1). Reaction of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)] (1) with [Bu(4)N]X (X = Cl, Br, I, NCS) occurs by reduction and substitution, yielding [Bu(4)N](3)[Ta(6)Cl(12)X(6)], where the clusters with X = Br, I, and NCS are new. Spectroscopic (IR and UV-vis) evidence indicates that the reduced cluster core {Ta(6)Cl(12)}(2+) is produced in reaction mixtures of 1 with the halide and pseudohalide ions. Concomitant substitution of the triflate ligands of 1 by X(-) occurs and the rates for the overall reduction and substitution increase in the order X(-) = Cl(-) < Br(-) < NCS(-) < I(-) < CN(-). Reduction of 1 with ferrocene followed by addition of [Bu(4)N]O(2)CCH(3) produces the new cluster [Ta(6)Cl(12)(O(2)CCH(3))(6)](3)(-) isolated as the tetrabutylammonium salt. Cyclic voltammetry and UV-vis spectroscopy on the new clusters [Bu(4)N](3)[Ta(6)Cl(12)X(6)] (X = Br, I, NCS, and O(2)CCH(3)) are reported. Crystal data for [Bu(4)N](3)[Ta(6)Cl(12)(NCS)(6)].CH(2)Cl(2): monoclinic, space group, P2(1)/c (No. 14); a = 25.855(6) Å, b = 21.843(6) Å, c = 16.423(3) Å; beta = 100.03(2) degrees; V = 9133(3) Å(3); Z = 4.

  10. High stability of the goldalloy fullerenes: A density functional theory investigation of M12@Au20 (M = Na, Al, Ag, Sc, Y, La, Lu, and Au) clusters

    International Nuclear Information System (INIS)

    Zhang Meng; Feng Xiao-Juan; Zhao Li-Xia; Zhang Hong-Yu; Luo You-Hua

    2012-01-01

    Discovering highly stable metal fullerenes such as the celebrated C 60 is interesting in cluster science as they have potential applications as building blocks in new nanostructures. We here investigated the structural and electronic properties of the fullerenes M 12 @Au 20 (M = Na, Al, Ag, Sc, Y, La, Lu, and Au), using a first-principles investigation with the density functional theory. It is found that these compound clusters possess a similar cage structure to the icosahedral Au 32 fullerene. La 12 @Au 20 is found to be particularly stable among these clusters. The binding energy of La 12 @Au 20 is 3.43 eV per atom, 1.05 eV larger than that in Au 32 . The highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap of La 12 @Au 20 is only 0.31 eV, suggesting that it should be relatively chemically reactive. (condensed matter: structural, mechanical, and thermal properties)

  11. Origin of the p-type character of AuCl3 functionalized carbon nanotubes

    KAUST Repository

    Murat, Altynbek

    2014-02-13

    The microscopic origin of the p-type character of AuCl3 functionalized carbon nanotubes (CNTs) is investigated using first-principles self-interaction corrected density functional theory (DFT). Recent DFT calculations suggest that the p-type character of AuCl3 functionalized CNTs is due to the Cl atoms adsorbed on the CNTs. We test this hypothesis and show that adsorbed Cl atoms only lead to a p-type character for very specific concentrations and arrangements of the Cl atoms, which furthermore are not the lowest energy configurations. We therefore investigate alternative mechanisms and conclude that the p-type character is due to the adsorption of AuCl4 molecules. The unraveling of the exact nature of the p-doping adsorbates is a key step for further development of AuCl3 functionalized CNTs in water sensor applications. © 2014 American Chemical Society.

  12. Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyltrimethylsilane and triphenylphosphine

    Directory of Open Access Journals (Sweden)

    Fei Wang

    2014-02-01

    Full Text Available Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods.Results: The combination of (chlorodifluoromethyltrimethylsilane (TMSCF2Cl and triphenylphosphine (PPh3 can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyltrimethylsilane (TMSCF2Br and (trifluoromethyltrimethylsilane (TMSCF3 in this reaction.Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.

  13. Electronic and vibrational signatures of the Au102(p-MBA)44 cluster.

    Science.gov (United States)

    Hulkko, Eero; Lopez-Acevedo, Olga; Koivisto, Jaakko; Levi-Kalisman, Yael; Kornberg, Roger D; Pettersson, Mika; Häkkinen, Hannu

    2011-03-23

    Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations for a model cluster Au(102)(SMe)(44) based on the time-dependent density functional theory in the linear-response regime and using the known structure of Au(102)(p-MBA)(44). The measured and calculated molar absorption coefficients in the NIR-vis region are comparable, within a factor of 2, in the absolute scale. Several characteristic features are observed in the absorption in the range of 1.5-3.5 eV. The onset of the electronic transitions in the mid-IR region is experimentally observed at 0.45 ± 0.05 eV which compares well with the lowest calculated transition at 0.55 eV. Vibrations in the ligand layer give rise to fingerprint IR features below the onset of low-energy metal-to-metal electronic transitions. Partial exchange of the p-MBA ligand to glutathione does not affect the onset of the electronic transitions, which indicates that the metal core of the cluster is not affected by the ligand exchange. The full spectroscopic characterization of the Au(102)(p-MBA)(44) reported here for the first time gives benchmarks for further studies of manipulation and functionalization of this nanocluster to various applications.

  14. A study on the redox, spectroscopic, and photophysical characteristics of a series of octahedral hexamolybdenum(ii) clusters: [{Mo6X8}Y6]2- (X, Y = Cl, Br, or I).

    Science.gov (United States)

    Akagi, Soichiro; Fujii, Sho; Kitamura, Noboru

    2018-01-23

    We report a systematic study on the redox, spectroscopic, and photophysical properties of a series of [{Mo 6 X 8 }Y 6 ] 2- (X, Y = Cl, Br, or I. 1-9). All of the [{Mo 6 X 8 }Y 6 ] 2- clusters show intense and long-lived phosphorescence in both CH 3 CN and crystalline phases at 298 K. We found that the emission quantum yields (Φ em ) of 1-9 increase in the sequences X = Cl Br Br Br < Cl for given {Mo 6 X 8 } 4+ -core clusters. The present data demonstrate that arbitrary combinations of X and Y in [{Mo 6 X 8 }Y 6 ] 2- could tune τ em and Φ em in the ranges of 85-300 μs and 0.09-0.47, respectively. Both capping (X) and terminal ligand (Y) effects on the photophysical properties of the clusters are discussed on the basis of the energy gap (i.e., emission energy) dependence of the nonradiative decay rate constant.

  15. An alkaline tin(II) halide compound Na{sub 3}Sn{sub 2}F{sub 6}Cl: Synthesis, structure, and characterization

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Pifu [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Luo, Siyang [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Huang, Qian; Yang, Yi [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Jiang, Xingxing [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Liang, Fei [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Chen, Chuangtian [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Lin, Zheshuai, E-mail: zslin@mail.ipc.ac.cn [Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China)

    2017-04-15

    A new alkali tin(II) halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. This compound crystallizes trigonally in space group of R-3c (167), and processes a zero-dimensional (0D) structure consisted of Na{sup +} cations, Cl{sup −} anions and the isolated [SnF{sub 3}]{sup -} trigonal pyramids in which the stereochemically active 5s{sup 2} lone pair electrons are attached to the Sn{sup 2+} cations. Interestingly, the [SnF{sub 3}]{sup −} trigonal pyramids are parallel arranged in the a-b plane, while oppositely arranged in line with rotation along the c- axis. Moreover, the energy bandgap, thermal stability and electronic structure of Na{sub 3}Sn{sub 2}F{sub 6}Cl are characterized and the results reveal that this compound has and indirect bandgap of 3.88 eV and is stable under 270 °C. - Graphical abstract: A zero-dimensional alkaline tin halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. Interestingly, both the anions and cations coordinating polyhedra exhibit order arranged with the [SnF{sub 3}]{sup -} trigonal pyramids rotating along the c- axis.

  16. A density functional theory study on structures, stabilities, and electronic and magnetic properties of Au{sub n}C (n = 1–9) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Xiao-Fei; Yan, Li-Li; Huang, Teng; Hong, Yu; Miao, Shou-Kui [Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics & Fine Mechanics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Peng, Xiu-Qiu [School of Environmental Science & Optoelectronic Technology, University of Science and Technology of China, Hefei, Anhui 230026 (China); Liu, Yi-Rong, E-mail: liuyirong@aiofm.ac.cn [Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics & Fine Mechanics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); Huang, Wei, E-mail: huangwei6@ustc.edu.cn [Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics & Fine Mechanics, Chinese Academy of Sciences, Hefei, Anhui 230031 (China); School of Environmental Science & Optoelectronic Technology, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2016-06-15

    The equilibrium geometric structures, relative stabilities, electronic stabilities, and electronic and magnetic properties of the Au{sub n}C and Au{sub n+1} (n = 1–9) clusters are systematically investigated using density functional theory (DFT) with hyper-generalized gradient approximation (GGA). The optimized geometries show that one Au atom added to the Au{sub n−1}C cluster is the dominant growth pattern for the Au{sub n}C clusters. In contrast to the pure gold clusters, the Au{sub n}C clusters are most stable in a quasi-planar or three-dimensional (3D) structure because the C dopant induces the local non-planarity, with exceptions of the Au{sub 6,8}C clusters who have 2D structures. The analysis of the relative and electronic stabilities reveals that the Au{sub 4}C and Au{sub 6} clusters are the most stable in the series of studied clusters, respectively. In addition, a natural bond orbital (NBO) analysis shows that the charges in the Au{sub n}C clusters transfer from the Au{sub n} host to the C atom. Moreover, the Au and C atoms interact with each other mostly via covalent bond rather than ionic bond, which can be confirmed through the average ionic character of the Au–C bond. Meanwhile, the charges mainly transfer between 2s and 2p orbitals within the C atom, and among 5d, 6s, and 6p orbitals within the Au atom for the Au{sub n}C clusters. As for the magnetic properties of the Au{sub n}C clusters, the total magnetic moments are 1 μ{sub B} for n = odd clusters, with the total magnetic moments mainly locating on the C atoms for Au{sub 1,3,9}C and on the Au{sub n} host for Au{sub 5,7}C clusters. However, the total magnetic moments of the Au{sub n}C clusters are zero for n = even clusters. Simultaneously, the magnetic moments mainly locate on the 2p orbital within the C atom and on the 5d, 6s orbitals within the Au atom.

  17. Optical contrast spectra studies for determining thickness of stage-1 graphene-FeCl{sub 3} intercalation compounds

    Energy Technology Data Exchange (ETDEWEB)

    Han, Wen-Peng, E-mail: han-wenpeng@163.com, E-mail: yunze.long@163.com; Yan, Xu; Zhao, Hui [College of Physics, Qingdao University, Qingdao 266071 (China); Li, Qiao-Qiao; Lu, Yan [State Key Laboratory for Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083 (China); Long, Yun-Ze, E-mail: han-wenpeng@163.com, E-mail: yunze.long@163.com [College of Physics, Qingdao University, Qingdao 266071 (China); Collaborative Innovation Center for Low-Dimensional Nanomaterials and Optoelectronic Devices, Qingdao University, Qingdao 266071 (China)

    2016-07-15

    Because of novel features in their structural, electronic, magnetic and optical properties, especially potential applications in nanoelectronics, the few-layer graphene intercalation compounds (FLGICs) have been intensively studied recently. In this work, the dielectric constant of the doped graphene of stage-1 FeCl{sub 3}-GIC is obtained by fitting the optical contrast spectra. And fully intercalated stage-1 FeCl{sub 3}-FLGICs were prepared by micromechanical cleavage method from graphite intercalation compounds (GICs) for the first time. Finally, we demonstrated that the thickness of stage-1 FeCl{sub 3}-GICs by micromechanical cleavage can be determined by optical contrast spectra. This method also can be used to other FLGICs, such as SbCl{sub 5}-FLGICs and AuCl{sub 5}-FLGICs, etc.

  18. Group IB Organometallic Chemistry XXXIII: ArAuPPh3, ArAu(CNR), (ArAu)n and Ar4Cu2Au2 compounds in which the aryl group contains 2-MeO, 2,6-(MeO)2, 2-Me2N, 2-Me2NCH2 and (S)- or (R)-2-Me2NCHMe substituents as potential ligands

    NARCIS (Netherlands)

    Koten, G. van; Schaap, C.A.; Jastrzebski, J.T.B.H.; Noltes, J.G.

    1980-01-01

    The synthesis and structural characterization by }1{H NMR and }1{}9{}7{Au Mossbauer spectroscopy as well as by chiral labelling of the built-in ligands of three different types of arylgold(I) compounds is described.}1{}9{}7{Au Mossbauer data revealed that the benzyl- and arylgold(I)

  19. Triangular Zn{sub 3} and Ga{sub 3} units in Sr{sub 2}Au{sub 6}Zn{sub 3}, Eu{sub 2}Au{sub 6}Zn{sub 3}, Sr{sub 2}Au{sub 6}Ga{sub 3}, and Eu{sub 2}Au{sub 6}Ga{sub 3}. Structure, magnetism, {sup 151}Eu Moessbauer and {sup 69;71}Ga solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gerke, Birgit; Niehaus, Oliver; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Korthaus, Alexander; Haarmann, Frank [RWTH Aachen Univ. (Germany). Inst. fuer Anorganische Chemie

    2016-08-01

    The gold-rich intermetallic compounds Sr{sub 2}Au{sub 6}Zn{sub 3}, Eu{sub 2}Au{sub 6}Zn{sub 3}, Sr{sub 2}Au{sub 6}Ga{sub 3}, and Eu{sub 2}Au{sub 6}Ga{sub 3} were synthesized from the elements in sealed tantalum ampoules in induction or muffle furnaces. The europium compounds are reported for the first time and their structures were refined from single crystal X-ray diffractometer data: Sr{sub 2}Au{sub 6}Zn{sub 3} type, R anti 3c, a = 837.7(1), c = 2184.5(4) pm, wR2 = 0.0293, 572 F{sup 2} values for Eu{sub 2}Au{sub 6.04}Zn{sub 2.96} and a = 838.1(2), c = 2191.7(5) pm, wR2 = 0.0443, 513 F{sup 2} values for Eu{sub 2}Au{sub 6.07}Ga{sub 2.93} with 20 variables per refinement. The structures consist of a three-dimensional gold network with a 6R stacking sequence, similar to the respective diamond polytype. The cavities of the network are filled in a ratio of 2:1 by strontium (europium) atoms and Ga{sub 3} (Zn{sub 3}) triangles in an ordered manner. Sr{sub 2}Au{sub 6}Zn{sub 3} and Sr{sub 2}Au{sub 6}Ga{sub 3} are diamagnetic with room temperature susceptibilities of -3.5 x 10{sup -4} emu mol{sup -1}. Temperature dependent susceptibility and {sup 151}Eu Moessbauer spectroscopic measurements show a stable divalent ground state for both europium compounds. Eu{sub 2}Au{sub 6}Zn{sub 3} and Eu{sub 2}Au{sub 6}Ga{sub 3} order antiferromagnetically below Neel temperatures of 16.3 and 12.1 K, respectively. Anisotropic electrical conductivity of Sr{sub 2}Au{sub 6}Ga{sub 3} is proven by an alignment of the crystallites in the magnetic field. Orientation-dependent {sup 69;71}Ga NMR experiments combined with quantum mechanical calculations (QM) give evidence for a highly anisotropic charge distribution of the Ga atoms.

  20. Mechanism of H2O-Induced Conductance Changes in AuCl4-Functionalized CNTs

    KAUST Repository

    Murat, Altynbek

    2015-04-30

    We employ ab initio self-interaction corrected density functional theory combined with the nonequilibrium Green\\'s function method to study the electronic and quantum transport properties of carbon nanotubes (CNTs) functionalized with AuCl4 molecules. In particular, we investigate the electronic structure and characterize the conductance for different concentrations and configurations of randomly distributed AuCl4 molecules with and without the adsorption of H2O. We thus propose a mechanism that explains the origin of the recently observed resistivity changes of AuCl4-functionalized CNTs upon H2O adsorption. We find that water adsorption shifts the highest occupied Cl and Au states down in energy and thereby reduces the scattering of the electrons around the Fermi energy, hence enhancing the conductivity. Our results help in the development of highly sensitive nanoscale H2O vapor sensors based on AuCl4-functionalized CNTs. © 2015 American Chemical Society.

  1. Magnetic Properties of the S=2 Heisenberg Antiferromagnetic Chain Compound MnCl3(bpy)

    International Nuclear Information System (INIS)

    Hagiwara, M; Idutsu, Y; Honda, Z; Yamamoto, S

    2012-01-01

    We report the results of magnetic susceptibilities at temperatures between 2 and 300 K, and magnetization in magnetic fields of up to 52 T on polycrystalline samples of MnCl 3 (bpy) (bpy=2, 2'-bipyridine) and the comparison with numerical calculations. This compound is one of the rare examples of the spin 2 quasi-one-dimensional Heisenberg antiferromagnet, and the magnetic properties of tiny single crystal samples were reported previously. The temperature dependence of magnetic susceptibility and the magnetization curve after subtracting the contribution of magnetic impurity are well fitted to those calculated by a quantum Monte Carlo method with the intrachain exchange constant J/k B =31.2 K and the g-value g=2.02 which are comparable to reported values (J/k B =34.8±1.6 K and g=2.04±0.04).

  2. The Elusive Palladium-Diazo Adduct Captured: Synthesis, Isolation and Structural Characterization of [(ArNHC-PPh2 )Pd(η2 -N2 C(Ph)CO2 Et)].

    Science.gov (United States)

    Rull, Silvia G; Álvarez, Eleuterio; Fructos, Manuel R; Belderrain, Tomás R; Pérez, Pedro J

    2017-06-07

    The first example of a diazo palladium adduct is reported. The complexes [(ArNHC-PPh 2 )M(η 2 -N 2 C(Ph)CO 2 Et)] (M=Ni, 3; M=Pd, 4; ArNHC-PPh 2 =3-(2,6-diisopropylphenyl)-1-[(diphenylphosphino)ethyl]imidazol-2-ylidene) were prepared by ligand exchange with styrene-coordinated precursors [(ArNHC-PPh 2 )M(styrene)] (M=Ni, 1; M=Pd, 2). Complex 4 was fully characterized, including X-ray analyses; this constitutes the first example of a diazo adduct compound with palladium, thereby closing the gap between Groups 8 and 10 regarding this type of compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

    Science.gov (United States)

    Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

    2004-09-07

    The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

  4. Formation of methane versus benzene in the reactions of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) yielding thorium-carbene or thorium-ylide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Rungthanaphatsophon, Pokpong; Behrle, Andrew C.; Barnes, Charles L.; Walensky, Justin R. [Department of Chemistry, University of Missouri, Columbia, MO (United States); Bathelier, Adrien; Castro, Ludovic; Maron, Laurent [Toulouse Univ. and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO (France)

    2017-10-09

    The reaction of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with the phosphonium salts [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C{sub 5}Me{sub 5}){sub 2}Th[CHPPh{sub 3}]X, rare terminal phosphorano-stabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds (∼2.30 Aa) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C{sub 5}Me{sub 5}){sub 2}Th[κ{sup 2}-(C,C{sup '})-(CH{sub 2})(CH{sub 2})PPh{sub 2}]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH{sub 3}PPh{sub 3}]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Bis(2,6-dimethylpyridine-κNgold(I tetrachloridoaurate(III

    Directory of Open Access Journals (Sweden)

    Hamid Reza Khavasi

    2008-10-01

    Full Text Available In the cation of the title compound, [Au(C7H9N2][AuCl4], the AuI atom is two-coordinated in a linear arrangement by two N atoms from two 2,6-dimethylpyridine ligands. In the anion, the AuIII atom has a virtually square-planar coordination geometry. The Au atoms both are located on centers of inversion. The crystal structure involves intermolecular C—H...Cl hydrogen bonds.

  6. Infrared investigation of the phonon spectrum in the frustrated spin cluster compound FeTe{sub 2}O{sub 5}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Pfuner, F; Degiorgi, L [Laboratorium fuer Festkoerperphysik, ETH Zuerich, CH-8093 Zuerich (Switzerland); Berger, H; Forro, L [Institut de Physique de la Matiere Complexe (IPMC), EPF Lausanne, CH-1015 Lausanne (Switzerland)

    2009-09-16

    We present our optical investigations on the frustrated spin cluster compound FeTe{sub 2}O{sub 5}Cl, which develops a long-range antiferromagnetic order below 10 K. We measure the optical reflectivity from the far-infrared to the ultraviolet with polarized light. We focus our attention on the lattice dynamics by discussing the infrared-active modes. Our findings reveal a polarization dependence of the vibrational modes but which do not seem to be affected by structural anomalies linked to the magnetically ordered state at low temperatures.

  7. Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4

    International Nuclear Information System (INIS)

    Fucugauchi, L.A.; Millan, S.; Mondragon, A.; Solache-Rios, M.

    1994-01-01

    The chemical effects of 98 Mo(n, γ) 99 Mo reaction on molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical applications in the enrichment of 99 Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo 6 Cl 8 )Cl 4 ] appears to offer good prospects. (author) 14 refs.; 2 figs

  8. Synthesis and stability of monolayer-protected Au38 clusters

    NARCIS (Netherlands)

    Toikkanen, O.; Ruiz, V.; Rönnholm, G.; Kalkkinen, N.; Liljeroth, P.W.; Quinn, B.M.

    2008-01-01

    A synthesis strategy to obtain monodisperse hexanethiolate-protected Au38 clusters based on their resistance to etching upon exposure to a hyperexcess of thiol is reported. The reduction time in the standard Brust−Schiffrin two-phase synthesis was optimized such that Au38 were the only clusters that

  9. Long-term adaptation of methanol-fed thermophilic (55°C) sulfate-reducing reactors to NaCl

    NARCIS (Netherlands)

    Vallero, M.V.G.; Lettinga, G.; Lens, P.N.L.

    2003-01-01

    A laboratory-scale upflow anaerobic sludge bed (UASB) reactor was operated during 273 days at increasing NaCl concentrations (0.5-12.5 g NaCl l(-1)) to assess whether the stepwise addition of the salt NaCl results in the acclimation of that sludge. The 6.5-1 thermophilic (55 degreesC), sulfidogenic

  10. Synthesis and characterization of several molybdenum chloride cluster compounds

    Energy Technology Data Exchange (ETDEWEB)

    Beers, W.W.

    1983-06-01

    Investigation into the direct synthesis of Mo/sub 4/Cl/sub 8/(P(C/sub 2/H/sub 5/)/sub 3/)/sub 4/ from Mo/sub 2/(OAc)/sub 4/ led to a synthetic procedure that produces yields greater than 80%. The single-crystal structure disclosed a planar rectangular cluster of molybdenum atoms. Metal-metal bond distances suggest that the long edges of the rectangular cluster should be considered to be single bonds and the short metal-metal bonds to be triple bonds. This view is reinforced by an extended Hueckel calculation. Attempts to add a metal atom to Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ to form Mo/sub 5/Cl/sub 10/(PR/sub 3/)/sub 3/ led instead to a compound with the composition Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/. Solution and reflectance uv-visible spectra and x-ray photoelectron spectra suggest that tetranuclear molybdenum units are present. The facile reaction between Mo/sub 8/Cl/sub 16/(PR/sub 3/)/sub 4/ and PR/sub 3/ imply that the linkage between tetrameric units is weak.

  11. Substrate-dependent Au{sub x} cluster: A new insight into Au{sub x}/CeO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Kong-Jie; Yang, Yan-Ju [School of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Lang, Jia-Jian [School of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Engineering Laboratory of Specialty Fibers and Nuclear Energy Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); Teng, Bo-Tao, E-mail: tbt@zjnu.cn [School of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Wu, Feng-Min [School of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004 (China); Du, Shi-Yu [Engineering Laboratory of Specialty Fibers and Nuclear Energy Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); Wen, Xiao-Dong, E-mail: wxd@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China)

    2016-11-30

    Graphical abstract: 2D Au{sub x} (x < 10) on CeO{sub 2}(110) are more stable than 3D ones, while the stability trend changes for x ≥ 10; Au{sub x} (x ≤ 4) prefer to monatomically disperse on CeO{sub 2}(100) and aggregate to 3D clusters for x > 4. - Highlights: • The stable structures of Au{sub x}/CeO{sub 2} are dependent of index surfaces of CeO{sub 2}. • Au{sub x} prefers to monatomically disperse on CeO{sub 2}(100) at low coverage. • Au{sub x} aggregates to 3D clusters on CeO{sub 2}(100) at high coverage. • 2D Au{sub x} (x < 10) are more stable than the 3D ones on CeO{sub 2}(110). • The effects on the stability of Au{sub x}/CeO{sub 2} are systematically discussed. - Abstract: To theoretically study the structures of metal clusters on oxides is very important and becomes one of the most challenging works in computational heterogeneous catalysis since many factors affect their structures and lead to various possibilities. In this work, it is very interesting to find that the stable structures and stability evolution of Au{sub x} clusters on ceria are varied with different index surfaces of CeO{sub 2}. The corresponding reasons in chemical, geometric and electronic properties are systematically explored. Au{sub x} (x = 1–4) clusters prefer to separately disperse at the O-O bridge sites on CeO{sub 2}(100) due to the low coordination number of surface O; while aggregate due to the strong Au–Au attractions when x is larger than 4. Owing to the uniform distribution of O-O bridge sites on CeO{sub 2}(111) and (100), the most stable configurations of Au{sub x} are 3D structures with bottom atoms more than top ones when x is larger than 4. However, 2D configurations of Au{sub x}/CeO{sub 2}(110) (x < 10) are more stable than the corresponding 3D structures due to the particular O-O arrangement on CeO{sub 2}(110). 3D Au{sub x} clusters across O-O-Y lines are suggested as the most stable configurations for Au{sub x}/CeO{sub 2}(110) (x ≥ 10). The present

  12. Local 3d Electronic Structures of Co-Based Complexes with Medicinal Molecules Probed by Soft X-ray Absorption

    Science.gov (United States)

    Yamagami, Kohei; Fujiwara, Hidenori; Imada, Shin; Kadono, Toshiharu; Yamanaka, Keisuke; Muro, Takayuki; Tanaka, Arata; Itai, Takuma; Yoshinari, Nobuto; Konno, Takumi; Sekiyama, Akira

    2017-07-01

    We have examined the local 3d electronic structures of Co-Au multinuclear complexes with the medicinal molecules d-penicillaminate (d-pen) [Co{Au(PPh3)(d-pen)}2]ClO4 and [Co3{Au3(tdme)(d-pen)3}2] by Co L2,3-edge soft X-ray absorption (XAS) spectroscopy, where PPh3 denotes triphenylphosphine and tdme stands for 1,1,1-tris[(diphenylphosphino)methyl]ethane. The Co L2,3-edge XAS spectra indicate the localized ionic 3d electronic states in both materials. The experimental spectra are well explained by spectral simulation for a localized Co ion under ligand fields with the full multiplet theory, which verifies that the ions are in the low-spin Co3+ state in the former compound and in the high-spin Co2+ state in the latter.

  13. The influence of internal degrees of freedom on the unimolecular decay of the molecule-cluster compound Au8+CH3OH

    Science.gov (United States)

    Vogel, M.; Hansen, K.; Herlert, A.; Schweikhard, L.; Walther, C.

    2002-06-01

    Time-resolved photodissociation measurements of the sequential reaction Au8+CH3OH→Au8+→Au7+ and the direct reaction Au8+→Au7+ have been performed for several excitation energies. The production rates and yields of the final state Au7+ in the sequential process are strongly influenced by the excitation energy deposited into the evaporated methanol molecule during the initial fragmentation step. Both the rate constants and yields can be fitted with a single parameter, the cluster-methanol binding energy.

  14. Systematic Study of Au6 to Au12 Gold Clusters on MgO(100) F Centers Using Density-Functional Theory

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Hammer, Bjørk

    2012-01-01

    We present an optimized genetic algorithm used in conjunction with density-functional theory in the search for stable gold clusters and O2 adsorption ensembles in F centers at MgO(100). For Au8 the method recovers known structures and identifies several more stable ones. When O2 adsorption...

  15. Reaction of ReH sub 7 (PPh sub 3 ) sub 2 with silanes: Preparation and characterization of the first silyl polyhydride complexes, ReH sub 6 (SiR sub 3 )(PPh sub 3 ) sub 2 (SiR sub 3 = SiPh sub 3 , SiEt sub 3 , SiHEt sub 2 )

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Xiaoliang; Baudry, D.; Boydell, P.; Charpin, P.; Nierlich, M.; Ephritikhine, M.; Crabtree, R.H. (Yale Univ., New Haven, CT (USA) CEA-CEN Saclay, Gif-sur-Yvette (France))

    1990-04-18

    Reaction of silanes with ReH{sub 7}(PPh{sub 3}){sub 2} (1) gives the novel rhenium silyl hexahydride complexes ReH{sub 6}(SiR{sub 3})(PPh{sub 3}){sub 2} (SiR{sub 3} = SiPh{sub 3} (2a), SiEt{sub 3} (2b), SiHEt{sub 2} (2c)), which have been fully characterized by IR and {sup 1}H, {sup 31}P, and {sup 13}C NMR spectroscopy and, in the case of 2a, by single-crystal x-ray crystallography. The spectroscopic and x-ray diffraction data suggest that 2a-c probably have a classical nine-coordinate tricapped trigonal-prismatic structure with the two phosphine ligands and the silyl group occupying the three equatorial sites and the six hydride ligands occupying the six axial positions. 2a has been obtained in two crystalline forms, one solvated (CH{sub 2}Cl{sub 2}) and the other unsolvated, and structures were determined on both. The crystal structures of crystals of unsolvated 2a and 2a {times} CH{sub 2} Cl{sub 2} are reported. The Re-Si bond lengths, 2.474 (4) {angstrom} (2a) and 2.475 (4) {angstrom} (2a {times} CH{sub 2}Cl{sub 2}), are shorter than the sum of the covalent radii of the Re and Si atoms (2.65 {angstrom}), which is unusual for a transition-metal silyl complex with a formal d{sup 0} configuration. 35 refs., 2 figs., 4 tabs.

  16. Synthesis and Structural Characterization of [Ir4(m-CO(CO7{m4-h3-Ph2PC(HC(PhPCBut}(m-PPh2]: Alkyne-Phosphaalkyne Coupling and Formation of a Novel 2-phosphabutadienylphosphine Ligand

    Directory of Open Access Journals (Sweden)

    Araujo Maria Helena

    1998-01-01

    Full Text Available Reaction of [Ir4(mu-H(CO9(Ph2PCºCPh(mu-PPh2] 1 with PºCBu t in CH2Cl2, at 35 °C, for 4 h yields the novel compound [Ir4(mu-CO(CO7{mu4-eta³-Ph2PC(HC(PhPCBu t}(mu-PPh2] 2, which contains the 2-phosphabutadienylphosphine chain. Compound 2 is also formed upon thermolysis of [Ir4(CO10(Ph2PCºCPh(PPh2H] 3 in the presence of PºCBu t in thf, at 40 °C, for 48 h. Small amounts of [Ir4(mu-CO(CO7(mu3-eta²-HCCPh(mu-PPh22] 4 are always obtained from both reactions, because of the competing rates of the transformations of 1 and 3 into 4 and of their reactions with PºCBu t. Compound 2 was characterized by analytical and spectroscopic studies such as FAB ms, ¹H, 31P,13C, 2D31P-¹H HETCOR, nOe difference and DEPT NMR experiments, which led to its formulation and established the coupling between the coordinated Ph2PCºCPh and PºCBu t and the migration of the hydride to the Calpha of the Ph2PCºCPh ligand. However, it was impossible to establish unambiguously if cleavage of the P-Csp bond of the Ph2PCºCPh ligand had occurred and the mode of interaction of the organophosphorus chain. An X-ray diffraction study of compound 2 established a butterfly arrangement of iridium atoms with the new ligand interacting with the metal framework via four sigma bonds and the PPh2 phosphorus lone pair.

  17. Photodetachment and UV-Vis spectral properties of Cl2rad -·nHO clusters: Extrapolation to bulk

    Science.gov (United States)

    Pathak, A. K.; Mukherjee, T.; Maity, D. K.

    2008-03-01

    Vertical detachment energy (VDE) and UV-Vis spectra of Cl2rad -·nHO clusters ( n = 1-11) are reported based on first principle electronic structure calculations. VDE of the hydrated clusters are calculated following second order Moller-Plesset perturbation (MP2) as well as coupled cluster theory with 6-311++G(d,p) set of basis function. The excess electron in these hydrated clusters is mainly localized over the solute Cl atoms. A linear relationship is obtained for VDE vs. ( n + 2.6) -1/3 and bulk VDE of Cl2rad - aqueous solution is calculated as 10.61 eV at CCSD(T) level of theory. UV-Vis spectra of these hydrated clusters are calculated applying CI with single electron (CIS) excitation procedure. Simulated UV-Vis spectra of Cl2rad -·10HO cluster is noted to be in excellent agreement with the reported spectra of Cl2rad - (aq) system, λmax for Cl2rad -·11HO system is calculated to be red shifted though.

  18. DFT study on stability and H{sub 2} adsorption activity of bimetallic Au{sub 79−n}Pd{sub n} (n = 1–55) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xuejing [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Tian, Dongxu, E-mail: tiandx@dlut.edu.cn [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Meng, Changgong [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

    2013-03-29

    Highlights: ► Stability of Pd substitution type is face > mid-edge > corner > edge. ► H{sub 2} adsorption activity is in contrast with the stability of Pd substitution type. ► Non-activated dissociation of H{sub 2} occurs in Au{sub 36}Pd{sub 43−3} with high thermal stability. ► ε{sub d} agrees with that Pd at edge and corner are more active than face and mid-edge. - Abstract: The stability and H{sub 2} adsorption activity of bimetallic Au{sub 79−n}Pd{sub n} (n = 1–55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H{sub 2} adsorption activity is corner ≈ edge > mid-edge > face. The Au{sub 36}Pd{sub 43} (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H{sub 2} non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ε{sub d} and the adsorption energies, the ε{sub d} order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites.

  19. Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8.

    Science.gov (United States)

    Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Ramello, Stefano; Samaritani, Simona

    2008-02-04

    The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.

  20. Imaging C. elegans with thiolated tryptophan-based NIR fluorescent gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Barman, Apurba Kr. [Indian Institute of Technology Kanpur, Department of Chemistry (India); Chaturbedi, Amaresh; Subramaniam, K. [Indian Institute of Technology Kanpur, Department of Biological Sciences and Bioengineering (India); Verma, Sandeep, E-mail: sverma@iitk.ac.in [Indian Institute of Technology Kanpur, Department of Chemistry (India)

    2013-11-15

    Multidentate, thiolated, tryptophan-containing peptide conjugates were synthesized for the preparation of gold nanoclusters (AuNCs). Precursor Au{sub 11}(PPh{sub 3}){sub 8}Cl{sub 3} was prepared by the reduction of HAuCl{sub 4}, followed by the use of tryptophan-containing peptide conjugates in ligand displacement reactions, to afford near-infrared fluorescent AuNCs. The emission maxima for these newly synthesized AuNCs were ∼715 nm. AuNCs were characterized with the help of UV–Vis, FTIR, fluorescence and MALDI analysis. FTIR spectra showed that the ligands bind to Au atoms through Au–S bonds, while MALDI mass spectra revealed that the clusters consisted of 20–23 Au atoms. Introduction of hydrophilic –COOH groups engendered water solubility to these AuNCs, enabling bioimaging applications. We demonstrate fluorescence imaging of the nematode C. elegans and confirm distribution of these AuNCs in nematode gut with the help of green fluorescent protein co-localization experiments.

  1. Determination of the Np(IV)-Np(III) normal potential in fused LiCl-CsCl (55-45%) by absorption spectrophotometry

    International Nuclear Information System (INIS)

    Lysy, R.; Duyckaerts, G.

    1977-01-01

    The following reaction Np 4+ + 1/2 H 2 + Cl - reversible Np 3+ + HCl has been studied quantitatively in fused LiCl-CsCl (55-45 mol %) in the temperature range of 450-600 0 C, by visible and near IR absorption spectrophotometry. At 450 deg C, the equilibrium constant equals K = 7.4 atmsup(1/2). The mean values of ΔH and ΔS in the temperature range of 450-600 deg C are: ΔH = (35.6+-10.3) kJ mol -1 , ΔS=(65.5+-13.0)J mol -1 K -1 [fr

  2. Atomic characterization of Au clusters in vapor-liquid-solid grown silicon nanowires

    International Nuclear Information System (INIS)

    Chen, Wanghua; Roca i Cabarrocas, Pere; Pareige, Philippe; Castro, Celia; Xu, Tao; Grandidier, Bruno; Stiévenard, Didier

    2015-01-01

    By correlating atom probe tomography with other conventional microscope techniques (scanning electron microscope, scanning transmission electron microscope, and scanning tunneling microscopy), the distribution and composition of Au clusters in individual vapor-liquid-solid grown Si nanowires is investigated. Taking advantage of the characteristics of atom probe tomography, we have developed a sample preparation method by inclining the sample at certain angle to characterize the nanowire sidewall without using focused ion beam. With three-dimensional atomic scale reconstruction, we provide direct evidence of Au clusters tending to remain on the nanowire sidewall rather than being incorporated into the Si nanowires. Based on the composition measurement of Au clusters (28% ± 1%), we have demonstrated the supersaturation of Si atoms in Au clusters, which supports the hypothesis that Au clusters are formed simultaneously during nanowire growth rather than during the cooling process

  3. Atomic characterization of Au clusters in vapor-liquid-solid grown silicon nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wanghua; Roca i Cabarrocas, Pere [Laboratoire de Physique des Interfaces et Couches Minces (LPICM), UMR 7647, CNRS, Ecole Polytechnique, 91128 Palaiseau (France); Pareige, Philippe; Castro, Celia [Groupe de Physique des Matériaux (GPM), Université et INSA de Rouen, UMR 6634, CNRS, Av. de l' Université, BP 12, 76801 Saint Etienne du Rouvray (France); Xu, Tao; Grandidier, Bruno; Stiévenard, Didier [Institut d' Electronique et de Microélectronique et de Nanotechnologies (IEMN), UMR 8520, CNRS, Département ISEN, 41 bd Vauban, 59046 Lille Cedex (France)

    2015-09-14

    By correlating atom probe tomography with other conventional microscope techniques (scanning electron microscope, scanning transmission electron microscope, and scanning tunneling microscopy), the distribution and composition of Au clusters in individual vapor-liquid-solid grown Si nanowires is investigated. Taking advantage of the characteristics of atom probe tomography, we have developed a sample preparation method by inclining the sample at certain angle to characterize the nanowire sidewall without using focused ion beam. With three-dimensional atomic scale reconstruction, we provide direct evidence of Au clusters tending to remain on the nanowire sidewall rather than being incorporated into the Si nanowires. Based on the composition measurement of Au clusters (28% ± 1%), we have demonstrated the supersaturation of Si atoms in Au clusters, which supports the hypothesis that Au clusters are formed simultaneously during nanowire growth rather than during the cooling process.

  4. KONSUMSI PANGAN DAN GIZI SERTA SKOR POLA PANGAN HARAPAN (PPH PADA ANAK USIA SEKOLAH 7—12 TAHUN DI INDONESIA

    Directory of Open Access Journals (Sweden)

    Karina Indah Pertiwi

    2014-11-01

    Full Text Available ABSTRACTThis study was aimed to assess food consumption, nutrient intake, Nutritional Dietary Quality (NDQ, Desirable Dietary Pattern (DDP score, and correlation between DDP score and NDQ in school-age children 7—12 years old. The study was conducted by analyzing food consumption data of Basic Health Research 2010 collected through a 24-hour recall method. Subject obtained was 23,981 children. The results showed that most school-age children consume cereals (99.5% and a few consume oily seeds (1.9%. Most school-age children (more than 50.0% were deficit of energy, fat, carbohydrate, water, vitamin A, vitamin B1, vitamin B9, vitamin C, calcium, phosphor, and zinc. The mean of DDP score was 64.8±14.7. The mean of NDQ was 55.4±15.6. Statistical test results showed medium strong correlation between DDP score and NDQ (r=0.6.Keywords: desirable dietary pattern, food consumption, nutrient intake, school-age childrenABSTRAKPenelitian ini bertujuan untuk menilai konsumsi pangan, asupan gizi, mutu gizi konsumsi pangan (MGP, skor pola pangan harapan (PPH, dan korelasi antara skor PPH dan MGP pada anak usia sekolah 7—12 tahun. Penelitian ini dilakukan dengan menganalisis data konsumsi pangan Riset Kesehatan Dasar (Riskesdas 2010 yang dikumpulkan melalui metode recall 24 jam. Subjek yang didapatkan yaitu 23 981 anak. Hasil penelitian menunjukkan bahwa sebagian besar anak usia sekolah mengonsumsi padi-padian (99.5% dan sebagian kecil mengonsumsi buah/biji berminyak (1.9%. Sebagian besar anak usia sekolah (lebih dari 50.0% mengalami defisit energi, lemak, karbohidrat, air, vitamin A, vitamin B1, vitamin B9, vitamin C, kalsium, fosfor, dan zink. Rata-rata skor PPH anak usia sekolah yaitu 64.8±14.7. Rata-rata MGP anak usia sekolah yaitu 55.4±15.6. Hasil uji statistik menunjukkan korelasi yang cukup kuat antara skor PPH dan MGP (r=0.6.Kata kunci: anak usia sekolah, asupan gizi, konsumsi pangan, pola pangan harapan

  5. THE YOUNG OPEN CLUSTER BERKELEY 55

    Energy Technology Data Exchange (ETDEWEB)

    Negueruela, Ignacio; Marco, Amparo, E-mail: ignacio.negueruela@ua.es, E-mail: amparo.marco@ua.es [Departamento de Fisica, Ingenieria de Sistemas y Teoria de la Senal, Universidad de Alicante, Apdo. 99, E-03080 Alicante (Spain)

    2012-02-15

    We present UBV photometry of the highly reddened and poorly studied open cluster Berkeley 55, revealing an important population of B-type stars and several evolved stars of high luminosity. Intermediate-resolution far-red spectra of several candidate members confirm the presence of one F-type supergiant and six late supergiants or bright giants. The brightest blue stars are mid-B giants. Spectroscopic and photometric analyses indicate an age 50 {+-} 10 Myr. The cluster is located at a distance d Almost-Equal-To 4 kpc, consistent with other tracers of the Perseus Arm in this direction. Berkeley 55 is thus a moderately young open cluster with a sizable population of candidate red (super)giant members, which can provide valuable information about the evolution of intermediate-mass stars.

  6. Determination of {sup 55}Mn(n,γ){sup 56}Mn reaction cross-section at the neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Vansola, Vibha; Mukherjee, Surjit [M.S. University of Baroda, Vadodara (India). Dept. of Physics; Naik, Haladhara [Bhabha Atomic Research Center, Mumbai (India). Radiochemistry Div.; Suryanarayana, Saraswatula Venkata [Bhabha Atomic Research Center, Mumbai (India). Nuclear Physics Div.; Ghosh, Reetuparna; Badwar, Sylvia; Lawriniang, Bioletty Mary [North Eastern Hill Univ., Meghalaya (India). Dept. of Physics; Sheela, Yerraguntla Santhi [Manipal Univ. (India). Dept. of Statistics

    2016-07-01

    The {sup 55}Mn(n,γ){sup 56}Mn reaction cross-sections at the neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV were determined by using activation and off-line γ-ray spectrometric technique. The neutron energies of 1.12 and 2.12 MeV were generated from the {sup 7}Li(p,n) reaction by using the proton energies of 3 and 4 MeV from the folded tandem ion beam accelerator (FOTIA) at BARC. For the neutron energies of 3.12 and 4.12 MeV, the proton energies used were 5 and 6 MeV from the Pelletron facility at TIFR, Mumbai. The {sup 115}In(n,γ){sup 116m}In reaction cross-section was used as the neutron flux monitor. The {sup 55}Mn(n,γ){sup 56}Mn reaction cross-section at the neutron energies of 4.12 MeV are reported for the first time, whereas at 1.12, 2.12 and 3.12 MeV, they are in between the literature data. The {sup 55}Mn(n,γ){sup 56}Mn reaction cross-section was also calculated theoretically by using the computer code TALYS 1.6 and EMPIRE 3.2.2. The experimental data of present work are found to be in between the theoretical values of TALYS and EMPIRE.

  7. Effect of NaCl on thermophilic (55°C) methanol degradation in sulfate reducing granular sludge reactors

    NARCIS (Netherlands)

    Vallero, M.V.G.; Hulshoff Pol, L.W.; Lettinga, G.; Lens, P.N.L.

    2003-01-01

    The effect of NaCl on thermophilic (55degreesC) methanol conversion in the presence of excess of sulfate (COD/SO42-=0.5) was investigated in two 6.5L lab-scale upflow anaerobic sludge bed reactors inoculated with granular sludge previously not adapted to NaCl
    The effect of NaCl on thermophilic

  8. Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

    Science.gov (United States)

    Yao, Hiroshi; Iwatsu, Mana

    2016-04-05

    Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

  9. Carbon nanotubes-supported PtAu-alloy nanoparticles for electro-oxidation of formic acid with remarkable activity

    International Nuclear Information System (INIS)

    Bai Yancui; Zhang Weide; Chen Caihong; Zhang Jiaqi

    2011-01-01

    Research highlights: → Electro-oxidation of HCOOH over PtAu at lower potential, higher peak current. → The stability of the PtAu catalyst is high. → Au in the PtAu catalyst promotes utilization of Pt. - Abstract: PtAu-alloy nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) were successfully prepared by simultaneous reduction of H 2 PtCl 6 .6H 2 O and HAuCl 4 .3H 2 O with sodium borohydride as a reducing reagent and sodium citrate as a stabilizing reagent. The morphology and composition of the composite catalyst were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The results show that the PtAu alloy nanoparticles with an average diameter of about 3.5 nm and narrow size distribution are supported on MWCNTs. Electrocatalytic oxidation of formic acid at the PtAu/MWCNTs nanocomposite electrode was investigated in a solution containing 0.50 M H 2 SO 4 as a supporting electrolyte and 0.50 M formic acid by cyclic voltammogram and chronoamperometry. The results demonstrate that the PtAu/MWCNTs catalyst exhibits higher activity and stability for electro-oxidation of formic acid than the commercial Pt/C catalyst, reflecting by its lower onset potential (-0.05 V), oxidation mainly occurring in low potential range of -0.05 ± 0.65 V and higher peak current density of 3.12 mA cm -2 . The result of CO stripping voltammetry discloses that gold in the PtAu/MWCNTs nanocomposite enhances the catalytic activity and stability.

  10. Elastic properties of distorted triangular lattice KNiCl3-family compounds

    International Nuclear Information System (INIS)

    Nishiwaki, Yoichi; Hasegawa, Takumi; Machida, Kenichi; Takeuchi, Yoshio

    2006-01-01

    In order to discuss the condensation of the K 4 -mode in KNiCl 3 -family compounds, the temperature dependences of the elastic compliances of KNiCl 3 , RbMnBr 3 , RbFeBr 3 , and RbCoBr 3 were measured. In each compound, the temperature dependence of the elastic compliances s 33 showed a sharp discontinuity at the point of structural phase transition from a prototype P6 3 /mmc structure. The structural phase transitions of the KNiCl 3 -family compounds are induced by the condensation of the K 4 -mode at the Brilluoin zone boundary in the P6 3 /mmc structure. When the K 4 -mode is regarded as an order parameter η, the Landau free energy includes coupling term η 2 T 3 , where T 3 is an external stress. The experimental results were interpreted satisfactorily on the basis of a phenomenological Landau theory. (author)

  11. Direct, rapid and convenient synthesis of esters and thioesters using PPh{sub 3}/N-chlorobenzotriazole system

    Energy Technology Data Exchange (ETDEWEB)

    Rouhi-Saadabad, Hamed; Akhlaghinia, Batool, E-mail: akhlaghinia@um.ac.ir [Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad (Iran, Islamic Republic of)

    2014-02-15

    We have developed an efficient method for esterification and thioesterification of various carboxylic acids with different alcohols and thiols using PPh{sub 3}/N-chlorobenzotriazole mixed reagent in CH{sub 2}Cl{sub 2} at room temperature. (author)

  12. Synthesis of the water soluble ligands dmPTA and dmoPTA and the complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (dmPTA = N,N'-Dimethyl-1,3,5-triaza-7-phosphaadamantane, dmoPTA = 3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, HdmoPTA = 3,7-H-3,7-Dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane).

    Science.gov (United States)

    Mena-Cruz, Adrian; Lorenzo-Luis, Pablo; Romerosa, Antonio; Saoud, Mustapha; Serrano-Ruiz, Manuel

    2007-07-23

    The new water-soluble ligand dmPTA(OSO(2)CF(3))(2) (1) (dmPTA = N,N'-dimethyl-1,3,5-triaza-7-phosphaadamantane) has been synthesized by reaction of PTA with MeOSO(2)CF(3) in acetone (PTA = 1,3,5-triaza-7-phosphatricycle[3.3.1.1(3,7)]decane). The reaction of 1 with KOH gave rise to the new water-soluble ligand dmoPTA (3) (dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) by elimination of the -CH(2)- group located between both NCH(3) units. Compound dmPTA(BF(4))(2) (2) and complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (4) have also been synthesized, while compounds HdmoPTA(BF(4)) (3a) and [RuClCp(dmPTA)(PPh(3))](OSO(2)CF(3)) (5) were characterized but not isolated. The new ligands and the complex have been fully characterized by NMR, IR, elemental analysis, and X-ray crystal structure determination (ligand 1 and complex 4). The synthetic processes for 3 and 4 were studied.

  13. Aryldiazo complexes. Syntheses and reactions of new complexes of osmium and ruthenium

    International Nuclear Information System (INIS)

    Haymore, B.L.; Ibers, J.A.

    1975-01-01

    Aryldiazo complexes, [M(CO) 2 (NNPh)(PPh 3 ) 2 ][PF 6 ](M = Os, Ru; Ph = C 6 H 5 ), were prepared by allowing diazonium salts to react with M(CO) 3 (PPh 3 ) 2 . Infrared spectra of the Ru complex suggest the presence of two isomers both in solution and in the solid state. These complexes react with a variety of coordinating anions (X - ), to form MX(CO) 2 (NNPh)(PPh 3 ) 2 . The osmium derivatives have ν(NN) near 1455 cm -1 , which is the lowest value yet reported for a nonbridging aryldiazo ligand. The first aryldiazo--hydrido complexes, MH(CO) 2 (NNPh)(PPh 3 ) 2 and MH(CO)(NNPh)(PPh 3 ) 2 , were prepared by deprotonation of the respective phenyldiazene complexes, MH(CO) 2 (HNNPh)(PPh 3 ) 2 + and MH(CO)(HNNPh)(PPh 3 ) 3 + . The compound OsCl 3 (NNPh)(PPh 3 ) 2 was also prepared. A large number of the foregoing complexes were synthesized with selective 2 H and 15 N labels. Infrared and NMR spectra show MX(CO) 2 (NNPh)(PPh 3 ) 2 and the analogous hydrido complex to be pseudooctahedral with trans phosphine ligands, cis carbonyl ligands, and a doubly bent phenyldiazenido (NNPh - ) ligand. Similarly, MH(CO)(NNPh)(PPh 3 ) 2 possesses a trigonal-bipyramidal geometry with trans phosphine ligands and an equatorial, singly bent phenyldiazoniumato (NNPh + ) ligand. Isotopic substitution of the diazo ligand shows that ν(NN) is often vibrationally coupled with phenyl vibrational modes and that two or three bands sometimes shift upon 15 N substitution. Vibrational coupling was also observed in the higher energy region (1850 to 1900 cm -1 ) in the compound RuCl 3 (NNC 6 D 5 )(PPh 3 ) 2 . The wide range in the values of ν(NN), RuCl 3 (NNPh)(PPh 3 ) 2 (1882 cm -1 ) vs. RuCl(CO) 2 (NNPh)(PPh 3 ) 2 (1462 cm -1 ), indicates that the N--N stretching frequencies are sensitive to the electronic and steric environment of the diazo ligand. The aryldiazo complexes are compared with analogous, isoelectronic nitrosyl complexes of Os and Ru

  14. Adsorption of small NaCl clusters on surfaces of silicon nanostructures

    International Nuclear Information System (INIS)

    Amsler, Maximilian; Alireza Ghasemi, S; Goedecker, Stefan; Neelov, Alexey; Genovese, Luigi

    2009-01-01

    We have studied possible adsorption geometries of neutral NaCl clusters on the disordered surface of a large silicon model tip used in non-contact atomic force microscopy. The minima hopping method was used to determine low energy model tip configurations as well as ground state geometries of isolated NaCl clusters. The combined system was treated with density functional theory. Alkali halides have proven to be strong structure seekers and tend to form highly stable ground state configurations whenever possible. The favored adsorption geometry for four Na and four Cl atoms was found to be an adsorption of four NaCl dimers due to the formation of Cl-Si bonds. However, for larger NaCl clusters, the increasing energy required to dissociate the cluster into NaCl dimers suggests that adsorption of whole clusters in their isolated ground state configuration is preferred.

  15. Magnetic properties of nearly stoichiometric CeAuBi2 heavy fermion compound

    International Nuclear Information System (INIS)

    Adriano, C.; Jesus, C. B. R.; Pagliuso, P. G.; Rosa, P. F. S.; Grant, T.; Fisk, Z.; Garcia, D. J.

    2015-01-01

    Motivated by the interesting magnetic anisotropy found in the heavy fermion family CeTX 2 (T = transition metal and X = pnictogen), here, we study the novel parent compound CeAu 1−x Bi 2−y by combining magnetization, pressure dependent electrical resistivity, and heat-capacity measurements. The magnetic properties of our nearly stoichiometric single crystal sample of CeAu 1−x Bi 2−y (x = 0.92 and y = 1.6) revealed an antiferromagnetic ordering at T N  = 12 K with an easy axis along the c-direction. The field dependent magnetization data at low temperatures reveal the existence of a spin-flop transition when the field is applied along the c-axis (H c  ∼ 7.5 T and T = 5 K). The heat capacity and pressure dependent resistivity data suggest that CeAu 0.92 Bi 1.6 exhibits a weak heavy fermion behavior with strongly localized Ce 3+ 4f electrons. Furthermore, the systematic analysis using a mean field model including anisotropic nearest-neighbors interactions and the tetragonal crystalline electric field (CEF) Hamiltonian allows us to extract a CEF scheme and two different values for the anisotropic J RKKY exchange parameters between the Ce 3+ ions in this compound. Thus, we discuss a scenario, considering both the anisotropic magnetic interactions and the tetragonal CEF effects, in the CeAu 1−x Bi 2−y compounds, and we compare our results with the isostructural compound CeCuBi 2

  16. Quantum chemical study of the interaction of elemental Hg with small neutral, anionic and cationic Aun (n = 1–6) clusters

    International Nuclear Information System (INIS)

    Siddiqui, Shamoon Ahmad; Bouarissa, Nadir; Rasheed, Tabish; Al-Assiri, M.S.

    2013-01-01

    Graphical abstract: Binding energies as a function of cluster size for Au n Hg, Au n Hg + and Au n Hg − complexes. Highlights: ► Hg adsorption of neutral and charged Au n (n = 1–6) clusters has been discussed. ► Size and charged state of cluster significantly affect the Hg adsorption. ► Transfer of electron mainly found from s orbital of Hg to s orbital of Au. - Abstract: Adsorption of elemental mercury (Hg) on small neutral, cationic and anionic gold clusters (Au n , n = 1–6) has been studied by using the density functional theory (DFT). Results of this investigation show that frontier molecular orbital theory is a useful tool to predict the selectivity of Hg adsorption. It is found that adsorption of Hg on neutral, cationic and anionic Au n (n = 1–6) clusters are thermodynamically favorable. The binding energies of Hg on the cationic Au n clusters are greater than those on the neutral and anionic clusters. Natural bond orbital (NBO) analysis indicates that the flow of electrons in the neutral and charged clusters is mainly due to the s orbitals of Hg and Au. Results of NBO analysis also indicate that the binding energy of Hg with Au n clusters is directly proportional to the charge transfer, i.e. greater is the charge transfer, higher is the binding energy

  17. Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

    Science.gov (United States)

    Uruş, Serhan

    2016-12-15

    The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Point-Defect Mediated Bonding of Pt Clusters on (5,5) Carbon Nanotubes

    DEFF Research Database (Denmark)

    Wang, J. G.; Lv, Y. A.; Li, X. N.

    2009-01-01

    The adhesion of various sizes of Pt clusters on the metallic (5,5) carbon nanotubes (CNTs) with and without the point defect has been investigated by means of density functional theory (DFT). The calculations show that the binding energies of Pt-n (n = 1-6) clusters on the defect free CNTs are mo...

  19. Further Insight into the Lability of MeCN Ligands of Cytotoxic Cycloruthenated Compounds: Evidence for the Antisymbiotic Effect Trans to the Carbon Atom at the Ru Center.

    Science.gov (United States)

    Barbosa, Ana Soraya Lima; Werlé, Christophe; Colunga, Claudia Olivia Oliva; Rodríguez, Cecilia Franco; Toscano, Ruben Alfredo; Le Lagadec, Ronan; Pfeffer, Michel

    2015-08-03

    The two MeCN ligands in [Ru(2-C6H4-2'-Py-κC,N)(Phen, trans-C)(MeCN)2]PF6 (1), both trans to a sp(2) hybridized N atom, cannot be substituted by any other ligand. In contrast, the isomerized derivative [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(MeCN)2]PF6 (2), in which one MeCN ligand is now trans to the C atom of the phenyl ring orthometalated to Ru, leads to fast and quantitative substitution reactions with several monodentate ligands. With PPh3, 2 affords [Ru(2-C6H4-2'-Py-κC,N)(Phen, cis-C)(PPh3)(MeCN)]PF6 (3), in which PPh3 is trans to the C σ bound to Ru. Compound 3 is not kinetically stable, because, under thermodynamic control, it leads to 4, in which the PPh3 is trans to a N atom of the Phen ligand. Dimethylsulfoxide (DMSO) can also substitute a MeCN ligand in 2, leading to 5, in which DMSO is coordinated to Ru via its S atom trans to the N atom of the Phen ligand, the isomer under thermodynamic control being the only compound observed. We also found evidence for the fast to very fast substitution of MeCN in 2 by water or a chloride anion by studying the electronic spectra of 2 in the presence of water or NBu4Cl, respectively. An isomerization related to that observed between 3 and 4 is also found for the known monophosphine derivative [Ru(2-C6H4-2'-Py-κC,N)(PPh3, trans-C)(MeCN)3]PF6 (10), in which the PPh3 is located trans to the C of the cyclometalated 2-phenylpyridine, since, upon treatment by refluxing MeCN, it leads to its isomer 11, [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(MeCN)3]PF6. Further substitutions are also observed on 11, whereby N^N chelates (N^N = 2,2'-bipyridine and phenanthroline) substitute two MeCN ligands, affording [Ru(2-C6H4-2'-Py-κC,N)(PPh3, cis-C)(N^N)(MeCN)]PF6 (12a and 12b). Altogether, the behavior of the obtained complexes by ligand substitution reactions can be rationalized by an antisymbiotic effect on the Ru center, trans to the C atom of the cyclometalated unit, leading to compounds having the least nucleophilic ligand trans to C

  20. Investigation of the magnetic structure of KFeCl3, KFeBr3, Rb2MnCl4, and Rb3Mn2Cl7 compounds with magnetic correlations in one and two dimensions

    International Nuclear Information System (INIS)

    Gurewitz, E.

    1976-12-01

    The crystallographic structure of KFeCl 3 and KFeBr 3 consists of (FeCl) - octahedra packed in isolated zigzagging chains. These compounds order antiferromagnetically at Tsub(N) approximately 16 deg K and Tsub(N) approximately 9.5 deg K, respectively. Below Tsub(N) the Fe 2+ magnetic moments within a chain are ferromagnetically coupled, parallel to the chain axis, while the chains are coupled antiferromagnetically. In the temperatures Tsub(N) 3 has magnetic correlations within the chains only, whereas the correlations between the chains are negligible. Moessbauer effect measurements at these temperatures show a distinct hyperfine magnetic splitting, characteristic of relaxation phenomena. Cs 2 MnCl 4 , Rb 2 MnCl 4 and Rb 3 Mn 2 Cl 7 belong to the Asub(n+1)Bsub(n)Xsub(3n+1) family of compounds, with the Dsub(4h)sup(17) space group. These compounds order antiferromagnetically at Tsub(N) approximately 55 deg K for Cs 2 MnCl 4 and Rb 2 MnCl 4 , and Tsub(N) approximately 64.5 deg K for Rb 3 Mn 2 Cl 7 . Below Tsub(N) each Mn 2+ moment is along the c-axis and is coupled antiferromagnetically to the moments of its nearest neighbours (nn). These compounds behave like a two-dimensional antiferromagnet at T >= Tsub(N). Neutron scans of the reciprocal space exhibit rods of reflections along c vectorsup(*). The negligible interactions between next nn sets of MnCl 2 layers, a distance c vector apart, yield both in Rb 2 MnCl 4 and in Rb 3 Mn 2 Cl 7 , two distinctive magnetic structures (polytypes) below Tsub(N). (author)

  1. Group 11 Metal Compounds with Tripodal Bis(imidazole Thioether Ligands. Applications as Catalysts in the Oxidation of Alkenes and as Antimicrobial Agents

    Directory of Open Access Journals (Sweden)

    Armando Varela-Ramírez

    2011-08-01

    Full Text Available New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole thioether ligand (N-methyl-4,5-diphenyl-2-imidazolyl2C(OMeC(CH32S(tert-Bu ({BITOMe,StBu}, 2. The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI, AuIII, AgI, CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3, [Au{BITOMe,StBu}Cl] (4, [Ag{BITOMe,StBu}X] (X = OSO2CF3- 5, PF6- 6 and [Cu{BITOMe,StBu}Cl2] (7 have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the neutral dinuclear mixed AuIII-AuI species [Au2{BITOMe,S}Cl3] (8 were obtained and its crystal structure was determined by X-ray diffraction studies. The structure shows a AuIII center coordinated to the pincer ligand through one N and the S atom. The soft AuI center coordinates to the ligand through the same S atom that has lost the tert-butyl group, thus becoming a thiolate ligand. The short distance between the AuI-AuIII atoms (3.383 Å may indicate a weak metal-metal interaction. Complexes 2-7 and the previously described CuI compound [Cu{BITOMe,StBu}]PF6 (9 have been evaluated in the oxidation of biphenyl ethylene with tert-butyl hydrogen peroxide (TBHP as the oxidant. Results have shown that the AuI and AgI complexes 4 and 6 (at 10 mol % loading are the more active catalysts in this oxidative cleavage. The antimicrobial activity of compounds 2-5, 7 and 9 against Gram-positive and Gram-negative bacteria and yeast has also been evaluated. The new gold and silver compounds display moderate to high antibacterial activity, while the copper derivatives are mostly inactive. The gold and silver complexes were also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing HeLa human cervical carcinoma cells. The compounds displayed a

  2. Synthesis and spectroscopic and structural characterization of the monomeric diborylphosphine and diphosphinoborane compounds PhP(BMes2)2 and MesB(PPh2)2 (Mes = 2,4,6-Me3C6H2)

    International Nuclear Information System (INIS)

    Bartlett, R.A.; Dias, H.V.R.; Power, P.P.

    1988-01-01

    The synthesis and spectroscopic and first x-ray structural characterization of a diborylphosphine, PhP(BMes 2 ) 2 (1), and a diphosphinoborane, MesB(PPh 2 ) 2 (2), are described. The structure of 1 has a planar core that involves the phosphorus and two boron atoms and also the five substituent carbons. In addition, the B-P bond lengths are shortened, which suggests a close structural analogy between 1 and the allyl cation. In the case of 2, although the boron remains planar, both phosphorus centers are pyramidal with slightly longer B-P bonds than in 1. Both 1 and 2 are the first examples of their respective classes of compound to be well characterized. Crystal data with Mo Kα radiation (λ = 0.71069 /angstrom/) at 130 K are as follows. 1: a = 14.302 (4) /angstrom/, b = 15.701 (3) /angstrom/, c = 16.601 (6) /angstrom/, β = 109.61 (2)/degrees/; monoclinic, space group C2/c, Z = 4, R = 0.059. 2: a = 7.815 (2) /angstrom/, b = 8.723 (2) /angstrom/, c = 40.147 (10) /angstrom/, β = 94.90 (2)/degrees/; monoclinic, space group P2 1 /n, Z = 4, R = 0.041. A listing of available 11 B and 31 P NMR data on compounds involving triply connected boron and phosphorus centers is also provided and discussed in the context of the data for 1 and 2. 25 references, 2 figures, 4 tables

  3. Influence of gold species (AuCl4(-) and AuCl2(-)) on self-assembly of PS-b-P2VP in solutions and morphology of composite thin films fabricated at the air/liquid interfaces.

    Science.gov (United States)

    Zhao, Xingjuan; Wang, Qian; Zhang, Xiaokai; Lee, Yong-Ill; Liu, Hong-Guo

    2016-01-21

    Composite thin films doped with Au species were fabricated at an air/liquid interface via a series of steps, including the mass transfer of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) across the liquid/liquid interface between a DMF/CHCl3 solution and an aqueous solution containing either AuCl4(-) or AuCl2(-), self-assembly of PS-b-P2VP in a mixed DMF-water solution, and adsorption and further self-organization of the formed aggregates at the air/liquid interface. This is a new approach for fabricating composite polymer films and can be completed within a very short time. AuCl4(-) and AuCl2(-) ions were found to significantly influence the self-assembly behavior of the block copolymer and the morphologies of the composite films, leading to the formation of nanowire arrays and a foam structure at the air/liquid interface, respectively, which originated from rod-like micelles and microcapsules that had formed in the respective solutions. The effect of the metal complex was analyzed based on the packing parameters of the amphiphilic polymer molecules in different microenvironments and the interactions between the pyridine groups and the metal chloride anions. In addition, these composite thin films exhibited stable and durable performance as heterogeneous catalysts for the hydrogenation of nitroaromatics in aqueous solutions.

  4. Investigation of the exotic clusters production in Au-Au collisions at √sNN = 200 GeV

    International Nuclear Information System (INIS)

    Besliu, Calin

    2004-01-01

    Recently experimental signals on some exotic clusters (diquarks, pentaquarks and others) have been obtained. Taking into account the experimental results on some new phenomena observed in Au-Au collisions at RHIC-BNL energies, we propose here an analysis of the formation of the exotic clusters using the experimental data obtained in the BRAHMS Experiment from RHIC-BNL. The suppression of the hadronic resonances and the production of some exotic clusters or resonances (diquarks, dibaryons, pentaquarks) could be possible, taking into account the kaons and antiprotons abundances. The experimental results obtained in Au-Au collisions at √s NN = 200 GeV using the BRAHMS experimental setup indicate a very weak weight of the classical resonances (under 2% all). On the other hand, the analysis of the proton-proton, proton-antiproton, kaon-proton, proton-pion-pion combinations, in the final state, indicates the existence of some pentaquarks and meso-baryon states (I = 5/2). These very preliminary results are in agreement with the results mentioned previously. (author)

  5. Design, Synthesis, and Characterization of Novel Thiol-Derivatized Ibuprofen Monolayer Protected Gold Clusters

    International Nuclear Information System (INIS)

    Lee, K.H.; Lee, K.H.; Lin, Y.Sh.; Huang, P.J.

    2013-01-01

    A series of new thiol-derivatized ibuprofen monolayer protected gold clusters have been prepared by amidation of ibuprofen with alkyl alcohol or aminophenol affording the carboxamide, N-hydroxyalkyl amide 2, and N-hydroxyphenyl amide 6, which were then tosylate with p-toluenesulfonyl chloride at hydroxyl group to give 3 and 7. Reactions of 3 and 7 with NaSH afforded the mercapto derivatives 4 and 8. Conducting Brust’s reaction with a 3:1 mole ratio of thiolate ibuprofen/ AuCl 4 - yielded polydisperse thiol-derivatized ibuprofen-MPCs 5 and 9. All compounds have been identified by NMR, MS, UV, and IR spectroscopies. Compounds 4 and 8 and the MPCs 5 and 9 have been investigated by using the method of 1 H NMR spectroscopy. The broadening of the signals from 0.8 to 2.0 ppm in 1 H NMR spectrum of MPCs 5 and 9 confirmed the success of the conjugation of thiol-containing derivatives with nano gold cluster.

  6. Pt/Au nanoalloy supported on alumina and chlorided alumina: DFT and experimental analysis

    Science.gov (United States)

    Sharifi, N.; Falamaki, C.; Ghorbanzadeh Ahangari, M.

    2018-04-01

    Density functional theory (DFT) was used to explore the adsorption of Pt/Au nanoalloy onto a pure and chlorided γ-Al2O3(110) surface, which has been applied in numerous catalytic reactions. First, we considered the adsorption properties of Pt clusters (n ≤ 5) onto the Al2O3(110) surface to determine the most stable Pt cluster on alumina surface in reforming processes. After full structural relaxations of Pt clusters at various configurations on alumina, our computed results expressed that the minimum binding energy (‑5.67 eV) is accrued for Pt4 cluster and the distance between the nearest Pt atom in the cluster to the alumina surface is equal to 1.13 Å. Then, we investigated the binding energies, geometries, and electronic properties of adsorbed Aun clusters (n ≤ 6) on the γ-Al2O3(110) surface. Our studied showed that Au5 was the most thermodynamically stable structure on γ-Al2O3. Finally, we inspected these properties for adsorbed Au clusters onto the Pt4-decorated alumina (Aun/Pt4-alumina) system. The binding energy of the Au4/Pt4-alumina system was ‑5.01 eV, and the distance between Au4 cluster and Pt4-alumina was 1.33 Å. The Au4/Pt4alumina system was found to be the most stable nanometer-sized catalyst design. At last, our first-principles calculations predicted that the best position of embedment Cl on the Au4/Pt4-alumina.

  7. On ternary intermetallic aurides. CaAu{sub 2}Al{sub 2}, SrAu{sub 2-x}Al{sub 2+x} and Ba{sub 3}Au{sub 5+x}Al{sub 6-x}

    Energy Technology Data Exchange (ETDEWEB)

    Stegemann, Frank [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Benndorf, Christopher [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Institut fuer Physikalische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Institut fuer Mineralogie, Kristallographie und Materialwissenschaften, Universitaet Leipzig (Germany); Zhang, Yuemei; Fokwa, Boniface P.T. [Department of Chemistry, University of California, Riverside, CA (United States); Bartsch, Manfred; Zacharias, Helmut [Physikalisches Institut, Westfaelische Wilhelms-Universitaet Muenster (Germany); Eckert, Hellmut [Institut fuer Physikalische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos, SP (Brazil); Janka, Oliver [Institut fuer Anorganische und Analytische Chemie, Westfaelische Wilhelms-Universitaet Muenster (Germany); Institut fuer Chemie, Carl von Ossietzky Universitaet Oldenburg (Germany)

    2017-11-17

    The intermetallic compound CaAu{sub 2}Al{sub 2}, and the members of the solid solutions SrAu{sub 2-x}Al{sub 2+x} (0 ≤ x ≤ 0.33) and Ba{sub 3}Au{sub 5+x}Al{sub 6-x} (x = 0, 0.14, 0.49) were synthesized from the elements in sealed tantalum ampoules. The Ca compound crystallizes with the orthorhombic ThRu{sub 2}P{sub 2} type structure, whereas the targeted SrAu{sub 2}Al{sub 2} was found to form a solid solution according to SrAu{sub 2-x}Al{sub 2+x}. For the Ba system no ''BaAu{sub 2}Al{sub 2}'' was found, however, Ba{sub 3}Au{sub 5+x}Al{sub 6-x} was discovered to crystallize in the monoclinic space group C2/c with its own structure type. The samples were investigated by powder X-ray diffraction and their crystal structures were refined on the basis of single-crystal X-ray diffraction data. All compounds were characterized furthermore by susceptibility measurements. The crystallographic aluminum sites of CaAu{sub 2}Al{sub 2} and Ba{sub 3}Au{sub 5}Al{sub 6} can be differentiated by {sup 27}Al solid state NMR spectra on the basis of their different electric field gradients, in agreement with theoretical calculations. The electron transfer from the alkaline earth metals and the aluminum atoms onto the gold atoms was investigated by X-ray photoelectron spectroscopy (XPS) classifying these intermetallics as aurides, in full agreement with the calculated Bader charges. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Cosensitization Properties of Glutathione-Protected Au25 Cluster on Ruthenium Dye-Sensitized TiO2 Photoelectrode

    Directory of Open Access Journals (Sweden)

    Kazuya Nakata

    2013-01-01

    Full Text Available Cosensitization by glutathione-protected Au25 clusters on Ru complex, N719-sensitized TiO2 photoelectrodes is demonstrated. Glutathione-protected Au25 clusters showed no significant changes in properties after adsorption onto TiO2 particles, as confirmed by optical absorption spectroscopy, transmission electron microscopy, and laser desorption/ionization mass spectrometry. Adsorption property of the glutathione-protected Au25 clusters depends on the pH, which affects the incident photon-to-current conversion efficiency (IPCE of the TiO2 photoelectrode containing Au25 clusters. When pH 7. The IPCE of a TiO2 photoelectrode sensitized by both glutathione-protected Au25 clusters and N719 was increased compared with photoelectrodes containing either glutathione-protected Au25 clusters or N719, which suggests that glutathione-protected Au25 clusters act as a coadsorbent for N719 on TiO2 photoelectrodes. This is also supported by the results that the IPCE of N719-sensitized TiO2 photoelectrodes increased upon addition of glutathione. Furthermore, cosensitization by glutathione-protected Au25 clusters on N719-sensitized TiO2 photoelectrodes allows that wavelength of photoelectric conversion was extended to the near infrared (NIR region. These results suggest that glutathione-protected Au25 clusters act not only as a coadsorbent to increase IPCE but also as an NIR-active sensitizer.

  9. Ultrafast relaxation dynamics of electrons in Au clusters capped with dodecanethiol molecules

    International Nuclear Information System (INIS)

    Hamanaka, Y.; Fukagawa, K.; Tai, Y.; Murakami, J.; Nakamura, A.

    2006-01-01

    We have investigated electron relaxation dynamics of size-selected Au clusters capped by dodecanethiol molecules in the cluster sizes of 28-142 atoms using femtosecond pump-probe spectroscopy. Absorption spectra of 28-71-atom clusters show discrete peaks due to the optical transitions between quantized states, while an absorption band due to the surface plasmon is observed in 142-atom clusters. In the differential absorption spectra measured by the pump-probe experiments, a large redshift of 140 meV lasting over 10 ps and absorption bleaching decaying within 2 ps are observed at the absorption peaks of 28-atom clusters. The redshift is ascribed to a charge transfer between Au clusters and dodecanethiol molecules adsorbed on the cluster surface, and the bleaching is due to blocking of the optical transitions between the ground state and the occupied electronic states due to the Pauli's-exclusion principle. Such behavior is in contrast to the 142-atom clusters, where the cooling of hot electrons generated by photo-excitation determines the relaxation dynamics. These results indicate molecular properties of the 28-atom Au cluster-dodecanethiol system

  10. A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.

    Science.gov (United States)

    Negishi, Yuichi; Nakazaki, Tafu; Malola, Sami; Takano, Shinjiro; Niihori, Yoshiki; Kurashige, Wataru; Yamazoe, Seiji; Tsukuda, Tatsuya; Häkkinen, Hannu

    2015-01-28

    We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.

  11. Cluster models of aqueous Na{sup +} and Cl{sup -} in sea water/ice

    Energy Technology Data Exchange (ETDEWEB)

    Michelsen, R.; Walker, R. [Randolph-Macon College, Department of Chemistry (United States); Shillady, D., E-mail: quantummechanicsllc@msn.com [Virginia Commonwealth University, Department of Chemistry (United States)

    2012-10-15

    In this article, we present finite cluster models of aqueous solutes [NaCl(H{sub 2}O){sub 10}, NaCl(H{sub 2}O){sub 5}, and (H{sub 2}O){sub 6}] in terms of molecular geometry and vibrational spectra for interpretation of experimental infrared spectra of NaCl brine solutions. The quantum chemistry program GAMESS is used to optimize the model clusters to a local minimum energy gradient of less than 5.0d-6 hartrees/bohr with B3LYP in a gaussian basis of 6-31G(d,p). Harmonic frequencies are computed for comparison with the infrared spectra measured by attenuated total reflection of a temperature-controlled Ge plate under a layer of cold brine solution. The motivation for this research is to understand the mechanism by which freezing seawater excludes halide ions (mainly Cl{sup -}) and why the O-H stretching region of the spectra changes with temperature. Frost flowers, sea ice, and snow in marine environments contain concentrated halides in liquid brine at their surfaces which lead to catalytic destruction of low-altitude ozone in the polar regions of the Earth.

  12. A method for hydrogenating and carbonylizing unsaturated compounds in the presence of catalysts based on phosphine and metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Briggs, J C; Dyer, G

    1982-12-22

    The hydrogenation of unsaturated organic compounds or the attachment to them of CO is accomplished with contact with a synthesis gas in the presence of a stereospecific catalyst (Kt), a compound of a metal of the platinum group (preferably Rhodium, but also Platinum, Palladium, Ruthenium or Iridium) and an asymmetrical bis-phosphine of the formula A-(CH2)n-B, where A and B are phosphine groups. R2P and R'2P or RRhP, where R is an aryl radical, R' is aralkyl, alcarylic or alkyl radical, n = 1 to 10, or an asymmetrical monophosphine of the formula R2-R'P. The complex compound also includes Hydrogen, CO and (or) halogen (preferably Chlorine) as ligands. The physical properties of the obtained complex compounds of the carbonylchlorbisphosphines or Rh are presented: trans-(RhC1-(CO)(Ph2P(CH2)6PPh2))2; trans-(RhC1(CO)(C2H5PhP-(CH2)6PPh2))2; trans-(RhC1(CO)(cycloC6H11PhP(CH2)6-PPh2))2; trans-(RhC1(CO)(C2H5PhP(CH2)4PPh2)2; trans-(RhC1(CO)(C2H5PhP(Ch2))2 and PhC1(CO)4(p-C6H4CH2)2P(Ch2)6PPh2). The isolated complexes are light yellow crystalline substances.

  13. Detection of a Double Relic in the Torpedo Cluster: SPT-CL J0245-5302

    Science.gov (United States)

    Zheng, Q.; Johnston-Hollitt, M.; Duchesne, S. W.; Li, W. T.

    2018-06-01

    The Torpedo cluster, SPT-CL J0245-5302 (S0295) is a massive, merging cluster at a redshift of z = 0.300, which exhibits a strikingly similar morphology to the Bullet cluster 1E 0657-55.8 (z = 0.296), including a classic bow shock in the cluster's intra-cluster medium revealed by Chandra X-ray observations. We present Australia Telescope Compact Array data centred at 2.1 GHz and Murchison Widefield Array data at frequencies between 72 MHz and 231 MHz which we use to study the properties of the cluster. We characterise a number of discrete and diffuse radio sources in the cluster, including the detection of two previously unknown radio relics on the cluster periphery. The average spectral index of the diffuse emission between 70 MHz and 3.1 GHz is α =-1.63_{-0.10}^{+0.10} and a radio-derived Mach number for the shock in the west of the cluster is calculated as M = 2.04. The Torpedo cluster is thus a double relic system at moderate redshift.

  14. A GMBCG GALAXY CLUSTER CATALOG OF 55,424 RICH CLUSTERS FROM SDSS DR7

    International Nuclear Information System (INIS)

    Hao Jiangang; Annis, James; Johnston, David E.; McKay, Timothy A.; Evrard, August; Siegel, Seth R.; Gerdes, David; Koester, Benjamin P.; Rykoff, Eli S.; Rozo, Eduardo; Wechsler, Risa H.; Busha, Michael; Becker, Matthew; Sheldon, Erin

    2010-01-01

    We present a large catalog of optically selected galaxy clusters from the application of a new Gaussian Mixture Brightest Cluster Galaxy (GMBCG) algorithm to SDSS Data Release 7 data. The algorithm detects clusters by identifying the red-sequence plus brightest cluster galaxy (BCG) feature, which is unique for galaxy clusters and does not exist among field galaxies. Red-sequence clustering in color space is detected using an Error Corrected Gaussian Mixture Model. We run GMBCG on 8240 deg 2 of photometric data from SDSS DR7 to assemble the largest ever optical galaxy cluster catalog, consisting of over 55,000 rich clusters across the redshift range from 0.1 < z < 0.55. We present Monte Carlo tests of completeness and purity and perform cross-matching with X-ray clusters and with the maxBCG sample at low redshift. These tests indicate high completeness and purity across the full redshift range for clusters with 15 or more members.

  15. A GMBCG galaxy cluster catalog of 55,880 rich clusters from SDSS DR7

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Jiangang; McKay, Timothy A.; Koester, Benjamin P.; Rykoff, Eli S.; Rozo, Eduardo; Annis, James; Wechsler, Risa H.; Evrard, August; Siegel, Seth R.; Becker, Matthew; Busha, Michael; /Fermilab /Michigan U. /Chicago U., Astron. Astrophys. Ctr. /UC, Santa Barbara /KICP, Chicago /KIPAC, Menlo Park /SLAC /Caltech /Brookhaven

    2010-08-01

    We present a large catalog of optically selected galaxy clusters from the application of a new Gaussian Mixture Brightest Cluster Galaxy (GMBCG) algorithm to SDSS Data Release 7 data. The algorithm detects clusters by identifying the red sequence plus Brightest Cluster Galaxy (BCG) feature, which is unique for galaxy clusters and does not exist among field galaxies. Red sequence clustering in color space is detected using an Error Corrected Gaussian Mixture Model. We run GMBCG on 8240 square degrees of photometric data from SDSS DR7 to assemble the largest ever optical galaxy cluster catalog, consisting of over 55,000 rich clusters across the redshift range from 0.1 < z < 0.55. We present Monte Carlo tests of completeness and purity and perform cross-matching with X-ray clusters and with the maxBCG sample at low redshift. These tests indicate high completeness and purity across the full redshift range for clusters with 15 or more members.

  16. Synthesis of new dithiacobaltaborane clusters derived from arachno-6,8-S2B7H9

    International Nuclear Information System (INIS)

    Kang, S.O.; Sneddon, L.G.

    1988-01-01

    A series of air-stable dithiacobaltaborane clusters has been isolated from either the reaction of the arachno-S 2 B 7 H 8 - anion with cobalt chloride and pentamethylcyclopentadienide or the reaction of neutral arachno-6,8-S 2 B 7 H 9 with cobalt atoms and pentamethylcyclopentadiene. Thus, the reaction of arachno-S 2 B 7 H 8 - with CoCl 2 and C 5 (CH 3 ) 5 - in THF gave, as the major products, the triple-decker compound nido-4,6-η-C 5 (CH 3 ) 52 Co 2 -3,5-S 2 B 2 H 2 (I) and the 11-vertex cluster nido-8,10(η-C 5 (CH 3 ) 5 ) 2 Co 2 -7,9-S 2 B 7 H 7 (III). Also isolated in smaller amounts were a chloride derivative of I, nido-1-Cl-4,6-(η-C 5 (CH 3 ) 5 ) 2 Co 2 -3,5-S 2 B 2 H (II), two isomers of III, nido-3,10-(η-C 5 (CH 3 ) 5 ) 2 Co 2 -7,9-S 2 B 7 H 7 (IV) and nido-3,5-(η-C 5 (CH 3 ) 5 ) 2 Co 2 -7,9-S 2 B 7 H 7 (V), and the eight-boron cluster nido-8-(η-C 5 (CH 3 ) 5 )Co-7,9-S 2 B 8 H 8 (VI). Other trace products of the reaction included the six-boron clusters nido-5,8-(η-C 5 (CH 3 ) 5 ) 2 Co 2 -6,9-S 2 B 6 H 6 (VII) and arachno-7-(η-C 5 (CH 3 ) 5 )Co-6,8-S 2 B 6 H 8 (VIII). Compound III was found to isomerize at 250 degree C to IV, which could then be converted to V at 300 degree C. The reaction of cobalt atoms with arachno-6,8-S 2 B 7 H 9 in the presence of pentamethylcyclopentadiene gave VIII as the major product; however, a number of other clusters including I, V, VI, and [(η-C 5 (CH 3 ) 5 ) 2 Co] + [(SB 10 H 10 ) 2 Co] - were isolated in trace amounts. 16 references, 6 figures, 3 tables

  17. Water Solubility of Plutonium and Uranium Compounds and Residues at TA-55

    International Nuclear Information System (INIS)

    Reilly, Sean Douglas; Smith, Paul Herrick; Jarvinen, Gordon D.; Prochnow, David Adrian; Schulte, Louis D.; DeBurgomaster, Paul Christopher; Fife, Keith William; Rubin, Jim; Worl, Laura Ann

    2016-01-01

    Understanding the water solubility of plutonium and uranium compounds and residues at TA-55 is necessary to provide a technical basis for appropriate criticality safety, safety basis and accountability controls. Individual compound solubility was determined using published solubility data and solution thermodynamic modeling. Residue solubility was estimated using a combination of published technical reports and process knowledge of constituent compounds. The scope of materials considered includes all compounds and residues at TA-55 as of March 2016 that contain Pu-239 or U-235 where any single item in the facility has more than 500 g of nuclear material. This analysis indicates that the following materials are not appreciably soluble in water: plutonium dioxide (IDC=C21), plutonium phosphate (IDC=C66), plutonium tetrafluoride (IDC=C80), plutonium filter residue (IDC=R26), plutonium hydroxide precipitate (IDC=R41), plutonium DOR salt (IDC=R42), plutonium incinerator ash (IDC=R47), uranium carbide (IDC=C13), uranium dioxide (IDC=C21), U 3 O 8 (IDC=C88), and uranium filter residue (IDC=R26). This analysis also indicates that the following materials are soluble in water: plutonium chloride (IDC=C19) and uranium nitrate (IDC=C52). Equilibrium calculations suggest that PuOCl is water soluble under certain conditions, but some plutonium processing reports indicate that it is insoluble when present in electrorefining residues (R65). Plutonium molten salt extraction residues (IDC=R83) contain significant quantities of PuCl 3 , and are expected to be soluble in water. The solubility of the following plutonium residues is indeterminate due to conflicting reports, insufficient process knowledge or process-dependent composition: calcium salt (IDC=R09), electrorefining salt (IDC=R65), salt (IDC=R71), silica (IDC=R73) and sweepings/screenings (IDC=R78). Solution thermodynamic modeling also indicates that fire suppression water buffered with a commercially-available phosphate

  18. Water Solubility of Plutonium and Uranium Compounds and Residues at TA-55

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, Sean Douglas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Smith, Paul Herrick [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Jarvinen, Gordon D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Prochnow, David Adrian [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Schulte, Louis D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; DeBurgomaster, Paul Christopher [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Fife, Keith William [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Rubin, Jim [Los Alamos National Lab. (LANL), Los Alamos, NM (United States; Worl, Laura Ann [Los Alamos National Lab. (LANL), Los Alamos, NM (United States

    2016-06-13

    Understanding the water solubility of plutonium and uranium compounds and residues at TA-55 is necessary to provide a technical basis for appropriate criticality safety, safety basis and accountability controls. Individual compound solubility was determined using published solubility data and solution thermodynamic modeling. Residue solubility was estimated using a combination of published technical reports and process knowledge of constituent compounds. The scope of materials considered includes all compounds and residues at TA-55 as of March 2016 that contain Pu-239 or U-235 where any single item in the facility has more than 500 g of nuclear material. This analysis indicates that the following materials are not appreciably soluble in water: plutonium dioxide (IDC=C21), plutonium phosphate (IDC=C66), plutonium tetrafluoride (IDC=C80), plutonium filter residue (IDC=R26), plutonium hydroxide precipitate (IDC=R41), plutonium DOR salt (IDC=R42), plutonium incinerator ash (IDC=R47), uranium carbide (IDC=C13), uranium dioxide (IDC=C21), U3O8 (IDC=C88), and uranium filter residue (IDC=R26). This analysis also indicates that the following materials are soluble in water: plutonium chloride (IDC=C19) and uranium nitrate (IDC=C52). Equilibrium calculations suggest that PuOCl is water soluble under certain conditions, but some plutonium processing reports indicate that it is insoluble when present in electrorefining residues (R65). Plutonium molten salt extraction residues (IDC=R83) contain significant quantities of PuCl3, and are expected to be soluble in water. The solubility of the following plutonium residues is indeterminate due to conflicting reports, insufficient process knowledge or process-dependent composition: calcium salt (IDC=R09), electrorefining salt (IDC=R65), salt (IDC=R71), silica (IDC=R73) and sweepings/screenings (IDC=R78). Solution thermodynamic modeling also indicates that fire suppression water buffered with a

  19. CLUSTER DYNAMICS LARGELY SHAPES PROTOPLANETARY DISK SIZES

    Energy Technology Data Exchange (ETDEWEB)

    Vincke, Kirsten; Pfalzner, Susanne, E-mail: kvincke@mpifr-bonn.mpg.de [Max Planck Institute for Radio Astronomy, Auf dem Hügel 69, D-53121 Bonn (Germany)

    2016-09-01

    To what degree the cluster environment influences the sizes of protoplanetary disks surrounding young stars is still an open question. This is particularly true for the short-lived clusters typical for the solar neighborhood, in which the stellar density and therefore the influence of the cluster environment change considerably over the first 10 Myr. In previous studies, the effect of the gas on the cluster dynamics has often been neglected; this is remedied here. Using the code NBody6++, we study the stellar dynamics in different developmental phases—embedded, expulsion, and expansion—including the gas, and quantify the effect of fly-bys on the disk size. We concentrate on massive clusters (M {sub cl} ≥ 10{sup 3}–6 ∗ 10{sup 4} M {sub Sun}), which are representative for clusters like the Orion Nebula Cluster (ONC) or NGC 6611. We find that not only the stellar density but also the duration of the embedded phase matters. The densest clusters react fastest to the gas expulsion and drop quickly in density, here 98% of relevant encounters happen before gas expulsion. By contrast, disks in sparser clusters are initially less affected, but because these clusters expand more slowly, 13% of disks are truncated after gas expulsion. For ONC-like clusters, we find that disks larger than 500 au are usually affected by the environment, which corresponds to the observation that 200 au-sized disks are common. For NGC 6611-like clusters, disk sizes are cut-down on average to roughly 100 au. A testable hypothesis would be that the disks in the center of NGC 6611 should be on average ≈20 au and therefore considerably smaller than those in the ONC.

  20. Alternative synthetic route for the heterometallic CO-releasing [Sb@Rh12(CO27]3− icosahedral carbonyl cluster and synthesis of its new unsaturated [Sb@Rh12(CO24]4− and dimeric [{Sb@Rh12Sb(CO25}2Rh(CO2PPh3]7− derivatives

    Directory of Open Access Journals (Sweden)

    Cristina Femoni

    2016-10-01

    Full Text Available The hetero-metallic [Sb@Rh12(CO27]3− cluster has been known as for over three decades thanks to Vidal and co-workers, and represents the first example of an E-centered (E=heteroatom icosahedral rhodium carbonyl cluster. However, its synthesis required high temperature (140–160 °C and elevated CO pressure (400 atm. Applying the redox condensation method for cluster preparation, we herein report a new synthetic, high-yield route for preparing [Sb@Rh12(CO27]3− under much milder conditions of temperature and pressure. Notably, when the same synthesis was carried out under N2 instead of CO atmosphere, the new isostructural but unsaturated derivative [Sb@Rh12(CO24]4− was obtained, for which we report the full X-ray structural characterization. This species represents one of the few examples of an icosahedral cluster disobeying the electron-counting Wade-Mingos rules, possessing less than the expected 170 cluster valence electrons (CVEs. Judging from IR monitoring, the two species can be obtained one from the other by switching between N2 and CO atmosphere, making [Sb@Rh12(CO27]3− a spontaneous CO-releasing molecule. Finally, the study of the chemical reactivity of [Sb@Rh12(CO27]3− with PPh3 allowed us to obtain the new [{Sb@Rh12Sb(CO25}2Rh(CO2PPh3]7− dimeric compound, for which we herein report the full X-ray structural and 31P NMR analyses.

  1. Electrocrystallization of Au nanoparticles on glassy carbon from HClO4 solution containing [AuCl4]-

    International Nuclear Information System (INIS)

    Komsiyska, L.; Staikov, G.

    2008-01-01

    The mechanism and kinetics of electrocrystallization of Au nanoparticles on glassy carbon (GC) were investigated in the system GC/1 mM KAuCl 4 + 0.1 M HClO 4 . Experimental results show that the gold electrodeposition follows the so-called Volmer-Weber growth mechanism involving formation and growth of 3D Au nanoparticles on an unmodified GC substrate. The analysis of current transients shows that at relatively positive electrode potentials (E ≥ 0.84 V) the deposition kinetics corresponds to the theoretical model for progressive nucleation and diffusion-controlled 3D growth of Au nanoparticles. The potential dependence of the nucleation rate extracted from the current transients is in agreement with the atomistic theory of nucleation. At sufficiently negative electrode potentials (E ≤ 0.64 V) the nucleation frequency becomes very high and the nucleation occurs instantaneously. Based on this behaviour is applied a potentiostatic double-pulse routine, which allows controlled electrodeposition of Au nanoparticles with a relatively narrow size distribution

  2. Enhancement of photocurrents due to the oxidation of water and organic compounds at BiZn2VO6 particulate thin film electrodes by treatment with a TiCl4 solution

    International Nuclear Information System (INIS)

    Liu Haimei; Imanishi, Akihito; Yang Wensheng; Nakato, Yoshihiro

    2010-01-01

    Photocurrents due to water oxidation at BiZn 2 VO 6 (E g 2.4 eV) particulate thin film electrodes were largely enhanced by pre-treatment with an aqueous TiCl 4 solution. Photocurrents for BiZn 2 VO 6 electrodes with no TiCl 4 treatment were also enhanced by the addition of organic compounds such as methanol and trimethyl amine to the aqueous electrolyte. Interestingly, such enhanced photocurrents by organic compounds were further enhanced by the TiCl 4 pre-treatment. EDAX and SEM investigations showed the formation of a flock-like TiO 2 overlayer on BiZn 2 VO 6 particles after the TiCl 4 treatment. The photocurrent enhancement by the TiCl 4 pre-treatment is thus mainly attributed to the necking effect of the flock-like TiO 2 overlayer, which facilitates the transport of photogenerated electrons within the BiZn 2 VO 6 particulate thin film electrode.

  3. Relaxation processes in optically excites metal clusters; Relaxationsprozesse in optisch angeregten Metallclustern

    Energy Technology Data Exchange (ETDEWEB)

    Stanzel, J.

    2007-08-10

    The present work is concerned with the dynamics of optically excited metal clusters in the gas phase. Small mass-selected gold and tungsten cluster anions (Au{sup -}{sub n}, n=5-8, 14, 20 and W{sup -}{sub n}, n=3-14) are studied using femtosecond time-resolved photoelectron spectroscopy. Depending on the electronic structure in the valence region as well as on the optical excitation energy fundamentally different relaxation processes are observed. In small gold cluster anions excited with 1.56 eV an isolated electronically excited state is populated. The time-dependent measurements are strongly sizedependent and open insights into photoinduced geometry changes of the nuclear framework. Oscillatory vibrational wavepacket motion in Au{sup -}{sub 5}, an extremely longlived ({tau} >90 ns) electronically excited state in Au{sup -}{sub 6} as well as photoinduced melting in Au{sup -}{sub 7} and Au{sup -}{sub 8} is monitored in real time. By increasing the OPTICAL excitation energy to 3.12 eV a completely different scenario is observed. A multitude of electronically excited states can be reached upon optical excitation and as a consequence electronic relaxation processes that take place on a time scale of 1 ps are dominating. This is shown for Au{sup -}{sub 7}, Au{sup -}{sub 14} and Au{sup -}{sub 20}. Compared to gold clusters, tungsten clusters are characterized by a significantly higher electronic density of states in the valence region. Therefore electronic relaxation processes are much more likely and take place on a significantly faster time scale. The fast electronic relaxation processes are distinguished from pure vibrational relaxation. It is shown that already in the four atomic tungsten cluster W{sup -}{sub 4} electronic relaxation processes take place on a time scale of 30 fs. In all investigated tungsten cluster anions (W{sup -}{sub n}, n=3-14) an equilibrium between electronic and vibrational system is reached within around 1 ps after optical excitation which

  4. Probing the electronic structure and Au—C chemical bonding in AuCn− and AuCnH− (n = 2, 4, and 6) using high-resolution photoelectron spectroscopy

    International Nuclear Information System (INIS)

    León, Iker; Ruipérez, Fernando; Ugalde, Jesus M.; Wang, Lai-Sheng

    2016-01-01

    We report a joint photoelectron spectroscopy and theoretical study on AuC 4 − , AuC 6 − , and AuC n H − (n = 2, 4, and 6) using high-resolution photoelectron imaging and ab initio calculations. The ground state of AuC 2 H − , AuC 4 H − , and AuC 6 H − is found to be linear, while that of AuC 4 − and AuC 6 − is bent. All the species are found to be linear in their neutral ground states. The electron affinities (EAs) are measured to be 3.366(1) and 3.593(1) eV for AuC 4 and AuC 6 , respectively. Both bending and stretching frequencies are resolved in the spectra of AuC 4 − and AuC 6 − . High-resolution data of AuC n H − reveal major vibrational progressions in the Au—C stretching and bending modes. AuC 2 H − has a ground state stretching frequency of 445(10) cm −1 and a bending frequency of 260(10) cm −1 ; AuC 4 H − has a ground state stretching frequency of 340(10) cm −1 ; AuC 6 H − has a ground state stretching frequency of 260(10) cm −1 and a bending frequency of 55(10) cm −1 . The EAs are measured to be 1.475(1), 1.778(1), and 1.962(1) eV for AuC 2 H, AuC 4 H, and AuC 6 H, respectively. The strength of the Au—C bond decreases as the number of carbon atoms increases. The current study provides a wealth of electronic structure information about AuC 4 − , AuC 6 − , and AuC n H − (n = 2, 4, and 6) and their corresponding neutrals.

  5. Size control in the synthesis of 1-6 nm gold nanoparticles via solvent-controlled nucleation.

    Science.gov (United States)

    Song, Jieun; Kim, Dukhan; Lee, Dongil

    2011-11-15

    We report a facile synthetic route for size-controlled preparation of gold nanoparticles. Nearly monodisperse gold nanoparticles with core diameters of 1-6 nm were obtained by reducing AuP(Phenyl)(3)Cl with tert-butylamine borane in the presence of dodecanethiol in the solvent mixture of benzene and CHCl(3). Mechanism studies have shown that the size control is achieved by the solvent-controlled nucleation in which the nuclei concentration increases with increasing the fraction of CHCl(3), leading to smaller particles. It was also found that, following the solvent-controlled nucleation, particle growth occurs via ligand replacement of PPh(3) on the nuclei by Au(I)thiolate generated by the digestive etching of small particles. This synthetic strategy was successfully demonstrated with other alkanethiols of different chain length with which size-controlled, monodisperse gold nanoparticles were prepared in remarkable yield without requiring any postsynthesis treatments.

  6. Genome Wide Transcriptome Analysis reveals ABA mediated response in Arabidopsis during Gold (AuCl4- treatment

    Directory of Open Access Journals (Sweden)

    Devesh eShukla

    2014-11-01

    Full Text Available The unique physico-chemical properties of gold nanoparticles (AuNPs find manifold applications in diagnostics, medicine and catalysis. Chemical synthesis produces reactive AuNPs and generates hazardous by-products. Alternatively, plants can be utilized to produce AuNPs in an eco-friendly manner. To better control the biosynthesis of AuNPs, we need to first understand the detailed molecular response induced by AuCl4- In this study, we carried out global transcriptome analysis in root tissue of Arabidopsis grown for 12- hours in presence of gold solution (HAuCl4 using the novel unbiased Affymetrix exon array. Transcriptomics analysis revealed differential regulation of a total of 704 genes and 4900 exons. Of these, 492 and 212 genes were up- and downregulated, respectively. The validation of the expressed key genes, such as glutathione-S-transferases, auxin responsive genes, cytochrome P450 82C2, methyl transferases, transducin (G protein beta subunit, ERF transcription factor, ABC, and MATE transporters, was carried out through quantitative RT-PCR. These key genes demonstrated specific induction under AuCl4- treatment relative to other heavy metals, suggesting a unique plant-gold interaction. GO enrichment analysis reveals the upregulation of processes like oxidative stress, glutathione binding, metal binding, transport, and plant hormonal responses. Changes predicted in biochemical pathways indicated major modulation in glutathione mediated detoxification, flavones and derivatives, and plant hormone biosynthesis. Motif search analysis identified a highly significant enriched motif, ACGT, which is an abscisic acid responsive core element (ABRE, suggesting the possibility of ABA- mediated signaling. Identification of abscisic acid response element (ABRE points to the operation of a predominant signaling mechanism in response to AuCl4- exposure. Overall, this study presents a useful picture of plant-gold interaction with an identification of

  7. Synthesis and characterization of [Ru(η6-C6Me6)Cl2(CNPy)] and [Cl2(η6-C6Me6)Ru-(μ-CNPy)-Ru(η6-C6Me6)Cl2] and reactivity of [Ru(η6-C6Me6)Cl2(CNPy)] with various bases

    International Nuclear Information System (INIS)

    Pandey, D.S.; Sahay, A.N.; Agarwala, U.C.

    1996-01-01

    Reactions of [(Ru(η 6 -C 6 Me 6 )Cl 2 ) 2 ] with 4-cyanopyridine leads to the formation of neutral mono and dimeric complexes viz., [Ru(η 6 C 6 Me 6 )Cl 2 (CNPy)] (I) and [Cl 2 (η 6 -C 6 Me 6 ) Ru-(μ-CNPy)-Ru(η 6 -C 6 Me 6 )Cl 2 ] (II). Complex (I) undergoes metathetical reactions with EPh 3 (E=P, As and Sb) and N-donor heterocyclic bases yielding corresponding substitutional products which have been characterized by elemental analyses and spectroscopic: (IR, UV/vis, 1 H and 13 C NMR) studies. (author). 21 refs., 1 tab

  8. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    International Nuclear Information System (INIS)

    Sun Xiaonan; Silly, Fabien

    2010-01-01

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22x√(3)) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22x√(3)). Local atomic hexagonal packing has also been observed in the NaCl(1 0 0) layer. At submonolayer NaCl coverage, PTCDA forms two-dimensional islands on the Au(1 1 1) surface and nucleate preferentially at the NaCl island step edges. When the Au surface is fully covered with NaCl layers, PTCDA molecules form three-dimensional molecular clusters decorating the step edges of NaCl layers.

  9. NaCl islands decorated with 2D or 3D 3,4,9,10-perylene-tetracarboxylic-dianhydride nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Sun Xiaonan [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); Silly, Fabien, E-mail: Fabien.silly@cea.fr [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands); CEA, IRAMIS, SPCSI, Nanostructures and Organic Semiconductors Laboratory, F-91191 Gif-sur-Yvette (France); UPMC, IPCM, UMR CNRS 7201, 4 place Jussieu, F-75005 Paris (France)

    2010-01-15

    The formation of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) nanostrutures on Au(1 1 1)-(22x{radical}(3)) covered with NaCl islands has been studied using scanning tunneling microscopy (STM). Atomically resolved STM images show that NaCl grows as (1 0 0)-terminated layers on Au(1 1 1)-(22x{radical}(3)). Local atomic hexagonal packing has also been observed in the NaCl(1 0 0) layer. At submonolayer NaCl coverage, PTCDA forms two-dimensional islands on the Au(1 1 1) surface and nucleate preferentially at the NaCl island step edges. When the Au surface is fully covered with NaCl layers, PTCDA molecules form three-dimensional molecular clusters decorating the step edges of NaCl layers.

  10. Maternal morbidity and mortality due to primary PPH-experience at ayub teaching hospital abbottabad

    International Nuclear Information System (INIS)

    Naz, H.; Sarwar, I.; Nisa, A.U.

    2008-01-01

    Postpartum Haemorrhage (PPH) remains a significant cause of maternal mortality and morbidity like hypovolemic shock, anaemia, multi organ failure, consumptive coagulopathy, disseminated intra vascular coagulation (DIC), blood transfusion related complications and hysterectomy leading to loss of childbearing potential. The present study was conducted to determine the frequency of PPH and the associated maternal morbidity at the Department of Gynaecology Unit B, Ayub Teaching Hospital Abbottabad. The study was carried out in the Department of Obstetrics and Gynaecology Unit B of the Ayub teaching Hospital Abbottabad from 18th April 2006 to 17 July 2006. The study population included all cases admitted with primary PPH during the study period. For calculation of frequencies, the total number of deliveries in the setting during the study period was used. All subjects underwent a complete obstetrical clinical workup comprising of history, general physical examination, abdominal and pelvic examination, relevant laboratory investigations. The maternal condition was assessed and managed according to established hospital protocols which included both pharmacological and surgical intervention. All maternal complications were noted and recorded on pre-designed proformas. Data was entered and analyzed by computer. A total of 50 cases of primary PPH were recorded during the study period. The frequency of PPH was calculated as 7.1%. The major cause of PPH was uterine atony found in 29 (58%) cases, followed by cervical, vaginal and perineal tears in 12 (24%) cases. Initially all patients were managed pharmacologically followed by surgical intervention. Subtotal (haemostatic) hysterectomy was performed in 10 (20%) cases. Maternal morbidity was detected in 31 (62%) of cases; the major morbidities were DIC in 3 (6%) cases. Acute renal failure in 3 (6%) patients and shock in 2 (9.9%) cases and anaemia in 20 (90.1%) cases. The study concludes that the frequency of primary PPH in this

  11. Size exclusion chromatography for semipreparative scale separation of Au38(SR)24 and Au40(SR)24 and larger clusters.

    Science.gov (United States)

    Knoppe, Stefan; Boudon, Julien; Dolamic, Igor; Dass, Amala; Bürgi, Thomas

    2011-07-01

    Size exclusion chromatography (SEC) on a semipreparative scale (10 mg and more) was used to size-select ultrasmall gold nanoclusters (<2 nm) from polydisperse mixtures. In particular, the ubiquitous byproducts of the etching process toward Au(38)(SR)(24) (SR, thiolate) clusters were separated and gained in high monodispersity (based on mass spectrometry). The isolated fractions were characterized by UV-vis spectroscopy, MALDI mass spectrometry, HPLC, and electron microscopy. Most notably, the separation of Au(38)(SR)(24) and Au(40)(SR)(24) clusters is demonstrated.

  12. Syntheses, structures and third-order non-linear optical properties of homometal clusters containing molybdenum

    International Nuclear Information System (INIS)

    Li Yong; Lu Jing; Cui Xiaobing; Xu Jiqing; Li Kechang; Sun Huaying; Li Guanghua; Pan Lingyun; Yang Qingxin

    2005-01-01

    Both the homometal cluster [P(ph 4 )] 2 [Mo 2 O 2 (μ-S) 2 (S 2 ) 2 ] (1) and [Mo 2 O 2 (μ-S) 2 (Et 2 dtc) 2 ] (2) (Et 2 dtc=diethyl-dithiocarbamate) were successfully synthesized by low-temperature solid-state reactions. X-ray single-crystal diffraction studies suggest that compound (1) is a dinuclear anion cluster, and compound (2) is a dinuclear neutral cluster. The two compounds were characterized by elemental analyses, IR spectra and UV-Vis spectra. The third-order non-linear optical (NLO) properties of the clusters were also investigated and all exhibited nice non-linear absorption and self-defocusing performance with moduli of the hyperpolarizabilities 5.145x10 -30 esu for (1) and 5.428x10 -30 esu for (2)

  13. X-ray Absorption Spectroscopy Combined with Time-Dependent Density Functional Theory Elucidates Differential Substitution Pathways of Au(I) and Au(III) with Zinc Fingers.

    Science.gov (United States)

    Abbehausen, Camilla; de Paiva, Raphael Enoque Ferraz; Bjornsson, Ragnar; Gomes, Saulo Quintana; Du, Zhifeng; Corbi, Pedro Paulo; Lima, Frederico Alves; Farrell, Nicholas

    2018-01-02

    A combination of two elements' (Au, Zn) X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TD-DFT) allowed the elucidation of differential substitution pathways of Au(I) and Au(III) compounds reacting with biologically relevant zinc fingers (ZnFs). Gold L 3 -edge XAS probed the interaction of gold and the C-terminal Cys 2 HisCys finger of the HIV-1 nucleocapsid protein NCp7, and the Cys 2 His 2 human transcription factor Sp1. The use of model compounds helped assign oxidation states and the identity of the gold-bound ligands. The computational studies accurately reproduced the experimental XAS spectra and allowed the proposition of structural models for the interaction products at early time points. The direct electrophilic attack on the ZnF by the highly thiophilic Au(I) resulted in a linear P-Au-Cys coordination sphere after zinc ejection whereas for the Sp1, loss of PEt 3 results in linear Cys-Au-Cys or Cys-Au-His arrangements. Reactions with Au(III) compounds, on the other hand, showed multiple binding modes. Prompt reaction between [AuCl(dien)] 2+ and [Au(dien)(DMAP)] 3+ with Sp1 showed a partially reduced Au center and a final linear His-Au-His coordination. Differently, in the presence of NCp7, [AuCl(dien)] 2+ readily reduces to Au(I) and changes from square-planar to linear geometry with Cys-Au-His coordination, while [Au(dien)(DMAP)] 3+ initially maintains its Au(III) oxidation state and square-planar geometry and the same first coordination sphere. The latter is the first observation of a "noncovalent" interaction of a Au(III) complex with a zinc finger and confirms early hypotheses that stabilization of Au(III) occurs with N-donor ligands. Modification of the zinc coordination sphere, suggesting full or partial zinc ejection, is observed in all cases, and for [Au(dien)(DMAP)] 3+ this represents a novel mechanism for nucleocapsid inactivation. The combination of XAS and TD-DFT presents the first direct experimental

  14. Antimicrobial photodynamic activity and cytocompatibility of Au25(Capt18 clusters photoexcited by blue LED light irradiation

    Directory of Open Access Journals (Sweden)

    Miyata S

    2017-04-01

    Full Text Available Saori Miyata,1 Hirofumi Miyaji,1 Hideya Kawasaki,2 Masaki Yamamoto,2 Erika Nishida,1 Hiroko Takita,3 Tsukasa Akasaka,4 Natsumi Ushijima,3 Toshihiko Iwanaga,5 Tsutomu Sugaya1 1Department of Periodontology and Endodontology, Hokkaido University Graduate School of Dental Medicine, Kita-ku, Sapporo, 2Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita-shi, Osaka, 3Support Section for Education and Research, Hokkaido University Graduate School of Dental Medicine, 4Department of Biomedical, Dental Materials and Engineering, Graduate School of Dental Medicine, Hokkaido University, 5Department of Anatomy, Laboratory of Histology and Cytology, Hokkaido University Graduate School of Medicine, Kita-ku, Sapporo, Japan Abstract: Antimicrobial photodynamic therapy (aPDT has beneficial effects in dental treatment. We applied captopril-protected gold (Au25(Capt18 clusters as a novel photosensitizer for aPDT. Photoexcited Au clusters under light irradiation generated singlet oxygen (1O2. Accordingly, the antimicrobial and cytotoxic effects of Au25(Capt18 clusters under dental blue light-emitting diode (LED irradiation were evaluated. 1O2 generation of Au25(Capt18 clusters under blue LED irradiation (420–460 nm was detected by a methotrexate (MTX probe. The antimicrobial effects of photoexcited Au clusters (0, 5, 50, and 500 µg/mL on oral bacterial cells, such as Streptococcus mutans, Aggregatibacter actinomycetemcomitans, and Porphyromonas gingivalis, were assessed by morphological observations and bacterial growth experiments. Cytotoxicity testing of Au clusters and blue LED irradiation was then performed against NIH3T3 and MC3T3-E1 cells. In addition, the biological performance of Au clusters (500 µg/mL was compared to an organic dye photosensitizer, methylene blue (MB; 10 and 100 µg/mL. We confirmed the 1O2 generation ability of Au25(Capt18 clusters through the fluorescence

  15. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-11-14

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  16. Photoabsorption spectra of (Mo/W)@Au12Si60 clusters from time-dependent DFT calculations

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2013-01-01

    The electronic structure and photoabsorption spectrum of encapsulated (Mo/W)@Au12Si60 clusters are theoretically investigated via static and time-dependent density functional theory. The photoabsorption spectrum is calculated both at the scalar relativistic and spin-orbit coupling levels. The encapsulated (Mo/W)@Au12 clusters interact with the Si and thus stabilize the Si60 cage. The spin-orbit coupling strongly affects the optical properties of (Mo/W)@Au12 clusters as it leads to a splitting of spectral lines together with an intensity redistribution, whereas the spectra of (Mo/W)@Au12Si60 clusters show hardly any difference. The nanoscale properties thus can be tuned by choosing the endohedral metal atom, while keeping the optical properties unaffected. © 2013 American Chemical Society.

  17. Metal cluster compounds - chemistry and importance; clusters containing isolated main group element atoms, large metal cluster compounds, cluster fluxionality

    International Nuclear Information System (INIS)

    Walther, B.

    1988-01-01

    This part of the review on metal cluster compounds deals with clusters containing isolated main group element atoms, with high nuclearity clusters and metal cluster fluxionality. It will be obvious that main group element atoms strongly influence the geometry, stability and reactivity of the clusters. High nuclearity clusters are of interest in there own due to the diversity of the structures adopted, but their intermediate position between molecules and the metallic state makes them a fascinating research object too. These both sites of the metal cluster chemistry as well as the frequently observed ligand and core fluxionality are related to the cluster metal and surface analogy. (author)

  18. Rigid, non-porous and tunable hybrid p-aminobenzoate/TiO2 materials: Toward a fine structural determination of the immobilized RhCl(Ph3)3 complex

    KAUST Repository

    Espinas, Jeff

    2015-05-01

    By exchange of ligands, Wilkinson complex RhCl(PPh3)3 are immobilized on p-aminobenzoate/TiO2 with different organic loading (6, 11 and 16%). This new hybrid material exhibit a linear correlation between the ligand content of the starting TiO2 and the rhodium loading, showing the accessibility of all surfaces amines fonctions on the non-porous parent materials. 1H, 13C, and 1D, 2D INAQUEDATE refocused and J-resolved 31P solid-state NMR confirm the well-defined structure [(≡TiO)2(n{right tail}2-O2C-C6H4-NH2)RhCl-cis-(PPh3)2]. New immobilized catalysts show interesting activity in cyclohexene hydroformylation.

  19. Rigid, non-porous and tunable hybrid p-aminobenzoate/TiO2 materials: Toward a fine structural determination of the immobilized RhCl(Ph3)3 complex

    KAUST Repository

    Espinas, Jeff; Rahal, Raed; Abou-Hamad, Edy; El Eter, Mohamad; Basset, Jean-Marie

    2015-01-01

    By exchange of ligands, Wilkinson complex RhCl(PPh3)3 are immobilized on p-aminobenzoate/TiO2 with different organic loading (6, 11 and 16%). This new hybrid material exhibit a linear correlation between the ligand content of the starting TiO2 and the rhodium loading, showing the accessibility of all surfaces amines fonctions on the non-porous parent materials. 1H, 13C, and 1D, 2D INAQUEDATE refocused and J-resolved 31P solid-state NMR confirm the well-defined structure [(≡TiO)2(n{right tail}2-O2C-C6H4-NH2)RhCl-cis-(PPh3)2]. New immobilized catalysts show interesting activity in cyclohexene hydroformylation.

  20. A highly sensitive fluorescence quenching method for perphenazine detection based on its catalysis of K{sub 2}S{sub 2}O{sub 8} oxidizing rhodamine 6G

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lihong; Huang, Qitong; Lin, Changqing [Department of Food and Biological Engineering, Zhangzhou Institute of Technology, Zhangzhou, 363000 (China); Lin, Xiaofeng [College of Chemistry and Environment, Minnan Normal University, Zhangzhou, 363000 (China); Huang, Yiqun [Zhangzhou Affiliated Hospital of Fujian Medical University, Zhangzhou 363000 (China); Liu, Jiaming, E-mail: mnsdljm@163.com [College of Chemistry and Environment, Minnan Normal University, Zhangzhou, 363000 (China); Ma, Xudong, E-mail: maxudong005@hotmail.com [Zhangzhou Affiliated Hospital of Fujian Medical University, Zhangzhou 363000 (China)

    2014-12-15

    In this paper, the fluorescence spectra of Rhod 6G (rhodamine 6G)–K{sub 2}S{sub 2}O{sub 8}–PPH (perphenazine) were studied. We found that Rhod 6G existed in the form of Rhod 6G{sup +} under the conditions of 60 °C, 10 min and pH 5.42, and Rhod 6G{sup +} can emit strong and stable fluorescence. Further study showed that when PPH and Rhod 6G{sup +} coexisted, the ester exchange reaction carried out between -OH of PPH and -COOC{sub 2}H{sub 5} of Rhod 6G{sup +} to produced Rhod 6G{sup +}–PPH compound. More interestingly, K{sub 2}S{sub 2}O{sub 8} could oxidize Rhod 6G{sup +} and quench its RTP signal, while PPH was oxidized to red compound PPH′ by K{sub 2}S{sub 2}O{sub 8}, and Rhod 6G{sup +}–PPH′ and PPH were produced in the ester exchange reaction between the -OH of PPH′ and the -COOC{sub 2}H{sub 5} of Rhod 6G{sup +}–PPH. In the above process, PPH catalyzed K{sub 2}S{sub 2}O{sub 8} oxidizing Rhod 6G, which caused the fluorescence signal of the system to quench sharply. Hence, a catalytic fluorescence quenching method for the determination of residual PPH has been developed based on the its catalyzing K{sub 2}S{sub 2}O{sub 8} oxidize rhodamine 6G. This sensitive, accurate, simple and selective fluorescence quenching method was used to determine residual PPH in biological samples with the results consisting with those obtained by high performance liquid chromatography (HPLC), showing good accuracy. The structures of Rhod 6G{sup +}, PPH and Rhod 6G{sup +}–PPH were characterized by infrared spectra. The reaction mechanism of the determination of PPH was also discussed. - Highlights: • Fluorescence for the determination of perphenazine (PPH) had been established. • This method had high sensitivity (limit of detection was 3.3×10{sup −14} g mL{sup −1}). • This method had been applied to determination of PPH in biological samples. • Structures of Rhod 6G{sup +}, PPH and Rhod 6G{sup +}–PPH were characterized by infrared spectra. • Mechanism

  1. Facile synthetic approach for 5-aryl-9-hydroxypyrano [3,2-f] indole-2(8H-one

    Directory of Open Access Journals (Sweden)

    Cheng Wang

    2016-11-01

    Full Text Available An appropriate method for the synthesis of 5-aryl-9-hydroxypyrano[3,2-f]indole-2(8H-one was described. The targeted compounds were obtained starting from vanillin via nine steps. Interestingly, in the final cyclization step, the intermediate 4-(2-halogeno phenyl-7-methoxy-1H-indole-6-yl propiolate could convert directly into the final product in one step reaction using PtCl4 or Pd(PPh34/trifluoroacetic acid as catalysts. The possible catalytic mechanism for PtCl4 and Pd(PPh34/trifluoroacetic acid was discussed.

  2. Point-Defect Mediated Bonding of Pt Clusters on (5,5) Carbon Nanotubes

    DEFF Research Database (Denmark)

    Wang, J. G.; Lv, Y. A.; Li, X. N.

    2009-01-01

    The adhesion of various sizes of Pt clusters on the metallic (5,5) carbon nanotubes (CNTs) with and without the point defect has been investigated by means of density functional theory (DFT). The calculations show that the binding energies of Pt-n (n = 1-6) clusters on the defect free CNTs are more......). The stronger orbital hybridization between the Pt atom and the carbon atom shows larger charge transfers on the defective CNTs than on the defect free CNTs, which allows the strong interaction between Pt clusters and CNTs. On the basis of DFT calculations, CNTs with point defect can be used as the catalyst...

  3. Biosynthesis of gold nanoparticles by Aspergillum sp. WL-Au for degradation of aromatic pollutants

    Science.gov (United States)

    Qu, Yuanyuan; Pei, Xiaofang; Shen, Wenli; Zhang, Xuwang; Wang, Jingwei; Zhang, Zhaojing; Li, Shuzhen; You, Shengnan; Ma, Fang; Zhou, Jiti

    2017-04-01

    A simple method for synthesis of gold nanoparticles (AuNPs) using Aspergillum sp. WL-Au was presented in this study. According to UV-vis spectra and transmission electron microscopy images, the shape and size of AuNPs were affected by different parameters, including buffer solution, pH, biomass and HAuCl4 concentrations. Phosphate sodium buffer was more suitable for extracellular synthesis of AuNPs, and the optimal conditions for AuNPs synthesis were pH 7.0, biomass 100 mg/mL and HAuCl4 3 mM, leading to the production of spherical and pseudo-spherical nanoparticles. The biosynthesized AuNPs possessed excellent catalytic activities for the reduction of 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, o-nitroaniline and m-nitroaniline in the presence of NaBH4, and the catalytic rate constants were calculated to be 6.3×10-3 s-1, 5.5×10-3 s-1, 10.6×10-3 s-1, 8.4×10-3 s-1 and 13.8×10-3 s-1, respectively. The AuNPs were also able to catalyze the decolorization of various azo dyes (e.g. Cationic Red X-GRL, Acid Orange II and Acid scarlet GR) using NaBH4 as the reductant, and the decolorization rates reached 91.0-96.4% within 7 min. The present study should provide a potential candidate for green synthesis of AuNPs, which could serve as efficient catalysts for aromatic pollutants degradation.

  4. Origin of the p-type character of AuCl3 functionalized carbon nanotubes

    KAUST Repository

    Murat, Altynbek; Rungger, Ivan; Jin, Chengjun; Sanvito, Stefano; Schwingenschlö gl, Udo

    2014-01-01

    The microscopic origin of the p-type character of AuCl3 functionalized carbon nanotubes (CNTs) is investigated using first-principles self-interaction corrected density functional theory (DFT). Recent DFT calculations suggest that the p

  5. Geometrical Structures and Electronic Properties of Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl Clusters

    Directory of Open Access Journals (Sweden)

    Yanfei Hu

    2018-04-01

    Full Text Available Based on the unbiased CALYPSO (Crystal structure Analysis by Particle Swarm Optimization structure searching method in combination with density functional theory (DFT, the geometrical structures and electronic properties are investigated theoretically for Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl clusters. The PBE0 exchange-correlation functional and the 6-311G(d basis set is carried out to determine global minima on potential energy surfaces. The relative stabilities of the clusters are examined by the binding energies and substitution reaction. Following the predictions of the Jellium model, the Ga5B cluster with the 18 valence electrons is the most stable structure. At last, with the obtained lowest energy structures, some physical properties such as electrons transfer, molecular orbitals, and total and partial densities of states are discussed, respectively.

  6. Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

    Science.gov (United States)

    Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

    2010-06-21

    The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

  7. BRIGHT STRONGLY LENSED GALAXIES AT REDSHIFT z ∼ 6-7 BEHIND THE CLUSTERS ABELL 1703 AND CL0024+16

    International Nuclear Information System (INIS)

    Zheng, W.; Bradley, L. D.; Ford, H. C.; Shu, X.W.; Bouwens, R. J.; Illingworth, G. D.; BenItez, N.; Broadhurst, T.; Zitrin, A.; Frye, B.; Infante, L.; Jee, M. J.; Motta, V.

    2009-01-01

    We report on the discovery of three bright, strongly lensed objects behind Abell 1703 and CL0024+16 from a dropout search over 25 arcmin 2 of deep NICMOS data, with deep ACS optical coverage. They are undetected in the deep ACS images below 8500 A and have clear detections in the J and H bands. Fits to the ACS, NICMOS, and IRAC data yield robust photometric redshifts in the range z ∼ 6-7 and largely rule out the possibility that they are low-redshift interlopers. All three objects are extended, and resolved into a pair of bright knots. The bright i-band dropout in Abell 1703 has an H-band AB magnitude of 23.9, which makes it one of the brightest known galaxy candidates at z > 5.5. Our model fits suggest a young, massive galaxy only ∼60 million years old with a mass of ∼10 10 M sun . The dropout galaxy candidates behind CL0024+16 are separated by 2.''5 (∼2 kpc in the source plane), and have H-band AB magnitudes of 25.0 and 25.6. Lensing models of CL0024+16 suggest that the objects have comparable intrinsic magnitudes of AB ∼27.3, approximately one magnitude fainter than L* at z ∼ 6.5. Their similar redshifts, spectral energy distribution, and luminosities, coupled with their very close proximity on the sky, suggest that they are spatially associated, and plausibly are physically bound. Combining this sample with two previously reported, similarly magnified galaxy candidates at z ∼ 6-8, we find that complex systems with dual nuclei may be a common feature of high-redshift galaxies.

  8. Modeling the pinning of Au and Ni clusters on graphite

    NARCIS (Netherlands)

    Smith, R.; Nock, C.; Kenny, S.D.; Belbruno, J.J.; Di Vece, M.; Paloma, S.; Palmer, R.E.

    2006-01-01

    The pinning of size-selected AuN and NiN clusters on graphite, for N=7–100, is investigated by means of molecular dynamics simulations and the results are compared to experiment and previous work with Ag clusters. Ab initio calculations of the binding of the metal adatom and dimers on a graphite

  9. Direct atomic imaging and density functional theory study of the Au24Pd1 cluster catalyst.

    Science.gov (United States)

    Bruma, A; Negreiros, F R; Xie, S; Tsukuda, T; Johnston, R L; Fortunelli, A; Li, Z Y

    2013-10-21

    In this study we report a direct, atomic-resolution imaging of calcined Au24Pd1 clusters supported on multiwall carbon nanotubes by employing aberration-corrected scanning transmission electron microscopy. Using gold atoms as mass standards, we confirm the cluster size to be 25 ± 2, in agreement with the Au24Pd1(SR)18 precursor used in the synthesis. Concurrently, a Density-Functional/Basin-Hopping computational algorithm is employed to locate the low-energy configurations of free Au24Pd1 cluster. Cage structures surrounding a single core atom are found to be favored, with a slight preference for Pd to occupy the core site. The cluster shows a tendency toward elongated arrangements, consistent with experimental data. The degree of electron transfer from the Pd dopant to Au is quantified through a Löwdin charge analysis, suggesting that Pd may act as an electron promoter to the surrounding Au atoms when they are involved in catalytic reactions.

  10. Is the largest aqueous gold cluster a superatom complex? Electronic structure & optical response of the structurally determined Au146(p-MBA)57.

    Science.gov (United States)

    López-Lozano, Xóchitl; Plascencia-Villa, G; Calero, G; Whetten, R L; Weissker, Hans-Christian

    2017-12-07

    The new water-soluble gold cluster Au 146 (p-MBA) 57 , the structure of which has been recently determined at sub-atomic resolution by Vergara et al., is the largest aqueous gold cluster ever structurally determined and likewise the smallest cluster with a stacking fault. The core presents a twinned truncated octahedron, while additional peripheral gold atoms follow a C 2 rotational symmetry. According to the usual counting rules of the superatom complex (SAC) model, the compound attains a number of 92 SAC electrons if the overall net charge is 3- (three additional electrons). As this is the number of electrons required for a major shell closing, the question arises of whether Au 146 (p-MBA) 57 should be regarded as a superatom complex. Starting from the experimental coordinates we have analyzed the structure using density-functional theory. The optimized (relaxed) structure retains all the connectivity of the experimental coordinates, while removing much of its irregularities in interatomic distances, thereby enhancing the C 2 -symmetry feature. On analyzing the angular-momentum-projected states, we show that, despite a small gap, the electronic structure does not exhibit SAC model character. In addition, optical absorption spectra are found to be relatively smooth compared to the example of the Au 144 (SR) 60 cluster. The Au 146 (SR) 57 does not derive its stability from SAC character; it cannot be considered as a superatom complex.

  11. Fabrication of Pt/Au concentric spheres from triblock copolymer.

    Science.gov (United States)

    Koh, Haeng-Deog; Park, Soojin; Russell, Thomas P

    2010-02-23

    Dispersion of an aqueous H(2)PtCl(6) solution into a trifluorotoluene (TFT) solution of a polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) triblock copolymer produced an emulsion-induced hollow micelle (EIHM), comprising a water nanodroplet stabilized by PEO, H(2)PtCl(6)/P2VP, and PS, sequentially. The following addition of an aqueous LiAuCl(4) solution into the dispersion led to a coordination of LiAuCl(4) and PEO. The resulting spherical EIHM structure was transformed to a hollow cylindrical micelle by the fusion of spherical EIHM with the addition of methanol. This structural transition was reversible by the alternative addition of methanol and TFT. Oxygen plasma was used to generate Pt/Au concentric spheres and hollow cylindrical Pt/Au nano-objects.

  12. Au11Re: A hollow or endohedral binary cluster?

    Science.gov (United States)

    MacLeod Carey, Desmond; Muñoz-Castro, Alvaro

    2018-06-01

    In this letter, we discussed the plausible formation of [Au11Re] as a superatom with an electronic structure accounted by the 1S21P61D10 shell order, denoting similar stability to [W@Au12]. The possible hollow or endohedral structures show a variable HOMO-LUMO gap according to the given structure (from 0.33 to 1.30 eV, at the PBE/ZORA level). Our results show that the energy minimum is an endohedral arrangement, where Re is encapsulated in a D3h-Au11 cage, retaining a higher gold-dopant stoichiometric ratio. This approach is useful for further rationalization and design of novel superatoms expanding the libraries of endohedral clusters.

  13. Application of a parallel genetic algorithm to the global optimization of medium-sized Au-Pd sub-nanometre clusters

    Science.gov (United States)

    Hussein, Heider A.; Demiroglu, Ilker; Johnston, Roy L.

    2018-02-01

    To contribute to the discussion of the high activity and reactivity of Au-Pd system, we have adopted the BPGA-DFT approach to study the structural and energetic properties of medium-sized Au-Pd sub-nanometre clusters with 11-18 atoms. We have examined the structural behaviour and stability as a function of cluster size and composition. The study suggests 2D-3D crossover points for pure Au clusters at 14 and 16 atoms, whereas pure Pd clusters are all found to be 3D. For Au-Pd nanoalloys, the role of cluster size and the influence of doping were found to be extensive and non-monotonic in altering cluster structures. Various stability criteria (e.g. binding energies, second differences in energy, and mixing energies) are used to evaluate the energetics, structures, and tendency of segregation in sub-nanometre Au-Pd clusters. HOMO-LUMO gaps were calculated to give additional information on cluster stability and a systematic homotop search was used to evaluate the energies of the generated global minima of mono-substituted clusters and the preferred doping sites, as well as confirming the validity of the BPGA-DFT approach.

  14. Electronic structure of structural open derivatives of the [Mo6X14]2- cluster: [Mo5Cl13]2- and [Mo4I11]2-

    International Nuclear Information System (INIS)

    Miessner, H.; Korol'kov, D.V.

    1983-01-01

    The electronic structure of structural open derivatives of the [Mo 6 X 14 ] 2 - -cluster [Mo 5 Cl 13 ] 2 - and [Mo 4 I 11 ] 2 - has been studied by the EHMO method. In [Mo 5 Cl 13 ] 2 - 9 occupied MO's with dominant Mo4d character are responsible for the formation of the 8 metal-metal bonds. In [Mo 4 I 11 ] 2 - the stronger covalent character of the Mo-I bonds affects the localization and the energy of molecular orbitals and also the charge distribution. The metal-metal bonds are formed by 8 MO's containing considerable participation of halogen AO's contrary to the chloride cluster. There is no bonding between the Mo atoms at the wing tips of the Mo 4 butterfly and the reason for decreasing the dihedral angle between the Mo 3 planes in [Mo 4 I 11 ] 2 - compared with the octahedral angle is apparently the stabilization of the whole system (Mo-Mo and Mo-I bonds). The unpaired electron occupies in both clusters a slightly antibonding (with regard to the Mo-Mo bonds) orbital. (author)

  15. Uptake of Au(III) Ions by Aluminum Hydroxide and Their Spontaneous Reduction to Elemental Gold (Au(0)).

    Science.gov (United States)

    Yokoyama; Matsukado; Uchida; Motomura; Watanabe; Izawa

    2001-01-01

    The behavior of AuCl(4)(-) ions during the formation of aluminum hydroxide at pH 6 was examined. With an increase in NaCl concentration, the content of gold taken up by aluminum hydroxide decreased, suggesting that chloro-hydroxy complexes of Au(III) ion were taken up due to the formation of Al-O-Au bonds. It was found unexpectedly that the Au(III) ions taken up were spontaneously reduced to elemental gold without addition of a specific reducing reagent and then colloidal gold particles were formed. The mechanisms for the uptake of Au(III) ions by aluminum hydroxide and for their spontaneous reduction are discussed. Copyright 2001 Academic Press.

  16. Bonding properties of FCC-like Au 44 (SR) 28 clusters from X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rui [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Chevrier, Daniel M. [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Zeng, Chenjie [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Jin, Rongchao [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Zhang, Peng [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.

    2017-11-01

    Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal core (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.

  17. Measurement and Modeling of Setschenow Constants for Selected Hydrophilic Compounds in NaCl and CaCl2 Simulated Carbon Storage Brines.

    Science.gov (United States)

    Burant, Aniela; Lowry, Gregory V; Karamalidis, Athanasios K

    2017-06-20

    Carbon capture, utilization, and storage (CCUS), a climate change mitigation strategy, along with unconventional oil and gas extraction, generates enormous volumes of produced water containing high salt concentrations and a litany of organic compounds. Understanding the aqueous solubility of organic compounds related to these operations is important for water treatment and reuse alternatives, as well as risk assessment purposes. The well-established Setschenow equation can be used to determine the effect of salts on aqueous solubility. However, there is a lack of reported Setschenow constants, especially for polar organic compounds. In this study, the Setschenow constants for selected hydrophilic organic compounds were experimentally determined, and linear free energy models for predicting the Setschenow constant of organic chemicals in concentrated brines were developed. Solid phase microextraction was employed to measure the salting-out behavior of six selected hydrophilic compounds up to 5 M NaCl and 2 M CaCl 2 and in Na-Ca-Cl brines. All compounds, which include phenol, p-cresol, hydroquinone, pyrrole, hexanoic acid, and 9-hydroxyfluorene, exhibited log-linear behavior up to these concentrations, meaning Setschenow constants previously measured at low salt concentrations can be extrapolated up to high salt concentrations for hydrophilic compounds. Setschenow constants measured in NaCl and CaCl 2 brines are additive for the compounds measured here; meaning Setschenow constants measured in single salt solutions can be used in multiple salt solutions. The hydrophilic compounds in this study were selected to elucidate differences in salting-out behavior based on their chemical structure. Using data from this study, as well as literature data, linear free energy relationships (LFERs) for prediction of NaCl, CaCl 2 , LiCl, and NaBr Setschenow constants were developed and validated. Two LFERs were improved. One LFER uses the Abraham solvation parameters, which include

  18. Computational study of AuSi{sub n} (n=1-9) nanoalloy clusters invoking DFT based descriptors

    Energy Technology Data Exchange (ETDEWEB)

    Ranjan, Prabhat; Kumar, Ajay [Department of Mechatronics, Manipal University Jaipur Dehmi Kalan, Jaipur-303007 (India); Chakraborty, Tanmoy, E-mail: tanmoy.chakraborty@jaipur.manipal.edu, E-mail: tanmoychem@gmail.com [Department of Chemistry, Manipal University Jaipur Dehmi Kalan, Jaipur-303007 (India)

    2016-04-13

    Nanoalloy clusters formed between Au and Si are topics of great interest today from both scientific and technological point of view. Due to its remarkable catalytic, electronic, mechanical and magnetic properties Au-Si nanoalloy clusters have extensive applications in the field of microelectronics, catalysis, biomedicine, and jewelry industry. Density Functional Theory (DFT) is a new paradigm of quantum mechanics, which is very much popular to study the electronic properties of materials. Conceptual DFT based descriptors have been invoked to correlate the experimental properties of nanoalloy clusters. In this venture, we have systematically investigated AuSi{sub n} (n=1-9) nanoalloy clusters in the theoretical frame of the B3LYP exchange correlation. The experimental properties of AuSi{sub n} (n=1-9) nanoalloy clusters are correlated in terms of DFT based descriptors viz. HOMO-LUMO gap, Electronegativity (χ), Global Hardness (η), Global Softness (S) and Electrophilicity Index (ω). The calculated HOMO-LUMO gap exhibits interesting odd-even alteration behaviour, indicating that even numbered clusters possess higher stability as compare to their neighbour odd numbered clusters. This study also reflects a very well agreement between experimental bond length and computed data.

  19. Cluster - ClEST | LSDB Archive [Life Science Database Archive metadata

    Lifescience Database Archive (English)

    Full Text Available switchLanguage; BLAST Search Image Search Home About Archive Update History Data ...e File name: clest_cluster.zip File URL: ftp://ftp.biosciencedbc.jp/archive/clest/LATEST/clest_cluster.zip F...ownload License Update History of This Database Site Policy | Contact Us Cluster - ClEST | LSDB Archive ...

  20. Raman spectra of the system TeCl4-SbCl5

    International Nuclear Information System (INIS)

    Brockner, W.; Demiray, A.F.

    1980-01-01

    Raman spectra of the solid and molten TeCl 4 . SbCl 5 addition compound and of some TeCl 4 -SbCl 5 mixtures have been recorded. Two modifications of the crystalline TeCl 4 -SbCl 5 compound have been found. The structure of the melt can be described by the equilibrium TeCl 3 + + SbCl 6 - reversible TeCl 4 + SbCl 5 lying on the left side. Mixtures with other stoichiometry contain the 1:1 adduct only and excess TeCl 4 or SbCl 5 , respectively. Such melts are built up by the ionic species TeCl 3 + and SbCl 6 - also and TeCl 4 or SbCl 5 according to stoichiometry. (author)

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

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  2. The Atacama Cosmology Telescope: ACT-CL J0102-4915 'EL GORDO', A Massive Merging Cluster at Redshift 0.87

    Science.gov (United States)

    Menanteau, Felipe; Hughes, John P.; Sifon, Cristobal; Hilton, Matt; Gonzalez, Jorge; Infante, Leopoldo; Barrientos, L. Felipe; Baker, Andrew J.; Bond, John R.; Das, Sudeep; hide

    2012-01-01

    We present a detailed analysis from new multi-wavelength observations of the exceptional galaxy cluster ACT-CL J0102-4915, likely the most massive, hottest, most X-ray luminous and brightest Sunyaev-Zel'dovich (SZ) effect cluster known at redshifts greater than 0.6. The Atacama Cosmology Telescope (ACT) collaboration discovered ACT-CL J0102-4915 as the most significant Sunyaev-Zeldovich (SZ) decrement in a sky survey area of 755 square degrees. Our VLT/FORS2 spectra of 89 member galaxies yield a cluster redshift, z = 0.870, and velocity dispersion, sigma(sub gal) = 1321+/-106 km s-1. Our Chandra observations reveal a hot and X-ray luminous system with an integrated temperature of T(sub X) = 14.5+/-1.0 keV and 0.5-2.0 keV band luminosity of L(sub X) = (2.19+/-0.11)×10(sup 45) h(sup -2)(sub 70) erg s-1. We obtain several statistically consistent cluster mass estimates; using empirical mass scaling relations with velocity dispersion, X-ray Y(sub X), and integrated SZ distortion, we estimate a cluster mass of M(sub 200a) = (2.16+/-0.32)×1015 h(sup -1)(sub 70) solar mass. We constrain the stellar content of the cluster to be less than 1% of the total mass, using Spitzer IRAC and optical imaging. The Chandra and VLT/FORS2 optical data also reveal that ACT-CL J0102-4915 is undergoing a major merger between components with a mass ratio of approximately 2 to 1. The X-ray data show significant temperature variations from a low of 6.6+/-0.7 keV at the merging low-entropy, high-metallicity, cool core to a high of 22+/-6 keV. We also see a wake in the X-ray surface brightness and deprojected gas density caused by the passage of one cluster through the other. Archival radio data at 843 MHz reveal diffuse radio emission that, if associated with the cluster, indicates the presence of an intense double radio relic, hosted by the highest redshift cluster yet. ACT-CL J0102-4915 is possibly a high-redshift analog of the famous Bullet Cluster. Such a massive cluster at this redshift

  3. Digital Signal Processing Based on a Clustering Algorithm for Ir/Au TES Microcalorimeter

    Science.gov (United States)

    Zen, N.; Kunieda, Y.; Takahashi, H.; Hiramoto, K.; Nakazawa, M.; Fukuda, D.; Ukibe, M.; Ohkubo, M.

    2006-02-01

    In recent years, cryogenic microcalorimeters using their superconducting transition edge have been under development for possible application to the research for astronomical X-ray observations. To improve the energy resolution of superconducting transition edge sensors (TES), several correction methods have been developed. Among them, a clustering method based on digital signal processing has recently been proposed. In this paper, we applied the clustering method to Ir/Au bilayer TES. This method resulted in almost a 10% improvement in the energy resolution. Conversely, from the point of view of imaging X-ray spectroscopy, we applied the clustering method to pixellated Ir/Au-TES devices. We will thus show how a clustering method which sorts signals by their shapes is also useful for position identification

  4. Synthesis and Structure Determination of a New Au20 Nanocluster Protected by Tripodal Tetraphosphine Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jing [Brown Univ., Providence, RI (United States); Zhang, Qianfan [Brown Univ., Providence, RI (United States); Williard, Paul G. [Brown Univ., Providence, RI (United States); Wang, Lai-Sheng [Brown Univ., Providence, RI (United States)

    2014-03-31

    We report the synthesis and structure determination of a new Au20 nanocluster coordinated by four tripodal tetraphosphine (PP3) ligands {PP3 = tris[2-(diphenylphosphino)ethyl]phosphine}. Single-crystal Xray crystallography and electrospray ionization mass spectrometry show that the cluster assembly can be formulated as [Au20(PP3)4]Cl4. The Au20 cluster consists of an icosahedral Au13 core and a seven-Au-atom partial outer shell arranged in a local C3 symmetry. One PP3 ligand coordinates to four Au atoms in the outer shell, while the other three PP3 ligands coordinate to one Au atom from the outer shell and three Au atoms from the surface of the Au13 core, giving rise to an overall chiral 16-electron Au cluster core with C3 symmetry.

  5. Geometric, stability, and electronic properties of gold-doped Pd clusters (Pd{sub n}Au, n = 3~20)

    Energy Technology Data Exchange (ETDEWEB)

    Huan, Hao; Chen, Yan; Wang, Tao; Ye, Xiang, E-mail: yexiang@shnu.edu.cn [Shanghai Normal University, Department of Physics (China); Gu, Xiao, E-mail: gx@cqu.edu.cn [Chongqing University, Department of Applied Physics (China)

    2016-11-15

    The structure, stability, and electronic properties of Pd{sub n}Au (n = 3~20) clusters are studied by density functional theory. The results show that the clusters studied here prefer three-dimensional structures even with very small atom number. It is found that the binding energies of Pd{sub n}Au clusters are higher than the corresponding pure Pd{sub n} clusters with the same atom number. Most Pd{sub n}Au clusters studied here are magnetic with magnetic moments ranging from 1.0 to 7.0 μ{sub B.} The dissociation energies of Pd atoms are lower than the doped gold atom, that is the doped Au atom will increase the mother clusters stability and activity.

  6. Synthesis, crystal structures, and characterization of double complex salts [Au(en)2][Rh(NO2)6]·2H2O and [Au(en)2][Rh(NO2)6

    Science.gov (United States)

    Plyusnin, Pavel E.; Makotchenko, Evgenia V.; Shubin, Yury V.; Baidina, Iraida A.; Korolkov, Ilya V.; Sheludyakova, Liliya A.; Korenev, Sergey V.

    2015-11-01

    Double complex salts of rhodium(III) and gold(III) of the composition [Au(en)2][Rh(NO2)6]·2H2O (1) and [Au(en)2][Rh(NO2)6] (2) have been prepared. Crystal structures of the compounds have been determined by single crystal X-ray diffraction. The compounds have been characterized by PXRD, IR, far-IR, CHN and DTA. The complexes have a layered structures. The presence of water in 1 makes the structure of the hydrated DCS less dense as compared to the anhydrous one. The environment of the cation and the anion in the two structures is the same, oxygen atoms of the nitro groups are involved in hydrogen bonds N-H⋯O, N⋯O distances being approximately the same. The structures of 1 and 2 are notable in having shortened contacts between the gold atoms and the oxygen atoms of the nitro groups of the neighboring complex anions. The thermal behavior of the complexes in a hydrogen atmosphere was investigated. The final product of thermolysis prepared at the temperature 600°C is a two-phase mixture of pure metallic gold and the solid solution Rh0.93Au0.07.

  7. N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3

    Directory of Open Access Journals (Sweden)

    Felix S. Geitner

    2017-07-01

    Full Text Available We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene compounds of the germanium-rich metalloid clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3. NHCDippCu{η3Ge9R3} with R = Si(iPr3 (1 represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(iBu3 or Si(TMS3. The coordination of the [NHCDippCu]+ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge9] cluster. Furthermore, a series of novel Zintl cluster coinage metal NHC compounds of the type (NHCM2{η3Ge9RI2} (RI = Si(TMS3 M = Cu, Ag and Au; NHC = NHCDipp or NHCMes is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12Ge17 with Si(TMS3Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au, or via a homogenous reaction using the preformed bis-silylated cluster K2[Ge9(Si(TMS32] and the corresponding NHCMCl (M = Cu, Ag, Au complex. The molecular structures of NHCDippCu{η3Ge9(Si(iPr33} (1 and (NHCDippCu2{η3-Ge9(Si(TMS32} (2 were determined by single crystal X-ray diffraction methods. In 2, the coordination of the [NHCDippCu]+ moieties to the cluster unit takes place via both open triangular faces of the [Ge9] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (1H, 13C, 29Si and ESI-MS.

  8. Synthesis, structure and isomerism of three-bridge exo-nido-osmacarborane clusters

    International Nuclear Information System (INIS)

    Kolomnikova, G.D.; Petrovskij, P.V.; Sorokin, P.V.; Dolgushin, F.M.; Yanovskij, A.I.; Chizhevskij, I.T.

    2001-01-01

    The structure and isomerism of exo-nido-osmacarboranes prepared by reaction between coordination-unsaturated complex OsCl 2 (PPh 3 ) 3 (Ph-phenyl) in benzene at 20 deg C and K + -salts of nido-dicarbaundecarborate anions were studied by the methods of 1 H and 11 B NMR (including usual and two-dimensional spectra) and X-ray diffraction analysis. It was ascertained that in the compounds prepared osmium-containing group is bound with nido-carborane ligand via three-center bonds, open pentagonal plane of carborane ligand being retained in the isomers. In it nature isomerism in the compounds mentioned is geometrical cis-trans-isomerism [ru

  9. Production of Au clusters by plasma gas condensation and their incorporation in oxide matrixes by sputtering

    Science.gov (United States)

    Figueiredo, N. M.; Serra, R.; Manninen, N. K.; Cavaleiro, A.

    2018-05-01

    Gold clusters were produced by plasma gas condensation method and studied in great detail for the first time. The influence of argon flow, discharge power applied to the Au target and aggregation chamber length on the size distribution and deposition rate of Au clusters was evaluated. Au clusters with sizes between 5 and 65 nm were deposited with varying deposition rates and size dispersion curves. Nanocomposite Au-TiO2 and Au-Al2O3 coatings were then deposited by alternating sputtering. These coatings were hydrophobic and showed strong colorations due to the surface plasmon resonance effect. By simulating the optical properties of the nanocomposites it was possible to identify each individual contribution to the overall surface plasmon resonance signal. These coatings show great potential to be used as high performance localized surface plasmon resonance sensors or as robust self-cleaning decorative protective layers. The hybrid method used for depositing the nanocomposites offers several advantages over co-sputtering or thermal evaporation processes, since a broader range of particle sizes can be obtained (up to tens of nanometers) without the application of any thermal annealing treatments and the properties of clusters and matrix can be controlled separately.

  10. Systematic Study on the Self-Assembled Hexagonal Au Voids, Nano-Clusters and Nanoparticles on GaN (0001.

    Directory of Open Access Journals (Sweden)

    Puran Pandey

    Full Text Available Au nano-clusters and nanoparticles (NPs have been widely utilized in various electronic, optoelectronic, and bio-medical applications due to their great potentials. The size, density and configuration of Au NPs play a vital role in the performance of these devices. In this paper, we present a systematic study on the self-assembled hexagonal Au voids, nano-clusters and NPs fabricated on GaN (0001 by the variation of annealing temperature and deposition amount. At relatively low annealing temperatures between 400 and 600°C, the fabrication of hexagonal shaped Au voids and Au nano-clusters are observed and discussed based on the diffusion limited aggregation model. The size and density of voids and nano-clusters can systematically be controlled. The self-assembled Au NPs are fabricated at comparatively high temperatures from 650 to 800°C based on the Volmer-Weber growth model and also the size and density can be tuned accordingly. The results are symmetrically analyzed and discussed in conjunction with the diffusion theory and thermodynamics by utilizing AFM and SEM images, EDS maps and spectra, FFT power spectra, cross-sectional line-profiles and size and density plots.

  11. Controlled assembly and single electron charging of monolayer protected Au144 clusters: an electrochemistry and scanning tunneling spectroscopy study

    Science.gov (United States)

    Bodappa, Nataraju; Fluch, Ulrike; Fu, Yongchun; Mayor, Marcel; Moreno-García, Pavel; Siegenthaler, Hans; Wandlowski, Thomas

    2014-11-01

    Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups exposed by the Au-MPCs enable their immobilization on Pt(111) substrates. By varying the humidity during their deposition, samples coated by stacks of compact monolayers of Au-MPCs or decorated with individual, laterally separated Au-MPCs are obtained. DPV experiments with stacked monolayers of Au144-MPCs and EC-STS experiments with laterally separated individual Au144-MPCs are performed both in aqueous and ionic liquid electrolytes. Lower capacitance values were observed for individual clusters compared to ensemble clusters. This trend remains the same irrespective of the composition of the electrolyte surrounding the Au144-MPC. However, the resolution of the energy level spacing of the single clusters is strongly affected by the proximity of neighboring particles.Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups

  12. THE ATACAMA COSMOLOGY TELESCOPE: ACT-CL J0102–4915 'EL GORDO', A MASSIVE MERGING CLUSTER AT REDSHIFT 0.87

    International Nuclear Information System (INIS)

    Menanteau, Felipe; Hughes, John P.; Baker, Andrew J.; Sifón, Cristóbal; González, Jorge; Infante, Leopoldo; Felipe Barrientos, L.; Hilton, Matt; Bond, John R.; Hajian, Amir; Nolta, Michael R.; Das, Sudeep; Devlin, Mark J.; Marsden, Danica; Dunkley, Joanna; Hincks, Adam D.; Kosowsky, Arthur; Marriage, Tobias A.; Moodley, Kavilan; Niemack, Michael D.

    2012-01-01

    We present a detailed analysis from new multi-wavelength observations of the exceptional galaxy cluster ACT-CL J0102–4915, likely the most massive, hottest, most X-ray luminous and brightest Sunyaev-Zel'dovich (SZ) effect cluster known at redshifts greater than 0.6. The Atacama Cosmology Telescope (ACT) collaboration discovered ACT-CL J0102–4915 as the most significant SZ decrement in a sky survey area of 755 deg 2 . Our Very Large Telescope (VLT)/FORS2 spectra of 89 member galaxies yield a cluster redshift, z = 0.870, and velocity dispersion, σ gal = 1321 ± 106 km s –1 . Our Chandra observations reveal a hot and X-ray luminous system with an integrated temperature of T X = 14.5 ± 0.1 keV and 0.5-2.0 keV band luminosity of L X = (2.19 ± 0.11) × 10 45 h –2 70 erg s –1 . We obtain several statistically consistent cluster mass estimates; using empirical mass scaling relations with velocity dispersion, X-ray Y X , and integrated SZ distortion, we estimate a cluster mass of M 200a = (2.16 ± 0.32) × 10 15 h –1 70 M ☉ . We constrain the stellar content of the cluster to be less than 1% of the total mass, using Spitzer IRAC and optical imaging. The Chandra and VLT/FORS2 optical data also reveal that ACT-CL J0102–4915 is undergoing a major merger between components with a mass ratio of approximately 2 to 1. The X-ray data show significant temperature variations from a low of 6.6 ± 0.7 keV at the merging low-entropy, high-metallicity, cool core to a high of 22 ± 6 keV. We also see a wake in the X-ray surface brightness and deprojected gas density caused by the passage of one cluster through the other. Archival radio data at 843 MHz reveal diffuse radio emission that, if associated with the cluster, indicates the presence of an intense double radio relic, hosted by the highest redshift cluster yet. ACT-CL J0102–4915 is possibly a high-redshift analog of the famous Bullet cluster. Such a massive cluster at this redshift is rare, although consistent

  13. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X. J.; Xue, X. L.; Jia, Yu [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Guo, Z. X. [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Department of Chemistry and London Centre for Nanotechnology, University College London, London WC1H (United Kingdom); Li, S. F., E-mail: sflizzu@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang, Zhenyu, E-mail: zhangzy@ustc.edu.cn [ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gao, Y. F., E-mail: ygao7@utk.edu [Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-07

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N} clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  14. Lithiation of prochiral 2,2'-dichloro-5,5'-dibromo-4,4'-bipyridine as a tool for the synthesis of chiral polyhalogenated 4,4'-bipyridines.

    Science.gov (United States)

    Mamane, Victor; Aubert, Emmanuel; Peluso, Paola; Cossu, Sergio

    2013-08-02

    Lithiation of the achiral tetrahalogenated 4,4'-bipyridine 1 with alkyllithiums was investigated. n-BuLi was found to induce either the chlorine-directed deprotolithiation reaction alone or with a concomitant halogen-lithium exchange furnishing after iodine trapping chiral 4,4'-bipyridines 2 and 6, respectively. The role of n-BuLi in the deprotolithiation process of 1 was elucidated on the basis of isolated secondary derivatives. After deprotolithiation, the lithiated species could be trapped by different electrophiles such as MeI, TMSCl, MeSSMe, R3SnCl (R = Me or n-Bu), and PPh2Cl. Moreover, 4,4'-bipyridine 2 was submitted to cross-coupling reactions (Suzuki and Sonogashira) which occurred selectively at the carbon-iodine bond. All compounds of this new family of atropisomeric 4,4'-bipyridines were separated by chiral HPLC (high-performance liquid chromatography), and the absolute configurations of obtained enantiomers were mainly assigned by XRD (X-ray diffraction) using anomalous dispersion.

  15. Intense fluorescence of Au 20

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Chongqi; Harbich, Wolfgang; Sementa, Luca; Ghiringhelli, Luca; Apra, Edoardo; Stener, Mauro; Fortunelli, Alessandro; Brune, Harald

    2017-08-21

    Ligand-protected Au clusters are non-bleaching fluorescence markers in bio- and medical applications. We show that their fluorescence is an intrinsic property of the Au cluster itself. We find a very intense and sharp fluorescence peak located at λ =739.2 nm (1.68 eV) for Au20 clusters in a Ne matrix held at 6 K. The fluorescence reflects the HOMO-LUMO diabatic bandgap of the cluster. The cluster shows a very rich absorption fine structure reminiscent of well defined molecule-like quantum levels. These levels are resolved since Au20 has only one stable isomer (tetrahedral), therefore our sample is mono-disperse in cluster size and conformation. Density-functional theory (DFT) and time-dependent DFT calculations clarify the nature of optical absorptionand predict both main absorption peaks and intrinsic fluorescence in good agreement with experiment.

  16. NaNO3/NaCl Oxidant and Polyethylene Glycol (PEG) Capped Gold Nanoparticles (AuNPs) as a Novel Green Route for AuNPs Detection in Electrochemical Biosensors.

    Science.gov (United States)

    López-Marzo, Adaris M; Hoyos-de-la-Torre, Raquel; Baldrich, Eva

    2018-03-20

    Gold nanoparticles (AuNPs) have been exploited as signal-producing tags in electrochemical biosensors. However, the electrochemical detection of AuNPs is currently performed using corrosive acid solutions, which may raise health and environmental concerns. Here, oxidant salts, and specifically the environmentally friendly and occupational safe NaNO 3 /NaCl mixture, have been evaluated for the first time as potential alternatives to the acid solutions traditionally used for AuNPs electrooxidation. In addition, a new strategy to improve the sensitivity of the biosensor through PEG-based ligand exchange to produce less compact and easier to oxidize AuNPs immunoconjugates is presented too. As we show, the electrochemical immunosensor using NaNO 3 /NaCl measurement solution for AuNPs electrooxidation and detection, coupled to the employment of PEG-capped nanoimmunoconjugates, produced results comparable to classical HCl detection. The procedure developed was next tested for human matrix metallopeptidase-9 (hMMP9) analysis, exhibiting a 0.18-23 ng/mL linear range, a detection limit of 0.06 ng/mL, and recoveries between 95 and 105% in spiked human plasma. These results show that the procedure developed is applicable to the analysis of protein biomarkers in blood plasma and could contribute to the development of more environmentally friendly AuNP-based electrochemical biosensors.

  17. Synthesis and characterization of technetium(III) complexes with nitrogen heterocycles by O atom transfer from oxotechnetium(V) cores. Crystal structures of mer-[Cl3(pic)3Tc] and mer-[Cl3(pic)(PMe2Ph)2Tc] (pic = 4-picoline). Electrochemical parameters fore the reduction of TcII, TcIII, and TcIV

    International Nuclear Information System (INIS)

    Lu, Jun; Yamano, Akahito; Clarke, M.J.

    1990-01-01

    The combination of pyridine ligands, (OCl 4 Tc) - , and O atom acceptors of different cone angles, such as PMe 2 Ph or PPh 3 , results in Tc III complexes that vary in the coordination of the phosphine ligand. The compounds mer[Cl 3 (4-picoline) 3 Tc] and mer-(Cl 3 (4-picoline)(PMe 2 Ph) 2 Tc) have been obtained in good yield and have been characterized spectroscopically and by single-crystal x-ray diffraction. The crystal structure data are reported. Linear correlations of technetium reduction potentials in DMF with electrochemical ligand additivity parameters (E L 's) have been obtained for the Tc II,I , Tc III,II , and Tc IV,III couples. The slope and intercept (S M , I M ) pairs for each technetium oxidation-reduction couple, respectively, are (1.39, -2.07), (1.29, -0.91), and (1.00, 0.65). 32 refs., 3 figs., 6 tabs

  18. Study of NaBH4 reaction with RhCl3·4H2O and H2PtCl6·6H2O in dimethylformamide

    International Nuclear Information System (INIS)

    Khain, V.S.; Val'kova, V.P.

    1988-01-01

    Data on study of NaBH 4 reactions with RhCl 3 x4H 2 O and H 2 PtCl 6 x6H 2 O in dimethylformamide, which is a good solvent of both complex hydride and compounds of platinum metals are presented. Rhodium (3) and platinum (4) reduction by sodium tetrahydridoborate in dimethylformamide proceeds quantitatively up to element state. Depositions of powder-like rhodium and platinum or their sols stable up to 8 months are formed depending on the ratio of concentrations of the reacting substances. Stoichiometry of redox-reactions is established based on spectrophotometric, gasovolumetric measurements,

  19. Bright Strongly Lensed Galaxies at Redshift z ~ 6-7 behind the Clusters Abell 1703 and CL0024+16

    Science.gov (United States)

    Zheng, W.; Bradley, L. D.; Bouwens, R. J.; Ford, H. C.; Illingworth, G. D.; Benítez, N.; Broadhurst, T.; Frye, B.; Infante, L.; Jee, M. J.; Motta, V.; Shu, X. W.; Zitrin, A.

    2009-06-01

    We report on the discovery of three bright, strongly lensed objects behind Abell 1703 and CL0024+16 from a dropout search over 25 arcmin2 of deep NICMOS data, with deep ACS optical coverage. They are undetected in the deep ACS images below 8500 Å and have clear detections in the J and H bands. Fits to the ACS, NICMOS, and IRAC data yield robust photometric redshifts in the range z ~ 6-7 and largely rule out the possibility that they are low-redshift interlopers. All three objects are extended, and resolved into a pair of bright knots. The bright i-band dropout in Abell 1703 has an H-band AB magnitude of 23.9, which makes it one of the brightest known galaxy candidates at z > 5.5. Our model fits suggest a young, massive galaxy only ~60 million years old with a mass of ~1010 M sun. The dropout galaxy candidates behind CL0024+16 are separated by 2farcs5 (~2 kpc in the source plane), and have H-band AB magnitudes of 25.0 and 25.6. Lensing models of CL0024+16 suggest that the objects have comparable intrinsic magnitudes of AB ~27.3, approximately one magnitude fainter than L* at z ~ 6.5. Their similar redshifts, spectral energy distribution, and luminosities, coupled with their very close proximity on the sky, suggest that they are spatially associated, and plausibly are physically bound. Combining this sample with two previously reported, similarly magnified galaxy candidates at z ~ 6-8, we find that complex systems with dual nuclei may be a common feature of high-redshift galaxies. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities of Research in Astronomy, Inc., under NASA contract NAS5-26555, and at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the Particle

  20. The assessment of the energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-Hexaazaisowurtzitane (CL-20) degradability in soil

    International Nuclear Information System (INIS)

    Strigul, Nikolay; Braida, Washington; Christodoulatos, Christos; Balas, Wendy; Nicolich, Steven

    2006-01-01

    CL-20 is a relatively new energetic compound with applications in explosive and propellant formulations. Currently, information about the fate of CL-20 in ecological systems is scarce. The aim of this study is to evaluate the biodegradability of CL-20 in soil environments. Four soils were used where initial CL-20 concentrations (above water solubility) ranged from 125 to 1500 mg of CL-20 per kg dry soil (corresponding to the concentrations derived from unexploded ordnance, low order detonation, or manufacturing spills). CL-20 appears to be biodegradable in soil under anaerobic conditions, and additions of organic substrates can substantially accelerate this process. However, CL-20 is not degraded in soil under aerobic conditions kept in the dark at temperatures up to 30 deg. C without organic amendments. Additions of starch or cellulose promote the biodegradation of CL-20 under aerobic conditions. Soil microbial community mediated biodegradation and plant uptake appears to enhance CL-20 biodegradation, the latter suggesting a possible route for CL-20 to entry in the food chain. - Biodegradation and plant uptake suggest possible entry of CL-20 into food chain

  1. The Atacama Cosmology Telescope: ACT-CL J0102-4215 "El Gordo," a Massive Merging Cluster at Redshift 0.87

    Science.gov (United States)

    Menanteau, Felipe; Hughes, John Pl; Baker, Andrew J.; Sifon, Cristobal; Gonzalez, Jorge; Infante, Leopoldo; Barrientos, L. Felipe; Hilton, Matt; Das, Sudeep; Spergel, David N.; hide

    2011-01-01

    We present a detailed analysis from new multi-wavelength observations of the exceptional galaxy cluster ACT-CL J0102-4915, likely the most massive, hottest, most X-ray luminous and brightest Sunyaev-Zel'dovich (SZ) effect cluster known at redshifts greater than 0.6. The Atacama Cosmology Telescope (ACT) collaboration discovered ACT-CL J0102-4915 as the most significant Sunyaev-Zeldovich (SZ) decrement in a sky survey area of 755 square degrees. Our VLT/FORS2 spectra of 89 member galaxies yield a cluster redshift, z = 0.870, and velocity dispersion, sigma(gal) +/- 1321 106 km s-1. Our Chandra observations reveal a hot and X-ray luminous system with an integrated temperature of T(X) = 14:5 +/- 0:1 keV and 0.5 2.0 keV band luminosity of L(X) = (2:19 0:11) 1045 h(exp -2)70erg s-1. We obtain several statistically consistent cluster mass estimates; using empirical mass scaling relations with velocity dispersion, X-ray Y(X) , and integrated SZ distortion, we estimate a cluster mass of M(200) = (2:16 +/- 0:32) 10(exp 15) h(exp-1) 70M compared to the Sun. We constrain the stellar content of the cluster to be less than 1% of the total mass, using Spitzer IRAC and optical imaging. The Chandra and VLT/FORS2 optical data also reveal that ACT-CL J0102-4915 is undergoing a major merger between components with a mass ratio of approximately 2 to 1. The X-ray data show significant temperature variations from a low of 6:6 +/- 0:7 keV at the merging low-entropy, high-metallicity, cool core to a high of 22 +/- 6 keV. We also see a wake in the X-ray surface brightness and deprojected gas density caused by the passage of one cluster through the other from which we estimate a merger speed of around 1300 km s(exp -1) for an assumed merger timescale of 1 Gyr. ACTCL J0102-4915 is possibly a high-redshift analog of the famous Bullet Cluster. Such a massive cluster at this redshift is rare, although consistent with the standard CDM cosmology in the lower part of its allowed mass range. Massive

  2. Preparation and characterization of a layered perovskite-type organic-inorganic hybrid compound (C8NH6-CH2CH2NH3)2CuCl4

    International Nuclear Information System (INIS)

    Zheng Yingying; Wu Gang; Deng Meng; Chen Hongzheng; Wang Mang; Tang, B.-Z.

    2006-01-01

    The organic-inorganic hybrid compound (C 8 NH 6 -CH 2 CH 2 NH 3 ) 2 CuCl 4 (AEI-CuCl 4 ) was synthesized from ethanol solution containing copper chloride and 3-2-(aminoethyl) indole hydrochloride (AEI-HCl). High order diffraction peaks corresponding to (0 0 l; l = 2, 4, 6, ...) observed in the X-ray diffraction profile of AEI-CuCl 4 indicated the formation of hybrid crystal with layered perovskite structure. The organic-inorganic hybrid crystal thin film can be easily prepared by spin-coating method from the ethanol solution of the AEI-CuCl 4 perovskite and it showed characteristic absorptions of CuCl-based layered perovskite centered at 288 and 388 nm, as well as the photoluminescence peak at around 420 nm. The unaided-eye-detectable blue fluorescence emission comes from the cooperation of AEI-HCl and AEI-CuCl 4 perovskite, in which protonized aminoethyl indole dominates the shape of the spectrum and the enhancement of emission intensity is due to the formation of the perovskite structure. The thermal analysis presented that the AEI-CuCl 4 perovskite started to melt at 182 deg. C, together with the beginning of the decomposition of the hybrids. Compared with the organic-inorganic perovskite hybrids reported previously, the AEI-CuCl 4 perovskite shows a novel stepwise decomposition behavior

  3. THE ATACAMA COSMOLOGY TELESCOPE: ACT-CL J0102-4915 'EL GORDO', A MASSIVE MERGING CLUSTER AT REDSHIFT 0.87

    Energy Technology Data Exchange (ETDEWEB)

    Menanteau, Felipe; Hughes, John P.; Baker, Andrew J. [Department of Physics and Astronomy, Rutgers University, 136 Frelinghuysen Rd, Piscataway, NJ 08854 (United States); Sifon, Cristobal; Gonzalez, Jorge; Infante, Leopoldo; Felipe Barrientos, L. [Departamento de Astronomia y Astrofisica, Facultad de Fisica, Pontificia Universidad Catolica de Chile, Casilla 306, Santiago 22 (Chile); Hilton, Matt [School of Physics and Astronomy, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Bond, John R.; Hajian, Amir; Nolta, Michael R. [Canadian Institute for Theoretical Astrophysics, University of Toronto, Toronto, ON M5S 3H8 (Canada); Das, Sudeep [Berkeley Center for Cosmological Physics, LBL and Department of Physics, University of California, Berkeley, CA 94720 (United States); Devlin, Mark J.; Marsden, Danica [Department of Physics and Astronomy, University of Pennsylvania, 209 South 33rd Street, Philadelphia, PA 19104 (United States); Dunkley, Joanna [Department of Astrophysics, Oxford University, Oxford, OX1 3RH (United Kingdom); Hincks, Adam D. [Joseph Henry Laboratories of Physics, Jadwin Hall, Princeton University, Princeton, NJ 08544 (United States); Kosowsky, Arthur [Physics and Astronomy Department, University of Pittsburgh, 100 Allen Hall, 3941 O' Hara Street, Pittsburgh, PA 15260 (United States); Marriage, Tobias A. [Department of Physics and Astronomy, The Johns Hopkins University, Baltimore, MD 21218-2686 (United States); Moodley, Kavilan [Astrophysics and Cosmology Research Unit, School of Mathematical Sciences, University of KwaZulu-Natal, Durban 4041 (South Africa); Niemack, Michael D. [NIST Quantum Devices Group, 325 Broadway Mailcode 817.03, Boulder, CO 80305 (United States); and others

    2012-03-20

    We present a detailed analysis from new multi-wavelength observations of the exceptional galaxy cluster ACT-CL J0102-4915, likely the most massive, hottest, most X-ray luminous and brightest Sunyaev-Zel'dovich (SZ) effect cluster known at redshifts greater than 0.6. The Atacama Cosmology Telescope (ACT) collaboration discovered ACT-CL J0102-4915 as the most significant SZ decrement in a sky survey area of 755 deg{sup 2}. Our Very Large Telescope (VLT)/FORS2 spectra of 89 member galaxies yield a cluster redshift, z = 0.870, and velocity dispersion, {sigma}{sub gal} = 1321 {+-} 106 km s{sup -1}. Our Chandra observations reveal a hot and X-ray luminous system with an integrated temperature of T{sub X} = 14.5 {+-} 0.1 keV and 0.5-2.0 keV band luminosity of L{sub X} = (2.19 {+-} 0.11) Multiplication-Sign 10{sup 45} h{sup -2}{sub 70} erg s{sup -1}. We obtain several statistically consistent cluster mass estimates; using empirical mass scaling relations with velocity dispersion, X-ray Y{sub X}, and integrated SZ distortion, we estimate a cluster mass of M{sub 200a} = (2.16 {+-} 0.32) Multiplication-Sign 10{sup 15} h{sup -1}{sub 70} M{sub Sun }. We constrain the stellar content of the cluster to be less than 1% of the total mass, using Spitzer IRAC and optical imaging. The Chandra and VLT/FORS2 optical data also reveal that ACT-CL J0102-4915 is undergoing a major merger between components with a mass ratio of approximately 2 to 1. The X-ray data show significant temperature variations from a low of 6.6 {+-} 0.7 keV at the merging low-entropy, high-metallicity, cool core to a high of 22 {+-} 6 keV. We also see a wake in the X-ray surface brightness and deprojected gas density caused by the passage of one cluster through the other. Archival radio data at 843 MHz reveal diffuse radio emission that, if associated with the cluster, indicates the presence of an intense double radio relic, hosted by the highest redshift cluster yet. ACT-CL J0102-4915 is possibly a high

  4. Imaging with Mass Spectrometry: A SIMS and VUV-Photoionization Study of Ion-Sputtered Atoms and Clusters from GaAs and Au

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Lynelle; Zhou, Jia; Wilson, Kevin R.; Leone, Stephen R.; Ahmed, Musahid

    2008-12-05

    A new mass spectrometry surface imaging method is presented in which ion-sputtered neutrals are postionized by wavelength-tunable vacuum ultraviolet (VUV) light from a synchrotron source. Mass spectra and signal counts of the photoionized neutrals from GaAs (100) and Au are compared to those of the secondary ions. While clusters larger than dimers are more efficiently detected as secondary ions, certain species, such as As2, Au and Au2, are more efficiently detected through the neutral channel. Continuously tuning the photon wavelength allows photoionization efficiency (PIE) curves to be obtained for sputtered Asm (m=1,2) and Aun (n=1-4). From the observed ionization thresholds, sputtered neutral As and Au show no clear evidence of electronic excitation, while neutral clusters have photoionization onsets shifted to lower energies by ~;;0.3 eV. These shifts are attributed to unresolved vibrational and rotational excitations. High-spatial resolution chemical imaging with synchrotron VUV postionization is demonstrated at two different photon energies using a copper TEM grid embedded in indium. The resulting images are used to illustrate the use of tunable VUV light for verifying mass peak assignments by exploiting the unique wavelength-dependent PIE of each sputtered neutral species. This capability is valuable for identifying compounds when imaging chemically complex systems with mass spectrometry-based techniques.

  5. Development of the TeamOBS-PPH - targeting clinical performance in postpartum hemorrhage.

    Science.gov (United States)

    Brogaard, Lise; Hvidman, Lone; Hinshaw, Kim; Kierkegaard, Ole; Manser, Tanja; Musaeus, Peter; Arafeh, Julie; Daniels, Kay I; Judy, Amy E; Uldbjerg, Niels

    2018-06-01

    This study aimed to develop a valid and reliable TeamOBS-PPH tool for assessing clinical performance in the management of postpartum hemorrhage (PPH). The tool was evaluated using video-recordings of teams managing PPH in both real-life and simulated settings. A Delphi panel consisting of 12 obstetricians from the UK, Norway, Sweden, Iceland, and Denmark achieved consensus on (i) the elements to include in the assessment tool, (ii) the weighting of each element, and (iii) the final tool. The validity and reliability were evaluated according to Cook and Beckman. (Level 1) Four raters scored four video-recordings of in situ simulations of PPH. (Level 2) Two raters scored 85 video-recordings of real-life teams managing patients with PPH ≥1000 mL in two Danish hospitals. (Level 3) Two raters scored 15 video-recordings of in situ simulations of PPH from a US hospital. The tool was designed with scores from 0 to 100. (Level 1) Teams of novices had a median score of 54 (95% CI 48-60), whereas experienced teams had a median score of 75 (95% CI 71-79; p < 0.001). (Level 2) The intra-rater [intra-class correlation (ICC) = 0.96] and inter-rater (ICC = 0.83) agreements for real-life PPH were strong. The tool was applicable in all cases: atony, retained placenta, and lacerations. (Level 3) The tool was easily adapted to in situ simulation settings in the USA (ICC = 0.86). The TeamOBS-PPH tool appears to be valid and reliable for assessing clinical performance in real-life and simulated settings. The tool will be shared as the free TeamOBS App. © 2018 Nordic Federation of Societies of Obstetrics and Gynecology.

  6. 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.

  7. c-T phase diagram and Landau free energies of (AgAu)55 nanoalloy via neural-network molecular dynamic simulations.

    Science.gov (United States)

    Chiriki, Siva; Jindal, Shweta; Bulusu, Satya S

    2017-10-21

    For understanding the structure, dynamics, and thermal stability of (AgAu) 55 nanoalloys, knowledge of the composition-temperature (c-T) phase diagram is essential due to the explicit dependence of properties on composition and temperature. Experimentally, generating the phase diagrams is very challenging, and therefore theoretical insight is necessary. We use an artificial neural network potential for (AgAu) 55 nanoalloys. Predicted global minimum structures for pure gold and gold rich compositions are lower in energy compared to previous reports by density functional theory. The present work based on c-T phase diagram, surface area, surface charge, probability of isomers, and Landau free energies supports the enhancement of catalytic property of Ag-Au nanoalloys by incorporation of Ag up to 24% by composition in Au nanoparticles as found experimentally. The phase diagram shows that there is a coexistence temperature range of 70 K for Ag 28 Au 27 compared to all other compositions. We propose the power spectrum coefficients derived from spherical harmonics as an order parameter to calculate Landau free energies.

  8. Summary of gold nanoparticles obtained by reduction Au3+

    International Nuclear Information System (INIS)

    Corzo Lucioni, Alberto

    2012-01-01

    In the present investigation were synthesized nanoparticles (NPs) of gold by oxidation-reduction reactions at boiling temperature, starting from dilute solutions of acid tetrachloroauric: H[AuCl 4 ].3H 2 O as a precursor in the presence of organic reducing agents such as trisodium citrate: Na 3 C 6 H 5 O 7 .2H 2 O; potassium sodium tartrate: KNaC 4 H 4 O 6 .4H 2 O and sodium borohydride: inorganic reducing agent NaBH 4 . With the aim of evaluating the particle size according to the type of reducing agent, is designed a series of experiments in which the reducing agent is changed, keeping it constant concentrations, but varying the concentration of H[AuCl 4 ]. The particle size and the absorbance of the plasmon Au were measured in a particle size analyzer and a UV - visible, respectively. In turn, the effect of pH variation on the size of the NP Au, maintaining concentrations of H [AuCl 4 ] constant and reducing agent trisodium citrate, at different pH values under the same conditions. (author).

  9. Preparation and characterization of dimeric and tetrameric clusters of molybdenum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, T.R.

    1981-10-01

    The cyclo-addition of two Mo/sub 2/Cl/sub 4/(P(C/sub 6/H/sub 5/)/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ molecules has produced a new type of tetrameric molybdenum cluster, Mo/sub 4/Cl/sub 8/L/sub 4/. Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo/sub 4/X/sub 8/L/sub 4/ clusters where X = Cl, Br, I and L = PR/sub 3/, Po/sub 3/, RCN, CH/sub 3/OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/, R = C/sub 2/H/sub 5/, n-C/sub 4/H/sub 9/. The preparation of the analogous W/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ cluster from WCl/sub 4/ was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species. The attempted preparation of a tetrameric tungsten cluster from W/sub 2/(mhp)/sub 4/ was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W/sub 2/Cl/sub 2/(mhp)/sub 3/, was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms were situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W/sub 2//sup 4 +/ dimer containing a quadruple metal-metal bond.

  10. Determination of Au, Sb, As, Br, Na, K, Cd, Mn and Cl in rice from Vietnam by neutron activation analysis

    International Nuclear Information System (INIS)

    Tran Van, L.; Teherani, D.K.

    1988-01-01

    Gold, antimony, arsenic, bromine, sodium, potassium, cadmium, manganese and chlorine were determined by neutron activation analysis in various rice seed, brand layer and husk samples from Vietnam. The following concentration values were found: Au 0.05-0.28 ppm, Sb 0.05-1.08 ppm, As 0.08-0.94 ppm, Br 0.82-6.72 ppm, Na 16.71-25.71 ppm, K 2582-5163 ppm, Mn 19.26-33.43 ppm, Cd 0.51-2.42 ppm and Cl 205.20-828.61 ppm in rice seed. Statistically significant differences in Au, Sb, Cd contents were detected in rice seed and husk, as well as brand layer and husk. (author) 8 refs.; 3 figs

  11. Heat capacity of Sr10(PO4)6Cl2 and Ca10(PO4)6Cl2 by DSC

    International Nuclear Information System (INIS)

    Venkata Krishnan, R.; Jena, Hrudananda; Govindan Kutty, K.V.; Nagarajan, K.

    2008-01-01

    Strontium and calcium chloroapatites were synthesized by wet chemical method, characterized by X-ray diffraction and are found to be phase pure materials. The measured room temperature lattice parameter of Ca 10 (PO 4 ) 6 Cl 2 is a = 9.523 A, c = 6.855 A and for Sr 10 (PO 4 ) 6 Cl 2 is a = 9.876 A, c = 7.188 A. Heat capacity measurements were carried out on Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 by DSC in the temperature range 298-800 K. The heat capacity values of Sr 10 (PO 4 ) 6 Cl 2 is higher at all temperatures than Ca 10 (PO 4 ) 6 Cl 2 . Enthalpy and entropy increments were computed. Heat capacity values of Ca 10 (PO 4 ) 6 Cl 2 and Sr 10 (PO 4 ) 6 Cl 2 at 298 K are 758 and 868 J K -1 mol -1 , respectively

  12. On silvation and thermal transformations of B10H12(PPh3)2

    International Nuclear Information System (INIS)

    Il'inchik, E.A.; Dunaev, S.T.; Myakishev, K.G.; Asanov, I.P.

    1994-01-01

    It is shown, that exchange reaction between B 10 H 12 (SMe 2 ) 2 and triphenylphospohine is benzene leads to formation of B 10 H 12 (PPh 3 ) 2 xPh solvate during B 10 H 12 (PPh 3 ) 2 synthesis. B 10 H 12 (PPh 3 ) 2 x0.7CHCl 3 is prepared by recrystallization of the latest solvate from chloroform, B 10 H 12 (PPh 3 ) 2 - from acetone. The composition is fixed after vacuum drying (1.3 Pa; 60 deg). In all cases, prepared crystals are amorphous ones. Pyrolysis of B 10 H 12 (PPh 3 ) 2 at 250 deg is accompained by the loss of 4 hydrogen and 0.05 triphenylphosphine moles. Besides hydrogen, benzene and methane are determined in gaseous phase. Formation of boron carbide and phosphide in solid phase at 750 deg isn't observed

  13. Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine.

    Science.gov (United States)

    Shang, Rong; Saito, Souta; Jimenez-Halla, J Oscar C; Yamamoto, Yohsuke

    2018-04-17

    Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.

  14. Reaction of organic ytterbium derivatives with alkyl- and arylhalogenides

    International Nuclear Information System (INIS)

    Rybakova, L.F.; Syutkina, O.P.; Garbar, A.V.; Petrov, Eh.S.

    1988-01-01

    Interaction of a series of organic halogenides with organic bivalent ytterbium derivatives (like Grignard reagent, RYbX, where R=CH 3 , C 6 H 5 ; X=Br, I) under metal complex catalysis is studied. Aromatic and aliphatic ytterbium derivatives undergo a reaction of cross combination with organic iodides and bromides under catalysis by NiCl 2 (PPh 3 ) 2 and Pd(PPh 3 ) 4 complexes. Therewith organo-ytterbium compounds quantitatively react with alkyl (aryl) iodides, bromine substitution for iodine in arylhalogenides results in decrease of yield of cross-combination products. Reactions of organo-ytterbium compounds with organic halogenides are more effectively catalysed by nickel complexes than by palladium ones

  15. Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} and Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63}: The diversity of pseudo 5-fold symmetries in the Na–Au–Ga system

    Energy Technology Data Exchange (ETDEWEB)

    Smetana, Volodymyr; Corbett, John D., E-mail: jcorbett@iastate.edu; Miller, Gordon J.

    2013-11-15

    The Na-rich part (∼30% Na) of the Na–Au–Ga system between NaAu{sub 2}, NaGa{sub 4}, and Na{sub 22}Ga{sub 39} has been found to contain the ternary phases Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} (I) and Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63} (II), according to the results of single crystal X-ray diffraction measurements. I is orthorhombic, Cmcm, a=5.3040(1), b=24.519(5), c=14.573(3) Å, and contains a network of clusters with local 5-fold symmetry along the a-axis. Such clusters are frequent building units in decagonal quasicrystals and their approximants. II is rhombohedral, R3{sup ¯}m, a=16.325(2), c=35.242(7) Å, and contains building blocks that are structurally identical to the Bergman-type clusters as well as fused icosahedral units known with active metals, triels and late transition elements. II also contains a polycationic network with elements of the clathrate V type structure. Tight-binding electronic structure calculations using linear muffin–tin-orbital (LMTO) methods on idealized models of I and II indicate that both compounds are metallic with evident pseudogaps at the corresponding Fermi levels. The overall Hamilton bond populations are generally dominated by Au–Ga and Au–Au bonds in I and by Ga–Ga bonds in II; moreover, the Na–Au and Na–Ga contributions in I are unexpectedly large, ∼20% of the total. A similar involvement of sodium in covalent bonding has also been found in the electron-richer i-Na{sub 13}Au{sub 12}Ga{sub 15} quasicrystal approximant. - Graphical abstract: Multiply-endohedral Bergman-related clusters in the structure of Na{sub 17}Au{sub 5.9(1)}Ga{sub 46.6.} Display Omitted - Highlights: • Two new compounds with the local 5-fold symmetry have been investigated. • Na{sub 8}Au{sub 9.8(4)}Ga{sub 7.2} is an orthorhombic approximant of the Na{sub 13}Au{sub 12}Ga{sub 15} quasicrystal. • Na{sub 17}Au{sub 5.87(2)}Ga{sub 46.63} represents a rhombohedral distortion of the Bergman-type phases.

  16. New Cepheid variables in the young open clusters Berkeley 51 and Berkeley 55

    Science.gov (United States)

    Lohr, M. E.; Negueruela, I.; Tabernero, H. M.; Clark, J. S.; Lewis, F.; Roche, P.

    2018-05-01

    As part of a wider investigation of evolved massive stars in Galactic open clusters, we have spectroscopically identified three candidate classical Cepheids in the little-studied clusters Berkeley 51, Berkeley 55 and NGC 6603. Using new multi-epoch photometry, we confirm that Be 51 #162 and Be 55 #107 are bona fide Cepheids, with pulsation periods of 9.83±0.01 d and 5.850±0.005 d respectively, while NGC 6603 star W2249 does not show significant photometric variability. Using the period-luminosity relationship for Cepheid variables, we determine a distance to Be 51 of 5.3^{+1.0}_{-0.8} kpc and an age of 44^{+9}_{-8} Myr, placing it in a sparsely-attested region of the Perseus arm. For Be 55, we find a distance of 2.2±0.3 kpc and age of 63^{+12}_{-11} Myr, locating the cluster in the Local arm. Taken together with our recent discovery of a long-period Cepheid in the starburst cluster VdBH222, these represent an important increase in the number of young, massive Cepheids known in Galactic open clusters. We also consider new Gaia (data release 2) parallaxes and proper motions for members of Be 51 and Be 55; the uncertainties on the parallaxes do not allow us to refine our distance estimates to these clusters, but the well-constrained proper motion measurements furnish further confirmation of cluster membership. However, future final Gaia parallaxes for such objects should provide valuable independent distance measurements, improving the calibration of the period-luminosity relationship, with implications for the distance ladder out to cosmological scales.

  17. [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

    KAUST Repository

    Alhilaly, Mohammad J.; Bootharaju, Megalamane Siddaramappa; Joshi, Chakra Prasad; Besong, Tabot M.D.; Emwas, Abdul-Hamid M.; Juarez-Mosqueda, Rosalba; Kaappa, Sami; Malola, Sami; Adil, Karim; Shkurenko, Aleksander; Hakkinen, Hannu; Eddaoudi, Mohamed; Bakr, Osman

    2016-01-01

    Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.

  18. [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

    KAUST Repository

    Alhilaly, Mohammad J.

    2016-10-13

    Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.

  19. Simultaneous voltammetric determination of dopamine and ascorbic acid using multivariate calibration methodology performed on a carbon paste electrode modified by a mer-[RuCl3(dppb)(4-pic)] complex

    International Nuclear Information System (INIS)

    Santos, Poliana M.; Sandrino, Bianca; Moreira, Tiago F.; Wohnrath, Karen; Nagata, Noemi; Pessoa, Christiana A.

    2007-01-01

    The preparation and electrochemical characterization of a carbon paste electrode (CPE) modified with mer-[Ru0Cl 3 (dppb)(4-pic)] (dppb=Ph 2 P(CH 2 ) 4 PPh 2 , 4-pic=CH 3 C 5 H 4 N), referred to as Rupic, were investigated. The CPE/Rupic system displayed only one pair of redox peaks, with a midpoint potential at 0.28 V vs. Ag/AgCl, which were ascribed to Ru III /Ru II charge transfer. This modified electrode presented the property of electrocatalysing the oxidation of dopamine (DA) and ascorbic acid (AA) at 0.35 V and 0.30 V vs. Ag/AgCl, respectively. Because the oxidation for both AA and DA practically occurred at the same potential, distinguishing between them was difficult with cyclic voltammetry. This limitation was overcome using Partial Least Square Regression (PLSR), which allowed us, with the optimised models, to determine four synthetic samples with prediction errors (RMSEP) of 5.55 X 10 -5 mol L -1 and 7.48 X 10 -6 mol L -1 for DA and AA, respectively. (author)

  20. Haloacyl complexes of boron, [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I).

    Science.gov (United States)

    Finze, Maik; Bernhardt, Eduard; Willner, Helge; Lehmann, Christian W

    2005-11-04

    The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6-311+G(d)].

  1. The electric dipole moments in the ground states of gold oxide, AuO, and gold sulfide, AuS.

    Science.gov (United States)

    Zhang, Ruohan; Yu, Yuanqin; Steimle, Timothy C; Cheng, Lan

    2017-02-14

    The B 2 Σ - - X 2 Π 3/2 (0,0) bands of a cold molecular beam sample of gold monoxide, AuO, and gold monosulfide, AuS, have been recorded at high resolution both field free and in the presence of a static electric field. The observed electric field induced splittings and shifts were analyzed to produce permanent electric dipole moments, μ→ el , of 2.94±0.06 D and 2.22±0.05 D for the X 2 Π 3/2 (v = 0) states of AuO and AuS, respectively. A molecular orbital correlation diagram is used to rationalize the trend in ground state μ→ el values for AuX (X = F, Cl, O, and S) molecules. The experimentally determined μ→ el are compared to those computed at the coupled-cluster singles and doubles (CCSD) level augmented with a perturbative inclusion of triple excitations (CCSD(T)) level of theory.

  2. Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

    Science.gov (United States)

    Hoshino, Takahiro; Isobe, Rina; Kaneko, Takuya; Matsuki, Yusuke; Nomiya, Kenji

    2017-08-21

    A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 }(P 2 W 15 Ti 3 O 61 ) 3 Ca(OH 2 ) 3 ] 19- (Ca 7 Ti 9 Trimer), was obtained as the Na 7 Ca 6 salt (NaCa-Ca 7 Ti 9 Trimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[P 2 W 15 Ti 3 O 59 (OH) 3 ] 9- " (Ti 3 Monomer). Ti 3 Monomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH 2 ) 3 groups and an encapsulated Cl - ion, [{P 2 W 15 Ti 3 O 59 (OH) 3 } 4 {μ 3 -Ti(H 2 O) 3 } 4 Cl] 21- (Ti 16 Tetramer). The Na 7 Ca 6 salt of Ca 7 Ti 9 Trimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution 183 W and 31 P NMR spectroscopy. X-ray crystallography revealed that the [Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 ] 9+ cluster cation was composed of six calcium cations linked by one μ 6 -carbonato anion and one μ 3 -OH - anion. The cluster cation was assembled, together with one calcium ion, on a trimeric species composed of three tri-Ti(IV)-substituted Wells-Dawson subunits linked by Ti-O-Ti bonds. Ca 7 Ti 9 Trimer is an unprecedented POM species containing an alkaline-earth-metal cluster cation and is the first example of alkaline-earth-metal ions clustered around a titanium(IV)-substituted POM.

  3. Light controllable catalytic activity of Au clusters decorated with photochromic molecules

    Science.gov (United States)

    Guo, Na; Meng Yam, Kah; Zhang, Chun

    2018-06-01

    By ab initio calculations, we show that when decorated with a photochromic molecule, the catalytic activity of an Au nanocluster can be reversibly controlled by light. The combination of a photochromic thiol-pentacarbonyl azobenzene (TPA) molecule and an Au8 cluster is chosen as a model catalyst. The TPA molecule has two configurations (trans and cis) that can be reversibly converted to each other upon photo-excitation. Our calculations show that when the TPA takes the trans configuration, the combined system (trans-Au8) is an excellent catalyst for CO oxidation. The reaction barrier of the catalyzed CO oxidation is less than 0.4 eV. While, the reaction barrier of CO oxidation catalyzed by cis-Au8 is very high (>2.7 eV), indicating that the catalyst is inactive. These results pave the way for a new class of light controllable nanoscale catalysts.

  4. Cluster-surface collisions: Characteristics of Xe55- and C20 - Si[111] surface bombardment

    International Nuclear Information System (INIS)

    Cheng, H.

    1999-01-01

    Molecular dynamics (MD) simulations are performed to study the cluster-surface collision processes. Two types of clusters, Xe 55 and C 20 are used as case studies of materials with very different properties. In studies of Xe 55 - Si[111] surface bombardment, two initial velocities, 5.0 and 10.0 km/s (normal to the surface) are chosen to investigate the dynamical consequences of the initial energy or velocity in the cluster-surface impact. A transition in the speed of kinetic energy propagation, from subsonic velocities to supersonic velocities, is observed. Energy transfer, from cluster translational motion to the substrate, occurs at an extremely fast rate that increases as the incident velocity increases. Local melting and amorphous layer formation in the surfaces are found via energetic analysis of individual silicon atoms. For C 20 , the initial velocity ranges from 10 to 100 km/s. The clusters are damaged immediately upon impact. Similar to Xe 55 , increase in the potential energy is larger than the increase in internal kinetic energy. However, the patterns of energy distribution are different for the two types of clusters. The energy transfer from the carbon clusters to Si(111) surface is found to be slower than that found in the Xe clusters. Fragmentation of the carbon cluster occurs when the initial velocity is greater than 30 km/s. At 10 km/s, the clusters show recrystallization at later times. The average penetration depth displays a nonlinear dependence on the initial velocity. Disturbance in the surface caused by C 20 is discussed and compared to the damage caused by Xe 55 . Energetics, structures, and dynamics of these systems are fully analyzed and characterized. copyright 1999 American Institute of Physics

  5. 9 CFR 55.6 - Mortgage against animals.

    Science.gov (United States)

    2010-01-01

    ... 9 Animals and Animal Products 1 2010-01-01 2010-01-01 false Mortgage against animals. 55.6 Section 55.6 Animals and Animal Products ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF... DISEASE Chronic Wasting Disease Indemnification Program § 55.6 Mortgage against animals. When cervids have...

  6. (Ph4P)S6—A Compound Containing the Cyclic Radical Anion S6.−

    NARCIS (Netherlands)

    Neumuller, F.; Schmock, R.; Kirmse, A.; Voigt, A.; Diefenbach, A.; Bickelhaupt, F.M.; Dehnicke, K.

    2000-01-01

    Two long S−S bonds link the two S3 fragments in the cyclic radical anion S6.−. This forms as orange‐red crystals with PPh4+ as the counterion in the reaction of sulfane with (tetraphenylphosphonium) hydrogen diazide. The anion has a chair conformation with C2h symmetry (see picture).

  7. Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

    Science.gov (United States)

    Jiménez-Díaz, Laura M.; Pérez, Luis A.

    2018-03-01

    In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

  8. Group IB Organometallic Chemistry XIX.Synthesis and characterization of mixed-organocopper cluster compounds R4R'2Cu6 containing aryl and acetylide ligands.

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1977-01-01

    Mixed-organocopper cluster compounds Ar4Cu6(CCR)2 (Ar = 2-Me2NC6H4, R = phenyl, 4-tolyl, 2,4-xylyl or mesityl) have been prepared in high yield by the ligand-substitution reaction of Ar4Cu6Br2 with two equivalents of LiCCR. Ar4Cu6(CCC6H4CH3-4)2 has also been prepared via the aryl¡ªarylacetylide

  9. Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

    International Nuclear Information System (INIS)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

    2006-01-01

    Near thermal energy reactive collisions of small mixed metal cluster cations Ag m Au n + (m+n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu 3 + and Ag 2 Au 2 + are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu 2 CO + . In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77 to 1.09 eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a ''head-on'' fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag 2 Au 2 + suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed

  10. Reduced sintering of mass-selected Au clusters on SiO2 by alloying with Ti: an aberration-corrected STEM and computational study

    DEFF Research Database (Denmark)

    Niu, Yubiao; Schlexer, Philomena; Sebök, Béla

    2018-01-01

    with a reactive metal, Ti. Mass-selected Au/Ti clusters (400 000 amu) and Au2057 clusters (405 229 amu) were produced with a magnetron sputtering, gas condensation cluster beam source in conjunction with a lateral time-of-flight mass filter, deposited onto a silica support and characterised by XPS and LEIS....... The sintering dynamics of mass-selected Au and Au/Ti alloy nanoclusters were investigated in real space and real time with atomic resolution aberration-corrected HAADF-STEM imaging, supported by model DFT calculations. A strong anchoring effect was revealed in the case of the Au/Ti clusters, because of a much...

  11. Reduced sintering of mass-selected Au clusters on SiO2 by alloying with Ti: an aberration-corrected STEM and computational study

    DEFF Research Database (Denmark)

    Niu, Yubiao; Schlexer, Philomena; Sebök, Béla

    2018-01-01

    Au nanoparticles represent the most remarkable example of a size effect in heterogeneous catalysis. However, a major issue hindering the use of Au nanoparticles in technological applications is their rapid sintering. We explore the potential of stabilizing Au nanoclusters on SiO2 by alloying them...... in the Au/Ti clusters, but in line with the model computational investigation, Au atoms were still present on the surface. Thus size-selected, deposited nanoalloy Au/Ti clusters appear to be promising candidates for sustainable gold-based nanocatalysis....

  12. 27 CFR 6.55 - Display service.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Display service. 6.55 Section 6.55 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS âTIED-HOUSEâ Unlawful Inducements Paying for Advertising, Display Or...

  13. Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

    Science.gov (United States)

    Armitt, David J; Bruce, Michael I; Gaudio, Maryka; Zaitseva, Natasha N; Skelton, Brian W; White, Allan H; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A; Roberts, Rachel L; Hartl, Frantisek; Low, Paul J

    2008-12-21

    Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp (); Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational

  14. Density functional study of the stability and magnetic behaviour of Au{sub n}TM{sup +} clusters (TM=Au,Sc,Ti,V,Cr,Mn,Fe; 1{<=}n{<=}9)

    Energy Technology Data Exchange (ETDEWEB)

    Torres, M.B. [Dpto. de Matematicas y Computacion, Univ. de Burgos, Avda. de Cantabria s/n, 09006-Burgos (Spain); Fernandez, E.M.; Balbas, L.C. [Dpto. de Fisica Teorica, Univ. de Valladolid, Prado de la Magdalena s/n, 47011-Valladolid (Spain)

    2005-03-01

    We study the element- and size-dependent electron stability of Au{sub n}TM{sup +} clusters (TM=Sc,Ti,V,Cr,Mn,Fe,Au; 1{<=}n{<=}9) by means of first-principles density functional calculations. The interplay between the cluster atomic arrangements and their electronic and magnetic structure is investigated for the few lower energy isomeric-states in dependence of the TM-atom and its environment in the cluster. We explain the experimental magic-numbers, observed recently, as well as the trend of the impurity local magnetic moment in dependence with the size of the cluster and the position of the impurity in the host. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  15. CO Oxidation by Subnanometer AgxAu3–x Supported Clusters via Density Functional Theory Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Negreiros, Fabio R.; Sementa, Luca; Barcaro, Giovanni; Vajda, S.; Apra, Edoardo; Fortunelli, Alessandro

    2012-09-07

    The activity of AgxAu3–x/MgO(100) clusters in CO oxidation is investigated computationally via systematic sampling techniques. It is found that these subnanometer species transform after ligand adsorption into reaction complexes which catalyze CO oxidation through a variety of different mechanisms, occurring via both Langmuir–Hinshelwood and Eley–Rideal paths and in some cases directly involving the oxide support. The alloyed Ag2Au1 cluster is proposed as the best catalyst in terms of efficiency and robustness.

  16. Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study.

    Science.gov (United States)

    Serebryanskaya, Tatiyana V; Novikov, Alexander S; Gushchin, Pavel V; Haukka, Matti; Asfin, Ruslan E; Tolstoy, Peter M; Kukushkin, Vadim Yu

    2016-05-18

    The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a system of H-bondings including one formed by each Cl(-) ion with CH2Cl2 or C2H4Cl2 molecules. The lengths and energies of these H-bonds in the chloride-haloalkane clusters were analyzed by DFT calculations (M06 functional) including AIM analysis. The crystal packing noticeably affected the geometry of the clusters, and energy of C-HCl(-) hydrogen bonds ranged from 1 to 6 kcal mol(-1). An exponential correlation (R(2) > 0.98) between the calculated Cl(-)H distances and the energies of the corresponding contacts was found and used to calculate hydrogen bond energies from the experimental Cl(-)H distances. Predicted energy values (3.3-3.9 kcal mol(-1) for the [Cl(CHCl3)2](-) cluster) are in a reasonable agreement with the energy of the Cl3C-HCl(-) bond estimated using ATRFTIR spectroscopy (2.7 kcal mol(-1)).

  17. Isotopic exchange in a neutron-irradiated mixed-valence compound: Tl3(I) Tl(III)Cl6

    International Nuclear Information System (INIS)

    Fernandez Valverde, S.; Duplatre, G.

    1977-01-01

    The initial distribution of Tl(I) and Tl(III) species, and its change on heating, have been investigated in solid thermal neutron-irradiated Th 4 Cl 6 . An initial ratio of 5/1 for 204 Tl(I)/ 204 Tl(III) is found and this remains constant for integral gamma-doses of 3 to 12 MRad. The variation of the 204 Tl(III) fraction with temperature is found identical to that observed in labelled Tl 4 Cl 6 for which a genuine isotopic exchange has previously been described. It is concluded that the recoil species are rapidly converted, after the recoil processes, into stable ions

  18. Electronic Structure of Au25 Clusters: Between Discrete and Continuous

    KAUST Repository

    Katsiev, Khabiboulakh

    2016-07-15

    Here, an approach based on synchrotron resonant photoemission is emplyed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states at the vicinity of the Fermi level. These observations are supported by DFT studies.

  19. Electronic Structure of Au25 Clusters: Between Discrete and Continuous

    KAUST Repository

    Katsiev, Khabiboulakh; Lozova, Nataliya; Wang, Lu; Katla, Saikrishna; Li, Ruipeng; Mei, Wai Ning; Skrabalak, Sara; Challa, Challa; Losovyj, Yaroslav

    2016-01-01

    Here, an approach based on synchrotron resonant photoemission is emplyed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states at the vicinity of the Fermi level. These observations are supported by DFT studies.

  20. Giant metal sputtering yields induced by 20-5000 keV/atom gold clusters

    International Nuclear Information System (INIS)

    Andersen, H.H.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Jacquet, D.; Le Beyec, Y.

    1997-01-01

    Very large non-linear effects have been found in cluster-induced metal sputtering over a broad projectile energy interval for the first time. Recently available cluster beams from tandem accelerators have allowed sputtering yield measurements to be made with Au 1 to Au 5 from 20 keV/atom to 5 MeV/atom. The cluster-sputtering yield maxima were found at the same total energy but not at the same energy/atom as expected. For Au 5 a yield as high as 3000 was reached at 150 keV/atom while the Au 1 yield was only 55 at the same velocity. The Sigmund-Claussen thermal spike theory, which fits published data at low energy, cannot reproduce our extended new data set. (author)

  1. Phase transitions and molecular motions in [Ni(ND3)6](ClO4)2

    International Nuclear Information System (INIS)

    Migdal-Mikuli, Anna; Mikuli, Edward; Gorska, Natalia; Kowalska, Aneta; Ulanski, Jacek

    2004-01-01

    [Ni(ND 3 ) 6 ](ClO 4 ) 2 has three solid phases between 100 and 300 K. The phase transitions temperatures at heating (T C1 h =164.1 K and T C2 h =145.1 K) are shifted, as compared to the non-deuterated compound, towards the lower temperature of ca. 8 and 5 K, respectively. The ClO 4 - anions perform fast, picosecond, isotropic reorientation with the activation energy of 6.6 kJ mol -1 , which abruptly slow down at T C1 c phase transition, during sample cooling. The ND 3 ligands perform fast uniaxial reorientation around the Ni-N bond in all three detected phases, with the effective activation energy of 2.9 kJ mol -1 . The reorientational motion of ND 3 is only slightly distorted at the T C1 phase transition due to the dynamical orientational order-disorder process of anions. The low value of the activation energy for the ND 3 reorientation suggests that this reorientation undergoes the translation-rotation coupling, which makes the barrier to the rotation of the ammonia ligands not constant but fluctuating. The phase polymorphism and the dynamics of the molecular reorientations of the title compound are similar but not quite identical with these of the [Ni(NH 3 ) 6 ](ClO 4 ) 2

  2. Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

    Energy Technology Data Exchange (ETDEWEB)

    Hammons, Casey [University of North Texas; Wang, Xiaoping [ORNL; Nesterov, Vladimir [University of North Texas; Richmond, Michael G. [University of North Texas

    2010-01-01

    The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 for 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.

  3. Ligand-protected gold clusters: the structure, synthesis and applications

    International Nuclear Information System (INIS)

    Pichugina, D A; Kuz'menko, N E; Shestakov, A F

    2015-01-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Au n with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au 15 and Au 25 ) and on anchorage to a support surface (Au 25 /SiO 2 , Au 20 /C, Au 10 /FeO x ) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR) n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters M x Au n L m (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR) x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active

  4. Ligand-protected gold clusters: the structure, synthesis and applications

    Science.gov (United States)

    Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

    2015-11-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

  5. Crystal growth and magnetic property of a new compound CeAu4Si2

    International Nuclear Information System (INIS)

    Nakashima, Hiroshi; Thamizhavel, Arumugam; Matsuda, Tatsuma D.; Haga, Yoshinori; Takeuchi, Tetsuya; Sugiyama, Kiyohiro; Settai, Rikio; Onuki, Yoshichika

    2006-01-01

    We have succeeded in growing a new ternary Ce compound CeAu 4 Si 2 . This compound crystallizes in the tetragonal crystal structure P4-bar m2 (-bar 1-bar 1-bar 5) with lattice parameters a=4.3304 -bar A and c=27.409 -bar A. The local environment around Ce atoms is similar to that of the well-known ThCr 2 Si 2 -type tetragonal structure in CeAu 2 Si 2 . Single crystals of CeAu 4 Si 2 were grown by the flux method using an Au 4.37 Si eutectic alloy as flux. Electrical resistivity, specific heat and magnetization measurements revealed a ferromagnetic ordering at T C =5.3 -bar K with a saturation moment of 1.7-bar μ B /Ce. Anisotropic features in the magnetic susceptibility and magnetization were well explained by a crystalline electric field (CEF) model. Estimated excitation energies from the ground state doublet to two excited doublets are 284 and 340-bar K, respectively

  6. The effect of CNTs on structures and catalytic properties of AuPd clusters for H2O2 synthesis.

    Science.gov (United States)

    Yang, Hua-feng; Xie, Peng-yang; Yu, Hui-you; Li, Xiao-nian; Wang, Jian-guo

    2012-12-28

    The structures and catalytic properties of AuPd clusters supported on carbon nanotubes (CNTs) for H(2)O(2) synthesis have been investigated by means of density functional theory calculations. Firstly, the structures of AuPd clusters are strongly influenced by CNTs, in which the bottom layers are mainly composed of Pd and the top layers are a mix of Au and Pd due to the stronger binding of Pd than Au on CNTs. Especially, it is found that O(2) adsorption on the Pd/CNTs interfacial sites is much weaker than that on the only Pd sites, which is in contrast to transition metal oxide (for example TiO(2), Al(2)O(3), CeO(2)) supported metal clusters. Furthermore, Pd ensembles on the interfacial sites have far superior catalytic properties for H(2)O(2) formation than those away from CNT supports due to the changes in electronic structures caused by the CNTs. Therefore, our study provides a physical insight into the enhanced role of carbon supports in H(2)O(2) synthesis over supported AuPd catalysts.

  7. Photoproduced fluorescent Au(I)@(Ag2/Ag3)-thiolate giant cluster: an intriguing sensing platform for DMSO and Pb(II).

    Science.gov (United States)

    Ganguly, Mainak; Mondal, Chanchal; Jana, Jayasmita; Pal, Anjali; Pal, Tarasankar

    2014-01-14

    Synergistic evolution of fluorescent Au(I)@(Ag2/Ag3)-thiolate core-shell particles has been made possible under the Sun in presence of the respective precursor coinage metal compounds and glutathione (GSH). The green chemically synthesized fluorescent clusters are giant (∼600 nm) in size and robust. Among all the common water miscible solvents, exclusively DMSO exhibits selective fluorescence quenching (Turn Off) because of the removal of GSH from the giant cluster. Again, only Pb(II) ion brings back the lost fluorescence (Turn On) leaving aside all other metal ions. This happens owing to the strong affinity of the sulfur donor of DMSO for Pb(II). Thus, employing the aqueous solution containing the giant cluster, we can detect DMSO contamination in water bodies at trace level. Besides, a selective sensing platform has emerged out for Pb(II) ion with a detection limit of 14 × 10(-8) M. Pb(II) induced fluorescence recovery is again vanished by I(-) implying a promising route to sense I(-) ion.

  8. Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

    Science.gov (United States)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

    2006-09-01

    Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

  9. Highly selective reactions of C(60)Cl(6) with thiols for the synthesis of functionalized [60]fullerene derivatives

    OpenAIRE

    Khakina, Ekaterina A; Yurkova, Anastasiya A; Peregudov, Alexander S; Troyanov, Sergey I; Trush, Vyacheslav V; Vovk, Andrey I; Mumyatov, Alexander V; Martynenko, Vyacheslav M; Balzarini, Jan; Troshin, Pavel A

    2012-01-01

    Chlorofullerene C(60)Cl(6) undergoes highly selective reactions with thiols forming compounds C(60)[SR](5)H with high yields. These reactions open up straightforward synthetic routes to many functionalized fullerene derivatives, e.g. water-soluble compounds showing interesting biological activities.

  10. Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

    Science.gov (United States)

    Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

    2015-06-01

    In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

  11. Behaviour of Au(I,III) cyanides on anion exchangers in the presence of Pd compounds

    International Nuclear Information System (INIS)

    Knothe, M.

    1985-01-01

    The behaviour of low concentrations of [Au(I)(CN) 2 ] - and [Au(III)(CN) 4 ] - in the presence of [Pd(NH 3 ) 4 ](NO 3 ) 2 when adsorbed by anionites has been studied with the aid of labelled Au compounds. The adsorption rate of Au decreased with increasing ageing of the feed solution, which was due to the conversion of gold cyanides into species not capable of being adsorbed. This conversion proceeded at a considerably lower rate when the cyanides of gold had been fixed on the ionite. Au(I) cyanides were always converted at a higher rate than Au(III) cyanides. Thus, an effective separation of Au cyanides by anionites is possible only in the Au(III) system. (author)

  12. Crystal structure, thermochromic and magnetic properties of organic-inorganic hybrid compound: (C7H7N2S)2CuCl4

    Science.gov (United States)

    Vishwakarma, Ashok K.; Kumari, Reema; Ghalsasi, Prasanna S.; Arulsamy, Navamoney

    2017-08-01

    The synthesis, thermal analysis, crystal structure and magnetic properties of (2-aminobenzothiazolium)2CuCl4, organic-inorganic hybrid compound, have been described. The compound crystallizes in the monoclinic space group P21/c with two formula units in a unit cell of dimensions a = 6.9522(4) Å, b = 9.6979(4) Å, c = 13.9633(6) Å, β = 97.849(3)° and volume 930.83(8) Å3 at 150(2) K. The structure consists of isolated nearly square planer [CuC14]2- units, with somewhat longer than normal Cusbnd Cl bond lengths [Cusbnd Cl (average) = 2.2711 Å]. The magnetic measurements of (2-aminobenzothiazolium)2CuCl4 using SQUID magnetometer show paramagnetic nature of the compound. Thermal measurements (TG-DTA and DSC) on this compound showed reversible phase transition at 83 °C. This transition is accompanied by the reversible change in colour of the prismatic crystal from green to dark brown, thermochromic behaviour. Temperature dependent EPR measurements on powdered sample ascertain change in coordination sphere around Cu(II) with shift in g|| = 2.150 and g⊥ = 2.071 at room temperature, typical of square planar, to g|| = 2.201 and g⊥ = 2.182 at 170 °C, typical of distorted tetrahedral geometry.

  13. Approximate treatment of semicore states in GW calculations with application to Au clusters.

    Science.gov (United States)

    Xian, Jiawei; Baroni, Stefano; Umari, P

    2014-03-28

    We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

  14. Approximate treatment of semicore states in GW calculations with application to Au clusters

    Energy Technology Data Exchange (ETDEWEB)

    Xian, Jiawei [SISSA – Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, I-34136 Trieste (Italy); Baroni, Stefano [SISSA – Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, I-34136 Trieste (Italy); CNR-IOM Democritos, Theory-Elettra group, Trieste (Italy); Umari, P., E-mail: paolo.umari@unipd.it [CNR-IOM Democritos, Theory-Elettra group, Trieste (Italy); Dipartimento di Fisica e Astronomia, Università di Padova, Via Marzolo 8, I-35131 Padova (Italy)

    2014-03-28

    We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.

  15. Approximate treatment of semicore states in GW calculations with application to Au clusters

    International Nuclear Information System (INIS)

    Xian, Jiawei; Baroni, Stefano; Umari, P.

    2014-01-01

    We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G 0 W 0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au 20 and Au 32 , that would be otherwise very difficult to deal with

  16. Simultaneous voltammetric determination of dopamine and ascorbic acid using multivariate calibration methodology performed on a carbon paste electrode modified by a mer-[RuCl{sub 3}(dppb)(4-pic)] complex

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Poliana M.; Sandrino, Bianca; Moreira, Tiago F.; Wohnrath, Karen; Nagata, Noemi; Pessoa, Christiana A. [Universidade Estadual de Ponta Grossa, PR (Brazil). Dept. de Quimica]. E-mail: capessoa@uepg.br

    2007-07-01

    The preparation and electrochemical characterization of a carbon paste electrode (CPE) modified with mer-[Ru0Cl{sub 3}(dppb)(4-pic)] (dppb=Ph{sub 2}P(CH{sub 2}){sub 4}PPh{sub 2}, 4-pic=CH{sub 3}C{sub 5}H{sub 4}N), referred to as Rupic, were investigated. The CPE/Rupic system displayed only one pair of redox peaks, with a midpoint potential at 0.28 V vs. Ag/AgCl, which were ascribed to Ru{sup III}/Ru{sup II} charge transfer. This modified electrode presented the property of electrocatalysing the oxidation of dopamine (DA) and ascorbic acid (AA) at 0.35 V and 0.30 V vs. Ag/AgCl, respectively. Because the oxidation for both AA and DA practically occurred at the same potential, distinguishing between them was difficult with cyclic voltammetry. This limitation was overcome using Partial Least Square Regression (PLSR), which allowed us, with the optimised models, to determine four synthetic samples with prediction errors (RMSEP) of 5.55 X 10{sup -5} mol L{sup -1} and 7.48 X 10{sup -6} mol L{sup -1} for DA and AA, respectively. (author)

  17. A high-density ammonia storage/delivery system based on Mg(NH3)6Cl2 for SCR-DeNOx in vehicles

    DEFF Research Database (Denmark)

    Elmøe, Tobias Dokkedal; Sørensen, Rasmus Zink; Quaade, Ulrich

    2006-01-01

    ammonia density of up to 93% of that of liquid ammonia. This provides a long lasting ammonia storage (approximate to 20000 km of driving per 6.2 L Mg(NH(3))(6)Cl(2) for an average medium-sized vehicle). The controlled thermal decomposition of Mg(NH(3))(6)Cl(2) was demonstrated. A small reactor......(NE(3))(6)Cl(2) ideal for use as an ammonia storage compound in both diesel and lean-burn gasoline-driven automobiles. (c) 2005 Elsevier Ltd. All rights reserved....

  18. Crystal Structure of Na3MoCl6

    Directory of Open Access Journals (Sweden)

    Martin Beran

    2011-07-01

    Full Text Available The ternary chloride Na3MoCl6 is obtained as red crystals from a disproportionation reaction of molybdenum dichloride, {Mo6}Cl12, in an acidic NaCl/AlCl3 melt at 350 °C. The crystal structure (trigonal, P-31c, a = 687.1(1, c = 1225.3(2 pm, Z = 2, V = 501,0(1 106 pm3 is that of Na3CrCl6: within a hexagonal closest-packing of chloride ions two thirds of the octahedral voids are filled between the AB double layers with Na+/Mo3+, and between the BA layers with Na+.

  19. A comparative study of Cu, Ag and Au doped CeO_2 in the total oxidation of volatile organic compounds (VOCs)

    International Nuclear Information System (INIS)

    Aboukaïs, Antoine; Skaf, Mira; Hany, Sara; Cousin, Renaud; Aouad, Samer; Labaki, Madona; Abi-Aad, Edmond

    2016-01-01

    Total oxidation of two Volatile Organic Compounds (VOCs), propylene and toluene, was investigated over M/CeO_2 catalysts, where M is a metal from IB group (i.e. Au, Ag, Cu), prepared by two different methods: the conventional wet impregnation and the deposition-precipitation. The catalysts have been characterized by means of total surface area (BET), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultra-violet-visible spectroscopy (DR-UV/Vis), and temperature-programmed reduction (TPR), in order to explain the differences observed in their catalytic activity towards the studied reactions. By comparing the two different preparation methods, the presence of metal in high oxidation state for gold and silver, and the presence of clusters for copper were the main factors responsible for the high catalytic activity. This latter was also found to be related, when comparing the different IB metals, to the values of the oxidation/reduction potential of the redox couples of the different metals. - Highlights: • IB metals (Au, Ag and Cu) were supported on ceria (CeO_2) by two different methods. • The solids were tested as catalysts for total oxidation of propylene and toluene. • The deposition-precipitation is better for Au whereas for Ag and Cu it is the impregnation. • High oxidation states of gold and silver and clusters of copper enhanced catalytic behavior. • Catalytic activity is linked to the oxidation/reduction potential of the redox IB couples.

  20. Tensile Strength of the Al-9%Si Alloy Modified with Na, F and Cl Compounds

    Directory of Open Access Journals (Sweden)

    T. Lipiński

    2010-01-01

    Full Text Available The modification of the Al-9%Si alloy with the use of a complex modifier containing Na, F and Cl was investigated in the study. The modifier was composed of NaCl, Na3AlF6 and NaF compounds. The modifier and the liquid Al-Si alloy were kept in the crucible for 15 minutes. The modifier's effect relative to the weight of the processed alloy on its tensile strength was presented in graphic form. The results of the study indicate that the complex modifier altered the investigated properties of the eutectic Al-9%Si alloy.

  1. Synthesis of axially chiral oxazoline-carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe(2).

    Science.gov (United States)

    Wang, Feijun; Li, Shengke; Qu, Mingliang; Zhao, Mei-Xin; Liu, Lian-Jun; Shi, Min

    2012-01-01

    Axially chiral oxazoline-carbene ligands with an N-naphthyl framework were successfully prepared, and their coordination behavior with AuCl·SMe(2) was also investigated, affording the corresponding Au(I) complexes in moderate to high yields.

  2. Novel multifunctional graphene sheets with encased Au/Ag nanoparticles for advanced electrochemical analysis of organic compounds.

    Science.gov (United States)

    Pruneanu, Stela; Biris, Alexandru R; Pogacean, Florina; Lazar, Diana Mihaela; Ardelean, Stefania; Watanabe, Fumyia; Dervishi, Enkeleda; Biris, Alexandru S

    2012-11-12

    This work is the first presentation of the synthesis of few-layer graphene decorated with gold and silver nanoparticles (Gr-Au-Ag) by chemical vapor deposition over a catalytic system formed of bimetallic Au-Ag nanoclusters supported on MgO and with methane used as the source of carbon. The sheetlike morphology of the graphene nanostructures, with mean sizes in the range of hundreds of nanometers, was observed by high-resolution electron microscopy. The distinctive feature found in all the samples was the regular rectangular or square shapes. This multi-component organic-inorganic nanomaterial was used to modify a platinum substrate and subsequently employed for the detection of carbamazepine, an anti-convulsion drug. UV/Vis spectroscopy revealed that a strong hypochromism occurred over time, after mixing solutions of graphene-Au-Ag with carbamazepine. This can be attributed to π-π stacking between the aromatic groups of the two compounds. Linear sweep voltammetry (LCV) provided evidence that the modified platinum substrate presented a significant electrocatalytic reaction toward the oxidation of carbamazepine. The intensity of the current was found to increase by up to 2.5 times, and the oxidation potential shifted from +1.5 to +1.35 V(Ag/AgCl) in comparison with the unmodified electrode. Electrochemical impedance spectroscopy (EIS) was further used to thoroughly assess the activity of the platinum electrode that was modified by the deposition of the Gr-Au-Ag composites in the presence of various concentrations of carbamazepine. The experimental EIS records were used for the generation of an equivalent electrical circuit, based on the charge-transfer resistance (R(ct)), Warburg impedance (Z(D)), solution resistance (R(s)), and a constant phase element (CPE) that characterizes the non-ideal interface capacitive responses. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Exploring the Photoreduction of Au(III) Complexes in the Gas-Phase

    Science.gov (United States)

    Marcum, Jesse C.; Kaufman, Sydney H.; Weber, J. Mathias

    2010-06-01

    We have used photodissociation spectroscopy to probe the electronic structure and photoreduction of Au(III) in gas-phase complexes containing Cl- and OH-. The gas-phase electronic spectrum of [AuCl_4]- closely resembles the aqueous solution spectrum, showing a lack of strong solvatochromic shifts. Substitution of Cl- ligands with OH- results in a strong blue shift, in agreement with ligand-field theory. Upon excitation, [AuCl_4]- can dissociate by loss of either one or two neutral Cl atoms, resulting in the reduction of gold from Au(III) to Au(II) and Au(I) respectively. The hydroxide substituted complex, [AuCl_2(OH)_2]-, demonstrates similar behavior but the only observable fragment channel is the loss of two neutral OH ligands, leading only to Au(I).

  4. Structures, stabilities, and electronic properties for rare-earth lanthanum doped gold clusters

    International Nuclear Information System (INIS)

    Zhao, Ya-Ru

    2015-01-01

    The structures, stabilities, and electronic properties of rare-earth lanthanum doped gold La 2 Au n (n = 1-9) and pure gold Au n (n ≤ 11) clusters have been investigated by using density functional theory. The optimized geometries show that the lowest energy structures of La 2 Au n clusters favour the 3D structure at n ≥ 3. The lanthanum atoms can strongly enhance the stabilities of gold clusters and tend to occupy the most highly coordinated position. By analysing the gap, vertical ionization potential, and chemical hardness, it is found that the La 2 Au 6 isomer possesses higher stability for small-sized La 2 Au n clusters (n = 1-9). The charges in the La 2 Au n clusters transfer from La atoms to the Au n host. In addition, Wiberg bond indices analysis reveals that the intensity of different bonds of La 2 Au n clusters exhibits a sequence of La-La bond > La-Au bond > Au-Au bond.

  5. Weak aurophilic interactions in a series of Au(III) double salts.

    Science.gov (United States)

    Chernyshev, Alexander N; Chernysheva, Maria V; Hirva, Pipsa; Kukushkin, Vadim Yu; Haukka, Matti

    2015-08-28

    In this work, several new examples of rare Au(III)Au(III) aurophilic contacts are reported. A series of gold(iii) double salts and complexes, viz. [AuX2(L)][AuX4] (L = 2,2'-bipyridyl, X = Cl , Br ; L = 2,2'-bipyrimidine, X = Cl , Br ; L = 2,2'-dipyridylamine, X = Cl , Br ), [AuX3(biq)] (biq = 2,2'-biquinoline, X = Cl , Br ), [LH][AuX4] (L = 2,2'-bipyridyl, X = Cl ; L = 2,2'-bipyrimidine, X = Cl ; L = 2,2'-dipyridylamine, X = Cl , Br ; L = 2,2'-biquinoline, X = Cl , Br ), [AuBr2(bpy)]2[AuBr4][AuBr2] , [AuCl2(bpm)][AuCl2] , (bpmH)2[AuBr4][AuBr2] , and (dpaH)[AuBr2] (, , and were reported earlier) was synthesized by coordination of a particular ligand to the Au(III) center and subsequent reduction of the formed product with acetone. Inspection of the X-ray structural data for , , and indicates that the Au(III) metal centers approach each other closer than the sum of their van der Waals radii, thus forming the aurophilic contacts, which were confirmed by topological charge density analysis according to the Quantum Theory of Atoms in Molecules (QTAIM). In , , and , such contacts are located only between the metal centers of the ion pair, whereas in , the aurophilic interactions form the cation-anion-anion array, and in , the aurophilicity exists between the gold atoms of the cations. It was also demonstrated that the interatomic distance alone is not a reliable measure of the aurophilic interactions, at least at the weakest limit of the interaction strength, and it needs to be complemented with structural analysis of the whole molecule and computational results.

  6. PRN 88-2: Clustering of Quaternary Ammonium Compounds

    Science.gov (United States)

    This Notice announces that EPA has clustered the Quaternary Ammonium Compounds into four groups for the purpose of testing chemicals to build a database that will support continued registration of the entire family of quaternary ammonium compounds

  7. No solid solution compounds in between the binaries. Syntheses and crystal structures of Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf; Schleid, Thomas [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2018-04-01

    The anion-mixed niobium tetrahalides Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2} were obtained by heating NbBr{sub 5} with NbCl{sub 5} and NbI{sub 5} with NbCl{sub 5}, respectively, in equimolar ratios with niobium metal in evacuated, torch-sealed silica ampoules at 720 K for 3 days. The orthorhombic title compounds form as very brittle black needles and were characterized by single-crystal X-ray diffraction [space group: Immm, Z=4; a=704.27(6), b=824.13(7), c=929.64(8) pm for Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and a=753.76(6), b=829.38(7) and c=983.41(8) pm for NbI{sub 2}Cl{sub 2}]. Surprisingly enough, these mixed-anionic halides are not isostructural with either NbCl{sub 4}, NbBr{sub 4} or NbI{sub 4}, but crystallize isotypically with TaI{sub 2}Cl{sub 2}, thus being examples for differential site occupancy stabilized materials. Structural features of other niobium(IV) halides are compiled and compared to those of Nb(Br{sub 0.62(4)}Cl{sub 0.38(4)}){sub 2}Cl{sub 2} and NbI{sub 2}Cl{sub 2}. Except for NbF{sub 4}, they all exhibit chains of trans-edge connected [NbX{sub 6}]{sup 2-} octahedra, which allow Peierls distortions to form Nb-Nb single bonds. The packing of these chains differ, however, depending on the actual halide or mixed-halide combination.

  8. Semiconducting La2AuP3, the metallic conductor Ce2AuP3, and other rare-earth gold phosphides Ln2AuP3 with two closely related crystal structures

    International Nuclear Information System (INIS)

    Eschen, M.; Kotzyba, G.; Kuennen, B.; Jeitschko, W.

    2001-01-01

    The compounds Ln 2 AuP 3 were synthesized by reaction of the elemental components in evacuated silica tubes. Their crystal structures were determined from single-crystal diffractometer data. The compounds with Ln = La, Ce, and Pr crystallize with an orthorhombic U 2 NiC 3 type structure (Pnma, Z = 4). The structure refinement for Ce 2 AuP 3 resulted in a = 774.14(6) pm, b = 421.11(4) pm, c = 1612.3(1) pm, R = 0.019 for 1410 structure factors and 38 variable parameters. For Pr 2 AuP 3 a residual of R = 0.024 was obtained. Nd 2 AuP 3 crystallizes with a monoclinic distortion of this structure: P2 1 /c, Z = 4, a = 416.14(4) pm, b = 768.87(6) pm, c = 1647.1(2) pm, β = 104.06(1) , R = 0.022 for 1361 F values and 56 variables. The near-neighbor coordinations of the two structures are nearly the same. In both structures the gold and phosphorus atoms form two-dimensionally infinite nets, where the gold atoms are tetrahedrally coordinated by phosphorus atoms with Au-P distances varying between 245.8 and 284.2 pm. Two thirds of the phosphorus atoms form pairs with single-bond distances varying between 217.7 and 218.9 pm. Thus, using oxidation numbers the structures can be rationalized with the formulas (Ln +3 ) 2 [AuP 3 ] -6 and (Ln +3 ) 2 Au +1 (P 2 ) -4 P -3 . Accordingly, La 2 AuP 3 is a diamagnetic semiconductor. Pr 2 AuP 3 is semi-conducting with an antiferromagnetic ground state, showing metamagnetism with a critical field of B c = 0.5(±0.1) T. In contrast, the cerium compound is a metallic conductor, even though its cell volume indicates that the cerium atoms are essentially trivalent, as is also suggested by the ferro- or ferrimagnetic behavior of the compound. (orig.)

  9. Two-Dimensional Cysteine and Cystine Cluster Networks on Au(111) Disclosed by Voltammetry and in Situ Scanning Tunneling Microscopy

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Chi, Qijin; Nielsen, Jens Ulrik

    2000-01-01

    Microscopic structures for molecular monolayers of L-cysteine and L-cystine assembled on Au(111) have been disclosed by employing electrochemistry and in situ scanning tunneling microscopy (STM). HighresolutionSTMimages show that the adlayers of both cyteine and cystine exhibit highly......-ordered networklike clusters with (3x3 6)R30° structure. By combining the surface coverage estimated from voltammetric data, each cluster is demonstrated to include six individual cysteine molecules or three cystine molecules. As a comparison, no cluster structure is observed for the 1-butanethiol adlayer prepared...... and examined under the same conditions as those for cysteine and cystine. This suggests that intermolecular and intramolecular hydrogen bonds among adsorbed cysteine or cystine molecules could be responsible for the origin of the cluster-network structures for the adlayers. Several models are proposed and used...

  10. Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

    Science.gov (United States)

    Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

    2010-12-20

    The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).

  11. A comparative study of Cu, Ag and Au doped CeO{sub 2} in the total oxidation of volatile organic compounds (VOCs)

    Energy Technology Data Exchange (ETDEWEB)

    Aboukaïs, Antoine, E-mail: aboukais@univ-littoral.fr [Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, ULCO, Equipe de Catalyse-UCEIV, MREI, 59140, Dunkerque (France); Skaf, Mira, E-mail: miraskaf@hotmail.com [Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, ULCO, Equipe de Catalyse-UCEIV, MREI, 59140, Dunkerque (France); Department of Chemistry, Faculty of Sciences, University of Balamand, P.O. Box 100, Deir El Balamand, Kelhat-Tripoli (Lebanon); Hany, Sara, E-mail: sarahani@hotmail.com [Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, ULCO, Equipe de Catalyse-UCEIV, MREI, 59140, Dunkerque (France); Cousin, Renaud, E-mail: Renaud.Cousin@univ-littoral.fr [Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, ULCO, Equipe de Catalyse-UCEIV, MREI, 59140, Dunkerque (France); Aouad, Samer, E-mail: Samer.Aouad@balamand.edu.lb [Department of Chemistry, Faculty of Sciences, University of Balamand, P.O. Box 100, Deir El Balamand, Kelhat-Tripoli (Lebanon); Labaki, Madona, E-mail: mlabaki@ul.edu.lb [Laboratory of Physical Chemistry of Materials (LCPM)/PR2N, Faculty of Sciences, Lebanese University, Fanar, PO Box 90656, Jdeidet El Metn (Lebanon); Abi-Aad, Edmond, E-mail: abiaad@univ-littoral.fr [Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, ULCO, Equipe de Catalyse-UCEIV, MREI, 59140, Dunkerque (France)

    2016-07-01

    Total oxidation of two Volatile Organic Compounds (VOCs), propylene and toluene, was investigated over M/CeO{sub 2} catalysts, where M is a metal from IB group (i.e. Au, Ag, Cu), prepared by two different methods: the conventional wet impregnation and the deposition-precipitation. The catalysts have been characterized by means of total surface area (BET), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultra-violet-visible spectroscopy (DR-UV/Vis), and temperature-programmed reduction (TPR), in order to explain the differences observed in their catalytic activity towards the studied reactions. By comparing the two different preparation methods, the presence of metal in high oxidation state for gold and silver, and the presence of clusters for copper were the main factors responsible for the high catalytic activity. This latter was also found to be related, when comparing the different IB metals, to the values of the oxidation/reduction potential of the redox couples of the different metals. - Highlights: • IB metals (Au, Ag and Cu) were supported on ceria (CeO{sub 2}) by two different methods. • The solids were tested as catalysts for total oxidation of propylene and toluene. • The deposition-precipitation is better for Au whereas for Ag and Cu it is the impregnation. • High oxidation states of gold and silver and clusters of copper enhanced catalytic behavior. • Catalytic activity is linked to the oxidation/reduction potential of the redox IB couples.

  12. Localization and orientation of heavy-atom cluster compounds in protein crystals using molecular replacement

    International Nuclear Information System (INIS)

    Dahms, Sven O.; Kuester, Miriam; Streb, Carsten; Roth, Christian; Sträter, Norbert; Than, Manuel E.

    2013-01-01

    A new approach is presented that allows the efficient localization and orientation of heavy-atom cluster compounds used in experimental phasing by a molecular replacement procedure. This permits the calculation of meaningful phases up to the highest resolution of the diffraction data. Heavy-atom clusters (HA clusters) containing a large number of specifically arranged electron-dense scatterers are especially useful for experimental phase determination of large complex structures, weakly diffracting crystals or structures with large unit cells. Often, the determination of the exact orientation of the HA cluster and hence of the individual heavy-atom positions proves to be the critical step in successful phasing and subsequent structure solution. Here, it is demonstrated that molecular replacement (MR) with either anomalous or isomorphous differences is a useful strategy for the correct placement of HA cluster compounds. The polyoxometallate cluster hexasodium α-metatungstate (HMT) was applied in phasing the structure of death receptor 6. Even though the HA cluster is bound in alternate partially occupied orientations and is located at a special position, its correct localization and orientation could be determined at resolutions as low as 4.9 Å. The broad applicability of this approach was demonstrated for five different derivative crystals that included the compounds tantalum tetradecabromide and trisodium phosphotungstate in addition to HMT. The correct placement of the HA cluster depends on the length of the intramolecular vectors chosen for MR, such that both a larger cluster size and the optimal choice of the wavelength used for anomalous data collection strongly affect the outcome

  13. WFC3 GRISM CONFIRMATION OF THE DISTANT CLUSTER Cl J1449+0856 AT (z) = 2.00: QUIESCENT AND STAR-FORMING GALAXY POPULATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Gobat, R.; Strazzullo, V.; Daddi, E. [Laboratoire AIM-Paris-Saclay, CEA/DSM-CNRS-Université Paris Diderot, Irfu/Service d' Astrophysique, CEA Saclay, Orme des Merisiers, F-91191 Gif sur Yvette (France); Onodera, M.; Carollo, M. [Institute for Astronomy, ETH Zürich Wolfgang-Pauli-strasse 27, 8093 Zürich (Switzerland); Renzini, A. [INAF-Osservatorio Astronomico di Padova Vicolo dell' Osservatorio 5, I-35122 Padova (Italy); Finoguenov, A. [University of Helsinki, P.O. Box 33 (Yliopistonkatu 4), FI-00014 Helsinki (Finland); Cimatti, A. [Università di Bologna, Dipartimento di Astronomia Via Ranzani 1, I-40127 Bologna (Italy); Scarlata, C. [School of Physics and Astronomy, University of Minnesota 116 Church Street Southeast, Minneapolis, MN 55455 (United States); Arimoto, N. [Subaru Telescope, National Astronomical Observatory of Japan 650 North A' ohoku Place, Hilo, HI 96720 (United States)

    2013-10-10

    We present deep Hubble Space Telescope Wide Field Camera 3 (HST/WFC3) slitless spectroscopic observations of the distant cluster Cl J1449+0856. These cover a single pointing with 18 orbits of G141 spectroscopy and F140W imaging, allowing us to derive secure redshifts down to M{sub 140} ∼ 25.5 AB and 3σ line fluxes of ∼5 × 10{sup –18} erg s{sup –1} cm{sup –2}. In particular, we were able to spectroscopically confirm 12 early-type galaxies (ETGs) in the field up to z ∼ 3, 6 of which are in the cluster core, which represents the first direct spectroscopic confirmation of quiescent galaxies in a z = 2 cluster environment. With 140 redshifts in a ∼6 arcmin{sup 2} field, we can trace the spatial and redshift galaxy distribution in the cluster core and background field. We find two strong peaks at z = 2.00 and z = 2.07, where only one was seen in our previously published ground-based data. Due to the spectroscopic confirmation of the cluster ETGs, we can now reevaluate the redshift of Cl J1449+0856 at z = 2.00, rather than z = 2.07, with the background overdensity being revealed to be sparse and {sup s}heet{sup -}like. This presents an interesting case of chance alignment of two close yet unrelated structures, each one preferentially selected by different observing strategies. With 6 quiescent or early-type spectroscopic members and 20 star-forming ones, Cl J1449+0856 is now reliably confirmed to be at z = 2.00. The identified members can now allow for a detailed study of galaxy properties in the densest environment at z = 2.

  14. Bis(2,2′-bipyridine[1,9-bis(diphenylphosphanyl-1,2,3,4,6,7,8,9-octahydropyrimido[1,2-a]pyrimidin-5-ium]ruthenium(II hexafluoridophosphate dibromide dichloromethane disolvate monohydrate

    Directory of Open Access Journals (Sweden)

    Alain Igau

    2013-12-01

    Full Text Available In the cation of the title complex, [Ru(C31H32N3P2(C10H8N22](PF6(Br2·2CH2Cl2·H2O, the ruthenium ion is coordinated in a distorted octahedral geometry by two 2,2′-bipyridine (bpy ligands and a chelating cationic N-diphenylphosphino-1,3,4,6,7,8-hexahydro-2-pyrimido[1,2-a]pyrimidine [(PPh22-hpp] ligand. The tricationic charge of the complex is balanced by two bromide and one hexafluoridophosphate counter-anions. The compound crystallized with two molecules of dichloromethane (one of which is equally disordered about a Cl atom and a water molecule. In the crystal, one of the Br anions bridges two water molecules via O—H...Br hydrogen bonds, forming a centrosymmetric diamond-shaped R42(8 motif. The cation and anions and the solvent molecules are linked via C—H...F, C—H...Br, C—H...Cl and C—H...O hydrogen bonds, forming a three-dimensional network.

  15. Structure and energetics of clusters relevant to thorium tetrachloride melts

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    2000-08-01

    We study within an ionic model the structure and the energetics of neutral and charged clusters which may exist as structural units in molten ThCl 4 and in its liquid mixtures with alkali chlorides, with reference to Raman scattering experiments by Photiadis and Papatheodorou. As stressed by these authors, the most striking facts for ThCl 4 in comparison with other tetrachlorides (and in particular with ZrCl 4 ) are the appreciable ionic conductivity of the pure melt and the continuous structural changes which occur in the melt mixtures with varying composition. After adjusting our model to data on the isolated ThCl 4 tetrahedral molecule, we evaluate (i) the Th 2 Cl 8 dimer and the singly charged species obtained by chlorine-ion transfer between two such neutral dimers; (ii) the ThCl 6 and ThCl 7 clusters both as charged anions and as alkali -compensated species; and (iii) various oligomers carrying positive or negative double charges. Our study shows that the characteristic structural properties of the ThCl 4 compound and of the alkali-Th chloride systems are the consequence of the relatively high ionic character of the binding, which is already evident in the isolated ThCl 4 molecular monomer. (author)

  16. Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

    Directory of Open Access Journals (Sweden)

    Ana Cláudia Bernardes Silva

    2003-06-01

    Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

  17. 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.

  18. CO oxidation on Alsbnd Au nano-composite systems

    Science.gov (United States)

    Rajesh, C.; Majumder, C.

    2018-03-01

    Using first principles method we report the CO oxidation behaviour of Alsbnd Au nano-composites in three different size ranges: Al6Au8, Al13Au42 and a periodic slab of Alsbnd Au(1 1 1) surface. The clusters prefer enclosed structures with alternating arrangement of Al and Au atoms, maximising Auδ-sbnd Alδ+ bonds. Charge distribution analysis suggests the charge transfer from Al to Au atoms, corroborated by the red shift in the density of states spectrum. Further, CO oxidation on these nano-composite systems was investigated through both Eley - Rideal and Langmuir Hinshelwood mechanism. While, these clusters interact with O2 non-dissociatively with an elongation of the Osbnd O bond, further interaction with CO led to formation of CO2 spontaneously. On contrary, the CO2 evolution by co-adsorption of O2 and CO molecules has a transition state barrier. On the basis of the results it is inferred that nano-composite material of Alsbnd Au shows significant promise toward effective oxidative catalysis.

  19. Oxytocin for preventing postpartum haemorrhage (PPH) in non-facility birth settings.

    Science.gov (United States)

    Pantoja, Tomas; Abalos, Edgardo; Chapman, Evelina; Vera, Claudio; Serrano, Valentina P

    2016-04-14

    Postpartum haemorrhage (PPH) is the single leading cause of maternal mortality worldwide. Most of the deaths associated with PPH occur in resource-poor settings where effective methods of prevention and treatment - such as oxytocin - are not accessible because many births still occur at home, or in community settings, far from a health facility. Likewise, most of the evidence supporting oxytocin effectiveness comes from hospital settings in high-income countries, mainly because of the need of well-organised care for its administration and monitoring. Easier methods for oxytocin administration have been developed for use in resource-poor settings, but as far as we know, its effectiveness has not been assessed in a systematic review. To assess the effectiveness and safety of oxytocin provided in non-facility birth settings by any way in the third stage of labour to prevent PPH. We searched the Cochrane Pregnancy and Childbirth Group's Trials Register, the WHO International Clinical Trials Registry Platform (ICTRP), ClinicalTrials.gov (12 November 2015), and reference lists of retrieved reports. All published, unpublished or ongoing randomised or quasi-randomised controlled trials comparing the administration of oxytocin with no intervention, or usual/standard care for the management of the third stage of labour in non-facility birth settings were considered for inclusion.Quasi-randomised controlled trials and randomised controlled trials published in abstract form only were eligible for inclusion but none were identified. Cross-over trials were not eligible for inclusion in this review. Two review authors independently assessed studies for eligibility, assessed risk of bias and extracted the data using an agreed data extraction form. Data were checked for accuracy. We included one cluster-randomised trial conducted in four rural districts in Ghana that randomised 28 community health officers (CHOs) (serving 2404 potentially eligible pregnant women) to the

  20. Microstructural evaluation of interfacial intermetallic compounds in Cu wire bonding with Al and Au pads

    International Nuclear Information System (INIS)

    Kim, Hyung Giun; Kim, Sang Min; Lee, Jae Young; Choi, Mi Ri; Choe, Si Hyun; Kim, Ki Hong; Ryu, Jae Sung; Kim, Sangshik; Han, Seung Zeon; Kim, Won Yong; Lim, Sung Hwan

    2014-01-01

    A comparative study on the difference in interfacial behavior of thermally aged Cu wire bonding with Al and Au pads was conducted using transmission electron microscopy. During high-temperature lifetime testing of Cu wire bonding with Al and Au pads at 175 °C for up to 2000 h, different growth rates and growth characteristics were investigated in the Cu–Al intermetallic compounds (IMCs), including CuAl 2 , CuAl and Cu 9 Al 4 , and in the Cu–Au IMCs, including (Au,Cu), Cu 3 Au and (Cu,Au). Because of the lower growth rates and greater ductility of Cu–Au IMCs compared to those of Cu–Al IMCs, the Cu wire bonding with the Au pad showed relatively better thermal aging properties of bond pull strength and ball shear strength than those with the Al pad counterpart. In this study, the coherent interfaces were found to retard the growth of IMCs, and a variety of orientation relationships between wire, pad and interfacial IMCs were identified

  1. Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

    KAUST Repository

    Baron, Marco

    2016-06-14

    Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and the crystal and molecular structures of (H3L . Cl)[CoCl4] and H2L[CuBr4] (L is 2,4,6-Tri(N,N-dimethylamino)methylphenol)

    International Nuclear Information System (INIS)

    Kovalchukova, O. V.; Stash, A. I.; Strashnova, S. B.; Romashkina, E. P.; Zaitsev, B. E.

    2010-01-01

    The complex compounds (H 3 L . Cl)[CoCl 4 ] (I) and H 2 L[CuBr 4 ] (II), where L is 2,4,6-tri(N,N-dimethylamino)methylphenol, were isolated in the crystalline state and studied by X-ray diffraction. The organic cations were found to be outer-sphere ligands. All three nitrogen atoms of the tertiary amino groups are protonated. In compound I, the H 3 L 3+ cation exists as the cis tautomer. In compound II, the H 2 L 2+ dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  4. Effect of tautomerism on Au-6-mercaptopurine nanocluster stability

    Science.gov (United States)

    Rashidpour, Neda; Kashid, Vikas; Shah, Vaishali

    2013-02-01

    We have investigated the stability of conjugated nanoparticles of Au-6-Mercaptopurine (6-MP) using ab initio density functional theory. We have studied the conjugation of the 6 tautomers of 6-MP via the different atomic sites with the gold nanoparticles. Our results show that the least stable tautomer has the strongest adsorption with the Au nanoparticles whereas the most stable tautomer has the weakest adsorption. We will discuss our results to explain the experimentally observed increased plasma half life time of the conjugated drug in vitro.

  5. Determination of the equilibrium constant of FeZrCl6 formation from FeCl3 and ZrCl4

    International Nuclear Information System (INIS)

    Berdonosov, S.S.; Kharisov, B.I.; Nikitin, M.I.

    1992-01-01

    Equilibrium pressures of chlorine formed in the course of reaction FeCl 3 +ZrCl 4 ↔ FeZrCl 6 +0.5 Cl 2 were determined at the temperatures of 250-325 deg C. The values of equilibrium constant K p of the reaction mentioned at the temperatures of 250, 275, 300 and 325 deg were calculated, taking into consideration the determined values of p Cl2 and literature data on equilibrium pressures of ZrCl 4 and FeCl 3 vapours

  6. MicroED Structure of Au146(p-MBA)57 at Subatomic Resolution Reveals a Twinned FCC Cluster.

    Science.gov (United States)

    Vergara, Sandra; Lukes, Dylan A; Martynowycz, Michael W; Santiago, Ulises; Plascencia-Villa, Germán; Weiss, Simon C; de la Cruz, M Jason; Black, David M; Alvarez, Marcos M; López-Lozano, Xochitl; Barnes, Christopher O; Lin, Guowu; Weissker, Hans-Christian; Whetten, Robert L; Gonen, Tamir; Yacaman, Miguel Jose; Calero, Guillermo

    2017-11-16

    Solving the atomic structure of metallic clusters is fundamental to understanding their optical, electronic, and chemical properties. Herein we present the structure of the largest aqueous gold cluster, Au 146 (p-MBA) 57 (p-MBA: para-mercaptobenzoic acid), solved by electron micro-diffraction (MicroED) to subatomic resolution (0.85 Å) and by X-ray diffraction at atomic resolution (1.3 Å). The 146 gold atoms may be decomposed into two constituent sets consisting of 119 core and 27 peripheral atoms. The core atoms are organized in a twinned FCC structure, whereas the surface gold atoms follow a C 2 rotational symmetry about an axis bisecting the twinning plane. The protective layer of 57 p-MBAs fully encloses the cluster and comprises bridging, monomeric, and dimeric staple motifs. Au 146 (p-MBA) 57 is the largest cluster observed exhibiting a bulk-like FCC structure as well as the smallest gold particle exhibiting a stacking fault.

  7. Localization and orientation of heavy-atom cluster compounds in protein crystals using molecular replacement.

    Science.gov (United States)

    Dahms, Sven O; Kuester, Miriam; Streb, Carsten; Roth, Christian; Sträter, Norbert; Than, Manuel E

    2013-02-01

    Heavy-atom clusters (HA clusters) containing a large number of specifically arranged electron-dense scatterers are especially useful for experimental phase determination of large complex structures, weakly diffracting crystals or structures with large unit cells. Often, the determination of the exact orientation of the HA cluster and hence of the individual heavy-atom positions proves to be the critical step in successful phasing and subsequent structure solution. Here, it is demonstrated that molecular replacement (MR) with either anomalous or isomorphous differences is a useful strategy for the correct placement of HA cluster compounds. The polyoxometallate cluster hexasodium α-metatungstate (HMT) was applied in phasing the structure of death receptor 6. Even though the HA cluster is bound in alternate partially occupied orientations and is located at a special position, its correct localization and orientation could be determined at resolutions as low as 4.9 Å. The broad applicability of this approach was demonstrated for five different derivative crystals that included the compounds tantalum tetradecabromide and trisodium phosphotungstate in addition to HMT. The correct placement of the HA cluster depends on the length of the intramolecular vectors chosen for MR, such that both a larger cluster size and the optimal choice of the wavelength used for anomalous data collection strongly affect the outcome.

  8. Investigation of Carbon Monoxide Adsorption on Cationic Gold- Palladium Clusters

    Science.gov (United States)

    Chen, Yang-Mei; Kuang, Xiao-Yu; Sheng, Xiao-Wei; Wang, Huai-Qian; Shao, Peng; Zhong, Min-Ming

    2013-11-01

    Density functional calculations have been performed for the carbon monoxide molecule adsorption on AunPd+m(n+m ≤ 6) clusters. In the process of CO adsorption, small Au clusters and Pd clusters tend to be an Au atom and three Pd atoms adsorption, respectively. For the mixed Au-Pd clusters, an Au atom, a Pd atom, two atoms consisted of an Au atom and a Pd atom, two Pd atoms, and three Pd atoms adsorption structures are displayed. The highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps and natural bond orbital charge population are calculated. Moreover, CO adsorption energy, CO stretching frequency, and CO bond length (upon adsorption) are also analysed in detail. The results predict that the adsorption strength of Au clusters with CO and the C-O vibration strength is enhanced and reduced after doping of Pd in the AunPdmCO+ complexes, respectively

  9. Identification and analytical characterization of nine synthetic cathinone derivatives N-ethylhexedrone, 4-Cl-pentedrone, 4-Cl-α-EAPP, propylone, N-ethylnorpentylone, 6-MeO-bk-MDMA, α-PiHP, 4-Cl-α-PHP, and 4-F-α-PHP.

    Science.gov (United States)

    Liu, Cuimei; Jia, Wei; Li, Tao; Hua, Zhendong; Qian, Zhenhua

    2017-08-01

    Clinical and forensic toxicology laboratories are continuously confronted by analytical challenges when dealing with the new psychoactive substances (NPS) phenomenon. In this study, the analytical characterization of nine synthetic cathinones is described: 2-(ethylamino)-1-phenylhexan-1-one (N-ethylhexedrone 1), 1-(4-chlorophenyl)-2-(methylamino)pentan-1-one (4-Cl-pentedrone 2), 1-(4-chlorophenyl)-2-(ethylamino)pentan-1-one (4-Cl-α-EAPP 3), 1-(3,4-methylenedioxyphenyl)-2-propylaminopropan-1-one (propylone 4), 1-(3,4-methylenedioxyphenyl)-2-ethylaminopentan-1-one (N-ethylnorpentylone 5), 1-(6-methoxy-3,4-methylenedioxyphenyl)-2-methylaminopropan-1-one (6-MeO-bk-MDMA 6), 4-methyl-1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PiHP 7), 1-(4-chlorophenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-Cl-α-PHP 8), and 1-(4-fluorophenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-F-α-PHP 9). The identification was based on ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (UHPLC-QTOF-MS), gas chromatography-mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR) spectroscopy. The mass-spectral fragmentations of these compounds following collision-induced dissociation (CID) and electron ionization (EI) were studied to assist forensic laboratories in identifying these compounds or other substances with similar structure in their case work. To our knowledge, no analytical data about the compounds 1-4, 7, and 8 have appeared until now, making this the first report on these compounds. The GC-MS data of 5, 6 and 9 has been reported, but this study added the LC-MS, Fourier Transform Infrared (FTIR) and NMR data for additional characterization. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  10. Autopistas: AU-1 25 de Mayo y AU-6 Perito Moreno

    Directory of Open Access Journals (Sweden)

    Editorial, Equipo

    1981-02-01

    Full Text Available Highways AU-1 and AU-6, approximately 17 km. long, were constructed for the purpose of solving the serious traffic problems in Buenos Aires, a city of nine million inhabitants and an evergrowing number of cars. A computer program was created for the design based on the geometric shape of the highway and the position of the supports. Using this, all elements composing the structure were calculated and the framework was sized. This programme made it possible to complete a stretch of 150 metres per week. The very rapid construction was carried out through self-supporting arches made of metallic beams held in place by brackets. The brackets were fitted in specially designed grooves in the major supports of the highway.

    Las autopistas AU-1 y AU-6, con una longitud aproximada de 17 km, se realizaron con objeto de resolver el grave problema de infraestructura vial del Municipio de Buenos Aires, ciudad de nueve millones de habitantes y con un parque de vehículos en rápido crecimiento. Para el proyecto se creó un programa de ordenador con el que, partiendo de la definición geométrica de la autopista y de la posición de las pilas, se calculan todos los elementos que componen la estructura y se dimensionan las armaduras. Este programa permitió proyectar un tramo (150 m por semana. La construcción, a un ritmo muy rápido, se llevó a cabo mediante cimbras autoportantes compuestas por vigas metálicas apoyadas sobre ménsulas, las cuales a su vez apoyan en unos nichos dejados en las pilas.

  11. Ferric hydroxide supported gold subnano clusters or quantum dots: enhanced catalytic performance in chemoselective hydrogenation.

    Science.gov (United States)

    Liu, Lequan; Qiao, Botao; Ma, Yubo; Zhang, Juan; Deng, Youquan

    2008-05-21

    An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and alpha,beta-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 degrees C and 1 MPa H2 in the hydrogenation of aromatic nitro compounds, a 96-99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2-6 times higher than that of the corresponding ferric oxide supported catalyst with 3-5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2-20 times higher than that of the corresponding ferric oxide Au catalyst.

  12. Uniform formation of Au coated polystyrene core-shell structure using metallization process

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyoungseob; Koo, Jonghyun; Roh, Yonghan, E-mail: yhroh@skku.edu

    2011-08-01

    There are several methods for the fabrication of core-shell particles, including chemical reduction and self-assembly. In this study, the chemical reduction method was used to fabricate 100 nm, Au-coated polystyrene nanoparticles. The formation of the gold layer was based on the increase of gold coverage by the reaction with aniline and HAuCl{sub 4}. This method allowed for efficient control of the gold coverage and led to relatively stable products. The formation of Au clusters on the surface of the 100 nm polystyrene beads was characterized by scanning electron microscope and high resolution tunneling electron microscope. As a result, the Au-coated nanoparticles can be used in various applications such as surface plasmon resonators, drug delivery systems and electronic optical devices.

  13. One-pot nucleation, growth, morphogenesis, and passivation of 1.4 nm Au nanoparticles on self-assembled rosette nanotubes.

    Science.gov (United States)

    Chhabra, Rahul; Moralez, Jesus G; Raez, Jose; Yamazaki, Takeshi; Cho, Jae-Young; Myles, Andrew J; Kovalenko, Andriy; Fenniri, Hicham

    2010-01-13

    A one-pot strategy for the nucleation, growth, morphogenesis, and passivation of 1.4 nm Au nanoparticles (NPs) on self-assembled rosette nanotubes (RNTs) is described. Tapping-mode atomic force microscopy, transmission electron microscopy, energy-dispersive X-ray analysis, and selected-area electron diffraction were used to establish the structure and organization of this hybrid material. Notably, we found that the Au NPs formed were nearly monodisperse clusters of Au(55) (1.4-1.5 nm) nestled in pockets on the RNT surface.

  14. The effect of Au amount on size uniformity of self-assembled Au nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Chen, S-H; Wang, D-C; Chen, G-Y; Chen, K-Y [Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology, Taiwan (China)

    2008-03-15

    The self-assembled fabrication of nanostructure, a dreaming approach in the area of fabrication engineering, is the ultimate goal of this research. A finding was proved through previous research that the size of the self-assembled gold nanoparticles could be controlled with the mole ratio between AuCl{sub 4}{sup -} and thiol. In this study, the moles of Au were fixed, only the moles of thiol were adjusted. Five different mole ratios of Au/S with their effect on size uniformity were investigated. The mole ratios were 1:1/16, 1:1/8, 1:1, 1:8, 1:16, respectively. The size distributions of the gold nanoparticles were analyzed by Mac-View analysis software. HR-TEM was used to derive images of self-assembled gold nanoparticles. The result reached was also the higher the mole ratio between AuCl{sub 4}{sup -} and thiol the bigger the self-assembled gold nanoparticles. Under the condition of moles of Au fixed, the most homogeneous nanoparticles in size distribution derived with the mole ratio of 1:1/8 between AuCl{sub 4}{sup -} and thiol. The obtained nanoparticles could be used, for example, in uniform surface nanofabrication, leading to the fabrication of ordered array of quantum dots.

  15. Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

    Science.gov (United States)

    Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

    2013-02-13

    Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  16. A benign route to fabricate nanoporous gold through electrochemical dealloying of Al-Au alloys in a neutral solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Qian; Wang Xiaoguang; Qi Zhen [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China); Wang Yan [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China); School of Materials Science and Engineering, University of Jinan, Jiwei Road 106, Jinan 250022 (China); Zhang Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)], E-mail: zh_zhang@sdu.edu.cn

    2009-11-01

    Nanoporous gold (NPG) ribbons have been fabricated through electrochemical dealloying of melt-spun Al-Au alloys with 20-50 at.% Au in a 10 wt.% NaCl aqueous solution under potential control at room temperature. The microstructures of NPG were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray (EDX) analysis. The microstructures of the NPG ribbons strongly depend upon the phase constitutions of the starting Al-Au alloys. The single-phase Al{sub 2}Au or AlAu intermetallic compound can be fully dealloyed, resulting in the formation of NPG with a homogeneous porous structure. The separate dealloying of Al{sub 2}Au and AlAu in the two-phase Al-45 Au alloy leads to the formation of NPG composites (NPGCs). In addition, the dealloying of the Al-20 Au alloy comprising {alpha}-Al and Al{sub 2}Au leads to the formation of NPG with bimodal channel size distributions. According to the ligament size, the surface diffusivity of Au adatoms along the alloy/electrolyte interface has been evaluated and increases with increasing applied potential. The dealloying mechanism in the neutral NaCl solution has been explained based upon pourbaix diagram and chloride ion effect.

  17. Efficient and Selective Reduction of Aromatic Nitro Compounds to Aromatic Amines by NbCl{sub 5}/Indium System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Kim, Duckil; Kim, Hyung Min; Kang, Sung Ho [Korea Univ., Seoul (Korea, Republic of)

    2012-09-15

    Aromatic amines find applicability in diverse fields including dyes, pharmaceuticals, agrochemicals, and photographic materials. To date, there are a variety of methods, which can be used to convert aromatic nitro compounds to their corresponding amines. Some of them include Cp{sub 2}TiCl{sub 2}/In, Al/NH{sub 4}Cl, (NH{sub 4}){sub 2}SO{sub 4}/NaBH{sub 4}, NiCl{sub 2}6H{sub 2}O/In, HI, Sm/I{sub 2}, In/NH{sub 4}Cl, B{sub 4}H{sub 10}/Pd/C, Co{sub 2}(CO){sub 8}/H{sub 2}O and In/HCl. However, most methods still lack the desired chemo-selectivity when other reducible functional groups are present in the nitroarene and often require long reaction times, or harsh reaction conditions. Consequently, efficient and selective methods for the reduction of aromatic nitro compounds continue to be developed. It has been reported that NbCl{sub 5}/Zn system is used as a reagent for reducing sulfoxides, epoxides, and amine N-oxides.12 Because of the close resemblance of indium to zinc in several respects, including first ionization potential, we considered that NbCl{sub 5}/In system can be an efficient reducing agent for the conversion of aromatic nitro compounds to the corresponding amines. Recently, indium metal has attracted much attention for its unique properties such as low toxicity and high stability in water and air compared with other metals. In continuation of our interest in exploring the utility of metal-metal salt system in organic synthesis, we would like to report an efficient and chemo-selective method for the reduction of various aromatic nitro compounds to the corresponding amines by treatment with NbCl{sub 5}/In system (eq. 1). The new reduction system was generated by the addition of indium powder to a stirred solution of niobium(V) chloride in THF under sonication. The generation of low-valent niobium species was examined at room temperature with an excess of indium metal. The observations suggest that this procedure can be applied for the chemo

  18. Constructing theoretical M-shell spectra for Mg-like Au through Cl-like Au ions in gold plasma diagnostics

    International Nuclear Information System (INIS)

    Hamasha, Safeia; Alshaiub, Rania

    2012-01-01

    The theoretical atomic structure and spectra data for electric dipole transitions in six gold ions (Au 67+ through Au 62+ ) are produced using the flexible atomic code (FAC). The produced data contain energy levels, radiative transition rates and oscillator strengths with Δn≠0 (n = 3 → 4, 5, 6, 7). All M-shell strong lines for the six gold ions are also identified. The produced data and constructed spectra revealed the presence of a wide variety of ionization stages of Au with several blended spectral lines in the spectral range (1.7-4.4 Å). Calculated energy levels are compared against published values, which were calculated using the multi-reference many body perturbation theory that includes higher order quantum electrodynamics corrections effects. Favorable agreement with <0.26% difference was observed.

  19. High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

    Science.gov (United States)

    Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

    2016-07-21

    In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

  20. Catalytic enhancement of gold nanocages induced by undercoordination-charge-polarization

    Directory of Open Access Journals (Sweden)

    Xi Zhang

    2017-05-01

    Full Text Available Principle behind the highest catalytic ability of the least coordinated gold remains a puzzle. With the aid of density functional theory calculations, we show that in 3-coordinated gold cages (i the Au–Au bond contracts by ∼5% in average, (ii the valance density-of-states shift up to Fermi level when the Au55 cluster turns into an Au12 cage, and (iii the activation energy for CO oxidation drops in sequence, Au55 cluster (13.6 Kcal/mol, Au42 cage (8.0 Kcal/mol, Au13(6.5 Kcal/mol, and Au12 cage (5.1 Kcal/mol, with comparing the reaction paths and spin states. The principle clarified here paves the way for the design of gold nanocatalyst.

  1. Crystal structures and luminescence of two cadmium-carboxylate cluster-based compounds with mixed ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui-Fang; Lei, Qian; Wang, Yu-Ling; Yin, Shun-Gao; Liu, Qing-Yan [College of Chemistry and Chemical Engineering and Key Lab. of Functional Small Organic Molecule of Ministry of Education, Jiangxi Normal Univ., Nanchang (China)

    2017-04-04

    Reactions of Cd(NO{sub 3}){sub 2}.4H{sub 2}O with 2-quinolinecarboxylic acid (H-QLC) in the presence of 1,4-benzenedicarboxylic acid (H{sub 2}-BDC) or 1,3,5-benzenetricarboxylic acid (H-BTC) in DMF/H{sub 2}O solvent afforded two compounds, namely, [Cd(QLC)(BDC){sub 1/2}(H{sub 2}O)]{sub n} (1) and [Cd(QLC)(BTC){sub 1/3}]{sub n} (2). Both compounds are two-dimensional (2D) frameworks but feature different cadmium-carboxylate clusters as a result of the presence of the polycarboxylate ligands with different geometries and coordination preference. The dinuclear Cd{sub 2}(QLC){sub 2} units in 1 are bridged by the pairs of bridging water ligands to give a one-dimensional (1D) chain, which is further linked by the second ligand of BDC{sup 2-} to form a 2D structure. Compound 2 is constructed from unique hexanuclear macrometallacyclic Cd{sub 6}(QLC){sub 6} clusters, which are linked by the surrounding BTC{sup 3-} ligands to generate a 2D structure. Photoluminescence studies showed both compounds exhibit ligand-centered luminescent emissions with emission maxima at 405 and 401 nm, respectively. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

    Science.gov (United States)

    Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

    2015-02-28

    Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

  3. Site-Selective Carving and Co-Deposition: Transformation of Ag Nanocubes into Concave Nanocrystals Encased by Au-Ag Alloy Frames.

    Science.gov (United States)

    Ahn, Jaewan; Wang, Daniel; Ding, Yong; Zhang, Jiawei; Qin, Dong

    2018-01-23

    We report a facile synthesis of Ag nanocubes with concave side faces and Au-Ag alloy frames, namely Ag@Au-Ag concave nanocrystals, by titrating HAuCl 4 solution into an aqueous mixture of Ag nanocubes, ascorbic acid (H 2 Asc), NaOH, and cetyltrimethylammonium chloride (CTAC) at an initial pH of 11.6 under ambient conditions. Different from all previous studies involving poly(vinylpyrrolidine), the use of CTAC at a sufficiently high concentration plays an essential role in carving away Ag atoms from the side faces through galvanic replacement. Concurrent co-deposition of Au and Ag atoms via chemical reduction at orthogonal sites on the surface of Ag nanocubes leads to the generation of Ag@Au-Ag concave nanocrystals with well-defined and controllable structures. Specifically, in the presence of CTAC-derived Cl - ions, the titrated HAuCl 4 is maintained in the AuCl 4 - species, enabling its galvanic replacement with the Ag atoms located on the side faces of nanocubes. The released Ag + ions can be retained in the soluble form of AgCl 2 - by complexing with the Cl - ions. Both the AuCl 4 - and AgCl 2 - in the solution are then reduced by ascorbate monoanion, a product of the neutralization reaction between H 2 Asc and NaOH, to Au and Ag atoms for their preferential co-deposition onto the edges and corners of the Ag nanocubes. Compared with Ag nanocubes, the Ag@Au-Ag concave nanocrystals exhibit much stronger SERS activity at an excitation of 785 nm, making it feasible to monitor the Au-catalyzed reduction of 4-nitrothiophenol by NaBH 4 in situ. When the Ag cores are removed, the concave nanocrystals evolve into Au-Ag nanoframes with controllable ridge thicknesses.

  4. Chemical effects of nuclear transformations in mixed crystals. 7. Chemical effects of the 35Cl(n,γ)36Cl nuclear reaction in K2ReCl6-K2ReBr6 mixed crystals

    International Nuclear Information System (INIS)

    Mueller, H.; Diefallah, E.H.M.; Martin, S.

    1981-01-01

    The solid-state reactions occurring during the moderation of recoiling 36 Cl, produced by the (n,γ) reaction, have been studied in K 2 ReCl 6 -K 2 ReBr 6 mixed crystals. The main reaction products are Re 36 ClCl 5 2- , Re 36 ClBr 5 2- , and 36 Cl - , but the more intimately mixed species Re 36 ClCl/sub n/Br/sub 5-n/ 2- (n = 1, 2, 3, 4) are found in significant amounts. The production of the different recoil-labeled species can be explained by elementary impact models: 6% of the recoils do not leave their original lattice site (primary retetion); between 6% and 23%, dependent upon the mixed-crystal composition, appear as interstitials; 31 to 48% give rise to direct displacement reactions of one halide ligand; and 40% produce larger disruption by substitution of at least two halide ligands. The results have been compared with Roessler's 38 Cl recoil experiments

  5. Carbetocin versus oxytocin in the management of atonic post partum haemorrhage (PPH) after vaginal delivery: a randomised controlled trial.

    Science.gov (United States)

    Maged, Ahmed Mohamed; Hassan, AbdelGany M A; Shehata, Nesreen A A

    2016-05-01

    The objective of this study is to compare the effectiveness and safety of carbetocin vs. oxytocin in the management of atonic post partum haemorrhage (PPH) after vaginal delivery. A prospective randomised study was conducted in which 100 pregnant women were randomised into 2 equal groups: group 1 received Carbetocin 100 µgm (Pabal(®) Ferring, UK) and group 2 received oxytocin 5 IU (Syntocinon(®), Novartis, Switzerland). The amount of blood loss and the need for other uterotonics were significantly lower in the carbetocin group (811 ± 389.17 vs. 1010 ± 525.66 and 10/50 vs. 21/50). There was no significant difference between the carbetocin and oxytocin groups regarding occurrence of major PPH (6 vs. 11), the need for blood transfusion (6 vs. 9), the difference between blood haemoglobin levels before delivery and 24 h after delivery (0.6 ± 0.28 vs. 0.56 ± 0.25), respectively. There was no significant difference between the 2 study groups regarding both systolic and diastolic blood pressure measured immediately after the drug administration and at 30 and 60 min later. Regarding the drugs side effects, there was no significant difference between the 2 groups in the occurrence of nausea, vomiting, tachycardia, flushing, dizziness, headache, shivering, metallic taste, dyspnea, palpitations and itching. Carbetocin is a better alternative to oxytocin in management of atonic PPH with non-significant hemodynamic changes or side effects .

  6. A Wide-Field, Broadband Imaging Survey of Butcher-Oemler Cluster Cl 0024+1654: The Catalog

    Science.gov (United States)

    Alexov, A.; Silva, D. R.; Pierce, M. J.

    2003-12-01

    Wide-field (20'×20') UBVI images of intermediate-redshift (z=0.39), Butcher-Oemler cluster Cl 0024+1654 have been obtained. These data probe the rest-frame mid-UV properties over a much larger area than previous studies of Cl 0024+1654. Using these data, a multicolor catalog of nonstellar objects, assumed to be galaxies, has been constructed and analyzed. Using statistical arguments, the observed galaxy sample is separated into field and cluster populations. The basic photometric properties of these populations are presented and discussed. The ``dropout'' objects (i.e., objects undetected in one or more photometric bands) in our catalog are also discussed. A description of the final UBVI images, as well as the object catalog, is provided in an appendix. In a second appendix the use of SExtractor in crowded fields, such as the core of Cl 0024+1654, is discussed. The specific issues of the mid-UV properties of red envelope cluster galaxies, as well as the possible detection of a faint blue cluster population, are discussed in a forthcoming companion paper by Silva, Alexov, & Pierce. The observations described were conducted at Kitt Peak National Observatory, National Optical Astronomy Observatory, which is operated by the Association of Universities for Research in Astronomy (AURA) Inc., under cooperative agreement with the National Science Foundation (NSF).

  7. Three new superconducting members of the family of tetramethyltetraselenafulvalene (TMTSF) salts: TMTSF2Cl04, TMTSF2SbF6, TMTSF2TaF6

    International Nuclear Information System (INIS)

    Parkin, S.S.P.; Ribault, M.; Jerome, D.; Bechgaard, K.

    1981-01-01

    Resistivity against temperature measurements are reported along the high-conductivity a axis of TMTSF 2 ClO 4 , TMTSF 2 SbF 6 and TMTSF 2 TaF 6 , under pressure and as a function of applied magnetic field, that show that all three compounds exhibit superconducting phase transitions near 1 K, when sufficient pressure is applied. TMTSF 2 SbF 6 and TMTSF 2 TaF 6 become superconducting above critical pressures of the order of 10 and 11 kbar respectively whereas a superconducting phase transition in TMTSF 2 ClO 4 is observed at much lower pressures (<3 kbar). The critical pressure above which the sc phase is stabilised can be correlated with the separation between the sheets of TMTSF molecules and anions. (author)

  8. THE RED SEQUENCE AT BIRTH IN THE GALAXY CLUSTER Cl J1449+0856 AT z = 2

    Energy Technology Data Exchange (ETDEWEB)

    Strazzullo, V.; Pannella, M. [Department of Physics, Ludwig-Maximilians-Universität, Scheinerstr. 1, D-81679 München (Germany); Daddi, E.; Valentino, F. [Irfu/Service d’Astrophysique, CEA Saclay, Orme des Merisiers, F-91191 Gif sur Yvette (France); Gobat, R. [School of Physics, Korea Institute for Advanced Study, Hoegiro 85, Dongdaemun-gu, Seoul 130-722 (Korea, Republic of); Dickinson, M. [National Optical Astronomy Observatory, 950 North Cherry Avenue, Tucson, AZ 85719 (United States); Renzini, A. [INAF-Osservatorio Astronomico di Padova, Vicolo dell’Osservatorio 5, I-35122, Padova (Italy); Brammer, G. [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Onodera, M.; Arimoto, N. [Subaru Telescope, National Astronomical Observatory of Japan, National Institutes of Natural Sciences (NINS), 650 North A’ohoku Place, Hilo, HI, 96720 (United States); Finoguenov, A. [Max-Planck-Institut für extraterrestrische Physik, Giessenbachstrasse 1, D-85748 Garching (Germany); Cimatti, A. [Dipartimento di Fisica e Astronomia, Universitá di Bologna, Viale Berti Pichat 6/2, I-30127, Bologna (Italy); Carollo, C. M., E-mail: vstrazz@usm.lmu.de [Institute for Astronomy, ETH Zürich, Wolfgang-Pauli-strasse 27, 8093 Zürich (Switzerland)

    2016-12-20

    We use Hubble Space Telescope /WFC3 imaging to study the red population in the IR-selected, X-ray detected, low-mass cluster Cl J1449+0856 at z = 2, one of the few bona fide established clusters discovered at this redshift, and likely a typical progenitor of an average massive cluster today. This study explores the presence and significance of an early red sequence in the core of this structure, investigating the nature of red-sequence galaxies, highlighting environmental effects on cluster galaxy populations at high redshift, and at the same time underlining similarities and differences with other distant dense environments. Our results suggest that the red population in the core of Cl J1449+0856 is made of a mixture of quiescent and dusty star-forming galaxies, with a seedling of the future red sequence already growing in the very central cluster region, and already characterizing the inner cluster core with respect to lower-density environments. On the other hand, the color–magnitude diagram of this cluster is definitely different from that of lower-redshift z ≲ 1 clusters, as well as of some rare particularly evolved massive clusters at similar redshift, and it is suggestive of a transition phase between active star formation and passive evolution occurring in the protocluster and established lower-redshift cluster regimes.

  9. Boosting the performance of Pt electro-catalysts toward formic acid electro-oxidation by depositing sub-monolayer Au clusters

    International Nuclear Information System (INIS)

    Bi Xuanxuan; Wang Rongyue; Ding Yi

    2011-01-01

    Highlights: → Au decoration on Pt nanoparticles simultaneously increases the activity and stability. → Sub-monolayer Au decoration changes the reaction path and results in the activity improvement. → Increasing the Au coverage will increase the specific activity. → Proper Au coverage results in a maximum mass specific activity. - Abstract: CO poisoning is the main obstacle to the application of Pt nanoparticles as anode catalysts in direct formic acid fuel cells (DFAFCs). Significant types of Pt alloys have been investigated, which often demonstrate evidently improved catalytic performance governed by difference mechanisms. By using a well-known electrochemical technique of under potential deposition and in situ redox replacement, sub-monolayer Au clusters are deposited onto Pt nanoparticle surfaces in a highly controlled manner, generating a unique surface alloy structure. Under optimum conditions, the modified Pt nanoparticles can exhibit greatly enhanced specific activity (up to 23-fold increase) at potential of -0.2 V vs. MSE toward formic acid electro-oxidation (FAEO). Interestingly, the mass specific activity can also be improved by a factor of 2.3 at potential of -0.35 V vs. MSE although significant amount of surface Pt atoms are covered by the overlayer Au clusters. The much enhanced catalytic activity can be ascribed to a Pt surface ensemble effect, which induces change of the reaction path. Moreover, the sub-monolayer Au coating on the surface also contributes to the enhanced catalyst durability by inhibiting the Pt oxidation. These results show great potential to rationally design more active and stable nanocatalysts by modifying the Pt surface with otherwise inactive materials.

  10. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    ... in the reduction of PPh2Cl to give [Ru(6-cymene)Cl2(PPh2H)] and the expected phosphinite. The yield of the hydride complex is highest when the alcohol is 1-phenyl-ethane-1,2-diol. All three half-sandwich complexes are characterized by X-ray crystallography. Surprisingly, the conversion of chlorodiphenylphosphine ...

  11. Synthesis, crystal structure, DFT studies, acid dissociation constant, and antimicrobial activity of methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate

    Science.gov (United States)

    Nural, Yahya; Gemili, Muge; Seferoglu, Nurgul; Sahin, Ertan; Ulger, Mahmut; Sari, Hayati

    2018-05-01

    A novel bicyclic thiohydantoin fused to pyrrolidine compound, methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate, was synthesized by the cyclization reaction of dimethyl 5,5-diphenylpyrrolidine-2,4-dicarboxylate and 4-chlorophenyl isothiocyanate in the presence of 4-(dimethylamino)pyridine to form methyl 2-(4-chlorophenyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate with concomitant addition reaction of the 4-chlorophenyl isothiocyanate in 79% yield. The structural characterization was performed by NMR, FT-IR, MS and HRMS techniques, and the stereochemistry of the compound was determined by single crystal X-ray diffraction study. In addition, the molecular structure and 1H and 13C NMR chemical shifts of the compound were obtained with the density functional theory and Hartree-Fock calculations. Acid dissociation constants of the compound were determined using potentiometric titration method in 25% (v/v) dimethyl sulfoxide-water hydroorganic solvent at 25 ± 0.1 °C, at an ionic background of 0.1 mol/L of NaCl using the HYPERQUAD computer program. Four acid dissociation constants were obtained for the compound, and we suggest that these acid dissociation constants are related to the NH, for two groups of enthiols and enol groups. Antimicrobial activity study was performed against S. aureus, B. subtilis, A. hydrophila, E. coli and A. baumannii as bacterial standard strains, and against M. tuberculosis H37Rv as mycobacterial strain. The compound exhibited antibacterial activity in the range of 31.25-62.5 μg/mL, and antimycobacterial activity with a MIC value of 40 μg/mL against the indicated strains.

  12. Water-soluble octahedral molybdenum cluster compounds Na2[Mo6I8(N3)6] and Na2[Mo6I8(NCS)6]: Syntheses, luminescence, and in vitro studies

    Czech Academy of Sciences Publication Activity Database

    Kirakci, Kaplan; Kubát, Pavel; Kučeráková, Monika; Šícha, Václav; Gbelcová, H.; Lovecká, P.; Grznárová, P.; Ruml, T.; Lang, Kamil

    2016-01-01

    Roč. 441, FEB (2016), s. 42-49 ISSN 0020-1693 R&D Projects: GA ČR GA13-05114S Institutional support: RVO:61388980 ; RVO:61388955 ; RVO:68378271 Keywords : Cluster compounds * Luminescence * Singlet oxygen * Toxicity Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W); CF - Physical ; Theoretical Chemistry (FZU-D) Impact factor: 2.002, year: 2016

  13. Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic perchlorates: (C6H18N3)·(ClO4)3H2O (I) and (C9H11N2)·ClO4(II)

    Science.gov (United States)

    Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Ferretti, V.; Ben Nasr, C.

    2018-06-01

    The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C6H18N3)·(ClO4)3·H2O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C9H11N2)·ClO4(II). Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 bar with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å3. Compound (II) has been found to belong to the P21/c space group of the monoclinic system, with a = 7.590 (3), b = 9.266 (3), c = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO4]- tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I). The crystal structures of (I) and (II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I), the ClO4- anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several Osbnd H⋯O and N-H⋯O interactions in compound (I). The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived.

  14. Structure and redox properties of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20 adsorbed on a silica surface. M05 computational study

    Directory of Open Access Journals (Sweden)

    Liudmyla K. Sviatenko

    2016-03-01

    Full Text Available The cluster approximation was applied at M05/tzvp level to model adsorption of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20 on (001 surface of α-quartz. Structures of the obtained CL-20–silica complexes confirm close to parallel orientation of the nitrocompound toward surface. The binding between CL-20 and silica surface was analyzed and bond energies were calculated applying the atoms in molecules (AIM method. Hydrogen bonds were found to significantly contribute in adsorption energy. An attaching of electron leads to significant deviation from coplanarity in complexes and to strengthening of hydrogen bonding. Redox properties of adsorbed CL-20 were compared with those of gas-phase and hydrated species by calculation of electron affinity, ionization potential, reduction Gibbs free energy, oxidation Gibbs free energy, reduction and oxidation potentials. It was shown that adsorbed CL-20 has lower ability to redox transformation as compared with hydrated one.

  15. The [Mo₆Cl14]2- Cluster is Biologically Secure and Has Anti-Rotavirus Activity In Vitro.

    Science.gov (United States)

    Rojas-Mancilla, Edgardo; Oyarce, Alexis; Verdugo, Viviana; Morales-Verdejo, Cesar; Echeverria, Cesar; Velásquez, Felipe; Chnaiderman, Jonas; Valiente-Echeverría, Fernando; Ramirez-Tagle, Rodrigo

    2017-07-05

    The molybdenum cluster [Mo₆Cl 14 ] 2- is a fluorescent component with potential for use in cell labelling and pharmacology. Biological safety and antiviral properties of the cluster are as yet unknown. Here, we show the effect of acute exposition of human cells and red blood cells to the molybdenum cluster and its interaction with proteins and antiviral activity in vitro. We measured cell viability of HepG2 and EA.hy926 cell lines exposed to increasing concentrations of the cluster (0.1 to 250 µM), by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay. Hemolysis and morphological alterations of red blood cells, obtained from healthy donors, exposed to the cluster (10 to 200 µM) at 37 °C were analyzed. Furthermore, quenching of tryptophan residues of albumin was performed. Finally, plaque formation by rotavirus SA11 in MA104 cells treated with the cluster (100 to 300 µM) were analyzed. We found that all doses of the cluster showed similar cell viability, hemolysis, and morphology values, compared to control. Quenching of tryptophan residues of albumin suggests a protein-cluster complex formation. Finally, the cluster showed antiviral activity at 300 µM. These results indicate that the cluster [Mo₆Cl 14 ] 2- could be intravenously administered in animals at therapeutic doses for further in vivo studies and might be studied as an antiviral agent.

  16. Bottom-up substitution assembly of AuF4-n0,-+nPO3 (n = 1-4): a theoretical study of novel oxyfluoride hyperhalogen molecules and anions AuF4-n(PO3)n0,-

    Science.gov (United States)

    Yang, Yi-fan; Cui, Zhong-hua; Ding, Yi-hong

    2014-06-01

    Compounds with high electron affinity, i.e. superhalogens, have continued to attract chemists' attention, due to their potential importance in fundamental chemistry and materials science. It has now proven very effective to build up novel superhalogens with multi-positively charged centres, which are usually called 'hyperhalogens'. Herein, using AuF4- and PO3 as the model building blocks, we made the first attempt to design the Au,P-based hyperhalogen anions AuF4-n(PO3)n- (n = 1-4) at the B3LYP/6-311+G(d)&SDD and CCSD(T)/6-311+G(d)&SDD (single-point) levels (6-311+G(d) for O, F, P and SDD for Au). Notably, for all the considered Au,P systems, the ground state bears a dioxo-bonded structure with n ≤ 3, which is significantly more stable than the usually presumed mono-oxo-bonded one. Moreover, the clustering of the -PO3 moieties becomes energetically favoured for n ≥ 3. The ground states of AuP4O120,- are the first reported cage-like oxide hyperhalogens. Thus, the -PO3 moiety cannot be retained during the 'bottom-up' assembly. The vertical detachment energy (VDE) value of the most stable AuF4-n(PO3)n- (n = 1-4) ranges from 7.16 to 8.20 eV, higher than the VDE values of the corresponding building blocks AuF4- (7.08 eV) and PO3- (4.69 eV). The adiabatic detachment energy values of these four hyperhalogens exceed 6.00 eV. Possible generation routes for AuF4-n(PO3)n- (n = 1-4) were discussed. The presently designed oxyfluorides not only enriches the family of hyperhalogens, but also demonstrates the great importance of considering the structural transformation during the superhalogen → hyperhalogen design such as for the present Au-P based systems.

  17. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    Science.gov (United States)

    Liu, Siqi; Xu, Yi-Jun

    2016-03-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

  18. Synthesis of nir-sensitive Au-Au{sub 2}S nanocolloids for drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Ren, L.; Chow, G.M

    2003-01-15

    Near IR (NIR) sensitive Au-Au{sub 2}S nanocolloids were prepared by mixing HAuCl{sub 4} and Na{sub 2}S in aqueous solutions. An anti-tumor drug, cis-platin, was adsorbed onto Au-Au{sub 2}S nanoparticle surface via the 11-mercaptoundecanoic acid (MUA) layers. The results show that the degree of adsorption of cis-platin onto Au-Au{sub 2}S nanoparticles was controlled by the solution pH value, and the drug release was sensitive to near-infrared irradiation. The cis-platin-loaded Au-Au{sub 2}S nanocolloids can be potentially applied as NIR activated drug delivery carrier.

  19. Some Peculiarities in the Interaction of $^{6}$He with $^{197}$Au and $^{206}$Pb

    CERN Document Server

    Penionzhkevich, Yu E; Demekhina, N A; Dlouhý, Z; Kalpakchieva, R; Kulko, A A; Lobastov, S P; Lukyanov, S M; Markaryan, E R; Maslov, V A; Muzycjka, Yu A; Oganessian, Yu T; Rassadov, D N; Skobelev, N K; Sobolev, Yu G; Ugryumov, V Yu; Vincour, J; Zholdybaev, T

    2005-01-01

    Excitation functions were measured for fusion followed by the evaporation of neutrons in the reactions $^{206}$Pb($^{6}$He, 2$n$)$^{210}$Po and $^{197}$Au($^{6}$He, $xn$)$^{203 - xn}$Tl, where $x$ = 2-7, as well as for the transfer reactions on a $^{197}$Au target with the formation of the $^{196}$Au, $^{198}$Au and $^{199}$Au isotopes. The experiment was carried out at the Dubna Radioactive Ion Beams (DRIBs) complex of FLNR, JINR. The $^{6}$He-beam intensity was about 5$\\cdot$10$^{6 }$ s$^{-1}$, the maximum energy being (60.3$\\pm $0.4) MeV. A significant increase in the cross section was observed below the Coulomb barrier for the fusion reaction with the evaporation of two neutrons compared to statistical model calculations. Unusual behaviour for the production of $^{198}$Au is observed, whereas the cross section for the formation of $^{199}$Au is very low. The analysis of the data in the framework of the statistical model for the decay of excited nuclei, which took into account the sequential fusion of $^{6...

  20. Semiconducting La{sub 2}AuP{sub 3}, the metallic conductor Ce{sub 2}AuP{sub 3}, and other rare-earth gold phosphides Ln{sub 2}AuP{sub 3} with two closely related crystal structures

    Energy Technology Data Exchange (ETDEWEB)

    Eschen, M.; Kotzyba, G.; Kuennen, B.; Jeitschko, W. [Anorganisch-Chemisches Inst. der Westfaelischen Wilhelms-Univ., Muenster (Germany)

    2001-07-01

    The compounds Ln{sub 2}AuP{sub 3} were synthesized by reaction of the elemental components in evacuated silica tubes. Their crystal structures were determined from single-crystal diffractometer data. The compounds with Ln = La, Ce, and Pr crystallize with an orthorhombic U{sub 2}NiC{sub 3} type structure (Pnma, Z = 4). The structure refinement for Ce{sub 2}AuP{sub 3} resulted in a = 774.14(6) pm, b = 421.11(4) pm, c = 1612.3(1) pm, R = 0.019 for 1410 structure factors and 38 variable parameters. For Pr{sub 2}AuP{sub 3} a residual of R = 0.024 was obtained. Nd{sub 2}AuP{sub 3} crystallizes with a monoclinic distortion of this structure: P2{sub 1}/c, Z = 4, a = 416.14(4) pm, b = 768.87(6) pm, c = 1647.1(2) pm, {beta} = 104.06(1) , R = 0.022 for 1361 F values and 56 variables. The near-neighbor coordinations of the two structures are nearly the same. In both structures the gold and phosphorus atoms form two-dimensionally infinite nets, where the gold atoms are tetrahedrally coordinated by phosphorus atoms with Au-P distances varying between 245.8 and 284.2 pm. Two thirds of the phosphorus atoms form pairs with single-bond distances varying between 217.7 and 218.9 pm. Thus, using oxidation numbers the structures can be rationalized with the formulas (Ln{sup +3}){sub 2}[AuP{sub 3}]{sup -6} and (Ln{sup +3}){sub 2}Au{sup +1}(P{sub 2}){sup -4}P{sup -3}. Accordingly, La{sub 2}AuP{sub 3} is a diamagnetic semiconductor. Pr{sub 2}AuP{sub 3} is semi-conducting with an antiferromagnetic ground state, showing metamagnetism with a critical field of B{sub c} = 0.5({+-}0.1) T. In contrast, the cerium compound is a metallic conductor, even though its cell volume indicates that the cerium atoms are essentially trivalent, as is also suggested by the ferro- or ferrimagnetic behavior of the compound. (orig.)

  1. Experimental and Theoretical Studies of the Factors Affecting the Cycloplatination of the Chiral Ferrocenylaldimine (SC-[(η5-C5H5Fe{(η5-C5H4–C(H=N–CH(Me(C6H5}

    Directory of Open Access Journals (Sweden)

    Concepción López

    2014-11-01

    Full Text Available The study of the reactivity of the enantiopure ferrocenyl Schiff base (SC-[FcCH=N–CH(Me(C6H5] (1 (Fc = (η5-C5H5Fe(η5-C5H4 with cis-[PtCl2(dmso2] under different experimental conditions is reported. Four different types of chiral Pt(II have been isolated and characterized. One of them is the enantiomerically pure trans-(SC-[Pt{κ1-N[FcCH=N–CH(Me(C6H5]}Cl2(dmso] (2a in which the imine acts as a neutral N-donor ligand; while the other three are the cycloplatinated complexes: [Pt{κ2-C,N [(C6H4–N=CHFc]}Cl(dmso] (7a and the two diastereomers {(Sp,SC and (Rp,SC} of [Pt{κ2-C,N[(η5-C5H3–CH=N–{CH(Me(C6H5}]Fe(η5-C5H5}Cl(dmso] (8a and 9a, respectively. Isomers 7a-9a, differ in the nature of the metallated carbon atom [CPh (in 7a or CFc (in 8a and 9a] or the planar chirality of the 1,2-disubstituted ferrocenyl unit (8a and 9a. Reactions of 7a–9a with PPh3 gave [Pt{κ2-C,N[(C6H4–N=CHFc]}Cl(PPh3] (in 7b and the diastereomers (Sp,SC and (Rp,SC of [Pt{κ2-C,N[(η5-C5H3–CH=N–{CH(Me(C6H5}] Fe(η5-C5H5}Cl(PPh3] (8b and 9b, respectively. Comparative studies of the electrochemical properties and cytotoxic activities on MCF7 and MDA-MB231 breast cancer cell lines of 2a and cycloplatinated complexes 7b-9b are also reported. Theoretical studies based on DFT calculations have also been carried out in order to rationalize the results obtained from the cycloplatination of 1, the stability of the Pt(II complexes and their electrochemical properties.

  2. Luminescence and scintillation properties of Rb2HfCl6 crystals

    International Nuclear Information System (INIS)

    Saeki, Keiichiro; Wakai, Yuki; Fujimoto, Yutaka; Koshimizu, Masanori; Asai, Keisuke; Yanagida, Takayuki; Nakauchi, Daisuke

    2016-01-01

    We developed a scintillator based on a Rb 2 HfCl 6 crystal as a ternary halide crystal with intrinsic luminescence. In the photoluminescence spectra, two emission bands are observed at 383 and 434 nm. The 434 nm emission band for Rb 2 HfCl 6 may be attributed to [HfCl 6 ] 2- complex ion or [ZrCl 6 ] 2- impurity, since the Rb 2 HfCl 6 contained Zr as impurity at 0.62 mol %. The radioluminescence band is observed at 420 nm and can be attributed to the same origin as the photoluminescence band at 434 nm. The scintillation decay-time constants were 0.84 and 5.4 μs. The light yield was estimated to be 24,100 photons/MeV. (author)

  3. Fluorescent Thiol-Derivatized Gold Clusters Embedded in Polymers

    Directory of Open Access Journals (Sweden)

    G. Carotenuto

    2013-01-01

    Full Text Available Owing to aurophilic interactions, linear and/or planar Au(I-thiolate molecules spontaneously aggregate, leading to molecular gold clusters passivated by a thiolate monolayer coating. Differently from the thiolate precursors, such cluster compounds show very intensive visible fluorescence characteristics that can be tuned by alloying the gold clusters with silver atoms or by conjugating the electronic structure of the metallic core with unsaturated electronic structures in the organic ligand through the sulphur atom. Here, the photoluminescence features of some examples of these systems are shortly described.

  4. Structure and Stability of GeAun, n = 1-10 clusters: A Density Functional Study

    International Nuclear Information System (INIS)

    Priyanka,; Dharamvir, Keya; Sharma, Hitesh

    2011-01-01

    The structures of Germanium doped gold clusters GeAu n (n = 1-10) have been investigated using ab initio calculations based on density functional theory (DFT). We have obtained ground state geometries of GeAu n clusters and have it compared with Silicon doped gold clusters and pure gold clusters. The ground state geometries of the GeAu n clusters show patterns similar to silicon doped gold clusters except for n = 5, 6 and 9. The introduction of germanium atom increases the binding energy of gold clusters. The binding energy per atom of germanium doped cluster is smaller than the corresponding silicon doped gold cluster. The HUMO-LOMO gap for Au n Ge clusters have been found to vary between 0.46 eV-2.09 eV. The mullikan charge analysis indicates that charge of order of 0.1e always transfers from germanium atom to gold atom.

  5. Ferromagnetic interactions in Ru(III)-nitronyl nitroxide radical complex: a potential 2p4d building block for molecular magnets.

    Science.gov (United States)

    Pointillart, Fabrice; Bernot, Kevin; Sorace, Lorenzo; Sessoli, Roberta; Gatteschi, Dante

    2007-07-07

    The reaction between [Ru(salen)(PPh3)Cl] and the 4-pyridyl-substituted nitronyl nitroxide radical (NITpPy) leads to the [Ru(salen)(PPh3)(NITpPy)](ClO4)(H2O)2 complex while the reaction with the azido anion (N3-) leads to the [Ru(salen)(PPh3)(N3)] complex 2 (where salen2- = N,N'-ethan-1,2-diylbis(salicylidenamine) and PPh3 = triphenylphosphine). Both compounds have been characterized by single crystal X-ray diffraction. The two crystal structures are composed by a [Ru(III)(salen)(PPh3)]+ unit where the Ru(III) ion is coordinated to a salen2- ligand and one PPh3 ligand in axial position. In 1 the Ru(III) ion is coordinated to the 4-pyridyl-substituted nitronyl nitroxide radical whereas in 2 the second axial position is occupied by the azido ligand. In both complexes the Ru(III) ions are in the same environment RuO2N3P, in a tetragonally elongated octhaedral geometry. The crystal packing of 1 reveals pi-stacking in pairs. While antiferromagnetic intermolecular interaction (J2 = 5.0 cm(-1)) dominates at low temperatures, ferromagnetic intramolecular interaction (J1 = -9.0 cm(-1)) have been found between the Ru(III) ion and the coordinated NITpPy.

  6. Au-Pt-Au nanoraspberry structures used for mercury ion detection

    Science.gov (United States)

    Huang, Jiang-Hao; Huang, Shuai; Wen, Xiaoyan; Li, Min; Lu, Haifei

    2017-12-01

    Detection of Hg2+ with high sensitivity is of great significance in the biochemical sensing field. Quantitative of Hg2+ was realized based on the influence of Hg2+ on the UV-vis absorption performance of Au-Pt-Au core-shell nanoraspberry (APA)-rhodamine-6G (R6G) structure. First, APA sol was added into R6G indicator solution and the UV-vis absorption signal intensity of R6G was evidently promoted. The signal intensity monotonously increased as more APA sol was added. However, when HgCl2 solution was introduced, the signal intensity declined. A linear relationship between Hg2+ concentration and signal intensity at 527 nm was revealed, based on which quantitative determination of Hg2+ could be realized. Hg2+ detection sensitivity was measured to be 0.031 a.u./M with a limit of detection of 10-7 M and the response time was 20 s. A high Hg2+ detection selectivity over Cu2+, Na+, Li+, and K+ was demonstrated. Due to its simplicity and high sensitivity, the proposed method could find an extensive application prospect in the Hg2+ detection field.

  7. Re4As6S3, a thio-spinel-related cluster system

    DEFF Research Database (Denmark)

    Besnard, Celine; Svensson, Christer; Ståhl, Kenny

    2003-01-01

    . The rhenium atoms form tetrahedral clusters linked via tetrahedral arsenic clusters to produce an NaCl-type arrangement. The oxidation state of rhenium is IV and the number of electrons shared by the rhenium atoms in the cluster is 12. The structure is based on an ordered defect thio-spinel A((1-x))B(2)X(4......) where the B-type atoms form tetrahedral clusters....

  8. Properties and electrochemical behaviors of AuPt alloys prepared by direct-current electrodeposition for lithium air batteries

    International Nuclear Information System (INIS)

    Zhang, Jinqiu; Li, Da; Zhu, Yiming; Chen, Miaomiao; An, Maozhong; Yang, Peixia; Wang, Peng

    2015-01-01

    AuPt catalyst has a prospective application in a lithium air battery because of its bi-function on catalyzing Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER). Electrodeposition is an in-situ convenient technology for catalyst preparation without chemical residue. In an acid electrolyte, AuPt alloy catalysts were electrodeposited on carbon paper. The effect of main salt concentration, electrodeposition time and current density were studied by deposit micromorphology observation, structure analyses and composition testing. Catalytic abilities of AuPt alloys were measured by cyclic voltammetry (CV) in an ionic liquid of EMI-TFSI/Li-TFSI [1- Ethyl - 3- methylimidazolium–bis (trifluoromethanesulphonyl) imide/lithium–bis (trifluoromethanesulphonyl) imide]. The electrochemical behaviors of Au, Pt and AuPt deposits were also measured. An optimized direct-current electrodeposition process of getting high active AuPt catalyst is concluded, which is an aqueous solution containing 6.7∼10 mmol · L −1 HAuCl 4 , 10∼13.3 mmol · L −1 H 2 PtCl 6 and 0.5 mol · L −1 H 2 SO 4 as the electrolyte, current density of 20mA · cm −2 and electrodeposition time of 8∼34 s. The co-deposition of AuPt alloy is an irregular co-deposition controlled by diffusion, while gold atoms enter the platinum’s crystal lattice in the structure of AuPt alloy. The increase of the concentration of H 2 PtCl 6 in the electrolyte, the extension of the electrodeposition time or the raise of the current density can improve the content of Pt in the deposit. The clusters’ diameters of AuPt catalysts decrease to 150∼250 nm by adjusting current densities during electrodeposition

  9. Chlorinated volatile organic compounds (Cl-VOCs) in environment - sources, potential human health impacts, and current remediation technologies.

    Science.gov (United States)

    Huang, Binbin; Lei, Chao; Wei, Chaohai; Zeng, Guangming

    2014-10-01

    Chlorinated volatile organic compounds (Cl-VOCs), including polychloromethanes, polychloroethanes and polychloroethylenes, are widely used as solvents, degreasing agents and a variety of commercial products. These compounds belong to a group of ubiquitous contaminants that can be found in contaminated soil, air and any kind of fluvial mediums such as groundwater, rivers and lakes. This review presents a summary of the research concerning the production levels and sources of Cl-VOCs, their potential impacts on human health as well as state-of-the-art remediation technologies. Important sources of Cl-VOCs principally include the emissions from industrial processes, the consumption of Cl-VOC-containing products, the disinfection process, as well as improper storage and disposal methods. Human exposure to Cl-VOCs can occur through different routes, including ingestion, inhalation and dermal contact. The toxicological impacts of these compounds have been carefully assessed, and the results demonstrate the potential associations of cancer incidence with exposure to Cl-VOCs. Most Cl-VOCs thus have been listed as priority pollutants by the Ministry of Environmental Protection (MEP) of China, Environmental Protection Agency of the U.S. (U.S. EPA) and European Commission (EC), and are under close monitor and strict control. Yet, more efforts will be put into the epidemiological studies for the risk of human exposure to Cl-VOCs and the exposure level measurements in contaminated sites in the future. State-of-the-art remediation technologies for Cl-VOCs employ non-destructive methods and destructive methods (e.g. thermal incineration, phytoremediation, biodegradation, advanced oxidation processes (AOPs) and reductive dechlorination), whose advantages, drawbacks and future developments are thoroughly discussed in the later sections. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Luminescence properties of copper(I), zinc(II) and cadmium(II) coordination compounds with picoline ligands

    Energy Technology Data Exchange (ETDEWEB)

    Małecki, Jan Grzegorz, E-mail: gmalecki@us.edu.pl; Maroń, Anna

    2017-06-15

    Mononuclear coordination compounds of copper(I) – [Cu(PPh{sub 3}){sub 2}(picoline)(NO{sub 3})], zinc(II) – [ZnCl{sub 2}(picoline){sub 2}] (picoline=3– and 4–methylpyridine) and polymeric cadmium(II) – [CdCl{sub 2}(β-picoline){sub 2}]{sub n} were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. Single crystal X-ray crystallography revealed distorted tetrahedral geometry around the central ions of the compounds. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. The emission of copper(I) compounds originated from metal-to-ligand charge transfer state combined with nitrato-to-picoline charge transfer state i.e. ({sup 1}(M+X)LCT). The presence of nitrato ligand in the coordination sphere of copper(I) compounds quenches the emission. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution). - Graphical abstract: Coordination compounds of copper(I), zinc(II) and polymeric cadmium(II) with picoline ligands were prepared and their luminescence properties in solid state and acetonitrile solutions were determined. The compounds exhibit green photoluminescence in solid state and in acetonitrile solutions. Emission of copper(I) compounds originated from {sup 1}(M+X)LCT state. Luminescence of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions (solid state, solution).

  11. Incorporation of μ3-CO3 into an MnIII/MnIV Mn12 cluster: {[(cyclam)MnIV(μ-O)2MnIII(H2O)(μ-OH)]6(μ3-CO3)2}Cl8·24H2O

    Science.gov (United States)

    Levaton, Ben B.; Olmstead, Marilyn M.

    2010-01-01

    The centrosymmetric title cluster, hexa­aquadi-μ3-carbonato-hexa­cyclamhexa-μ2-hydroxido-dodeca-μ2-oxido-hexa­mang­an­ese(IV)hexa­manganese(III) octa­chloride tetra­cosa­hydrate, [Mn12(CO3)2O12(OH)6(C10H24N4)6(H2O)6]Cl8·24H2O, has two μ3-CO3 groups that not only bridge octahedrally coordinated MnIII ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C—O distance of 1.294 (4) Å. The crystal packing is stabilized by O—H⋯Cl, O—H⋯O, N—H⋯Cl and N—H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol­ecules are disordered over 21 positions. PMID:21587382

  12. (Phosphinoalkyl)silanes. 4.(1) Hydrozirconation as a Non-Photochemical Route to (Phosphinopropyl)silanes: Facile Assembly of the Bis(3-(diphenylphosphino)propyl)silyl ("biPSi") Ligand Framework. Access to the Related Poly(3-(dimethylsilyl)propyl)phosphines R(n)()P(CH(2)CH(2)CH(2)SiMe(2)H)(3)(-)(n)() (n = 1, R = Ph; n = 0).

    Science.gov (United States)

    Zhou, Xiaobing; Stobart, Stephen R.; Gossage, Robert A.

    1997-08-13

    Treatment of SiEt(3)(CH=CH(2)) with ZrCp(2)HCl (Schwartz's reagent) followed by reaction with PPh(2)Cl provides a high-yield (75%) route to Ph(2)PCH(2)CH(2)SiEt(3), and accordingly hydrozirconation of CH(2)=CHCH(2)SiHMe(2) affords the intermediate ZrCp(2)(CH(2)CH(2)CH(2)SiHMe(2))Cl (2). The latter, which is very sensitive to hydrolysis and reacts with HCl forming SiHMe(2)Pr(n)() and with NBS or I(2) affording SiHMe(2)CH(2)CH(2)CH(2)X (X = Br (3), I (4)), behaves similarly with PPh(2)Cl, PPhCl(2), or PBr(3) undergoing cleavage to the known Ph(2)PCH(2)CH(2)CH(2)SiMe(2)H (i.e. chelH, A) and the novel bis- and tris(silylpropyl)phosphines PhP(CH(2)CH(2)CH(2)SiMe(2)H)(2) (5) and P(CH(2)CH(2)CH(2)SiMe(2)H)(3) (6), respectively, with concomitant formation of ZrCp(2)Cl(2). Corresponding hydroboration of allylsilanes is facile, but subsequent phosphine halide cleavage yields (phosphinoalkyl)silanes only as constituents of intractable mixtures. Hydrozirconation followed by phosphination with PPh(2)Cl also converts SiHMe(CH(2)CH=CH(2))(2) to SiHMe(CH(2)CH(2)CH(2)PPh(2))(2) (i.e. biPSiH, B) together with a propyl analogue Ph(2)PCH(2)CH(2)CH(2)SiMe(Pr(n)())H (7) of A (ca. 2:1 ratio), as well as SiH(CH(2)CH=CH(2))(3) to a mixture (ca. 5:2:1 ratio) of SiH(CH(2)CH(2)CH(2)PPh(2))(3) (i.e. triPSiH, C), a new analogue SiH(Pr(n)())(CH(2)CH(2)CH(2)PPh(2))(2) (8) of B, and a further analogue Ph(2)PCH(2)CH(2)CH(2)SiHPr(n)()(2) (9) of A. A further analogue SiH(2)(CH(2)CH(2)CH(2)PPh(2))(2) (10) of biPSiH (B) is obtained similarly starting from SiH(2)(CH(2)CH=CH(2))(2). Steric control of silylalkyl cleavage from 2 is indicated by the fact that, like PPh(2)Cl (which forms B), two further biPSiH analogues SiH(Me)[CH(2)CH(2)CH(2)P(n-hex)(2)](2) (11) and SiH(Me)(CH(2)CH(2)CH(2)PPhBz)(2) (12) were obtained using P(n-hex)(2)Cl (i.e. n-hex = CH(3)(CH(2))(4)CH(2)-) or PPhBzCl (i.e. Bz = -CH(2)C(6)H(5)), respectively, whereas neither PPr(i)(2)Cl nor PBu(t)(2)Cl led to (phosphinoalkyl)silane formation

  13. Cyclopentadienyl complexes of uranium(IV) chlorides. Crystal structures of trichloro(eta5-cyclopentadienyl)bis(triphenylphosphine oxide)uranium(IV) tetrahydrofuran solvate and of trichloro(eta5-cyclopentadienyl)bis(hexamethylphosphoramide)uranium(IV)

    International Nuclear Information System (INIS)

    Bagnall, K.W.; De Paoli, G.

    1984-01-01

    The crystal and molecular structures of [U(cp)Cl 3 (PPh 3 O) 2 ].thf (thf = tetrahydrofuran) (1) and [U(cp)Cl 3 (P(NMe 2 ) 3 O) 2 ] (cp = eta 5 -cyclopentadienyl) (2) have been determined from three-dimensional X-ray diffraction data. The results are presented. In both compounds the uranium atom is octahedrally co-ordinated with the two neutral ligands [PPh 3 O and P(NMe 2 ) 3 O] in cis positions; the chlorine atoms are in the mer arrangement and the cyclopentadienyl group is trans to one neutral ligand. The appearance of cis octahedral geometry in complexes of the type [U(cp)Cl 3 L 2 ] is discussed in terms of the operation of a possible trans effect. (author)

  14. A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

    Science.gov (United States)

    Usher, Al; McPhail, D. C.; Brugger, Joël

    2009-06-01

    The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0

  15. Preparations and characterization of some carbonyl-(1-cyanoethyl)ruthenium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Katsuma; Ochi, Naoyuki; Kitamura, Tsuneyuki; Sasada, Yoko [Nagasaki Univ. (Japan); Shinoda, Sumio

    1982-08-01

    A hydridoruthenium(II) complex (RuClH(CO)(PPh/sub 3/)/sub 3/) reacted easily with acrylonitrile and fumaronitrile to give chloro-bridged binuclear (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/) (2) and ((Ru(NCCH/sub 2/CHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/), respectively. Complex 2 reacted with 4-picoline (pic), Na(BHPz/sub 3/) (Pz = 1-pyrazolyl), Na(BPz/sub 4/), and Na(Et/sub 2/NCS/sub 2/).3H/sub 2/O to afford the corresponding (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(pic)(PPh/sub 3/))/sub 2/) (3), (Ru(MeCHCN)(BHPz/sub 3/)(CO)(PPh/sub 3/)) (accompanied by a small amount of (Ru/sub 2/(MeCHCN)/sub 2/Cl(BHPz/sub 3/)(CO)/sub 2/(PPh/sub 3/)/sub 4/)), (Ru/sub 2/(MeCHCN)/sub 2/Cl(BPz/sub 4/)(CO)/sub 2/(PPh/sub 3/)/sub 2/), and Na(Ru(MeCHCN)Cl(Et/sub 2/NCS/sub 2/)(CO)(PPh/sub 3/)), respectively. Complex 3 reacted with thallium (I) acetylacetonate (Tl(acac)), resulting in the formation of ((Ru(MeCHCN)(acac)(CO)(PPh/sub 3/))/sub 2/) and (Ru(MeCHCN)(acad)(CO)(pic)(PPh/sub 3/)). These new complexes were characterized by means of elemental analysis and spectroscopic data. The diastereoisomerism was also discussed as regards these (1-cyanoethyl)ruthenium(II) complexes.

  16. On the relation between Jahn-Teller ordering and charge ordering

    International Nuclear Information System (INIS)

    Eijndhoven, J.C.M van.

    1978-01-01

    This thesis compares the structures of KCusup(II)F 3 and Cs 2 Ausup(I)Ausup(III)Cl 6 . Both compounds have a structure that can be thought to result from a deformation of the cubic perovskite structure. The deformation of KCusup(II)F 3 is a result of a cooperative Jahn-Teller effect and the deformation of Cs 2 Ausup(I)Ausup(III)Cl 6 results in two sublattices. The structures of both compounds result from a continuous phase transition from the cubic pervskite structure due to a deformation of symmetry. Using local coordinates and a calculation of the electron-lattice interaction in a static approximation, four structure types were derived. One is the structure of Cs 2 AuAuCl 6 at ambient temperature and pressure and the second contains a group of structures corresponding to the structures found for KCuF 3 . The third structure type was recently suggested for Cs 2 AuAuCl 6 under pressure and the fourth has not been found experimentally. Two types show a Jahn-Teller ordering and the other two charge ordering (Auth./C.F.)

  17. Molecular dynamics computer simulation study of Pdn (n=13, 19, 38 and 55) clusters

    International Nuclear Information System (INIS)

    Karabacak, M.; Oezcelik, S.; Guevenc, Z.B.

    2002-01-01

    Using constant-energy molecular dynamics and thermal quenching simulations, we have studied minimum-energy structures and energetics, Pd n (n=13, 19, 38, and 55) clusters employing the Voter and Chen's version of parameterisation of the embedded-atom potential surface. Isomer statistics for Pdn ( n = 13 and 19 ) is obtained from 10000 initial independent configurations, which have been generated along high-energy trajectories (chosen energy values are high enough to melt the clusters). The thermal quenching technique is employed to remove the internal kinetic energy of the clusters. The locally stable isomers are separated from metastable ones. Probabilities belonging to sampling the basins of attractions of each isomers are computed, and then, isomers' energy spectra are analyzed

  18. The magmatic model for the origin of Archean Au-quartz vein ore systems: an assessment of the evidence

    International Nuclear Information System (INIS)

    Spooner, E.T.C.

    1991-01-01

    The magmatic model for the origin of Archean Au-quartz vein ore systems suggests that Au was derived by partition between silicate (± sulphide) melts of certain compositions and H 2 O-CO 2 -NaCl magmatic fluids. Supporting evidence includes partial/structural geological relationships, timing relationships, H and C isotope geochemistry, probable primary Au enrichment in the Lamaque stocks, and fluid inclusion volatile geochemistry. Evidence is currently negative with respect to various within- and sub-greenstone belt metamorphic/deep crustal fluid models for primary Au mineralization; however a U-Pb age for vein stage 3 sphene from the Camflo deposit, Quebec which is ∼ 55-60 Ma younger than the host stock at 2685-2680 Ma indicates dissolution/reprecipitation of Au by late, (?) upper crustal saline fluids. Evidence is accumulating that epithermal-meso thermal Au-Ag mineralization in island arc and cordilleran settings may also have been magmatically derived ± high level fluid mixing from calc-alkaline, shoshonitic and other igneous compositions. (author)

  19. Magnetic ordering of CoCl2-GIC, a spin ceramic: hierarchical successive transitions and the intermediate glassy phase

    International Nuclear Information System (INIS)

    Suzuki, Masatsugu; Suzuki, Itsuko S; Matsuura, Motohiro

    2007-01-01

    Stage-2 CoCl 2 -graphite intercalation compound (GIC) is a spin ceramic which shows hierarchical successive transitions at T cu (= 8.9 K) and T cl (= 7.0 K) from the paramagnetic phase into an intra-cluster (two-dimensional ferromagnetic) order with inter-cluster disorder and then to an inter-cluster (three-dimensional antiferromagnetic like) order over the whole system. The nature of the inter-cluster disorder was suggested to be of spin glass by nonlinear magnetic response analyses around T cu and by studies on dynamical aspects of ordering between T cu and T cl . Here, we present a further extensive examination of a series of time dependence of zero-field cooled magnetization M ZFC after the ageing protocol below T cu . The time dependence of the relaxation rates S ZFC (t) = (1/H) dM ZFC (t)/dlnt dramatically changes from the curves of simple spin glass ageing effect below T cl to those of two peaks above T cl . The characteristic relaxation behaviour apparently indicates that there coexist two different kinds of glassy correlated region below T cu

  20. Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation

    NARCIS (Netherlands)

    Guan, Y.; Hensen, E.J.M.

    2009-01-01

    Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au LIII edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold

  1. trans-(Cl)-[Ru(5,5'-diamide-2,2'-bipyridine)(CO)2 Cl2 ]: Synthesis, Structure, and Photocatalytic CO2 Reduction Activity.

    Science.gov (United States)

    Kuramochi, Yusuke; Fukaya, Kyohei; Yoshida, Makoto; Ishida, Hitoshi

    2015-07-06

    A series of trans-(Cl)-[Ru(L)(CO)2 Cl2 ]-type complexes, in which the ligands L are 2,2'-bipyridyl derivatives with amide groups at the 5,5'-positions, are synthesized. The C-connected amide group bound to the bipyridyl ligand through the carbonyl carbon atom is twisted with respect to the bipyridyl plane, whereas the N-connected amide group is in the plane. DFT calculations reveal that the twisted structure of the C-connected amide group raises the level of the LUMO, which results in a negative shift of the first reduction potential (Ep ) of the ruthenium complex. The catalytic abilities for CO2 reduction are evaluated in photoreactions (λ>400 nm) with the ruthenium complexes (the catalyst), [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine; the photosensitizer), and 1-benzyl-1,4-dihydronicotinamide (the electron donor) in CO2 -saturated N,N-dimethylacetamide/water. The logarithm of the turnover frequency increases by shifting Ep a negative value until it reaches the reduction potential of the photosensitizer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Experimental studies on cycling stable characteristics of inorganic phase change material CaCl6H2O-MgCl6H2O modified with SrCl6H2O and CMC

    Science.gov (United States)

    He, Meizhi; Yang, Luwei; Zhang, Zhentao

    2018-01-01

    By means of mass ratio method, binary eutectic hydrated salts inorganic phase change thermal energy storage system CaCl6H2O-20wt% MgCl6H2O was prepared, and through adding nucleating agent 1wt% SrCl6H2O and thickening agent 0.5wt% carboxy methyl cellulose (CMC), inoganic phase change material (PCM) modified was obtained. With recording cooling-melting curves simultaneously, this PCM was frozen and melted for 100 cycles under programmable temperature control. After per 10 cycles, the PCM was charaterized by differential scanning calorimeter (DSC), X-ray diffraction (XRD) and density meter, then analysing variation characteristics of phase change temperature, supercooling degree, superheat degree, latent heat, crystal structure and density with the increase of cycle index. The results showed that the average values of average phase change temperature for cooling and heating process were 25.70°C and 27.39°C respectively with small changes. The average values of average supercooling and superheat degree were 0.59°C and 0.49°C respectively, and the maximum value was 1.10°C. The average value and standard deviation of latent heat of fusion were 120.62 J/g and 1.90 J/g respectively. Non-molten white solid sediments resulted from phase separation were tachyhydrite (CaMg2Cl6·12H2O), which was characterized by XRD. Measuring density of the PCM after per 10 cycles, and the results suggested that the total mass of tachyhydrite was limited. In summary, such modified inoganic PCM CaCl6H2O-20wt% MgCl6H2O-1wt% SrCl6H2O-0.5wt% CMC could stay excellent circulation stability within 100 cycles, and providing reference value in practical use.

  3. Electronic structure, superconductivity, and spin fluctuations in the A15 compounds A3B: A = V, Nb; B = Ir,Pt,Au

    International Nuclear Information System (INIS)

    Jarlborg, T.; Junod, A.; Peter, M.

    1983-01-01

    The electronic structure of six A15 compounds V 3 Ir, V 3 Pt, V 3 Au, Nb 3 Ir, Nb 3 Pt, and Nb 3 Au has been determined by means of self-consistent semirelativistic linear muffin-tin orbital band calculations. Parameters related to superconductivity such as electron-phonon coupling, transition temperature, electronic specific heat, and magnetic exchange enhancement are derived from the electronic-structure results. Generally the results obtained agree well with experimental values, with the exception of Nb 3 Pt and V 3 Au. In the former compound the density of states (DOS) has a sharp increase at E/sub F/ making the exact DOS value uncertain. In V 3 Au the high calculated T/sub c/ and the Stoner factor indicate that spin fluctuations may be limiting the T/sub c/. .AE

  4. Cationic polyhydrido cluster complexes. Crystal and molecular structures of (Ir3(Ph2P(CH2)3PPh2)3(H)7(CO))2+ and (Ir3(Ph2P(CH2)2(2-py))3(H)7)2+

    International Nuclear Information System (INIS)

    Hsienhau Wang; Casalnuovo, A.L.; Johnson, B.J.; Mueting, A.M.; Pignolet, L.H.

    1988-01-01

    Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and 1 H and 31 P NMR spectroscopy (Ir 3 (dppp) 3 (H) 7 (CO)) 2+ (2) and (Ir3 (PN) 3 (H) 7)2+ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir 3 (dppp) 3 (H) 7 ) 2+ (1) in CH 2 Cl 2 solution and H 2 with (Ir(PN)(COD)) + (4) in CH 3 OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced from structural and 1 H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. 1 H NMR data with use of acetone-d 6 as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C 1 symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) angstrom) with one PN ligand chelated to each iridium atom. 1 H NMR analysis, with use of CD 2 Cl 2 as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C 3 symmetry. (Ir 3 (dppp) 3 (H) 7 (CH 3 C 6 H 4 NC)) 2+ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH 2 Cl 2 solution and characterized by ir and 1 H and 31 P NMR spectroscopy. 44 refs., 3 figs., 3 tabs

  5. Developing an aqueous approach for synthesizing Au and M@Au (M = Pd, CuPt) hybrid nanostars with plasmonic properties

    Science.gov (United States)

    Du, Jingshan; Yu, Junjie; Xiong, Yalin; Lin, Zhuoqing; Zhang, Hui; Yang, Deren

    Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make it attractive in optical, sensing, and biomedical applications. In this contribution, we report a general and facile strategy towards aqueous synthesis of Au and M@Au (M = Pd, CuPt) hybrid nanostars by reducing HAuCl4 with ethanolamine in the presence of cetyltrimethylammonium bromide (CTAB). According to electron microscopic observation and spectral monitoring, we found that the layered epitaxial growth mode (i.e., Frank-van der Merwe mechanism) contributes to the enlargement of the core, while, the random attachment of Au nanoclusters onto the cores accounts for the formation of the branches. Both of them are indispensable for the formation of the nanostars. The LSPR properties of the Au nanoparticles have been well investigated with morphology control via precursor amount and growth temperature. The Au nanostars showed improved surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G due to their sharp edges and tips, which were therefore confirmed as good SERS substrate to detect trace amount of molecules.

  6. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

    Science.gov (United States)

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-11-01

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at -0.65 V, -0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes.

  7. Intramolecular charge separation in spirobifluorene-based donor–acceptor compounds adsorbed on Au and indium tin oxide electrodes

    International Nuclear Information System (INIS)

    Heredia, Daniel; Otero, Luis; Gervaldo, Miguel; Fungo, Fernando; Dittrich, Thomas; Lin, Chih-Yen; Chi, Liang-Chen; Fang, Fu-Chuan; Wong, Ken-Tsung

    2013-01-01

    Surface photovoltage (SPV) measurements were performed with a Kelvin-probe in spirobifluorene-based donor (diphenylamine)–acceptor (dicyano or cyanoacrylic acid moieties) compounds adsorbed from highly diluted solutions onto Au and indium tin oxide electrode surfaces. Strong intramolecular charge separation (negative SPV signals up to more than 0.1 V) due to directed molecule adsorption was observed only for spirobifluorene donor–acceptor compounds with carboxylic acid moiety. SPV signals and onset energies of electronic transitions depended on ambience conditions. - Highlights: ► Fluorene donor–acceptor derivatives were adsorbed at Au and indium tin oxide. ► Surface photovoltage measurements were performed with a Kelvin-probe. ► Strong intra-molecular charge separation was observed. ► SPV signals depended on ambience conditions

  8. Production of strange clusters in relativistic heavy ion collisions

    International Nuclear Information System (INIS)

    Dover, C.B.; Baltz, A.J.; Pang, Yang; Schlagel, T.J.; Kahana, S.H.

    1993-02-01

    We address a number of issues related to the production of strangeness in high energy heavy ion collisions, including the possibility that stable states of multi-strange hyperonic or quark matter might exist, and the prospects that such objects may be created and detected in the laboratory. We make use of events generated by the cascade code ARC to estimate the rapidity distribution dN/dy of strange clusters produced in Si+Au and Au+Au collisions at AGS energies. These calculations are performed in a simple coalescence model, which yields a consistent description of the strange cluster (d, 3 HE, 3 H, 4 He) production at these energies. If a doubly strange, weakly bound ΛΛ dibaryon exists, we find that it is produced rather copiously in Au+Au collisions, with dN/dy ∼0.1 at raid-rapidity. If one adds another non-strange or strange baryon to a cluster, the production rate decreases by roughly one or two orders of magnitude, respectively. For instance, we predict that the hypernucleus ΛΛ 6 He should have dN/dy ∼5 x 10 -6 for Au+Au central collisions. It should be possible to measure the successive Λ → pπ- weak decays of this object. We comment on the possibility that conventional multi-strange hypernuclei may serve as ''doorway states'' for the production of stable configurations of strange quark matter, if such states exist

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-15

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

  10. Novel ruthenium methylcyclopentadienyl complex bearing a bipyridine perfluorinated ligand shows strong activity towards colorectal cancer cells.

    Science.gov (United States)

    Teixeira, Ricardo G; Brás, Ana Rita; Côrte-Real, Leonor; Tatikonda, Rajendhraprasad; Sanches, Anabela; Robalo, M Paula; Avecilla, Fernando; Moreira, Tiago; Garcia, M Helena; Haukka, Matti; Preto, Ana; Valente, Andreia

    2018-01-01

    Three new compounds have been synthesized and completely characterized by analytical and spectroscopic techniques. The new bipyridine-perfluorinated ligand L1 and the new organometallic complex [Ru(η 5 -MeCp)(PPh 3 ) 2 Cl] (Ru1) crystalize in the centrosymmetric triclinic space group P1¯. Analysis of the phenotypic effects induced by both organometallic complexes Ru1 and [Ru(η 5 -MeCp)(PPh 3 )(L1)][CF 3 SO 3 ] (Ru2), on human colorectal cancer cells (SW480 and RKO) survival, showed that Ru2 has a potent anti-proliferative activity, 4-6 times higher than cisplatin, and induce apoptosis in these cells. Data obtained in a noncancerous cell line derived from normal colon epithelial cells (NCM460) revealed an intrinsic selectivity of Ru2 for malignant cells at low concentrations, showing the high potential of this compound as a selective anticancer agent. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  11. Binding motif of terminal alkynes on gold clusters.

    Science.gov (United States)

    Maity, Prasenjit; Takano, Shinjiro; Yamazoe, Seiji; Wakabayashi, Tomonari; Tsukuda, Tatsuya

    2013-06-26

    Gold clusters protected by terminal alkynes (1-octyne (OC-H), phenylacetylene (PA-H) and 9-ethynyl-phenanthrene (EPT-H)) were prepared by the ligand exchange of small (diameter alkynes on Au clusters was investigated using various spectroscopic methods. FTIR and Raman spectroscopy revealed that terminal hydrogen is lost during the ligand exchange and that the C≡C bond of the alkynyl group is weakened upon attachment to the Au clusters. Acidification of the water phase after the ligand exchange indicated that the ligation of alkynyl groups to the Au clusters proceeds via deprotonation of the alkynes. A series of precisely defined Au clusters, Au34(PA)16, Au54(PA)26, Au30(EPT)13, Au35(EPT)18, and Au(41-43)(EPT)(21-23), were synthesized and characterized in detail to obtain further insight into the interfacial structures. Careful mass analysis confirmed the ligation of the alkynes in the dehydrogenated form. An upright configuration of the alkynes on Au clusters was suggested from the Au to alkyne ratios and photoluminescence from the excimer of the EPT ligands. EXAFS analysis implied that the alkynyl carbon is bound to bridged or hollow sites on the cluster surface.

  12. Optical properties of NbCl5 and ZnMg intercalated graphite compounds

    International Nuclear Information System (INIS)

    Jung, Eilho; Lee, Seokbae; Roh, Seulki; Kang, Jihoon; Park, Tuson; Hwang, Jungseek; Meng, Xiuqing; Tongay, Sefaattin

    2014-01-01

    We studied NbCl 5 and ZnMg alloy intercalated graphite compounds using an optical spectroscopy technique. These intercalated metallic graphite samples were quite challenging to obtain optical reflectance spectra since they were not flat and quite thin. By using both a new method and an in situ gold evaporation technique we were able to obtain reliable reflectance spectra of our samples in the far and mid infrared range (80–7000 cm −1 ). We extracted the optical constants including the optical conductivity and the dielectric function from the measured reflectance spectra using a Kramers–Kronig analysis. We also extracted the dc conductivity and the plasma frequencies from the optical conductivity and dielectric functions. NbCl 5 intercalated graphite samples show similar optical conductivity spectra as bare highly oriented pyrolytic graphite even though there are some differences in detail. ZnMg intercalated samples show significantly different optical conductivity spectra from the bare graphite. Optical spectroscopy is one of the most reliable experimental techniques to obtain the electronic band structures of materials. The obtained optical conductivities support the recent theoretically calculated electronic band structures of NbCl 5 and ZnMg intercalated graphite compounds. Our results also provide important information of electronic structures and charge carrier properties of these two new intercalated materials for applications. (paper)

  13. Grafting of a novel gold(III) complex on nanoporous MCM-41 and evaluation of its toxicity in Saccharomyces cerevisiae.

    Science.gov (United States)

    Fazaeli, Yousef; Amini, Mostafa M; Ashourion, Hamed; Heydari, Homayoun; Majdabadi, Abbas; Jalilian, Amir Reza; Abolmaali, Shamsozoha

    2011-01-01

    The goal of this research was to investigate the potential of newly synthesized gold complex trichloro(2,4,6-trimethylpyridine)Au(III) as an anticancer agent. The gold(III) complex was synthesized and grafted on nanoporous silica, MCM-41, to produce AuCl(3)@PF-MCM- 41 (AuCl(3) grafted on pyridine-functionalized MCM-41). The toxicity of trichloro(2,4,6- trimethylpyridine)Au(III) and AuCl(3)@PF-MCM-41 in Saccharomyces cerevisiae (as a model system) was studied. The gold(III) complex showed a mid cytotoxic effect on yeast viability. Using the drug delivery system, nanoporous MCM-41, the gold(III) complex became a strong inhibitor for growth of yeast cells at a very low concentration. Furthermore, the animal tests revealed a high uptake of AuCl(3)@PF-MCM-41 in tumor cells. The stability of the compound was confirmed in human serum.

  14. Gold cluster carbonyls: saturated adsorption of CO on gold cluster cations, vibrational spectroscopy, and implications for their structures.

    Science.gov (United States)

    Fielicke, André; von Helden, Gert; Meijer, Gerard; Pedersen, David B; Simard, Benoit; Rayner, David M

    2005-06-15

    We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au(n)(+) clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au(n)(+). Our findings are in agreement with the planar structures of the Au(n)(+) cluster cations with n < or = 7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au(n)(CO)(m)(+) complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au(n)(CO)(m)(+) complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au(n)(+), provide information on the structure of the Au(n)(+)-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.

  15. Crystal structures of two 1:2 dihydrate compounds of chloranilic acid with 2-carboxypyridine and 2-carboxyquinoline

    Directory of Open Access Journals (Sweden)

    Kazuma Gotoh

    2017-12-01

    Full Text Available The crystal structure of the 1:2 dihydrate compound of chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone with 2-carboxypyridine (another common name: picolinic acid; systematic name: pyridine-2-carboxylic acid, namely, 2C6H5.5NO20.5+·C6HCl2O4−·2H2O, (I, has been determined at 180 K, and the structure of the 1:2 dihydrate compound of chloranilic acid with 2-carboxyquinoline (another common name: quinaldic acid; systematic name: quinoline-2-carboxylic acid, namely, 2C10H7NO2·C6H2Cl2O4·2H2O, (II, has been redetermined at 200 K. This determination presents a higher precision crystal structure than the previously published structure [Marfo-Owusu & Thompson (2014. X-ray Struct. Anal. Online, 30, 55–56]. Compound (I was analysed as a disordered structure over two states, viz. salt and co-crystal. The salt is bis(2-carboxypyridinium chloranilate dihydrate, 2C6H6NO2+·C6Cl2O42−·2H2O, and the co-crystal is bis(pyridinium-2-carboxylate chloranilic acid dihydrate, 2C6H5NO2·C6H2Cl2O4·2H2O, including zwitterionic 2-carboxypyridine. In both salt and co-crystal, the water molecule links the chloranilic acid and 2-carboxypyridine molecules through O—H...O and N—H...O hydrogen bonds. The 2-carboxypyridine molecules are connected into a head-to-head inversion dimer by a short O—H...O hydrogen bond, in which the H atom is disordered over two positions. Compound (II is a 1:2 dihydrate co-crystal of chloranilic acid and zwitterionic 2-carboxyquinoline. The water molecule links the chloranilic acid and 2-carboxyquinoline molecules through O—H...O hydrogen bonds. The 2-carboxyquinoline molecules are connected into a head-to-tail inversion dimer by a pair of N—H...O hydrogen bonds.

  16. Fermi surfaces properties of AuAl2, AuGa2, and AuIn2 with the CaF2-type cubic structure

    Science.gov (United States)

    Nishimura, K.; Kakihana, M.; Suzuki, F.; Yara, T.; Hedo, M.; Nakama, T.; Ōnuki, Y.; Harima, H.

    2018-05-01

    We grew high-quality single crystals of AuAl2, AuGa2, and AuIn2 with the fluorite (CaF2)-type cubic structure and determined the Fermi surface properties by the de Haas-van Alphen (dHvA) experiments using full-potential LAPW bad calculations. The Fermi surface and optical properties for three compounds were once studied from an interest of colors because AuAl2 has a striking bright reddish-purple color, whereas AuGa2 and AuIn2 are, respectively, neutral and bluish. The detected dHvA frequencies in the present study are found to be in a wide range of (0.1-13)×107 Oe. The main dHvA branches for three compounds are in excellent agreement with the theoretical ones, but some dHvA branches with small dHvA frequencies are slightly deviated from the theoretical ones, especially in AuGa2 and AuIn2.

  17. Structural Characterizations of Palladium Clusters Prepared by Polyol Reduction of [PdCl4]2− Ions

    Directory of Open Access Journals (Sweden)

    Loredana Schiavo

    2016-01-01

    Full Text Available Palladium nanoparticles are of great interest in many industrial fields, ranging from catalysis and hydrogen technology to microelectronics, thanks to their unique physical and chemical properties. In this work, palladium clusters have been prepared by reduction of [PdCl4]2− ions with ethylene glycol, in the presence of poly(N-vinyl-2-pyrrolidone (PVP as stabilizer. The stabilizer performs the important role of nucleating agent for the Pd atoms with a fast phase separation, since palladium atoms coordinated to the polymer side-groups are forced at short distances during nucleation. Quasispherical palladium clusters with a diameter of ca. 2.6 nm were obtained by reaction in air at 90°C for 2 hours. An extensive materials characterization by transmission electron microscopy (TEM, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, and other characterizations (TGA, SEM, EDS-SEM, and UV-Vis has been performed in order to evaluate the structure and oxidation state of nanopalladium.

  18. Crystal structure of difluorochloronium hexafluoroniobate and hexafluorotantalate, ClF2NbF6 and ClF2TaF6

    International Nuclear Information System (INIS)

    Ehllern, A.M.; Antipin, M.Yu.; Sharabarin, A.V.; Struchkov, Yu.T.

    1991-01-01

    Crystal structure of ClF 2 NbF 6 (1) and ClF 2 TaF 6 (2) were investigated by the method of X-ray diffraction analysis. Salts 1 and 2 are isostructural, crystals are rhombic: a = 9.981(2) and 10.049(2), b = 5.781(1) and 5.775(1), c = 10.552(2) and 10.670(2) A, V = 608.9(3) and 619.2(3) A 3 , Z = 4, d calcd 3.058 and 3.952 g/cm 3 , sp. gr. Pcca. Both salts are characterized by ionic structure. Bond lengths and valent angles, general view of 1 crystal structure are presented

  19. Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbClCl·H2O

    Science.gov (United States)

    Ahmed, Houssem Eddine; Kamoun, Slaheddine

    2017-09-01

    The crystal structure of (C6H20N3)SbClCl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbClCl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

  20. AuPd Bimetallic Nanocrystals Embedded in Magnetic Halloysite Nanotubes: Facile Synthesis and Catalytic Reduction of Nitroaromatic Compounds

    Directory of Open Access Journals (Sweden)

    Lei Jia

    2017-10-01

    Full Text Available In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd. The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by transmission electron microscopy (TEM, high resolution TEM (HRTEM, energy-dispersive X-ray spectroscopy (EDS, and vibrating sample magnetometry (VSM analyses. The catalysts, fabricated by a cheap, environmentally friendly, and simple surfactant-free formation process, exhibited high activities during the reduction of 4-nitrophenol and various other nitroaromatic compounds. Moreover, the catalytic activities of the HNTs@Fe3O4@AuPd nanocatalysts were tunable via adjusting the atomic ratio of AuPd during the synthesis. As compared with the monometallic nanocatalysts (HNTs@Fe3O4@Au and HNTs@Fe3O4@Pd, the bimetallic alloyed HNTs@Fe3O4@AuPd nanocatalysts exhibited excellent catalytic activities toward the reduction of 4-nitrophenol (4-NP to 4-aminophenol. Furthermore, the as-obtained HNTs@Fe3O4@AuPd can be recycled several times, while retaining its functionality due to the stability and magnetic separation property.

  1. Ternary reduced-graphene-oxide/Bi2MoO6/Au nanocomposites with enhanced photocatalytic activity under visible light

    International Nuclear Information System (INIS)

    Bi, Jinhong; Fang, Wei; Li, Li; Li, Xiaofen; Liu, Minghua; Liang, Shijing; Zhang, Zizhong; He, Yunhui; Lin, Huaxiang; Wu, Ling; Liu, Shengwei; Wong, Po Keung

    2015-01-01

    A novel ternary nanocomposite photocatalyst consisted of reduced-graphene-oxide (RGO), Bi 2 MoO 6 and plasmonic Au nanoparticles were successfully fabricated by multiple steps including a simple solvothermal process and photochemical reduction process. RGO/Bi 2 MoO 6 /Au was characterized by X-ray powder diffraction patterns, transmission electron microscopy, UV–vis diffuse reflectance spectra, Raman spectroscopy and X-ray photoelectron spectroscopy. In comparison with Bi 2 MoO 6 , RGO/Bi 2 MoO 6 and Au/Bi 2 MoO 6 , RGO/Bi 2 MoO 6 /Au exhibits an enhanced photocatalytic activity for decomposition of Rhodamine B under visible light. The separation efficiency of the photogenerated holes and electrons on Bi 2 MoO 6 is promoted by the combined effect of both RGO and Au in the ternary composite, and thus enhances photocatalytic activity. The scavenger study revealed that both hole and superoxide are the major reactive species for the photocatalytic degradation of Rhodamine B using RGO/Bi 2 MoO 6 /Au photocatalyst. - Graphical abstract: A novel ternary nanocomposite photocatalyst consisted of reduced-graphene-oxide (RGO), Bi 2 MoO 6 and plasmonic Au nanoparticles were successfully fabricated by multiple steps including a simple solvothermal process and photochemical reduction process. The resulted ternary nanocomposites greatly enhanced the visible light photocatalytic properties compared to Bi 2 MoO 6 , RGO/Bi 2 MoO 6 or Au/Bi 2 MoO 6 binary systems. The improved photocatalytic activity was mainly attributed to the synergistic effect of Au and RGO with better separation of the photogenerated holes and electrons, resulting from the surface plasmonic resonance and extra strong electron magnetic field of Au nanoparticles and the high electron conductivity of RGO. - Highlights: • The ternary nanocomposites RGO/Bi 2 MoO 6 /Au were constructed for the first time. • RGO/Bi 2 MoO 6 /Au showed much higher visible photoactivity than RGO (Au)/Bi 2 MoO 6 . • The improved

  2. Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

    Science.gov (United States)

    Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

    2002-08-01

    Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic

  3. Electrochemical fabrication of clean dendritic Au supported Pt clusters for electrocatalytic oxidation of formic acid

    International Nuclear Information System (INIS)

    Xia Yue; Liu Jun; Huang Wei; Li Zelin

    2012-01-01

    Highlights: ► A smooth Au surface was rebuilt into clean dendrite via square wave potential pulses. ► It was performed in blank H 2 SO 4 solution without Au(III) species and other additives. ► Dendritic Au provided certain advantage for dispersing Pt due to its unique structure. ► Pt-decorated dendritic Au demonstrated high activity for the HCOOH electrooxidation. - Abstract: We report here the fabrication of clean dendritic gold (DG) directly on a smooth Au electrode via square wave potential pulses (SWPPs) in a blank H 2 SO 4 solution containing no Au(III) species and additives. The effects of potential range, frequency and duration time of SWPPs and H 2 SO 4 concentration on the construction of DG were systematically investigated. A possible mechanism was proposed to explain the growth of DG. The whole process was templateless and surfactantless, and therefore effectively avoided possible contaminations that occurred in other synthetic routes. Further, the prepared DG electrode functioned as a scaffold to support electrodeposited Pt clusters, producing Pt-decorated DG (Pt-DG) electrodes. The electrocatalytic properties of Pt-DG electrodes with various Pt loadings were examined for the oxidation of formic acid. The low Pt loading Pt-DG demonstrated different electrochemical behavior from that on Pt-decorated smooth gold (Pt-SG) and on Pt-decorated gold nanoparticles because there were more defect sites like steps and edges on the DG surface. Ensemble effect, as well as electronic effect, accounts for the improved electrocatalytic activity of low Pt loading Pt-DG.

  4. Surface defect free growth of a spin dimer TlCuCl{sub 3} compound crystals and investigations on its optical and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Gihun, E-mail: G.Ryu@fkf.mpg.de [Max Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart (Germany); Son, Kwanghyo [Max Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart (Germany)

    2016-05-15

    A defect-free high quality single crystal of spin dimer TlCuCl{sub 3} compound is firstly synthesized at the optimal growth temperature using the vertical Bridgman method. In this study, we clearly found that the cupric chloride is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C. The Cl{sup −}- related gas phase at the high temperature region also always gives rise to a pinhole-like surface defect at the surface of crystal. Therefore, we clearly verified an exotic anisotropic magnetic behavior (anisotropic ratio of M{sub b}/M{sub (201)} at 2 K, 7 T=10) using the defect-free TlCuCl{sub 3} crystals in this three-dimensional spin dimer TlCuCl{sub 3} compound, relatively stronger magnetic ordering in the H//b than that of H//(201) direction at above the transition magnetic field. - Graphical abstract: A single crystal of spin dimer TlCuCl{sub 3} compound with a defect free is successfully synthesized on the basis of TG/DTA result. We newly found that this cupric chloride compound is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C and Cl{sup −} related gas phases also give rise to the defects like a pinhole on the surface of TlCuCl{sub 3} crystal. Using the crystals with a surface defect free, we also clearly verified the crystal structure of spin dimer TlCuCl{sub 3} compound.

  5. Femtosecond Laser Fabricated Ag@Au and Cu@Au Alloy Nanoparticles for Surface Enhanced Raman Spectroscopy Based Trace Explosives Detection

    Directory of Open Access Journals (Sweden)

    Moram Sree Satya Bharati

    2018-03-01

    Full Text Available Herein we present results from our detailed studies on the fabrication of Ag@Au and Cu@Au alloy nanoparticles (NPs using the femtosecond laser ablation in liquid technique. The NPs were obtained by ablating the pure Ag, Cu targets (bulk in HAuCl4 (5 mM solution. The absorption properties of the obtained NPs colloids were characterized using UV-Visible absorption spectrometer and their size, shape, and crystallinity were investigated using the XRD, FESEM and TEM techniques. The fabricated NPs were utilized for sensing of explosive molecules such as 2,4,6-trinitrophenol (PA, 2,4-dinitrotoluene (DNT and a common dye methylene blue (MB using the surface enhanced Raman spectroscopy (SERS technique. The detection limit in terms of weight was as low as few nano-grams in the case of nitroaromatic explosive compounds (PA, DNT and few picograms in the case of a common dye molecule (MB. Typical enhancement factors achieved were estimated to be ~104, ~105, and ~107, respectively, for PA, DNT, and MB. The significance of the present work lies in exploring the performance of the prepared NPs being used as SERS substrates for explosives detection using a portable Raman instrument. Such capability enables one to carry the spectrometer to the point of interest in the field and evaluate any hazardous samples within a short period of time.

  6. Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

    Science.gov (United States)

    Lin, Qisheng; Miller, Gordon J

    2018-01-16

    Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural

  7. Spontaneous decoration of Au nanoparticles on micro-patterned reduced graphene oxide shaped by focused laser beam

    International Nuclear Information System (INIS)

    Wan, Y. C.; Tok, E. S.; Teoh, H. F.; Sow, C. H.

    2015-01-01

    We report a facile, two-step method for the micro-landscaping of Au nanoparticles(NPs) on reduced graphene oxide (rGO) film en route to micro-patterned Au(NPs)-rGO hybrid functional materials. This method employs a focused laser beam to first locally convert GO to rGO before immersing the micro-patterned GO-rGO film into HAuCl 4 solution. The rGO micro-pattern, shaped by the focused laser beam, serves as nucleation sites for the reduction of Au ions. The reduction mechanism that governs the decoration of Au NPs on rGO films is akin to electroless deposition process. In this instance, surface charges that are formed during laser reduction of GO to rGO provide active nucleation sites for Au 3+ ions to form Au NPs when HAuCl 4 solution is introduced. The number density, the size, and size distribution of the Au NPs can thus be directly tuned and preferentially anchored onto the rGO micro-pattern by varying the incident laser power, the scanning speed of the laser, or the concentration of HAuCl 4 . The resulting hybrid materials can be used as a substrate for Surface Enhanced Raman Spectroscopy (SERS). Using Rhodamine 6G as the test subject, we found an improvement of SERS enhancement over bare rGO of up to four times, depending on the size of the Au NPs

  8. Spontaneous decoration of Au nanoparticles on micro-patterned reduced graphene oxide shaped by focused laser beam

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Y. C.; Tok, E. S. [Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542 (Singapore); Teoh, H. F. [Graduate School of Integrative Sciences and Engineering, National University of Singapore, 28 Medical Drive, Singapore 117456 (Singapore); Sow, C. H. [Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542 (Singapore); Graduate School of Integrative Sciences and Engineering, National University of Singapore, 28 Medical Drive, Singapore 117456 (Singapore)

    2015-02-07

    We report a facile, two-step method for the micro-landscaping of Au nanoparticles(NPs) on reduced graphene oxide (rGO) film en route to micro-patterned Au(NPs)-rGO hybrid functional materials. This method employs a focused laser beam to first locally convert GO to rGO before immersing the micro-patterned GO-rGO film into HAuCl{sub 4} solution. The rGO micro-pattern, shaped by the focused laser beam, serves as nucleation sites for the reduction of Au ions. The reduction mechanism that governs the decoration of Au NPs on rGO films is akin to electroless deposition process. In this instance, surface charges that are formed during laser reduction of GO to rGO provide active nucleation sites for Au{sup 3+} ions to form Au NPs when HAuCl{sub 4} solution is introduced. The number density, the size, and size distribution of the Au NPs can thus be directly tuned and preferentially anchored onto the rGO micro-pattern by varying the incident laser power, the scanning speed of the laser, or the concentration of HAuCl{sub 4}. The resulting hybrid materials can be used as a substrate for Surface Enhanced Raman Spectroscopy (SERS). Using Rhodamine 6G as the test subject, we found an improvement of SERS enhancement over bare rGO of up to four times, depending on the size of the Au NPs.

  9. The glass transition, crystallization and melting in Au-Pb-Sb alloys

    Science.gov (United States)

    Lee, M. C.; Allen, J. L.; Fecht, H. J.; Perepezko, J. H.; Ohsaka, K.

    1988-01-01

    The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

  10. Microstructure and Thermal Properties of Polypropylene/Clay Nanocomposites with TiCl4/MgCl2/Clay Compound Catalyst

    Directory of Open Access Journals (Sweden)

    Limei Wang

    2015-01-01

    Full Text Available Polypropylene (PP/clay nanocomposites were synthesized by in situ intercalative polymerization with TiCl4/MgCl2/clay compound catalyst. Microstructure and thermal properties of PP/clay nanocomposites were studied in detail. Fourier transform infrared (FTIR spectra indicated that PP/clay nanocomposites were successfully prepared. Both wide-angle X-ray diffraction (XRD and transmission electron microscopy (TEM examination proved that clay layers are homogeneously distributed in PP matrix. XRD patterns also showed that the α phase was the dominate crystal phase of PP in the nanocomposites. Thermogravimetric analysis (TGA examinations confirmed that thermal stability of PP/clay nanocomposites was markedly superior to pure PP. Differential scanning calorimetry (DSC scans showed that the melt temperature and the crystallinity of nanocomposites were slightly lower than those of pure PP due to crystals imperfections.

  11. Electrochemistry of oxygen-free curium compounds in fused NaCl-2CsCl eutectic

    International Nuclear Information System (INIS)

    Osipenko, A.; Maershin, A.; Smolenski, V.; Novoselova, A.; Kormilitsyn, M.; Bychkov, A.

    2010-01-01

    This work presents the electrochemical study of Cm(III) in fused NaCl-2CsCl eutectic in the temperature range 823-1023 K. Transient electrochemical techniques such as cyclic, differential pulse and square wave voltammetry, and chronopotentiometry have been used in order to investigate the reduction mechanism of curium ions up to the metal. The results obtained show that the reduction reaction takes place in a single step Cm(III)+3e-bar →Cm(0). The diffusion coefficient of [CmCl 6 ] 3- complex ions was determined by cyclic voltammetry at different temperatures by applying the Berzins-Delahay equation. The validity of the Arrhenius law was also verified and the activation energy for diffusion was found to be 44.46 kJ/mol. The apparent standard electrode potential of the redox couple Cm(III)/Cm(0) was found by chronopotentiometry at several temperatures. The thermodynamic properties of curium trichloride have also been calculated.

  12. Understanding the structural properties and thermal stabilities of Au–Pd–Pt trimetallic clusters

    International Nuclear Information System (INIS)

    Zhao, Zheng; Li, Mingjiang; Cheng, Daojian; Zhu, Jiqin

    2014-01-01

    Highlights: • Structural properties of Au–Pd–Pt clusters are studied by Monte Carlo simulation. • Melting of Au–Pd–Pt clusters is studied by molecular dynamics simulation. • Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters. • Linear decrease in cluster melting point with the inverse cluster diameter. - Abstract: In this work, surface segregation phenomena of Au–Pd–Pt trimetallic clusters are investigated by using semi-grand Monte Carlo simulations based on the Gupta potential. It is found that Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters (6–24 at.% higher than the overall Au concentration), due to the competition among the surface energies of Au, Pd, and Pt. The melting properties of Au–Pd–Pt trimetallic clusters with different composition and size are investigated by using molecular dynamics simulations, based on the same Gupta potential. It is found that the Au–Pd–Pt trimetallic cluster with the highest melting point corresponds to the one with the most stable structure. In addition, linear decrease in cluster melting point with the inverse cluster diameter is predicted for both pure and trimetallic clusters, which is well-known as the Pawlow’s law

  13. The quaternary arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Hoffmann, Rolf-Dieter; Poettgen, Rainer [Univ. Muenster (Germany). Inst. fuer Anorganische und Analytische Chemie

    2016-07-01

    The quaternary gold arsenide oxides Ce{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} and Pr{sub 9}Au{sub 5-x}As{sub 8}O{sub 6} were synthesized from the rare earth elements (RE), rare earth oxides, arsenic and gold powder at maximum annealing temperatures of 1173 K. The structures were refined from single crystal X-ray diffractometer data: Pnnm, a=1321.64(6) pm, b=4073.0(3), c=423.96(2), wR2=0.0842, 3106 F{sup 2} values, 160 variables for Ce{sub 9}Au{sub 4.91(4)}As{sub 8}O{sub 6} and Pnnm, a=1315.01(4), b=4052.87(8), c=420.68(1) pm, wR2=0.0865, 5313 F{sup 2} values, 160 variables for Pr{sub 9}Au{sub 4.75(1)}As{sub 8}O{sub 6}. They represent a new structure type and show a further extension of pnictide oxide crystal chemistry. A complex polyanionic gold arsenide network [Au{sub 5}As{sub 8}]{sup 15-} (with some disorder in the gold substructure) is charge compensated with polycationic strands of condensed edge-sharing O rate at RE{sub 4/4} and O rate at RE{sub 4/3} tetrahedra ([RE{sub 4}O{sub 3}]{sub 2}{sup 12+}) as well as RE{sup 3+} cations in cavities.

  14. Reactions of R(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)]. A general and efficient entry to phosphanylphosphinidene complexes of platinum. Syntheses and structures of [(eta(2)-P=(i)Pr(2))Pt(p-Tol(3)P)(2)], [(eta(2)-P=(t)Bu(2))Pt(p-Tol(3)P)(2)], [{eta(2)-P=(N(i)Pr(2))(2)}Pt(p-Tol(3)P)(2)] and [{(Et(2)PhP)(2)Pt}(2)P(2)].

    Science.gov (United States)

    Domańska-Babul, Wioleta; Chojnacki, Jaroslaw; Matern, Eberhard; Pikies, Jerzy

    2009-01-07

    The reactions of lithium derivatives of diphosphanes R(2)P-P(SiMe(3))Li (R = (t)Bu, (i)Pr, Et(2)N and (i)Pr(2)N) with [(R'(3)P)(2)PtCl(2)] (R'(3)P = Et(3)P, Et(2)PhP, EtPh(2)P and p-Tol(3)P) proceed in a facile manner to afford side-on bonded phosphanylphosphinidene complexes of platinum [(eta(2)-P=R(2))Pt(PR'(3))(2)]. The related reactions of Ph(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)] did not yield [(eta(2)-P=PPh(2))Pt(PR'(3))(2)] and resulted mainly in the formation of [{(R'(3)P)(2)Pt}(2)P(2)], Ph(2)P-PLi-PPh(2), (Me(3)Si)(2)PLi and (Me(3)Si)(3)P. Crystallographic data are reported for the compounds [(eta(2)-P=R(2))Pt(p-Tol(3)P)(2)] (R = (t)Bu, (i)Pr, ((i)Pr(2)N)(2)P) and for [{(Et(2)PhP)(2)Pt}(2)P(2)].

  15. Local structure of disordered Au-Cu and Au-Ag alloys

    International Nuclear Information System (INIS)

    Frenkel, A. I.; Machavariani, V. Sh.; Rubshtein, A.; Rosenberg, Yu.; Voronel, A.; Stern, E. A.

    2000-01-01

    X-ray-absorption fine structure (XAFS) and x-ray-diffraction (XRD) measurements of disordered alloys Au x Cu 1-x and Au 0.5 Ag 0.5 prepared by melt spinning were performed. In the Au 0.5 Ag 0.5 alloy, no significant local deviations of the atoms from the average fcc lattice were detected while in Au x Cu 1-x alloys, significant deviations of atoms from the average fcc lattice were found. Mean-square vibrations of the Cu-Cu distances revealed by the XAFS in Au x Cu 1-x alloys indicate the weakening of contact between Cu atoms in the dilute limit. Our computer simulation for Au x Cu 1-x clusters of 10 5 atoms reproduces the main features of both the XAFS and XRD data

  16. Synthesis, Characterization and Biological Studies of New Phenyltin(IV) Dithiocarbamate Compounds

    International Nuclear Information System (INIS)

    Amirah Faizah Abdul Muthalib; Ibrahim Baba; Nazlina Ibrahim

    2015-01-01

    Nine chlorophenyl tin(IV) dithiocarbamate compounds of general formula PhSnCl[S 2 CNR ' R '' ] 2 (R ' = CH 3 , C 2 H 5 , C 7 H 7 and R ' = C 2 H 5 , C 6 H 11 , iC 3 H 7 , C 7 H 7 ) were prepared in one pot reaction of various secondary amine, carbon disulphide and phenyltin(1V) trichloride with the ratio of 2:2:1. These compounds have been characterized by elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, 1 H, 13 C NMR spectroscopy as well as single crystal X-ray crystallography. Data from X-ray crystallography showed that (C 6 H 5 )SnCl[S 2 CN(C 2 H 5 )(iC 3 H 7 )] 2 is six coordinated bonded with two chelating dithiocarbamate ligands in bidentate fashion, methyl-C and chloride atom thus form a distorted octahedral geometry. Five selected compounds, (C 6 H 5 )SnCl[S 2 CN(CH 3 )(C 2 H 5 )] 2 , (C 6 H 5 )SnCl[S 2 CN(CH 3 )(C 6 H 11 )] 2 , (C 6 H 5 )SnCl[S 2 CN(C 2 H 5 )(iC 3 H 7 )] 2 , (C 6 H 5 )SnCl[S 2 CN(C 7 H 7 )(iC 3 H 7 )] 2 and (C 6 H 5 )SnCl[S 2 CN(C 7 H 7 ) 2 ] 2 were screened for anticancer activity against Chang liver cells. These compounds were demonstrated no cytotoxic effect for all concentrations under the condition of the study with no IC 50 value. The minimum inhibitory concentration (MIC) and maximum bactericidal concentration (MBC) determinations for these five compounds used Escherichia coli and Pseudomonas aeruginosa as Gram negative bacteria together with Staphylococcus aureus and Staphylococcus epidermis as Gram positive bacteria. Compound (C 6 H 5 )SnCl[S 2 CN(CH 3 )(C 2 H 5 )] 2 was the most active compared to the other compounds by having the lowest MIC values of 1.25 mg/ mL and MBC value of 5.0 mg/ mL against E. Coli and S. Aureus bacteria. Compounds (C 6 H 5 )SnCl[S 2 CN(C 7 H 7 )(iC 3 H 7 )] 2 and (C 6 H 5 )SnCl[S 2 CN(C 7 H 7 ) 2 ] 2 that having a benzyl group showed their MIC and MBC values slightly higher compared to the other compounds againts certain bacteria indicating their low

  17. EDITORIAL: Cluster issue on Heusler compounds and devices Cluster issue on Heusler compounds and devices

    Science.gov (United States)

    Felser, Claudia; Hillebrands, Burkard

    2009-04-01

    This is the third cluster issue of Journal Physics D: Applied Physics devoted to half-metallic Heusler compounds and devices utilizing this class of materials. Heusler compounds are named after Fritz Heusler, the owner of a German copper mine, the Isabellenhütte, who discovered this class of materials in 1903 [1]. He synthesized mixtures of Cu2Mn alloys with various main group metals Z = Al, Si, Sn, Sb, which became ferromagnetic despite all constituents being non-magnetic. The recent success story of Heusler compounds began in 1983 with the discovery of the half-metallic electronic structure in NiMnSb [2] and Co2MnZ [3], making these and similar materials, in particular PtMnSb, also useful for magneto-optical data storage media applications due to their high Kerr rotation. The real breakthrough, however, came in 2000 with the observation of a large magnetoresistance effect in Co2Cr0.6Fe0.4Al [4]. The Co2YZ (Y = Ti, Cr, Mn, Fe) compounds are a special class of materials, which follow the Slater-Pauling rule [5], and most of them are half-metallic bulk materials. The electronic structure of Heusler compounds is well understood [6] and Curie temperatures up to 1100 K have been observed [7]. In their contribution to this cluster issue, Thoene et al predict that still higher Curie temperatures can be achieved. A breakthrough from the viewpoint of materials design is the synthesis of nanoparticles of Heusler compounds as reported in the contribution by Basit et al. Nano-sized half- metallic ferromagnets will open new directions for spintronic applications. The challenge, however, is still to produce spintronic devices with well defined interfaces to take advantage of the half-metallicity of the electrodes. Several groups have succeeded in producing excellent tunnel junctions with high magnetoresistance effects at low temperatures and decent values at room temperature [8-11]. Spin-dependent tunnelling characteristics of fully epitaxial magnetic tunnel junctions with a

  18. Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

    KAUST Repository

    Veenboer, Richard M. P.

    2017-09-08

    The synthesis and isolation of gold(I) precatalysts often requires the generation of several isolable intermediates as well as numerous purification steps. New protocols for the expedient synthesis of neutral [Au(OH)(NHC)] and [Au(CH2COCH3)(NHC)] species from [AuCl(NHC)] or [AuCl(DMS)] precursors bearing a variety of N-heterocyclic carbene (NHC) ligands are presented. These methods can be employed in a telescoping manner for the synthesis of catalytically relevant [Au(NTf2)(NHC)] and [Au(NHC)(NCCH3)][BF4] complexes. These attractive methods are straightforward and practical leading to various complexes in high isolated yields and purity.

  19. Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

    KAUST Repository

    Veenboer, Richard M. P.; Gasperini, Danila; Nahra, Fady; Cordes, David B.; Slawin, Alexandra M. Z.; Cazin, Catherine S. J.; Nolan, Steven P.

    2017-01-01

    The synthesis and isolation of gold(I) precatalysts often requires the generation of several isolable intermediates as well as numerous purification steps. New protocols for the expedient synthesis of neutral [Au(OH)(NHC)] and [Au(CH2COCH3)(NHC)] species from [AuCl(NHC)] or [AuCl(DMS)] precursors bearing a variety of N-heterocyclic carbene (NHC) ligands are presented. These methods can be employed in a telescoping manner for the synthesis of catalytically relevant [Au(NTf2)(NHC)] and [Au(NHC)(NCCH3)][BF4] complexes. These attractive methods are straightforward and practical leading to various complexes in high isolated yields and purity.

  20. Intense deep blue exciplex electroluminescence from NPB/TPBi:PPh3O-based OLEDs and their intrinsic degradation mechanisms (Conference Presentation)

    Science.gov (United States)

    Shinar, Joseph; Hippola, Chamika; Danilovic, Dusan; Bhattacharjee, Ujjal; Petrich, Jacob W.; Shinar, Ruth

    2016-09-01

    We describe intense and efficient deep blue (430 - 440 nm) exciplex emission from NPB/TPBi:PPh3O OLEDs where the luminous efficiency approaches 4 Cd/A and the maximal brightness exceeds 22,000 Cd/m2. Time resolved PL measurements confirm the exciplex emission from NPB:TPBi, as studied earlier by Monkman and coworkers [Adv. Mater. 25, 1455 (2013)]. However, the inclusion of PPh3O improves the OLED performance significantly. The effect of PPh3O on the EL and PL will be discussed. The NPB/TPBi:PPh3O-based OLEDs were also studied by optically and electrically detected magnetic resonance (ODMR and EDMR, respectively). In particular, the amplitude of the negative (EL- and current-quenching) spin 1/2 resonance, previously attributed to enhanced formation of strongly EL-quenching positive bipolarons, increases as the OLEDs degrade in a dry nitrogen atmosphere. This degradation mechanism is discussed in relation to degradation induced by hot polarons that are energized by exciton annihilation.

  1. Dual structural transition in small nanoparticles of Cu-Au alloy

    Science.gov (United States)

    Gafner, Yuri; Gafner, Svetlana; Redel, Larisa; Zamulin, Ivan

    2018-02-01

    Cu-Au alloy nanoparticles are known to be widely used in the catalysis of various chemical reactions as it was experimentally defined that in many cases the partial substitution of copper with gold increases catalytic activity. However, providing the reaction capacity of alloy nanoparticles the surface electronic structure strongly depends on their atomic ordering. Therefore, to theoretically determine catalytic properties, one needs to use a most real structural model complying with Cu-Au nanoparticles under various external influences. So, thermal stability limits were studied for the initial L12 phase in Cu3Au nanoalloy clusters up to 8.0 nm and Cu-Au clusters up to 3.0 nm at various degrees of Au atom concentration, with molecular dynamics method using a modified tight-binding TB-SMA potential. Dual structural transition L12 → FCC and further FCC → Ih is shown to be possible under the thermal factor in Cu3Au and Cu-Au clusters with the diameter up to 3.0 nm. The temperature of the structural transition FCC → Ih is established to decrease for small particles of Cu-Au alloy under the increase of Au atom concentration. For clusters with this structural transition, the melting point is found to be a linear increasing function of concentration, and for clusters without FCC → Ih structural transition, the melting point is a linear decreasing function of Au content. Thus, the article shows that doping Cu nanoclusters with Au atoms allows to control the forming structure as well as the melting point.

  2. Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

    Directory of Open Access Journals (Sweden)

    Arshid M. Ali

    2015-01-01

    Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

  3. Two-step crystal engineering of porous nets from [Cr3(μ 3-O)(RCO2)6] and [Cu3(μ 3-Cl)(RNH2)6Cl6] molecular building blocks

    KAUST Repository

    Elsaidi, Sameh K.

    2013-01-01

    Two porous nets have been prepared via a 2-step crystal engineering approach that links decorated trigonal prismatic [Cr3(μ 3-O)(CO2)6] and [Cu3(μ 3-Cl)(RNH2)6Cl6] molecular building blocks, MBBs. tp-PMBB-5-acs-1 is a rare example of a rigid acs underlying net whereas tp-PMBB-6-stp-1, an stp underlying net, exhibits free NH2 groups in its channels and a relatively high isosteric heat of adsorption for CO2. © 2013 The Royal Society of Chemistry.

  4. The Electronic Properties and L3 XANES of Au and Nano-Au

    International Nuclear Information System (INIS)

    Yiu, Y.M.; Zhang, P.; Sham, T.K.

    2004-01-01

    The electronic properties of Au crystal and nano Au have been investigated by theory and experiment. Molecularly capped nano-Au was synthesized using the two-phase method. Au nano-particles have been characterized by X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). They retain the fcc crystal structure. Their sizes have been determined to be in a range from 5.5 nm to 1.7 nm. The L3 X-ray Absorption Near Edge Structure (XANES) of nano-Au and Au foil have been recorded using synchrotron radiation, and examined by theoretical calculation based on the first principles. Both theory and experiment show that the nano-Au particles have essentially all the Au L3 XANES features of bulk Au in the near edge region with less pronounced resonance peaks. It is also shown that nano Au exhibits lower 4f binding energy than bulk Au in good agreement with quantum confined Au systems reported previously.

  5. Synthesis of binuclear rhodacarboranes from dianions 1,4- and 1,3-C6H4(CH2-9-C2H2B9H9-7,8-nido)22- and (Ph3P)3RhCl

    International Nuclear Information System (INIS)

    Zakharkin, L.I.; Zhigareva, G.G.

    1996-01-01

    Dianions 1,4 and 1,3-C 6 H 4 (CH 2 -9-C 2 H 2 B 9 H 9 -7,8-nido) 2 2- obtained from nido 7,8-dicarbollide-ion and 1,4-bis(bromomethyl) and 1,3-bis(bromomethyl)benzenes react with (Ph 3 P) 3 RhCl to give binuclear rhodacarboranes, 1,4- and 1,3-[3,3-(Ph 3 P) 2 -3-H-3,1,2-RhC 2 B 9 H 10 -4-CH 2 ] 2 C 6 H 6 with chemical reaction yield 85% and 87% respectively. 7 refs., 1 fig., 1 tab

  6. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    Science.gov (United States)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-12-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

  7. Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

    International Nuclear Information System (INIS)

    Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

    2015-01-01

    Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611}high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H_2PtCl_6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells. (paper)

  8. Absorption spectra and Faraday effect in Cs2NaNdCl6 and Cs2NaPrCl6 crystals

    International Nuclear Information System (INIS)

    Ehdel'man, I.S.; Galanov, E.K.; Kokov, I.T.; Malakhovskij, A.V.; Anistratov, A.T.

    1985-01-01

    The paper is devoted to studying absorption spectra and the Faraday effect in Cs 2 NaNdCl 6 and Cs 2 NaPrCl 6 crystals. The absorption spectra and Faraday effect were measured at room temperature in the range of 9000-30000 cmsup(-1) (0.33-1.2 μm) in 0-10 kOe magnetic fields. The absorption spectra produced contain several groups of intense absorption bands resulted from intraconfiguration electron transitions in rare-earth cations. The Faraday spectra in the whole range studied for both crystals have the form of smoothly dipping curves when increasing wavelength. The form of these curves testifies to prevailing contribution of strong electron transitions lying in a nearer UV region to the Faraday effect

  9. First-principles theory of short-range order in size-mismatched metal alloys: Cu-Au, Cu-Ag, and Ni-Au

    International Nuclear Information System (INIS)

    Wolverton, C.; Ozolins, V.; Zunger, A.

    1998-01-01

    We describe a first-principles technique for calculating the short-range order (SRO) in disordered alloys, even in the presence of large anharmonic atomic relaxations. The technique is applied to several alloys possessing large size mismatch: Cu-Au, Cu-Ag, Ni-Au, and Cu-Pd. We find the following: (i) The calculated SRO in Cu-Au alloys peaks at (or near) the left-angle 100 right-angle point for all compositions studied, in agreement with diffuse scattering measurements. (ii) A fourfold splitting of the X-point SRO exists in both Cu 0.75 Au 0.25 and Cu 0.70 Pd 0.30 , although qualitative differences in the calculated energetics for these two alloys demonstrate that the splitting in Cu 0.70 Pd 0.30 may be accounted for by T=0 K energetics while T≠0 K configurational entropy is necessary to account for the splitting in Cu 0.75 Au 0.25 . Cu 0.75 Au 0.25 shows a significant temperature dependence of the splitting, in agreement with recent in situ measurements, while the splitting in Cu 0.70 Pd 0.30 is predicted to have a much smaller temperature dependence. (iii) Although no measurements exist, the SRO of Cu-Ag alloys is predicted to be of clustering type with peaks at the left-angle 000 right-angle point. Streaking of the SRO peaks in the left-angle 100 right-angle and left-angle 1 (1) /(2) 0 right-angle directions for Ag- and Cu-rich compositions, respectively, is correlated with the elastically soft directions for these compositions. (iv) Even though Ni-Au phase separates at low temperatures, the calculated SRO pattern in Ni 0.4 Au 0.6 , like the measured data, shows a peak along the left-angle ζ00 right-angle direction, away from the typical clustering-type left-angle 000 right-angle point. (v) The explicit effect of atomic relaxation on SRO is investigated and it is found that atomic relaxation can produce significant qualitative changes in the SRO pattern, changing the pattern from ordering to clustering type, as in the case of Cu-Ag. copyright 1998 The American

  10. Facile preparation of amine and amino acid adducts of [60]fullerene using chlorofullerene C60Cl6 as a precursor.

    Science.gov (United States)

    Kornev, Alexey B; Khakina, Ekaterina A; Troyanov, Sergey I; Kushch, Alla A; Peregudov, Alexander; Vasilchenko, Alexey; Deryabin, Dmitry G; Martynenko, Vyacheslav M; Troshin, Pavel A

    2012-06-04

    We report a general synthetic approach to the preparation of highly functionalized amine and amino acid derivatives of [60]fullerene starting from readily available chlorofullerene C(60)Cl(6). The synthesized water-soluble amino acid derivative of C(60) demonstrated pronounced antiviral activity, while the cationic amine-based compound showed strong antibacterial action in vitro.

  11. Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

    Science.gov (United States)

    Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

    2013-01-07

    We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

  12. Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation.

    Science.gov (United States)

    Guan, Y; Hensen, E J M

    2009-11-07

    Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au L(III) edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold atoms upon reduction. The resulting gold clusters exhibit a very high intrinsic activity in the hydrogenation of 1,3-butadiene, which is at least one order of magnitude higher than that of the nanometre-sized gold particles in the non-leached parent catalyst. These findings point to a very strong structure sensitivity of the gold-catalyzed hydrogenation of dienes.

  13. Substitution reactions on cyclometallated iridium(I) triaryl-phosphite complexes and the formation of bis-monometallated triaryl-phosphite hydrido iridium(III) compounds

    Energy Technology Data Exchange (ETDEWEB)

    De Waal, D.J.A.; Singleton, E.; Van der Stok, E. (Council for Scientific and Industrial Research, Pretoria (South Africa). National Chemical Research Lab.)

    1981-01-01

    The compounds (Ir(P-C)(cod)L) (1) (P-C=P(OC/sub 6/H/sub 3/R-o)-(OC/sub 6/H/sub 4/R-o)/sub 2/; cod=1,5-cyclo-octadiene; L=P(OC/sub 6/H/sub 4/R-o)/sub 3/; R=H or Me) react with a range of tertiary phosphorus ligands in refluxing benzene to give (Ir(P-C)(cod)L') (2) (R=H;L'=PMe/sub 2/Ph,PMePh/sub 2/ or P(OMe)Ph/sub 2/ and R=Me;L'=PMe/sub 3/,PMe/sub 2/Ph,PMePh/sub 2/,PPh/sub 3/,Ph/sub 2/PCH/sub 2/CH/sub 2/AsPh/sub 2/,Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/,P(OMe)Ph/sub 2/,P(OC/sub 6/H/sub 4/Me-p)/sub 3/, or P(OCH/sub 2/)/sub 3/CMe). With carbon monoxide, diene replacement is effected in refluxing benzene to give cis-(Ir(P-C)(CO)/sub 2/L) (3a) (R=Me;L=P(OC/sub 6/H/sub 4/Me-o)/sub 3/) which readily converts to the transisomer (3b) in hot ethanol. With refluxing toluene as solvent, (1) and L'produce (IrH(P-C)/sub 2/L') (4) (R=H;L'=P(OPh)/sub 3/,P(OMe)Ph/sub 2/,PMePh/sub 2/, PPh/sub 3/, or P(C/sub 6/H/sub 4/Me-o)/sub 3/, and R=Me;L'=P(OMe)Ph/sub 2/,PMePh/sub 2/,P(OC/sub 6/H/sub 4/Me-o)/sub 3/,PPh/sub 3/,PCy/sub 3/ (Cy=cyclohexyl), or P(C/sub 6/H/sub 4/Me-o)/sub 3/), in which diene replacement is shown to be a function fo the size of L'. Proton n.m.r. and i.r. data are discussed in terms of possible structures.

  14. 22 CFR 312.655 - Individual.

    Science.gov (United States)

    2010-04-01

    ... 22 Foreign Relations 2 2010-04-01 2010-04-01 true Individual. 312.655 Section 312.655 Foreign Relations PEACE CORPS GOVERNMENTWIDE REQUIREMENTS FOR DRUG-FREE WORKPLACE (FINANCIAL ASSISTANCE) Definitions § 312.655 Individual. Individual means a natural person. ...

  15. Different Dimensional and Structural Variations in Coordination Compounds of Cadmium, Manganese and Nickel Constructed from the Ligand 2,2'-Bipyidine-3,3',6,6'-tetracarboxylic Acid (H{sub 4}bptc)

    Energy Technology Data Exchange (ETDEWEB)

    Xiang, Jing; Yang, Tiantian; Fu, Lulu; Luo, Ya; Wu, Jiashou [Yangtze Univ., Jingzhou (China)

    2013-09-15

    The reactions of hydrated CdCl{sub 2}, MnCl{sub 2}, and NiCl{sub 2} with 2,2'-bipyidine-3,3',6,6'-tetracarboxylic acid (H{sub 4}bptc) afforded the mononuclear [Cd{sup II}(H{sub 2}bptc)(H{sub 2}O){sub 3}]·H{sub 2}O (1), linear [Cd(H{sub 2}bptc)(H{sub 2}O)]·3H{sub 2}O{sub n} (2), 3-D hetero-bimetallic [NaCd(Hbptc)(H{sub 2}O)] (3), layer [Mn(H{sub 2}bptc)(H{sub 2}O)]n (4) and a dinuclear compound [Ni{sub 2}(H{sub 2}bptc)-(H{sub 2}O){sub 2}]·6H{sub 2}O (5). These compounds have been characterized by elemental analysis, IR, and their structures have been determined by X-ray crystallography. The thermal stabilities of 1-3 were measured by thermogravimetric analysis (TGA) and their solid state luminescence properties together with the free ligand H{sub 4}bptc were investigated at room temperature.

  16. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, L H; Lou, H B; Wang, X D; Debela, T T; Cao, Q P; Zhang, D X; Wang, S Y; Wang, C Z; Jiang, J Z

    2014-04-01

    The local atomic structure evolution in Al2Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt-Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al2Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of < 0,4,4,0 >, < 0,3, 6,0 > and < 0,4,4,2 > with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF2-type Al2Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al2Au alloy. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  17. Evolution of local atomic structure during solidification of Al2Au liquid: An ab initio study

    International Nuclear Information System (INIS)

    Xiong, L.H.; Lou, H.B.; Wang, X.D.; Debela, T.T.; Cao, Q.P.; Zhang, D.X.; Wang, S.Y.; Wang, C.Z.; Jiang, J.Z.

    2014-01-01

    The local atomic structure evolution in Al 2 Au alloy during solidification from 2000 K to 400 K was studied by ab initio molecular dynamics simulations and analyzed using the structure factor, pair correlation functions, bond angle distributions, the Honeycutt–Anderson (HA) index and Voronoi tessellation methods. It was found that the icosahedral-like clusters are negligible in the Al 2 Au stable liquid and supercooled liquid states, and the most abundant clusters are those having HA indices of 131 and 120 or Voronoi indices of 〈0, 4, 4, 0〉, 〈0, 3, 6, 0〉 and 〈0, 4, 4, 2〉 with coordination numbers of 8, 9 and 10, respectively. These clusters are similar to the local atomic structures in the CaF 2 -type Al 2 Au crystal, revealing the existence of structure heredity between liquid and crystalline phase in Al 2 Au alloy

  18. An Atomically Precise Au10 Ag2 Nanocluster with Red-Near-IR Dual Emission.

    Science.gov (United States)

    Lei, Zhen; Guan, Zong-Jie; Pei, Xiao-Li; Yuan, Shang-Fu; Wan, Xian-Kai; Zhang, Jin-Yuan; Wang, Quan-Ming

    2016-08-01

    A red-near-IR dual-emissive nanocluster with the composition [Au10 Ag2 (2-py-C≡C)3 (dppy)6 ](BF4 )5 (1; 2-py-C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10 Ag2 core that contains a planar Au4 (2-py-C≡C)3 unit sandwiched by two Au3 Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3 Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Observed damage during Argon gas cluster depth profiles of compound semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Barlow, Anders J., E-mail: anders.barlow@ncl.ac.uk; Portoles, Jose F.; Cumpson, Peter J. [National EPSRC XPS Users' Service (NEXUS), School of Mechanical and Systems Engineering, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2014-08-07

    Argon Gas Cluster Ion Beam (GCIB) sources have become very popular in XPS and SIMS in recent years, due to the minimal chemical damage they introduce in the depth-profiling of polymer and other organic materials. These GCIB sources are therefore particularly useful for depth-profiling polymer and organic materials, but also (though more slowly) the surfaces of inorganic materials such as semiconductors, due to the lower roughness expected in cluster ion sputtering compared to that introduced by monatomic ions. We have examined experimentally a set of five compound semiconductors, cadmium telluride (CdTe), gallium arsenide (GaAs), gallium phosphide (GaP), indium arsenide (InAs), and zinc selenide (ZnSe) and a high-κ dielectric material, hafnium oxide (HfO), in their response to argon cluster profiling. An experimentally determined HfO etch rate of 0.025 nm/min (3.95 × 10{sup −2} amu/atom in ion) for 6 keV Ar gas clusters is used in the depth scale conversion for the profiles of the semiconductor materials. The assumption has been that, since the damage introduced into polymer materials is low, even though sputter yields are high, then there is little likelihood of damaging inorganic materials at all with cluster ions. This seems true in most cases; however, in this work, we report for the first time that this damage can in fact be very significant in the case of InAs, causing the formation of metallic indium that is readily visible even to the naked eye.

  20. 7 CFR 1210.312 - Promotion.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 10 2010-01-01 2010-01-01 false Promotion. 1210.312 Section 1210.312 Agriculture... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE WATERMELON RESEARCH AND PROMOTION PLAN Watermelon Research and Promotion Plan Definitions § 1210.312 Promotion. Promotion means any...

  1. [Sb{sub 4}Au{sub 4}Sb{sub 4}]{sup 2−}: A designer all-metal aromatic sandwich

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Wen-Juan; You, Xue-Rui [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); Guo, Jin-Chang [Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000 (China); Li, Da-Zhi, E-mail: hj.zhai@sxu.edu.cn, E-mail: ldz005@126.com [Department of Chemical Engineering, Binzhou University, Binzhou 256603 (China); Wang, Ying-Jin [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); Department of Chemistry, Xinzhou Teachers University, Xinzhou 034000 (China); Sun, Zhong-Ming [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Zhai, Hua-Jin, E-mail: hj.zhai@sxu.edu.cn, E-mail: ldz005@126.com [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006 (China); State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan 030006 (China)

    2016-07-28

    We report on the computational design of an all-metal aromatic sandwich, [Sb{sub 4}Au{sub 4}Sb{sub 4}]{sup 2−}. The triple-layered, square-prismatic sandwich complex is the global minimum of the system from Coalescence Kick and Minima Hopping structural searches. Following a standard, qualitative chemical bonding analysis via canonical molecular orbitals, the sandwich complex can be formally described as [Sb{sub 4}]{sup +}[Au{sub 4}]{sup 4−}[Sb{sub 4}]{sup +}, showing ionic bonding characters with electron transfers in between the Sb{sub 4}/Au{sub 4}/Sb{sub 4} layers. For an in-depth understanding of the system, one needs to go beyond the above picture. Significant Sb → Au donation and Sb ← Au back-donation occur, redistributing electrons from the Sb{sub 4}/Au{sub 4}/Sb{sub 4} layers to the interlayer Sb–Au–Sb edges, which effectively lead to four Sb–Au–Sb three-center two-electron bonds. The complex is a system with 30 valence electrons, excluding the Sb 5s and Au 5d lone-pairs. The two [Sb{sub 4}]{sup +} ligands constitute an unusual three-fold (π and σ) aromatic system with all 22 electrons being delocalized. An energy gap of ∼1.6 eV is predicted for this all-metal sandwich. The complex is a rare example for rational design of cluster compounds and invites forth-coming synthetic efforts.

  2. The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

    Science.gov (United States)

    Gleeson, S. A.; Smith, M. P.

    2009-10-01

    We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

  3. Origin of selenium–gold interaction in F2CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH3): Synergistic effects

    International Nuclear Information System (INIS)

    Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong; Li, Hai-Bei

    2016-01-01

    Selenium–gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium–gold interaction by studying complexes F 2 CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH 3 ). The results showed that the formation of selenium–gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium–gold interaction. Interestingly, the chalcogen–gold interaction becomes stronger with the increase of chalcogen atomic mass in F 2 CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH 3 into F 2 CSe⋯AuY, in which selenium–gold interaction is weakened and selenium–nitrogen interaction is strengthened due to the synergistic effects.

  4. Molecular dynamics computer simulation study of Pd{sub n} (n=13, 19, 38 and 55) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Karabacak, M [Afyon Kocatepe University, Department of Physics, Afyon (Turkey); Oezcelik, S [Gazi University, Department of Physics, Ankara (Turkey); Guevenc, Z B [Cankaya University, Department of Electronics and Communication Engineering, Ankara (Turkey)

    2002-07-01

    Using constant-energy molecular dynamics and thermal quenching simulations, we have studied minimum-energy structures and energetics, Pd{sub n} (n=13, 19, 38, and 55) clusters employing the Voter and Chen's version of parameterisation of the embedded-atom potential surface. Isomer statistics for Pdn ( n = 13 and 19 ) is obtained from 10000 initial independent configurations, which have been generated along high-energy trajectories (chosen energy values are high enough to melt the clusters). The thermal quenching technique is employed to remove the internal kinetic energy of the clusters. The locally stable isomers are separated from metastable ones. Probabilities belonging to sampling the basins of attractions of each isomers are computed, and then, isomers' energy spectra are analyzed.

  5. 7 CFR 1250.312 - Marketing.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 10 2010-01-01 2010-01-01 false Marketing. 1250.312 Section 1250.312 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (MARKETING AGREEMENTS... Research and Promotion Order Definitions § 1250.312 Marketing. Marketing means the sale or other...

  6. 49 CFR 31.2 - Definitions.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false Definitions. 31.2 Section 31.2 Transportation Office of the Secretary of Transportation PROGRAM FRAUD CIVIL REMEDIES § 31.2 Definitions. ALJ means an... means any representation, certification, affirmation, document, record, or accounting or bookkeeping...

  7. Thermal And Gamma-Radiation Annealing Of The Iridium-192 Recoil Species In Crystalline Na{sub 2}IrCl{sub 6} {center_dot} 6H{sub 2}O; Recuit Thermique et par Rayonnement Gamma de l'espece {sup 192}Ir de Recul dans des Cristaux de Na{sub 2}IrCl{sub 6} * 6H{sub 2}O; 0422 0415 041f 041b 041e 0412 041e 0419 0418 0413 0410 041c 041c 0410 - 041e 0422 0416 0418 0413 041f 0420 041e 0414 0423 041a 0422 041e 0412 041e 0422 0414 0410 0427 0418 0418 0420 0418 0414 0418 042f -192 0412 041a 0420 0418 0421 0422 0410 041b 041b 0418 0427 0415 0421 041a 041e 041c Na{sub 2}IrCl{sub 6} {center_dot} 6H{sub 2}O; Regeneracion Termica y por Irradiacion Gamma de las Especies de Retroceso del Iridio-192 en Na{sub 2}IrCl{sub 6} {center_dot} 6H{sub 2}O Cristalino

    Energy Technology Data Exchange (ETDEWEB)

    Bell, Rita; Herr, W. [Kernforschungsanlage Juelich, Institut fuer Kernchemie der Universitaet Koeln, Cologne, Federal Republic of Germany (Germany)

    1965-04-15

    Ii is possible to separate by means of paper electrophoresis as many as 13 different recoil compounds from Na{sub 2}IrCl{sub 6}H{sub 2}O {center_dot} 6H{sub 2}O as a result of the nuclear reaction Ir{sup 191} (n, {gamma}) Ir{sup 192}. While most of them have anionic character, two of them act as Irwz-labelled cations. These carrier-free compounds have been studied as regards their behaviour towards reducing and oxidizing agents and aging in solution. Independently the hydrolysis of the hexachloro complexes of ter- and quadrivalent iridium, which had been labelled with Cl{sup 36} and Ir{sup 192}, was investigated. A comparison between these two series of results supported by further results from neutron activation analysis enables the recoil products to be identified mostly as octahedral complexes of Ir-III containing Cl{sup -}, H{sub 2}O and OH{sup -} ligands to a different extent. Evidently the water of crystallization plays an important role in the formation of the recoil species. The thermal annealing of these products at 120 Degree-Sign C shows a rapid decrease in the yields of the aquochloro, hydroxochloro and aquohydroxochloro complexes towards formation of the mother compound with the exception of the pentachloro complex. This complex decreases only after an initial increase, indicating that it is involved as an intermediate from other accompanying products during their annealing. Gamma-radiation annealing reveals many single steps whose general trend is a transition from lesser Cl-containing species to a higher Cl content leading finally to the hexachloro complex. This shows that the annealing process consists in the re-entering of Cl atoms (or ions) into the ligand sphere with the accompanying displacement of H{sub 2}O as well as OH (OH{sup -}). (author) [French] Il est possible de separer de Na{sub 2}IrCl{sub 6}(6H{sub 2}O), au moyen de l'electrophorese sur papier, jusqu'a 13 composes de recul resultant de la reaction nucleaire {sup 191}Ir(n, {gamma

  8. Probing the large-scale structure of the universe: an analysis of 55 bright southern clusters of galaxies

    International Nuclear Information System (INIS)

    Olowin, R.P.

    1985-01-01

    This dissertation presents the description of 55 bright, close (Z less than or equal to 0.1) clusters of galaxies as a homogeneous sample taken from a new effort to catalog galaxy clusters in the Southern Hemisphere. The positions of some 21,000 galaxies in clusters were cataloged along with visual magnitudes, morphological types, position angles of extended objects and pertinent remarks. For all of the clusters, various cluster parameters were determined and form the basis of comparative studies for these fundamental aggregates of matter in the universe. The aims of this study are to produce a homogeneous sample of galaxy clusters measured to a uniform limiting magnitude of m/sub v/ = 19.0 by means of a calibrated stepscale: catalogued with accurate positions relative to nearby astrometric standard stars; morphologically classified and population typed; and statistically analyzed in a uniform fashion to deduce certain cluster parameters. The cluster parameters of interest include an estimate of cluster distance, cluster center and cluster richness; galaxy distributions as a function of morphological type, magnitude distribution and core radius as determined by an isothermal gas sphere model

  9. Separating NaCl and AlCl6H2O Crystals from Acidic Solution Assisted by the Non-Equilibrium Phase Diagram of AlCl3-NaCl-H2O(-HCl Salt-Water System at 353.15 K

    Directory of Open Access Journals (Sweden)

    Huaigang Cheng

    2017-08-01

    Full Text Available Extracting AlCl6H2O from acid leaching solution through crystallization is one of the key processes to extracting aluminum from fly ash, coal gangue and other industrial solid wastes. However, the obtained products usually have low purity and a key problem is the lack of accurate data for phase equilibrium. This paper presented the non-equilibrium phase diagrams of AlCl3-NaCl-H2O (HCl salt-water systems under continuous heating and evaporation conditions, which were the main components of the acid leaching solution obtained through a sodium-assisted activation hydrochloric acid leaching process. The ternary system was of a simple eutonic type under different acidities. There were three crystalline regions; the crystalline regions of AlCl6H2O, NaCl and the mixture AlCl6H2O/NaCl, respectively. The phase diagram was used to optimize the crystallization process of AlCl6H2O and NaCl. A process was designed to evaporate and remove NaCl at the first stage of the evaporation process, and then continue to evaporate and crystallize AlCl6H2O after solid-liquid separation. The purities of the final salt products were 99.12% for NaCl and up to 97.35% for AlCl6H2O, respectively.

  10. Production of antimatter 5,6Li nuclei in central Au+Au collisions at sNN=200 GeV

    Directory of Open Access Journals (Sweden)

    Kai-Jia Sun

    2015-12-01

    Full Text Available Combining the covariant coalescence model and a blast-wave-like analytical parametrization for (anti-nucleon phase–space freezeout configuration, we explore light (anti-nucleus production in central Au+Au collisions at sNN=200 GeV. Using the nucleon freezeout configuration (denoted by FO1 determined from the measured spectra of protons (p, deutrons (d and 3He, we find the predicted yield of 4He is significantly smaller than the experimental data. We show this disagreement can be removed by using a nucleon freezeout configuration (denoted by FO2 in which the nucleons are assumed to freeze out earlier than those in FO1 to effectively consider the effect of large binding energy value of 4He. Assuming the binding energy effect also exists for the production of 5Li, Li‾5, 6Li and Li‾6 due to their similar binding energy values as 4He, we find the yields of these heavier (anti-nuclei can be enhanced by a factor of about one order, implying that although the stable (anti-6Li nucleus is unlikely to be observed, the unstable (anti-5Li nucleus could be produced in observable abundance in Au+Au collisions at sNN=200 GeV where it may be identified through the p–4He (p‾–He‾4 invariant mass spectrum. The future experimental measurement on (anti-5Li would be very useful to understand the production mechanism of heavier antimatter.

  11. Electrochemical properties of the MmNi3.55Mn0.4Al0.3Co0.75-xFex (x = 0.55 and 0.75) compounds

    International Nuclear Information System (INIS)

    Ben Moussa, M.; Abdellaoui, M.; Mathlouthi, H.; Lamloumi, J.; Guegan, A. Percheron

    2008-01-01

    The hydrogen storage alloys MmNi 3.55 Mn 0.4 Al 0.3 Co 0.75-x Fe x (x = 0.55 and 0.75) were used as negative electrodes in the Ni-MH accumulators. The chronopotentiommetry and the cyclic voltammetry were applied to characterize the electrochemical properties of these alloys. The obtained results showed that the substitution of the cobalt atoms by iron atoms has a good effect on the life cycle of the electrode. For the MmNi 3.55 Mn 0.4 Al 0.3 Co 0.2 Fe 0.55 compound, the discharge capacity reaches its maximum of 210 mAh/g after 12 cycles and then decreases to 190 mAh/g after 30 charge-discharge cycles. However, for the MmNi 3.55 Mn 0.4 Al 0.3 Fe 0.75 compound, the discharge capacity reaches its maximum of 200 mAh/g after 10 cycles and then decreases to 160 mAh/g after 30 cycles. The diffusion behavior of hydrogen in the negative electrodes made from these alloys was characterized by cyclic voltammetry after few activation cycles. The values of the hydrogen coefficient in MmNi 3.55 Mn 0.4 Al 0.3 Co 0.2 Fe 0.55 and MmNi 3.55 Mn 0.4 Al 0.3 Fe 0.75 are, respectively, equal to 2.96 x 10 -9 and 4.98 x 10 -10 cm 2 s -1 . However, the values of the charge transfer coefficients are, respectively, equal to 0.33 and 0.3. These results showed that the substitution of cobalt by iron decreases the reversibility and the kinetic of the electrochemical reaction in these alloys

  12. NMR study of distinct phase transitional behaviors in (CnH2n+1NH3)2SnCl6

    International Nuclear Information System (INIS)

    Lee, K. W.; Lee, C. E.; Choi, J. Y.; Kim, J.

    2005-01-01

    Phase transitions in bis-(n-C n H 2n+1 NH 3 ) 2 SnCl 6 , where the hydrocarbon part is analogous to lipid membrane, were investigated by means of 200-MHz 1 H nuclear magnetic resonance. As a result, critical fluctuations and molecular dynamics associated with the phase transitions, an order-disorder and a conformational phase transition, were distinguished in a wide temperature range. The critical dynamics, observed in the long-chain compounds but not in the short-chain compounds by laboratory frame spin-lattice relaxation measurements, is discussed in view of the chain length dependence of molecular dynamics.

  13. Small gold clusters on graphene, their mobility and clustering: a DFT study

    International Nuclear Information System (INIS)

    Amft, Martin; Sanyal, Biplab; Eriksson, Olle; Skorodumova, Natalia V

    2011-01-01

    Motivated by the experimentally observed high mobility of gold atoms on graphene and their tendency to form nanometer-sized clusters, we present a density functional theory study of the ground state structures of small gold clusters on graphene, their mobility and clustering. Our detailed analysis of the electronic structures identifies the opportunity to form strong gold-gold bonds and the graphene-mediated interaction of the pre-adsorbed fragments as the driving forces behind gold's tendency to aggregate on graphene. While clusters containing up to three gold atoms have one unambiguous ground state structure, both gas phase isomers of a cluster with four gold atoms can be found on graphene. In the gas phase the diamond-shaped Au 4 D cluster is the ground state structure, whereas the Y-shaped Au 4 Y becomes the actual ground state when adsorbed on graphene. As we show, both clusters can be produced on graphene by two distinct clustering processes. We also studied in detail the stepwise formation of a gold dimer out of two pre-adsorbed adatoms, as well as the formation of Au 3 . All reactions are exothermic and no further activation barriers, apart from the diffusion barriers, were found. The diffusion barriers of all studied clusters range from 4 to 36 meV only, and are substantially exceeded by the adsorption energies of - 0.1 to - 0.59 eV. This explains the high mobility of Au 1-4 on graphene along the C-C bonds.

  14. Synthesis and crystal structure of new K and Rb selenido/tellurido ferrate cluster compounds

    Energy Technology Data Exchange (ETDEWEB)

    Stueble, Pirmin; Berroth, Angela; Roehr, Caroline [Freiburg Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2016-08-01

    In the course of a systematic study of alkali iron chalcogenido salts containing clusters [Fe{sub 4}Q{sub 8}] a series of new mixed-valent potassium and rubidium selenido and tellurido ferrates(II/III) was synthesized by carefully heating the pure elements enclosed in sample tubes under an argon atmosphere up to maximum temperatures of 800-900 C. Their crystal structures have been determined by means of single crystal X-ray diffraction. The mixed-valent Fe{sup II/III} tellurido ferrates A{sub 7}[Fe{sub 4}Te{sub 8}] form three different structure types. All structures contain tetramers of four edge sharing [FeTe{sub 4}] tetrahedra, which are connected by common edges to form only slightly distorted tetrahedral [Fe{sub 4}Te{sub 8}]{sup 7-} anions ('stella quadrangula') with a [Fe{sub 4}Te{sub 4}] cubane core. In all cases, these anions are surrounded by 26 alkali cations, which are located at the eight corners and the midpoints of the six faces and 12 edges of a cube. The three crystal structures can thus be described by three different packings of cuboid moieties: The monoclinic rubidium compound Rb{sub 7}[Fe{sub 4}Te{sub 8}] (space group C2/c, a = 2000.16(7), b = 897.79(3), c = 1768.12(6) pm, β = 117.4995(10) , Z = 4, R1 = 0.0296) is isotypic to the known cesium tellurido and sulfido ferrates Cs{sub 7}[Fe{sub 4}(S/Te){sub 8}]. Depending on the temperature, K{sub 7}[Fe{sub 4}Te{sub 8}] forms two different but closely related new structure types: The tetragonal r.t. modification (space group P4{sub 2}/nmc, a = 1222.25(14), c = 872.1(2) pm, Z = 2, R1 = 0.0583) crystallizes in a supergroup of the orthorhombic l.t. (100 K) form (space group Pbcn, a = 1715.5, b = 866.76(3), c = 1715.50(7) pm, Z = 4, R1 = 0.0160). In all structures, the cluster centered cubes are stacked to form columns along the short (∼ 870 pm) axis. These columns are themselves densely packed with 4 (both K compounds) and 6 (A = Rb) adjacent face-sharing columns. According to these

  15. Electron attachment to oxygen, ozone and other compounds of atmospheric relevance as studied with ultra-high energy resolution

    International Nuclear Information System (INIS)

    Maerk, T.D.; Matejcik, S.; Kiendler, A.; Cicman, P.; Senn, G.; Skalny, J.; Stampfli, P.; Illenberger, E.; Chu, Y.; Stamatovic, A.

    1996-01-01

    The processes of electron attachment to oxygen, ozone, ozone/oxygen cluster and oxygen cluster as well as other compounds of atmospheric relevance (CF 2 Cl 2 , CHCl 3 and CCl 3 Br) were studied with ultra-high energy resolution crossed beam technique

  16. 40 CFR 81.312 - Hawaii.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 17 2010-07-01 2010-07-01 false Hawaii. 81.312 Section 81.312... AREAS FOR AIR QUALITY PLANNING PURPOSES Section 107 Attainment Status Designations § 81.312 Hawaii. Hawaii—TSP Designated area Does not meet primary standards Does not meet secondary standards Cannot be...

  17. Hydrogen-bonded clusters of 1, 1'-ferrocenedicarboxylic acid on Au(111) are initially formed in solution

    Science.gov (United States)

    Quardokus, Rebecca C.; Wasio, Natalie A.; Brown, Ryan D.; Christie, John A.; Henderson, Kenneth W.; Forrest, Ryan P.; Lent, Craig S.; Corcelli, Steven A.; Alex Kandel, S.

    2015-03-01

    Low-temperature scanning tunneling microscopy is used to observe self-assembled structures of ferrocenedicarboxylic acid (Fc(COOH)2) on the Au(111) surface. The surface is prepared by pulse-deposition of Fc(COOH)2 dissolved in methanol, and the solvent is evaporated before imaging. While the rows of hydrogen-bonded dimers that are common for carboxylic acid species are observed, the majority of adsorbed Fc(COOH)2 is instead found in six-molecule clusters with a well-defined and chiral geometry. The coverage and distribution of these clusters are consistent with a random sequential adsorption model, showing that solution-phase species are determinative of adsorbate distribution for this system under these reaction conditions.

  18. Synthesis of Au and Au/Cu alloy nanoparticles on multiwalled carbon nanotubes by using microwave irradiation

    International Nuclear Information System (INIS)

    Rangari, Vijaya K.; Dey, Sanchita; Jeelani, Shaik

    2010-01-01

    Gold nanoparticles and gold-copper alloy nanoparticles were synthesized by reduction of chloroauric acid (HAuCl_4.xH_2O) and co-reduction of chloroauric acid (HAuCl_4.xH_2O) and Copper(II) acetate [(CH_3COO)_2Cu.H_2O] by ethylene glycol through microwave irradiation technique. In this reaction ethylene glycol used as a solvent and also reducing agent. The cetyltrimethyl ammonium bromide (CTAB) used as surfactant. Au nanoparticles and Au-Cu nanoparticles on the surface of multiwalled carbon nanotube also produced by using same procedure. The XRD analysis confirmed the formation of Au and Au-Cu alloy nanoparticles on multiwalled carbon nanotubes(CNTs). The morphology and size of the particles were examined by the transmission electron microscopy. The EDS analysis on individual particles confirmed that the presence of two metals in a particle in case of alloy nanoparticle. The results presented here show that a variety of well defined metal and metal alloy nanoparticles can be produced by using the microwave polyol process with in a short period of time. (author)

  19. Density functionalized [RuII(NO)(Salen)(Cl)] complex: Computational photodynamics and in vitro anticancer facets.

    Science.gov (United States)

    Mir, Jan Mohammad; Jain, N; Jaget, P S; Maurya, R C

    2017-09-01

    Photodynamic therapy (PDT) is a treatment that uses photosensitizing agents to kill cancer cells. Scientific community has been eager for decades to design an efficient PDT drug. Under such purview, the current report deals with the computational photodynamic behavior of ruthenium(II) nitrosyl complex containing N, N'-salicyldehyde-ethylenediimine (SalenH 2 ), the synthesis and X-ray crystallography of which is already known [Ref. 38,39]. Gaussian 09W software package was employed to carry out the density functional (DFT) studies. DFT calculations with Becke-3-Lee-Yang-Parr (B3LYP)/Los Alamos National Laboratory 2 Double Z (LanL2DZ) specified for Ru atom and B3LYP/6-31G(d,p) combination for all other atoms were used using effective core potential method. Both, the ground and excited states of the complex were evolved. Some known photosensitizers were compared with the target complex. Pthalocyanine and porphyrin derivatives were the compounds selected for the respective comparative study. It is suggested that effective photoactivity was found due to the presence of ruthenium core in the model complex. In addition to the evaluation of theoretical aspects in vitro anticancer aspects against COLO-205 human cancer cells have also been carried out with regard to the complex. More emphasis was laid to extrapolate DFT to depict the chemical power of the target compound to release nitric oxide. A promising visible light triggered nitric oxide releasing power of the compound has been inferred. In vitro antiproliferative studies of [RuCl 3 (PPh 3 ) 3 ] and [Ru(NO)(Salen)(Cl)] have revealed the model complex as an excellent anticancer agent. From IC 50 values of 40.031mg/mL in former and of 9.74mg/mL in latter, it is established that latter bears more anticancer potentiality. From overall study the DFT based structural elucidation and the efficiency of NO, Ru and Salen co-ligands has shown promising drug delivery property and a good candidacy for both chemotherapy as well as

  20. 22 CFR 312.640 - Employee.

    Science.gov (United States)

    2010-04-01

    ... 22 Foreign Relations 2 2010-04-01 2010-04-01 true Employee. 312.640 Section 312.640 Foreign... § 312.640 Employee. (a) Employee means the employee of a recipient directly engaged in the performance of work under the award, including— (1) All direct charge employees; (2) All indirect charge...

  1. Potential use of SERS-assisted theranostic strategy based on Fe{sub 3}O{sub 4}/Au cluster/shell nanocomposites for bio-detection, MRI, and magnetic hyperthermia

    Energy Technology Data Exchange (ETDEWEB)

    Han, Yu; Lei, Sheng-lan [Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005 (China); Lu, Jian-hua [Department of Electronic Science, College of Physical Science and Technology, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance Research, Xiamen University, Xiamen 361005 (China); He, Yuan [Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005 (China); Chen, Zhi-wei, E-mail: chenzhiwei@xmu.edu.cn [Department of Electronic Science, College of Physical Science and Technology, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance Research, Xiamen University, Xiamen 361005 (China); Ren, Lei, E-mail: renlei@xmu.edu.cn [Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005 (China); State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005 (China); Fujian Collaborative Innovation Center for Exploitation and Utilization of Marine Biological Resources, Xiamen 361005 (China); Zhou, Xi [Department of Biomaterials, College of Materials, Xiamen University, Xiamen 361005 (China); Fujian Provincial Key Laboratory of Fire Retardant Materials, Xiamen University, Xiamen 361005 (China); Fujian Collaborative Innovation Center for Exploitation and Utilization of Marine Biological Resources, Xiamen 361005 (China)

    2016-07-01

    A surface-enhanced Raman scattering (SERS)-assisted theranostic strategy was designed based on a synthesized multifunctional Fe{sub 3}O{sub 4}/Au cluster/shell nanocomposite. This theranostic strategy was used for free prostate specific antigen (free-PSA) detection, magnetic resonance imaging (MRI), and magnetic hyperthermia. The lowest protein concentration detected was 1 ng mL{sup −1}, and the limit of detection (LOD) of the calculated PSA was 0.75 ng mL{sup −1}. Then, MRI was carried out to visualize the tumor cell. Lastly, magnetic hyperthermia was employed and revealed a favorable killing effect for the tumor cells. Thus, this SERS-assisted strategy based on a Fe{sub 3}O{sub 4}/Au cluster/shell nanocomposite showed great advantages in theranostic treatment. - Graphical abstract: Fe{sub 3}O{sub 4}/Au cluster/shell composite can be used for specific protein detection, magnetic resonance imaging and magnetic hyperthermia therapy. - Highlights: • We designed a SERS-assisted theranostic strategy based on the mutifunctional nanocomposites using gold shelled Fe{sub 3}O{sub 4} clusters. • Fe{sub 3}O{sub 4}/Au nanoparticles with theranostics and SERS for early diagnosis of PSA were reported for the first time. • The LOD of detection for PSA was lowed as 0.75 ng mL{sup −1}, and the total detection time was shorten to less than 1 h. • Fe{sub 3}O{sub 4} clusters had spin-spin (T{sub 2}) contrast enhancement and increased magnetic response. • Gold nanoshells supplied excellent chemical stability, biocompatibility, better heating property for magnetic hyperthermia.

  2. Electric field gradients in Hg compounds

    DEFF Research Database (Denmark)

    Arcisauskaité, Vaida; Knecht, Stefan; Sauer, Stephan P. A.

    2012-01-01

    &H functional performs best at both 4-component and ZORA levels. We furthermore observe that changes in the largest component of the diagonalised EFG tensor, Vzz, of linear HgCl2 show a slightly stronger dependence than the r-3 scaling upon bond length r(Hg-Cl) alterations. The 4-component/BH&H Vzz value of -9.......26 a.u. for a bent HgCl2 (¿ Cl-Hg-Cl = 120¿) is close to -9.60 a.u. obtained for the linear HgCl2 structure. Thus a point charge model for EFG calculations completely fails in this case. By means of a projection analysis of molecular orbital (MO) contributions to Vzz in terms of the atomic constituents...

  3. 31 CFR 312.1 - Authority.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false Authority. 312.1 Section 312.1 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) FISCAL SERVICE, DEPARTMENT... UNIONS AS FISCAL AGENTS OF THE UNITED STATES § 312.1 Authority. (a) Home Owners' Loan Act. Section 5(k...

  4. Collision geometry scaling of Au+Au pseudorapidity density from √(sNN )=19.6 to 200 GeV

    Science.gov (United States)

    Back, B. B.; Baker, M. D.; Ballintijn, M.; Barton, D. S.; Betts, R. R.; Bickley, A. A.; Bindel, R.; Budzanowski, A.; Busza, W.; Carroll, A.; Decowski, M. P.; García, E.; George, N.; Gulbrandsen, K.; Gushue, S.; Halliwell, C.; Hamblen, J.; Heintzelman, G. A.; Henderson, C.; Hofman, D. J.; Hollis, R. S.; Hołyński, R.; Holzman, B.; Iordanova, A.; Johnson, E.; Kane, J. L.; Katzy, J.; Khan, N.; Kucewicz, W.; Kulinich, P.; Kuo, C. M.; Lin, W. T.; Manly, S.; McLeod, D.; Mignerey, A. C.; Nouicer, R.; Olszewski, A.; Pak, R.; Park, I. C.; Pernegger, H.; Reed, C.; Remsberg, L. P.; Reuter, M.; Roland, C.; Roland, G.; Rosenberg, L.; Sagerer, J.; Sarin, P.; Sawicki, P.; Skulski, W.; Steinberg, P.; Stephans, G. S.; Sukhanov, A.; Tonjes, M. B.; Tang, J.-L.; Trzupek, A.; Vale, C.; van Nieuwenhuizen, G. J.; Verdier, R.; Wolfs, F. L.; Wosiek, B.; Woźniak, K.; Wuosmaa, A. H.; Wysłouch, B.

    2004-08-01

    The centrality dependence of the midrapidity charged particle multiplicity in Au+Au heavy-ion collisions at √(sNN )=19.6 and 200 GeV is presented. Within a simple model, the fraction of hard (scaling with number of binary collisions) to soft (scaling with number of participant pairs) interactions is consistent with a value of x=0.13±0.01 (stat) ±0.05 (syst) at both energies. The experimental results at both energies, scaled by inelastic p ( p¯ ) +p collision data, agree within systematic errors. The ratio of the data was found not to depend on centrality over the studied range and yields a simple linear scale factor of R200/19.6 =2.03±0.02 (stat) ±0.05 (syst) .

  5. CD33 monoclonal antibody conjugated Au cluster nano-bioprobe for targeted flow-cytometric detection of acute myeloid leukaemia

    Science.gov (United States)

    Retnakumari, Archana; Jayasimhan, Jasusri; Chandran, Parwathy; Menon, Deepthy; Nair, Shantikumar; Mony, Ullas; Koyakutty, Manzoor

    2011-07-01

    Protein stabilized gold nanoclusters (Au-NCs) are biocompatible, near-infrared (NIR) emitting nanosystems having a wide range of biomedical applications. Here, we report the development of a Au-NC based targeted fluorescent nano-bioprobe for the flow-cytometric detection of acute myeloid leukaemia (AML) cells. Au-NCs with ~ 25-28 atoms showing bright red-NIR fluorescence (600-750 nm) and average size of ~ 0.8 nm were prepared by bovine serum albumin assisted reduction-cum-stabilization in aqueous phase. The protein protected clusters were conjugated with monoclonal antibody against CD33 myeloid antigen, which is overexpressed in ~ 99.2% of the primitive population of AML cells, as confirmed by immunophenotyping using flow cytometry. Au-NC-CD33 conjugates having average size of ~ 12 nm retained bright fluorescence over an extended duration of ~ a year, as the albumin protein protects Au-NCs against degradation. Nanotoxicity studies revealed excellent biocompatibility of Au-NC conjugates, as they showed no adverse effect on the cell viability and inflammatory response. Target specificity of the conjugates for detecting CD33 expressing AML cells (KG1a) in flow cytometry showed specific staining of ~ 95.4% of leukaemia cells within 1-2 h compared to a non-specific uptake of ~ 8.2% in human peripheral blood cells (PBMCs) which are CD33low. The confocal imaging also demonstrated the targeted uptake of CD33 conjugated Au-NCs by leukaemia cells, thus confirming the flow cytometry results. This study demonstrates that novel nano-bioprobes can be developed using protein protected fluorescent nanoclusters of Au for the molecular receptor targeted flow cytometry based detection and imaging of cancer cells.

  6. CD33 monoclonal antibody conjugated Au cluster nano-bioprobe for targeted flow-cytometric detection of acute myeloid leukaemia

    International Nuclear Information System (INIS)

    Retnakumari, Archana; Jayasimhan, Jasusri; Chandran, Parwathy; Menon, Deepthy; Nair, Shantikumar; Mony, Ullas; Koyakutty, Manzoor

    2011-01-01

    Protein stabilized gold nanoclusters (Au-NCs) are biocompatible, near-infrared (NIR) emitting nanosystems having a wide range of biomedical applications. Here, we report the development of a Au-NC based targeted fluorescent nano-bioprobe for the flow-cytometric detection of acute myeloid leukaemia (AML) cells. Au-NCs with ∼ 25-28 atoms showing bright red-NIR fluorescence (600-750 nm) and average size of ∼ 0.8 nm were prepared by bovine serum albumin assisted reduction-cum-stabilization in aqueous phase. The protein protected clusters were conjugated with monoclonal antibody against CD33 myeloid antigen, which is overexpressed in ∼ 99.2% of the primitive population of AML cells, as confirmed by immunophenotyping using flow cytometry. Au-NC-CD33 conjugates having average size of ∼ 12 nm retained bright fluorescence over an extended duration of ∼ a year, as the albumin protein protects Au-NCs against degradation. Nanotoxicity studies revealed excellent biocompatibility of Au-NC conjugates, as they showed no adverse effect on the cell viability and inflammatory response. Target specificity of the conjugates for detecting CD33 expressing AML cells (KG1a) in flow cytometry showed specific staining of ∼ 95.4% of leukaemia cells within 1-2 h compared to a non-specific uptake of ∼ 8.2% in human peripheral blood cells (PBMCs) which are CD33 low . The confocal imaging also demonstrated the targeted uptake of CD33 conjugated Au-NCs by leukaemia cells, thus confirming the flow cytometry results. This study demonstrates that novel nano-bioprobes can be developed using protein protected fluorescent nanoclusters of Au for the molecular receptor targeted flow cytometry based detection and imaging of cancer cells.

  7. CD33 monoclonal antibody conjugated Au cluster nano-bioprobe for targeted flow-cytometric detection of acute myeloid leukaemia

    Energy Technology Data Exchange (ETDEWEB)

    Retnakumari, Archana; Jayasimhan, Jasusri; Chandran, Parwathy; Menon, Deepthy; Nair, Shantikumar; Mony, Ullas; Koyakutty, Manzoor, E-mail: manzoork@aims.amrita.edu, E-mail: ullasmony@aims.amrita.edu [Amrita Centre for Nanoscience and Molecular Medicine, Amrita Institute of Medical Science, Cochin 682 041 (India)

    2011-07-15

    Protein stabilized gold nanoclusters (Au-NCs) are biocompatible, near-infrared (NIR) emitting nanosystems having a wide range of biomedical applications. Here, we report the development of a Au-NC based targeted fluorescent nano-bioprobe for the flow-cytometric detection of acute myeloid leukaemia (AML) cells. Au-NCs with {approx} 25-28 atoms showing bright red-NIR fluorescence (600-750 nm) and average size of {approx} 0.8 nm were prepared by bovine serum albumin assisted reduction-cum-stabilization in aqueous phase. The protein protected clusters were conjugated with monoclonal antibody against CD33 myeloid antigen, which is overexpressed in {approx} 99.2% of the primitive population of AML cells, as confirmed by immunophenotyping using flow cytometry. Au-NC-CD33 conjugates having average size of {approx} 12 nm retained bright fluorescence over an extended duration of {approx} a year, as the albumin protein protects Au-NCs against degradation. Nanotoxicity studies revealed excellent biocompatibility of Au-NC conjugates, as they showed no adverse effect on the cell viability and inflammatory response. Target specificity of the conjugates for detecting CD33 expressing AML cells (KG1a) in flow cytometry showed specific staining of {approx} 95.4% of leukaemia cells within 1-2 h compared to a non-specific uptake of {approx} 8.2% in human peripheral blood cells (PBMCs) which are CD33{sup low}. The confocal imaging also demonstrated the targeted uptake of CD33 conjugated Au-NCs by leukaemia cells, thus confirming the flow cytometry results. This study demonstrates that novel nano-bioprobes can be developed using protein protected fluorescent nanoclusters of Au for the molecular receptor targeted flow cytometry based detection and imaging of cancer cells.

  8. Molecular assembly and magnetic dynamics of two novel Dy6 and Dy8 aggregates.

    Science.gov (United States)

    Guo, Yun-Nan; Chen, Xiao-Hua; Xue, Shufang; Tang, Jinkui

    2012-04-02

    Complexation of dysprosium(III) with the heterodonor chelating ligand o-vanillin picolinoylhydrazone (H(2)ovph) in the presence of a carbonato ligand affords two novel Dy(6) and Dy(8) clusters, namely, [Dy(6)(ovph)(4)(Hpvph)(2)Cl(4)(H(2)O)(2)(CO(3))(2)]·CH(3)OH·H(2)O·CH(3)CN (2) and [Dy(8)(ovph)(8)(CO(3))(4)(H(2)O)(8)]·12CH(3)CN·6H(2)O (3). Compound 2 is composed of three petals of the Dy(2) units linked by two carbonato ligands, forming a triangular prism arrangement, while compound 3 possesses an octanuclear core with an unprecedented tub conformation, in which Dy(ovph) fragments are attached to the sides of the carbonato core. The static and dynamic magnetic properties are reported and discussed. In the Dy(6) aggregate, three Dy(2) "skeletons", having been well preserved (see the scheme), contribute to the single-molecule-magnet behavior with a relatively slow tunneling rate, while the Dy(8) cluster only exhibits a rather small relaxation barrier.

  9. Design, synthesis and luminescence properties of Ba2 YB2 O6 Cl- and Ba2 YB2 O6 F-based phosphors.

    Science.gov (United States)

    Chen, Wanping; Yang, Xin; Liu, Yan; Dai, Xiaoyan

    2015-05-01

    Using a high-temperature solid-state reaction, the chlorine in Ba2 YB2 O6 Cl is gradually replaced by F, and a new compound with the nominal chemical formula Ba2 YB2 O6 F and two phosphors doped with Ce(3+) and Eu(3+) , respectively, are obtained. X-Ray diffraction and photoluminescence spectroscopy are used to characterize the as-synthesized samples. The as-synthesized Ba2 YB2 O6 Cl exhibits bright blue emission in the spectral range ~ 330-410 nm with a maximum around 363 nm under X-ray or UV excitation. Ba2 YB2 O6 F:0.01Ce(3+) exhibits blue emission in the range ~ 340-570 nm with a maximum around 383 nm. Ba2 YB2 O6 F:0.01Eu(3+) exhibits a predominantly (5) D0 -(7)  F2 emission (~610 nm) and the relative intensities of the (5) D0 -(7)  F0,1,2 emissions are tunable under different wavelength UV excitation. The luminescence behaviors of the two phosphors are explained simply in terms of the host composition and site occupancy probability of Ce(3+) and Eu(3+) , respectively. The results indicate that these phosphors have potential application as a blue phosphor or as a red phosphor. Copyright © 2014 John Wiley & Sons, Ltd.

  10. clusters

    Indian Academy of Sciences (India)

    environmental as well as technical problems during fuel gas utilization. ... adsorption on some alloys of Pd, namely PdAu, PdAg ... ried out on small neutral and charged Au24,26,27, Cu,28 ... study of Zanti et al.29 on Pdn (n = 1–9) clusters.

  11. Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

    Science.gov (United States)

    Hsu, K.-J.; Demore, W. B.

    1994-01-01

    Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

  12. In-Plane Angular Effect of Magnetoresistance of Quasi-One-Dimensional Organic Metals, (DMET) 2AuBr 2 and (TMTSF) 2ClO 4

    Science.gov (United States)

    Yoshino, Harukazu; Saito, Kazuya; Nishikawa, Hiroyuki; Kikuchi, Koichi; Kobayashi, Keiji; Ikemoto, Isao

    1997-08-01

    Comparative study is presented for the in-plane angular effect of magnetoresistance of quasi-one-dimensional organic conductors, (DMET)2AuBr2 and (TMTSF)2ClO4. The magnetoresistance for the magnetic and electrical fields parallel and perpendicular to the most conducting plane, respectively, was measured at 4.2 K and up to 7.0 T. (DMET)2AuBr2 shows an anomalous hump in the field-orientation dependence of the magnetoresistance for the magnetic field nearly parallel to the most conducting axis and this is very similar to what previously reported for (DMET)2I3. Weak anomaly was detected for the magnetoresistance of (TMTSF)2ClO4 in the Relaxed state, while no anomaly was observed in the SDW phase in the Quenched state. By comparing the numerical angular derivatives of the magnetoresistance, it is shown that the anomaly in the in-plane angular effect continuously develops from zero magnetic field and is closely related to the quasi-one-dimensional Fermi surface. A simple method is proposed to estimate the anisotropy of the transfer integral from the width of the hump anomaly.

  13. Electronic structure, Fermi surface topology and spectroscopic optical properties of LaBaCo{sub 2}O{sub 5.5} compound

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A.H. [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Al-Douri, Y. [Institute of Nano Electronic Engineering, University Malaysia Perlis, 01000 Kangar, Perlis (Malaysia); Khenata, R. [Laboratoire de Physique Quantique et de Modélisation Mathématique (LPQ3M), Département de Technologie, Université de Mascara, Mascara 29000 (Algeria); Khan, Wilayat; Khan, Saleem Ayaz [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic); Azam, Sikander, E-mail: sikander.physicst@gmail.com [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, Pilsen 306 14 (Czech Republic)

    2014-08-01

    We have investigated the electronic band structure, Fermi surface topology, chemical bonding and optical properties of LaBaCo{sub 2}O{sub 5.5} compound. The first-principle calculations based on density functional theory (DFT) by means of the full-potential linearized augmented plane-wave method were employed. The atomic positions of LaBaCo{sub 2}O{sub 5.5} compound were optimized by minimizing the forces acting on atoms. We employed the local density approximation (LDA), generalized gradient approximation (GGA) and Engel–Vosko GGA (EVGGA) to treat the exchange correlation potential by solving Kohn–Sham equations. Electronic structure and bonding properties are studied throughout the calculation of densities of states, Fermi surfaces and charge densities. Furthermore, the optical properties are investigated via the calculation of the dielectric tensor component in order to characterize the linear optical properties. Optical spectra are analyzed by means of the electronic structure, which provides theoretical understanding of the conduction mechanism of the investigated compound. - Highlights: • DFT-FPLAPW method used for calculating the properties of LaBaCo{sub 2}O{sub 5.5} compound. • This study shows that nature of the compound is metallic. • Crystallographic plane which shows covalent character of O–Co bond. • The optical properties were also calculated and analyzed. • The Fermi surface of LaBaCo{sub 2}O{sub 5.5} is composed of five bands crossing along Γ–Z direction.

  14. XAFS studies of monodisperse Au nanoclusters formation in the etching process

    International Nuclear Information System (INIS)

    Yang, Lina; Huang, Ting; Liu, Wei; Bao, Jie; Huang, Yuanyuan; Cao, Yuanjie; Yao, Tao; Sun, Zhihu; Wei, Shiqiang

    2016-01-01

    Understanding the formation mechanism of gold nanoclusters is essential to the development of their synthetic chemistry. Here, by using x-ray absorption fine-structure (XAFS) spectroscopy, UV-Vis and MS spectra, the formation process of monodisperse Au 13 nanoclusters is investigated. We find that a critical step involving the formation of smaller Au 8 -Au 11 metastable intermediate clusters induced by the HCl + HSR etching of the polydisperse Au n precursor clusters occurs firstly. Then these intermediate species undergo a size-growth to Au 13 cores, followed by a slow structure rearrangement to reach the final stable structure. This work enriches the understanding of cluster formation chemistry and may guide the way towards the design and the controllable synthesis of nanoclusters. (paper)

  15. Direct evidence of a multicentre halogen bond: unexpected contraction of the P-XXX-P fragment in triphenylphosphine dihalides.

    Science.gov (United States)

    Nikitin, Kirill; Müller-Bunz, Helge; Gilheany, Declan

    2013-02-18

    Triphenylhalophosphonium halides, Ph(3)PX(2), form crystals comprising bridged linear cations [Ph(3)P-X-X-X-PPh(3)](+) where the X(3) bridge is shortened from 6.56 Å in Cl-Cl-Cl to 6.37 Å in the Br-Br-Br system. It is proposed that this structure is stabilised by five-centre/six-electron (5c-6e) hypervalent interactions.

  16. TGA, Hirshfeld, Raman spectroscopy and computational studies of diethylammonium hexachloroplumbate [(C2H5)2NH2]2PbCl6

    Science.gov (United States)

    Ouasri, A.; El-Adel, L.; Zouihri, H.; Rhandour, A.; Jalbout, A. F.

    2018-04-01

    Diethylammonium hexachloroplumbate [(C2H5)2NH2]2PbCl6 was found to be monoclinic with P21/n (Z = 2) as space group at room temperature. The TGA analysis shows that this compound is slightly hygroscopic and presents moisture in itself. The Raman spectrum (50-4000 cm-1) of this compound recorded at room temperature was discussed on the basis of the factor group analysis using the structural data obtained recently [5]. The experimental frequencies are compared to those obtained by Density Functional Theory (DFT) by using the B3LYP functional and the 6-31G(d) (SDD) basis set. The thermodynamic properties and geometries of this compound have been determinated and characterized. The significant intermolecular interactions in the crystal structure are identified and analyzed using the Hirshfeld surface and fingerprint plots computational methods.

  17. Nanopore formation on Au coated pyramid under electron beam irradiations (plasmonic nanopore on pyramid

    Directory of Open Access Journals (Sweden)

    Seong Soo Choi

    2016-03-01

    Full Text Available There have been tremendous interests about the single molecule analysis using a sold-state nanopore. The solid-state nanopore can be fabricated either by drilling technique, or diffusion technique by using electron beam irradiations. The solid-state SiN nanopore device with electrical detection technique recently fabricated, however, the solid-state Au nanopore with optical detection technique can be better utilized as the next generation single molecule sensor. In this report, the nanometer size openings with its size less than 10 nm on the diffused membrane on the 200 nm Au pyramid were fabricated by using field emission scanning electron microscopy (FESEM electron beam irradiations, transmission electron microscopy (TEM, etc. After the sample was being kept under a room environment for several months, several Au (111 clusters with ~6 nm diameter formed via Ostwald ripening are observed using a high resolution TEM imaging. The nanopore with Au nanoclusters on the diffused membrane can be utilized as an optical nanopore device. Keywords: Electron beam irradiation, Surface diffusion, Carbon contamination, Au cluster, Ostwald ripening

  18. 9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

    Science.gov (United States)

    Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

    2013-05-14

    Reactions of 9,10-phenanthrenequinone (PQ) in toluene with [M(II)(PPh3)3X2] at 298 K afford green complexes, trans-[M(PQ)(PPh3)2X2] (M = Ru, X = Cl, 1; M = Os, X = Br, 2) in moderate yields. Reaction of anhydrous RhCl3 with PQ and PPh3 in boiling ethanol affords the dark brown paramagnetic complex, cis-[Rh(PQ)(PPh3)2Cl2] (3) in good yields. Diffusion of iodine solution in n-hexane to the trans-[Os(PQ) (PPh3)2(CO)(Br)] solution in CH2Cl2 generates the crystals of trans-[Os(PQ)(PPh3)2(CO)(Br)](+)I3(-), (4(+))I3(-)), in lower yields. Single crystal X-ray structure determinations of 1·2toluene, 2·CH2Cl2 and 4(+)I3(-), UV-vis/NIR absorption spectra, EPR spectra of 3, electrochemical activities and DFT calculations on 1, 2, trans-[Ru(PQ)(PMe3)2Cl2] (1Me), trans-[Os(PQ)(PMe3)2Br2] (2Me), cis-[Rh(PQ)(PMe3)2Cl2] (3Me) and their oxidized and reduced analogues including trans-[Os(PQ)(PMe3)2(CO)(Br)](+) (4Me(+)) substantiated that 1-3 are the 9,10-phenanthrenesemiquinone radical (PQ(˙-)) complexes of ruthenium(III), osmium(III) and rhodium(III) and are defined as trans/cis-[M(III)(PQ(˙-))(PPh3)2X2] with a minor contribution of the resonance form trans/cis-[M(II)(PQ)(PPh3)2X2]. Two comparatively longer C-O (1.286(4) Å) and the shorter C-C lengths (1.415(7) Å) of the OO-chelate of 1·2toluene and 2·CH2Cl2 and the isotropic fluid solution EPR signal at g = 1.999 of 3 are consistent with the existence of the reduced PQ(˙-) ligand in 1-3 complexes. Anisotropic EPR spectra of the frozen glasses (g11 = g22 = 2.0046 and g33 = 1.9874) and solids (g11 = g22 = 2.005 and g33 = 1.987) instigate the contribution of the resonance form, cis-[Rh(II)(PQ)(PPh3)2Cl2] in 3. DFT calculations established that the closed shell singlet (CSS) solutions of 1Me and 2Me are unstable due to open shell singlet (OSS) perturbation. However, the broken symmetry (BS) (1,1) Ms = 0 solutions of 1Me and 2Me are respectively 22.6 and 24.2 kJ mole(-1) lower in energy and reproduced the experimental bond

  19. First-principles study of SF_6 decomposed gas adsorbed on Au-decorated graphene

    International Nuclear Information System (INIS)

    Zhang, Xiaoxing; Yu, Lei; Gui, Yingang; Hu, Weihua

    2016-01-01

    Graphical abstract: - Highlights: • We theoretically investigated the decomposed gaseous components of sulfur hexafluoride (SF_6), namely, H_2S, SO_2, SOF_2, and SO_2F_2, adsorbed on pristine and Au-embedded graphene based on DFT-D, in which the van der Waals effect is considered. • H_2S, SO_2, SOF_2, and SO_2F_2 are chemisorption on Au-doped graphene, appreciably stronger than physisorption on pristine graphene in which the van der Waals dominates. • Only H_2S exhibits n-type doping to Au-graphene, whereas the rest gases exhibit p-type doping. The n-type and p-type sensing behaviors that Au-doped graphene displays to different gases play a crucial role in selective sensing application. • Magnetic moments fluctuate substantially in the original Au-graphene when H_2S and SO_2 are adsorbed. While the adsorption effects of SOF_2 and SO_2F_2 generate magnetism quenching. The different changes of magnetic moments in every adsorption system provide another approach to selective detection. • The charge transfer mechanism is deeply discussed in this paper. - Abstract: We theoretically investigated the decomposed gaseous components of sulfur hexafluoride (SF_6), namely, H_2S, SO_2, SOF_2, and SO_2F_2, adsorbed on pristine and Au-embedded graphene based on the revised Perdew–Burke–Ernzerhof calculation, which empirically includes a dispersion correction (DFT-D) for van der Waals interaction with standard generalized gradient approximation. Pristine graphene exhibits weak adsorption and absence of charge transfer, which indicates barely satisfactory sensing for decomposed components. The Au atom introduces magnetism to the pristine graphene after metal-embedded decoration as well as enhances conductivity. All four molecules induce certain hybridization between the molecules and Au-graphene, which results in chemical interactions. SOF_2 and SO_2F_2 exhibit a strong chemisorption interaction with Au-graphene, while H_2S and SO_2 exhibit quasi-molecular binding

  20. Geology, mineralization, and fluid inclusion study of the Kuru-Tegerek Au-Cu-Mo skarn deposit in the Middle Tien Shan, Kyrgyzstan

    Science.gov (United States)

    Soloviev, Serguei G.; Kryazhev, Sergey; Dvurechenskaya, Svetlana

    2018-02-01

    The Kuru-Tegerek Cu-Au-Mo deposit is situated in a system of Late Carboniferous subduction-related magmatic arcs of the Middle Tien Shan, which together constitute a metallogenic belt of Cu-Au-Mo (±W) porphyry, with local skarns, deposits. The deposit is related to magnetite-series gabbro-diorite to tonalite intrusion. It contains prograde magnesian and calcic skarns with abundant magnetite, associated with gabbro-diorite, and retrograde skarn with Cu mineralization, formed after intrusion of tonalite. Subsequent propylitic alteration introduced abundant chalcopyrite and pyrrhotite, and native Au culminating in zones overprinting magnetite and garnet skarn. Later quartz-muscovite-carbonate veins, formed after intrusion of late mafic quartz monzogabbro dikes, contain chalcopyrite, pyrite, arsenopyrite and other sulfides and sulfosalts, tellurides, and native Au. The earliest retrograde skarn garnet contains gaseous low-salinity (1.7-3.4 wt.% NaCl eq.) fluid inclusions homogenizing at 460-500 °C into vapor, indicating that the early fluid released from crystallizing magma was a low-density vapor. It was followed by more saline (4.0-5.0 wt.% NaCl eq.), high-temperature (400-440 °C) aqueous fluid, as fluid release from the magma progressed. Boiling of this fluid at temperatures of 420 to 370 °C and a pressure of 350-300 bar produced a low-salinity (0.6-1.2 wt.% NaCl eq.), essentially gaseous, and high-salinity (from 39 to 31 wt.% NaCl eq.) brine, with possible metal (including Cu) partitioning into both gaseous and aqueous-saline phases. Boiling was coeval with sulfide deposition in the retrograde skarn. The latest episode of the retrograde skarn stage included direct separation of saline ( 40-42 wt.% NaCl eq.) fluid from crystallizing magma. The separation of saline ( 40 to 14 wt.% NaCl eq.) fluids from a crystallizing magmatic melt continued during the propylitic stage, when fluid cooling from 370 to 320 °C, together with decreasing fO2, caused Cu and especially

  1. Moessbauer studies of non-linear excitations and gold cluster compounds

    International Nuclear Information System (INIS)

    Smit, H.H.A.

    1988-01-01

    Moessbauer effect spectroscopy has been applied to the study of three polynuclear gold cluster compounds. The resulting information on the local vibrational density of states has been compared to several models which take the finite size of the particles into consideration. 188 refs.; 34 figs.; 103 schemes; 8 tabs

  2. Rich Ground State Chemical Ordering in Nanoparticles: Exact Solution of a Model for Ag-Au Clusters

    DEFF Research Database (Denmark)

    Larsen, Peter Mahler; Jacobsen, Karsten Wedel; Schiøtz, Jakob

    2018-01-01

    We show that nanoparticles can have very rich ground state chemical order. This is illustrated by determining the chemical ordering of Ag-Au 309-atom Mackay icosahedral nanoparticles. The energy of the nanoparticles is described using a cluster expansion model, and a Mixed Integer Programming (MIP......) approach is used to find the exact ground state configurations for all stoichiometries. The chemical ordering varies widely between the different stoichiometries, and display a rich zoo of structures with non-trivial ordering....

  3. Electrochemical behavior of gold (III) in cyanide-free bath with 5,5′-dimethylhydantoin as complexing agent

    International Nuclear Information System (INIS)

    Yang Xiaowei; An Maozhong; Zhang Yunwang; Zhang Lin

    2011-01-01

    Highlights: ► The DMH gold plating electrolyte with good stability studied in this paper is cyanide-free and the influence of novel additive (pyridyl-compound) on the nucleation and growth of gold is also investigated. ► The electrochemical behavior of gold electrodeposition in DMH bath is firstly analyzed using cyclic voltammograms and chronoamperometry techniques. - Abstract: Gold electrodeposits are prepared in a cyanide-free bath with 5,5′-dimethylhydantoin (DMH) as complexing agent. The electrochemical behavior of the electrodeposition is then investigated together with the influence of additive A (pyridyl-compound) as an additive on the nucleation and growth of gold using electrochemical techniques on gold working electrode at different temperatures. Cyclic voltammogram consists of a single cathodic reduction wave at −0.62 V which corresponds to the reduction of Au(III) to Au without anodic oxidation wave observed. The diffusion coefficient of Au(III) in the bath is found to be ∼10 −6 cm 2 /s and the energy of activation (43 kJ/mol) is deduced from the cyclic voltammograms at different temperatures. The nucleation and growth of gold on gold working electrode is investigated by chronoamperometry. The progressive nucleation mechanism is found for gold deposition using Scharifker–Hills’ model with three-dimensional (3D) diffusion-controlled growth nucleation. The introduction of the additive A does not influence this mechanism. The gold electrodeposits are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cathodic polarization measurements. Experimental results indicate that additive A increases the cathodic polarization of bath, refines the grains of electrodeposit and changes the preferred orientation of electrodeposit from [1 1 1] direction to [2 0 0] direction.

  4. Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

    Science.gov (United States)

    Kuwata, Keith T.

    Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

  5. Mapping compound cosmic telescopes containing multiple projected cluster-scale halos

    Energy Technology Data Exchange (ETDEWEB)

    Ammons, S. Mark [Lawrence Livermore National Laboratory, Physics Division L-210, 7000 East Ave., Livermore, CA 94550 (United States); Wong, Kenneth C. [EACOA Fellow, Institute of Astronomy and Astrophysics, Academia Sinica (ASIAA), Taipei 10641, Taiwan (China); Zabludoff, Ann I. [Steward Observatory, University of Arizona, 933 Cherry Ave., Tucson, AZ 85721 (United States); Keeton, Charles R., E-mail: ammons1@llnl.gov, E-mail: kwong@as.arizona.edu, E-mail: aiz@email.arizona.edu, E-mail: keeton@physics.rutgers.edu [Department of Physics and Astronomy, Rutgers University, 136 Frelinghuysen Road, Piscataway, NJ 08854 (United States)

    2014-01-20

    Lines of sight with multiple projected cluster-scale gravitational lenses have high total masses and complex lens plane interactions that can boost the area of magnification, or étendue, making detection of faint background sources more likely than elsewhere. To identify these new 'compound' cosmic telescopes, we have found directions in the sky with the highest integrated mass densities, as traced by the projected concentrations of luminous red galaxies (LRGs). We use new galaxy spectroscopy to derive preliminary magnification maps for two such lines of sight with total mass exceeding ∼3 × 10{sup 15} M {sub ☉}. From 1151 MMT Hectospec spectra of galaxies down to i {sub AB} = 21.2, we identify two to three group- and cluster-scale halos in each beam. These are well traced by LRGs. The majority of the mass in beam J085007.6+360428 (0850) is contributed by Zwicky 1953, a massive cluster at z = 0.3774, whereas beam J130657.5+463219 (1306) is composed of three halos with virial masses of 6 × 10{sup 14}-2 × 10{sup 15} M {sub ☉}, one of which is A1682. The magnification maps derived from our mass models based on spectroscopy and Sloan Digital Sky Survey photometry alone display substantial étendue: the 68% confidence bands on the lens plane area with magnification exceeding 10 for a source plane of z{sub s} = 10 are [1.2, 3.8] arcmin{sup 2} for 0850 and [2.3, 6.7] arcmin{sup 2} for 1306. In deep Subaru Suprime-Cam imaging of beam 0850, we serendipitously discover a candidate multiply imaged V-dropout source at z {sub phot} = 5.03. The location of the candidate multiply imaged arcs is consistent with the critical curves for a source plane of z = 5.03 predicted by our mass model. Incorporating the position of the candidate multiply imaged galaxy as a constraint on the critical curve location in 0850 narrows the 68% confidence band on the lens plane area with μ > 10 and z{sub s} = 10 to [1.8, 4.2] arcmin{sup 2}, an étendue range comparable to that of

  6. Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water

    Science.gov (United States)

    Lau, Marcus; Haxhiaj, Ina; Wagener, Philipp; Intartaglia, Romuald; Brandi, Fernando; Nakamura, Junji; Barcikowski, Stephan

    2014-08-01

    Over three decades after the first synthesis of stabilized Au55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks.

  7. Ab Initio Theoretical Investigation on the Geometrical and Electronic Structures of AlAun-/0 (n = 2-4) Clusters%Ab Initio Theoretical Investigation on the Geometrical and Electronic Structures of AlAun-/0 (n = 2-4) Clusters

    Institute of Scientific and Technical Information of China (English)

    YAO Wen-Zhi; YAO Jian-Bin; LI Si-Dian

    2012-01-01

    A systematic density functional theory and wave function theory investigation on the geometrical and electronic properties of A1Aun0/" (n = 2-4) clusters has been performed in this work. A1Aun- anions prove to possess ground states of the V-shaped C2v A1Au2, umbrella-shaped C3v A1Au3, and perfect tetrahedral Td A1Au4", while their neutrals favor the V-shaped CEv A1Au2, perfect planar triangular D3h A1Au3, and severely distorted Cs A1Au4, respectively. Aluminum aurides appear to be analogous to the corresponding aluminum hydrides, expect C~ A1Au4. Molecular orbitals (MOs) analyses also support this conclusion. Detailed orbital analyses indicate that Au 6s makes 94-96% and Au 5d makes 6-4% contribution to the Au-based orbitals in A1-Au bonds, which is smaller than the BAun0/- series, partially reflecting the relativistic effect of gold. The one-electron detachment energies of the anions and characteristic stretching vibrational frequencies of A1-Au bonds between 100-400 cm-1 have been calculated to facilitate future experimental characterization of these clusters.

  8. Aspects of transmetallation reactions of 2-Me2NCH2C6H4- and 2,6-(Me2NCH2)-C6H3-metal (Pd,Pt,Hg,Tl) complexes with metal carboxylates and low-valent metal (Pd,Pt) complexes

    NARCIS (Netherlands)

    Koten, G. van; Ploeg, A.F.M.J. van der; Vrieze, K.

    1981-01-01

    A study has been made of reactions involving organometallic compounds containing ortho-Me{2}NCH{2} substituted aryl ligands. The single step syntheses of the new compounds [(2-Me{2}NCH{2}C{6}H{4}){2}TlCl], [ [{(S)-2-Me{2}NCH(Me)C{6}H{4}}{2}TlCl], [{(S)-2-Me{2}NCH(Me)C{6}H{4}}TlCl{2}], [{2,

  9. Effect of the partial NaCl substitution by other chloride salts on the volatile profile during the ripening of dry-cured lacón

    Directory of Open Access Journals (Sweden)

    Domínguez, R.

    2016-06-01

    Full Text Available The influence of three salting treatments (treatment II: 50% NaCl-50% KCl; III: 45% NaCl-25% KCl-20% CaCl2-10% MgCl2; IV: 30% NaCl-50% KCl-15% CaCl2-5% MgCl2 on the formation of volatile compounds throughout the process was studied and compared to those of a control “lacón” (treatment I: 100% NaCl. There was an intense formation of volatile compounds throughout the processing, particularly during the dry-ripening stage. The most abundant chemical family in all the formulations, in the final product was hydrocarbons followed by aldehydes. The total volatile compound release was more intense in the control “lacóns” (1164 AU_106·g-1dry matter than in “lacóns” from formulations II, III and IV (817-891 AUx106·g-1dry matter. The “lacóns” from formulation I showed the highest amounts of aldehydes. The “lacóns” from formulations I and II presented the highest amounts of hydrocarbons. The main conclusion is that the replacement of NaCl produces changes in the volatile profile and could be affect the aroma of “lacón”.Se estudió la influencia de tres tratamientos de salado (tratamiento II: 50 % NaCl-50 % KCl; III: 45 % NaCl-25 % KCl-20 % CaCl2-10 % MgCl2; IV: 30 % NaCl-50 % KCl-15 % CaCl2-5 % MgCl2 en la formación de compuestos volátiles durante la elaboración de lacón, en comparación con un control (tratamiento I: 100 % NaCl. Hubo una intensa formación de compuestos volátiles durante el procesado, principalmente durante la fase de secado-maduración. La familia química más abundante en el producto final fueron los hidrocarbonos, seguidos por los aldehídos. La liberación de volátiles fue más intensa en los lacones control (1164 AU_106·g-1 materia seca que en los otros lacones (817-891 AUx106· g-1 materia seca. Los lacones de la formulación I mostraron las mayores cantidades de aldehídos, y los lacones de las formulaciones I y II presentaron los mayores contenidos de hidrocarburos. La principal conclusi

  10. Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry.

    Science.gov (United States)

    Panyala, Nagender Reddy; Peña-Méndez, Eladia María; Havel, Josef

    2012-05-15

    Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m = 1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n = 2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m = 1-12), P(n)(+) (n = 2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n = 1, 2-88 (even numbers)), Au(2)P(n)(+) (n = 1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n = 1-6, 8, 9, 14), Au(4)P(n)(+) (n = 1-9, 14-16), Au(5)P(n)(+) (n = 1-6, 14, 16), Au(6)P(n)(+) (n = 1-6), Au(7)P(n)(+) (n = 1-7), Au(8)P(n)(+) (n = 1-6, 8), Au(9)P(n)(+) (n = 1-10), Au(10)P(n)(+) (n = 1-8, 15), Au(11)P(n)(+) (n = 1-6), and Au(12)P(n)(+) (n = 1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m = 1-5), P(n)(-) (n = 2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n = 4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n = 2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n = 6-11, 32), Au(4)P(n)(-) (n = 1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n = 1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of

  11. Theoretical study of the structure of a Ga{sub 6}N{sub 6} cluster

    Energy Technology Data Exchange (ETDEWEB)

    Song Bin; Cao Peilin; Li Baoxing

    2003-08-25

    The structures and energies of a Ga{sub 6}N{sub 6} cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics and simulated annealing techniques. We obtained 19 structures for a Ga{sub 6}N{sub 6} cluster. The most stable structure we obtained is a C{sub s} three-dimensional structure with a N{sub 2} and N{sub 3} subunits. The calculated results show that the existence of strong N-N bonds still dominates the structure of a Ga{sub 6}N{sub 6} cluster, supporting the previous result made by Kandalam et al. [J. Phys. Chem. B 106 (2002) 1945]. Through the calculation of the density of states we found that the most stable structure of Ga{sub 6}N{sub 6} clusters presented semiconductor-like properties.

  12. Chlorido(1,3-dimethylthiourea-κSbis(triphenylphosphine-κPcopper(I acetonitrile hemisolvate

    Directory of Open Access Journals (Sweden)

    Brian W. Skelton

    2009-08-01

    Full Text Available The title compound, [CuCl(C3H8N2S(C18H15P2]·0.5CH3CN, was prepared by the reaction of copper(I chloride with 1,3-dimethylthiourea (dmtu and triphenylphosphine (PPh3 in acetonitrile. The CuI atom has a distorted tetrahedral environment formed by two P atoms from triphenylphosphine, one S atom from the dmtu ligand and one Cl atom. In addition, the molecules exhibit intra- and intermolecular N—H...Cl interactions.

  13. Single-Crystal-to-Single-Crystal Anion Exchange in a Gadolinium MOF: Incorporation of POMs and [AuCl4]−

    Directory of Open Access Journals (Sweden)

    Javier López-Cabrelles

    2016-04-01

    Full Text Available The encapsulation of functional molecules inside porous coordination polymers (also known as metal-organic frameworks, MOFs has become of great interest in recent years at the field of multifunctional materials. In this article, we present a study of the effects of size and charge in the anion exchange process of a Gd based MOF, involving molecular species like polyoxometalates (POMs, and [AuCl4]−. This post-synthetic modification has been characterized by IR, EDAX, and single crystal diffraction, which have provided unequivocal evidence of the location of the anion molecules in the framework.

  14. Developing an aqueous approach for synthesizing Au and M@Au (M = Pd, CuPt) hybrid nanostars with plasmonic properties

    OpenAIRE

    Du, Jingshan; Yu, Junjie; Xiong, Yalin; Lin, Zhuoqing; Zhang, Hui; Yang, Deren

    2014-01-01

    Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make it attractive in optical, sensing, and biomedical applications. In this contribution, we report a general and facile strategy towards aqueous synthesis of Au and M@Au (M = Pd, CuPt) hybrid nanostars by reducing HAuCl4 with ethanolamine in the presence of cetyltrimethylammonium bromide (CTAB). According to electron microscopic observation and spectral monitoring, we found that the layered...

  15. A Distributed OpenCL Framework using Redundant Computation and Data Replication

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Junghyun [Seoul National University, Korea; Gangwon, Jo [Seoul National University, Korea; Jaehoon, Jung [Seoul National University, Korea; Lee, Jaejin [Seoul National University, Korea

    2016-01-01

    Applications written solely in OpenCL or CUDA cannot execute on a cluster as a whole. Most previous approaches that extend these programming models to clusters are based on a common idea: designating a centralized host node and coordinating the other nodes with the host for computation. However, the centralized host node is a serious performance bottleneck when the number of nodes is large. In this paper, we propose a scalable and distributed OpenCL framework called SnuCL-D for large-scale clusters. SnuCL-D's remote device virtualization provides an OpenCL application with an illusion that all compute devices in a cluster are confined in a single node. To reduce the amount of control-message and data communication between nodes, SnuCL-D replicates the OpenCL host program execution and data in each node. We also propose a new OpenCL host API function and a queueing optimization technique that significantly reduce the overhead incurred by the previous centralized approaches. To show the effectiveness of SnuCL-D, we evaluate SnuCL-D with a microbenchmark and eleven benchmark applications on a large-scale CPU cluster and a medium-scale GPU cluster.

  16. 7 CFR 58.312 - Churn rooms.

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 3 2010-01-01 2010-01-01 false Churn rooms. 58.312 Section 58.312 Agriculture Regulations of the Department of Agriculture (Continued) AGRICULTURAL MARKETING SERVICE (Standards....312 Churn rooms. Churn rooms in addition to proper construction and sanitation shall be so equipped...

  17. Isotopic exchange in mixed valence compounds in the solid state

    International Nuclear Information System (INIS)

    Fernandez Valverde, S.M.

    1986-01-01

    This work aims at the determination of isotopic exchange kinetics and mechanism in two mixed valence compounds: Cs 10 (Sbsup(V)Cl 6 ) (Sbsup(III)Cl 6 ) 3 and Tl 3 sup(I)(Tlsup(III)Cl 6 ). The synthesis of the first compound is very difficult because in most of the cases mixtures of chloroantimoniates are obtained. Exchange in Tl 4 Cl 6 labelled on Tlsup(III) is studied in detail by radiochemical analysis and physical techniques: ionic conductivity and positon annihilation. Cation vacancies are easily created in the lattice with formation enthalpy of 0.35 eV and migration enthalpy of 0.52 eV. Isochronic and isothermal exchange curves are described by a kinetic based on species diffusion. Models are given. Exchange is increased by grinding probably because extrinseque defects are introduced [fr

  18. First-principles investigations on the mechanical, thermal, electronic, and optical properties of the defect perovskites Cs2Sn X 6 ( X = Cl, Br, I)

    International Nuclear Information System (INIS)

    Huang Hai-Ming; Jiang Zhen-Yi; Luo Shi-Jun

    2017-01-01

    The mechanical properties, thermal properties, electronic structures, and optical properties of the defect perovskites Cs 2 Sn X 6 ( X = Cl, Br, I) were investigated by first-principles calculation using PBE and HSE06 hybrid functional. The optic band gaps based on HSE06 are 3.83 eV for Cs 2 SnCl 6 , 2.36 eV for Cs 2 SnBr 6 , and 0.92 eV for Cs 2 SnI 6 , which agree with the experimental results. The Cs 2 SnCl 6 , Cs 2 SnBr 6 , and Cs 2 SnI 6 are mechanically stable and they are all anisotropic and ductile in nature. Electronic structures calculations show that the conduction band consists mainly of hybridization between the halogen p orbitals and Sn 5s orbitals, whereas the valence band is composed of the halogen p orbitals. Optic properties indicate that these three compounds exhibit good optical absorption in the ultraviolet region, and the absorption spectra red shift with the increase in the number of halogen atoms. The defect perovskites are good candidates for probing the lead-free and high power conversion efficiency of solar cells. (paper)

  19. Extended mechanistic aspects on photoinitiated polymerization of 1,6-hexanediol diacrylate by hexaarylbisimidazoles and heterocyclic mercapto compounds.

    Science.gov (United States)

    Berdzinski, Stefan; Strehmel, Nadine; Lindauer, Heike; Strehmel, Veronika; Strehmel, Bernd

    2014-05-01

    Chlorine substituted hexaarylbisimidazole (o-Cl-HABI) efficiently initiates radical polymerization of multifunctional acrylic esters in the presence of a heterocyclic mercapto compound if the latter can form its tautomeric thione. Exposure of o-Cl-HABI results in lophyl radicals, which efficiently add to the thione in the first step while the second step releases a highly reactive thiyl radical from this intermediate. LC-MS and CID-MS measurements support this reaction scheme. Furthermore, photo-DSC experiments applying UV light between 320 and 380 nm showed that mercaptotriazole and phenylmercaptotriazole exhibited the best reactivity in the monomer 1,6-hexanediol diacrylate (HDDA) while alkyl substituted mercaptotriazoles showed less reactivity. Change of the triazole heterocycle by mercaptoimidazole resulted in a significant decrease of photoinitiation efficiency. This heterocycle does not form the corresponding thione in HDDA as shown by NMR measurements. Replacement of mercaptotriazole by an alkylthiol leads to a system showing the lowest photoinitiation efficiency in this series. Formation of thione structure in the case of heterocyclic mercapto compounds may cause higher reactivity of the heterocyclic mercapto compounds with the lophyl radical in the monomer chosen.

  20. Synthesis of Fulvic Acid-Coated Magnetite (Fe3O4–FA and Its Application for the Reductive Adsorption of [AuCl4]–

    Directory of Open Access Journals (Sweden)

    Philip Anggo Krisbiantoro

    2017-11-01

    Full Text Available Fulvic acid-coated magnetite (Fe3O4–FA has been synthesized through coprecipitation method using NH4OH. Synthesis conducted by cheap and environmentally friendly preparation used iron salts and extracted fulvic acid (FA from Peat soil of Rawa Pening, Central Java, Indonesia. Characterization using FT–IR indicated that the coating of FA on Fe3O4 occurred through the formation of chemical bond between iron of Fe3O4 and carboxyl group of FA. The XRD measurement indicated that coated Fe3O4 successfully dispersed in smaller size than uncoated Fe3O4, i.e. from 16.67 to 14.84 nm for Fe3O4 and Fe3O4–FA, respectively. Synthesized Fe3O4–FA has pHPZC 6.37 and stable at pH > 3.0. The extracted FA has total acidity 866.61 cmol kg–1, –COOH content 229.77 cmol kg–1 and –OH content 636.84 cmol kg–1. Fe3O4–FA has total acidity 494.86 cmol kg–1, –COOH content 67.80 cmol kg–1 and –OH content 427.06 cmol kg–1. The adsorption rate constant (k of [AuCl4]– on Fe3O4–A according to the Ho kinetic model was 8006.53 g mol–1 min–1. The adsorption capacity (qmax according to Langmuir isotherm model was 1.24 × 10–4 mol g–1. The presence of reduction towards the adsorbed [AuCl4]– was shown by the appearance of peaks at 2θ: 37.41; 43.66; 64.25, and 76.67° in the XRD diffractogram.

  1. Theoretical study of oxygen adsorption on pure Au-n+1(+) and doped MAun+ cationic gold clusters for M = Ti, Fe and n=3-7

    DEFF Research Database (Denmark)

    Torres, M. Begona; Fernandez Sanchez, Eva; Balbas, Luis C.

    2008-01-01

    A comparative study of the adsorption of an O-2 molecule on pure Au-n+1(+) and doped MAun+ cationic gold clusters for n = 3-7 and M = Ti, Fe is presented. The simultaneous adsorption of two oxygen atoms also was studied. This work was performed by means of first principles calculations based...... with adsorption energies of 0.56 and 0.69 eV, respectively. The ground-state geometry of Au-n(+) is almost unperturbed after O-2 adsorption. The electronic charge flows towards O-2 when the molecule is adsorbed in bridge positions and towards the gold cluster when O-2 is adsorbed on top of An atoms, and both...... with size n are rationalized in terms of O-O and O-M bond distances, as well as charge transfer between oxygen and cluster substrates. The spin multiplicity of those (MAunO2+)(ad) complexes with the highest O-2 adsorption energy is a maximum (minimum) for M = Fe (Ti), corresponding to parallel (anti...

  2. Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

    Science.gov (United States)

    Naumkin, F

    2006-06-07

    A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

  3. 31 CFR 586.312 - New investment.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false New investment. 586.312 Section 586.312 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF...) KOSOVO SANCTIONS REGULATIONS General Definitions § 586.312 New investment. The term new investment means...

  4. 8 CFR 312.1 - Literacy requirements.

    Science.gov (United States)

    2010-01-01

    ... 8 Aliens and Nationality 1 2010-01-01 2010-01-01 false Literacy requirements. 312.1 Section 312.1... FOR NATURALIZATION § 312.1 Literacy requirements. (a) General. Except as otherwise provided in... determining English proficiency, as outlined in paragraph(c) of this section. (c) Literacy examination—(1...

  5. 31 CFR 539.312 - United States.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false United States. 539.312 Section 539.312 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF... General Definitions § 539.312 United States. The term United States means the United States, its...

  6. Synthesis of furfural from xylose, xylan, and biomass using AlCl6H2O in biphasic media via xylose isomerization to xylulose.

    Science.gov (United States)

    Yang, Yu; Hu, Chang-Wei; Abu-Omar, Mahdi M

    2012-02-13

    Furfural was prepared in high yields (75 %) from the reaction of xylose in a water-tetrahydrofuran biphasic medium containing AlCl(3)·6H2O and NaCl under microwave heating at 140 °C. The reaction profile revealed the formation of xylulose as an intermediate en route to the dehydration product (furfural). The reaction under these conditions reached completion in 45 min. The aqueous phase containing AlCl(3)·6H(2)O and NaCl could be recycled multiple times (>5) without any loss of activity or selectivity for furfural. Extension of this biphasic reaction system to include xylan as the starting material afforded furfural in 64 % yield. The use of corn stover, pinewood, switchgrass, and poplar gave furfural in 55, 38, 56, and 64 % yield, respectively, at 160 °C. Even though AlCl(3)·6H(2)O did not affect the conversion of crystalline cellulose, moderate yields of the by-product 5-hydroxymethylfurfural (HMF) were noted. The highest HMF yield of 42 % was obtained from pinewood. The coproduction of HMF and furfural from biomass was attributed to the weakening of the cellulose network in the biomass, as a result of hemicellulose hydrolysis. The multifunctional capacity of AlCl(3)·6H(2)O (hemicellulose hydrolysis, xylose isomerization, and xylulose dehydration) in combination with its ease of recyclability make it an attractive candidate/catalyst for the selective synthesis of furfural from various biomass feedstocks. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The synthesis and crystal structures of the first rare-earth alkaline-earth selenite chlorides MNd10(SeO3)12Cl8 (M=Ca and Sr)

    International Nuclear Information System (INIS)

    Berdonosov, P.S.; Olenev, A.V.; Dolgikh, V.A.; Lightfoot, P.

    2007-01-01

    Two new alkaline-earth Nd selenite chlorides MNd 10 (SeO 3 ) 12 Cl 8 (M=Ca, Sr) were obtained using crystal growth from alkaline-earth chloride melts in quartz tubes. These new compounds crystallize in the orthorhombic system in space group C cca (no. 68). The compounds were studied by energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction. It was shown that both compounds adopt the same structure type, constructed by complex [M 11 (SeO 3 ) 12 ] 8+ slabs separated by chloride anion layers perpendicular to the longest cell parameter. The SeO 3 groups show a pyramidal shape and may be described as SeO 3 E tetrahedra. Such SeO 3 groups decorate the Nd-O skeletons forming the [M 11 (SeO 3 ) 12 ] 8+ slabs. - Graphical abstract: Two new alkaline-earth Nd selenite chlorides MNd 10 (SeO 3 ) 12 Cl 8 (M=Ca, Sr) were synthesized. These structures are constructed by [M 11 (SeO 3 ) 12 ] 8+ slabs separated by chloride anion layers

  8. sp magnetism in clusters of gold thiolates

    International Nuclear Information System (INIS)

    Ayuela, A; Hernando, A; Echenique, P M; Crespo, P; García, M A

    2012-01-01

    Using first-principles calculations, we consider the bond between thiolate and small Au clusters, with particular emphasis on the resulting magnetic moment. The moment of pure gold clusters is 1 μ B for clusters with an odd number of Au atoms and zero for those with an even number. The addition of the thiolate, having an odd number of electrons itself, shifts the phase of the odd-even oscillations so that particles with an even number of Au atoms now have unit moment. Surprisingly, gold thiolate exhibits a dramatic and non-intuitive distribution of charge and spin moment. Our results show that the S-Au bond is such that sulfur does not get charge and an electron is transferred to the Au cluster. This extra electron is mainly sp in character and resides in an electronic shell below the Au surface. The calculations suggest that any thiolate-induced magnetism occurs in the gold nanoparticle and not the thiolate, and can be controlled by modifying the thiolate coverage. (paper)

  9. 3-Amino-1,2,4-triazolium ion in [24(3at)]Cl and [24(3at)]2SnCl6·H2O. Comparative X-ray, vibrational and theoretical studies

    Science.gov (United States)

    Daszkiewicz, Marek; Marchewka, Mariusz K.

    2012-09-01

    Crystal structures of 3-amino-1,2,4-triazolium chloride and bis(3-amino-1,2,4-triazolium) hexachloridostannate monohydrate were determined by means of X-ray single crystal diffraction. The route of protonation of organic molecule and tautomer equilibrium constants for the cationic forms were calculated using B3LYP/6-31G* method. The most stable protonated species is 2,4-H2-3-amino-1,2,4-triazolium ion, 24(3at)+. Very good agreement between theoretical and experimental frequencies was achieved due to very weak interactions existing in studied compounds. Significantly weaker intermolecular interactions are found in [24(3at)]2SnCl6·H2O than in [24(3at)]Cl. The differences in strength of interactions are manifested in red and blue shifts for stretching and bending motions, respectively. PED calculations show that for 24(3at)+ ion the stretching type of motion of two Nringsbnd H bonds is independent, whereas bending is coupled.

  10. Human ClC-6 is a late endosomal glycoprotein that associates with detergent-resistant lipid domains.

    Directory of Open Access Journals (Sweden)

    Sofie Ignoul

    Full Text Available BACKGROUND: The mammalian CLC protein family comprises nine members (ClC-1 to -7 and ClC-Ka, -Kb that function either as plasma membrane chloride channels or as intracellular chloride/proton antiporters, and that sustain a broad spectrum of cellular processes, such as membrane excitability, transepithelial transport, endocytosis and lysosomal degradation. In this study we focus on human ClC-6, which is structurally most related to the late endosomal/lysomal ClC-7. PRINCIPAL FINDINGS: Using a polyclonal affinity-purified antibody directed against a unique epitope in the ClC-6 COOH-terminal tail, we show that human ClC-6, when transfected in COS-1 cells, is N-glycosylated in a region that is evolutionary poorly conserved between mammalian CLC proteins and that is located between the predicted helices K and M. Three asparagine residues (N410, N422 and N432 have been defined by mutagenesis as acceptor sites for N-glycosylation, but only two of the three sites seem to be simultaneously N-glycosylated. In a differentiated human neuroblastoma cell line (SH-SY5Y, endogenous ClC-6 colocalizes with LAMP-1, a late endosomal/lysosomal marker, but not with early/recycling endosomal markers such as EEA-1 and transferrin receptor. In contrast, when transiently expressed in COS-1 or HeLa cells, human ClC-6 mainly overlaps with markers for early/recycling endosomes (transferrin receptor, EEA-1, Rab5, Rab4 and not with late endosomal/lysosomal markers (LAMP-1, Rab7. Analogously, overexpression of human ClC-6 in SH-SY5Y cells also leads to an early/recycling endosomal localization of the exogenously expressed ClC-6 protein. Finally, in transiently transfected COS-1 cells, ClC-6 copurifies with detergent-resistant membrane fractions, suggesting its partitioning in lipid rafts. Mutating a juxtamembrane string of basic amino acids (amino acids 71-75: KKGRR disturbs the association with detergent-resistant membrane fractions and also affects the segregation of ClC-6

  11. Transformation of Au144(SCH2CH2Ph)60 to Au133(SPh-tBu)52 Nanomolecules: Theoretical and Experimental Study.

    Science.gov (United States)

    Nimmala, Praneeth Reddy; Theivendran, Shevanuja; Barcaro, Giovanni; Sementa, Luca; Kumara, Chanaka; Jupally, Vijay Reddy; Apra, Edoardo; Stener, Mauro; Fortunelli, Alessandro; Dass, Amala

    2015-06-04

    Ultrastable gold nanomolecule Au144(SCH2CH2Ph)60 upon etching with excess tert-butylbenzenethiol undergoes a core-size conversion and compositional change to form an entirely new core of Au133(SPh-tBu)52. This conversion was studied using high-resolution electrospray mass spectrometry which shows that the core size conversion is initiated after 22 ligand exchanges, suggesting a relatively high stability of the Au144(SCH2CH2Ph)38(SPh-tBu)22 intermediate. The Au144 → Au133 core size conversion is surprisingly different from the Au144 → Au99 core conversion reported in the case of thiophenol, -SPh. Theoretical analysis and ab initio molecular dynamics simulations show that rigid p-tBu groups play a crucial role by reducing the cluster structural freedom, and protecting the cluster from adsorption of exogenous and reactive species, thus rationalizing the kinetic factors that stabilize the Au133 core size. This 144-atom to 133-atom nanomolecule's compositional change is reflected in optical spectroscopy and electrochemistry.

  12. Human erythrocytes and neuroblastoma cells are affected in vitro by Au(III) ions

    International Nuclear Information System (INIS)

    Suwalsky, Mario; Gonzalez, Raquel; Villena, Fernando; Aguilar, Luis F.; Sotomayor, Carlos P.; Bolognin, Silvia; Zatta, Paolo

    2010-01-01

    Gold compounds are well known for their neurological and nephrotoxic implications. However, haematological toxicity is one of the most serious toxic and less studied effects. The lack of information on these aspects of Au(III) prompted us to study the structural effects induced on cell membranes, particularly that of human erythrocytes. AuCl 3 was incubated with intact erythrocytes, isolated unsealed human erythrocyte membranes (IUM) and molecular models of the erythrocyte membrane. The latter consisted of multibilayers of dimyristoylphosphatidylcholine and dimyristoylphosphatidylethanolamine, phospholipids classes located in the outer and inner monolayers of the human erythrocyte membrane, respectively. This report presents evidence that Au(III) interacts with red cell membranes as follows: (a) in scanning electron microscopy studies on human erythrocytes it was observed that Au(III) induced shape changes at a concentration as low as 0.01 μM; (b) in isolated unsealed human erythrocyte membranes Au(III) induced a decrease in the molecular dynamics and/or water content at the glycerol backbone level of the lipid bilayer polar groups in a 5-50 μM concentration range, and (c) X-ray diffraction studies showed that Au(III) in the 10 μm-1 mM range induced increasing structural perturbation only to dimyristoylphosphatidylcholine bilayers. Additional experiments were performed in human neuroblastoma cells SH-SY5Y. A statistically significant decrease of cell viability was observed with Au(III) ranging from 0.1 μM to 100 μM.

  13. On new ternary equiatomic scandium transition metal aluminum compounds ScTAl with T = Cr, Ru, Ag, Re, Pt, and Au

    Energy Technology Data Exchange (ETDEWEB)

    Radzieowski, Mathis; Janka, Oliver [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Haverkamp, Sandra [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; University of Sao Paulo, Sao Carlos, SP (Brazil). Inst. of Physics

    2016-08-01

    The new equiatomic scandium transition metal aluminides ScTAl for T = Cr, Ru, Ag, Re, Pt, and Au were obtained by arc-melting of the elements followed by subsequent annealing for crystal growth. The samples were studied by powder and single crystal X-ray diffraction. The structures of three compounds were refined from single crystal X-ray diffractometer data: ScCrAl, MgZn{sub 2} type, P6{sub 3}/mmc, a = 525.77(3), c = 858.68(5) pm, R{sub 1} = 0.0188, wR{sub 2} = 0.0485, 204 F{sup 2} values, 13 variables, ScPtAl, TiNiSi type, Pnma, a = 642.83(4), b = 428.96(2), c = 754.54(5) pm, R{sub 1} = 0.0326, wR{sub 2} = 0.0458, 448 F{sup 2} values, 20 variables and ScAuAl, HfRhSn type, P anti 62c, a = 722.88(4), c = 724.15(4) pm, R{sub 1} = 0.0316, wR{sub 2} = 0.0653, 512 F{sup 2} values, 18 variables. Phase pure samples of all compounds were furthermore investigated by magnetic susceptibility measurements, and Pauli-paramagnetism but no superconductivity was observed down to 2.1 K for all of them. The local structural features and disordering phenomena have been characterized by {sup 27}Al and {sup 45}Sc magic angle spinning (MAS) and static NMR spectroscopic investigations.

  14. Cytotoxicity, antimicrobial and antioxidant activity of eight compounds isolated from Entada abyssinica (Fabaceae).

    Science.gov (United States)

    Dzoyem, Jean P; Melong, Raduis; Tsamo, Armelle T; Tchinda, Alembert T; Kapche, Deccaux G W F; Ngadjui, Bonaventure T; McGaw, Lyndy J; Eloff, Jacobus N

    2017-03-06

    Entada abyssinica is a plant traditionally used against gastrointestinal bacterial infections. Eight compounds including three flavonoids, three terpenoids, a monoglyceride and a phenolic compound isolated from E. abyssinica were investigated for their cytotoxicity, antibacterial and antioxidant activity. Compounds 7 and 2 had remarkable activity against Salmonella typhimurium with the lowest respective minimum inhibitory concentration (MIC) values of 1.56 and 3.12 µg/mL. The antioxidant assay gave IC 50 values varied from 0.48 to 2.87 μg/mL in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, from 2.53 to 17.04 μg/mL in the 2,2'-Azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) assay and from 1.43 to 103.98 µg/mL in the FRAP assay. Compounds had relatively low cytotoxicity (LC 50 values ranging from 22.42 to 80.55 µg/mL) towards Vero cells. Ursolic acid had the most potent cytotoxicity against THP-1 and RAW 264.7 cells with LC 50 values of 9.62 and 4.56 μg/mL respectively, and selectivity index values of 7.32 and 15.44 respectively. Our findings suggest that among the terpenoid and flavonoid compounds studied, entadanin (compound 7) possess tremendous antibacterial activity against S. typhimurium and could be developed for the treatment of bacterial diseases.

  15. 31 CFR 596.312 - United States.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false United States. 596.312 Section 596.312 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF... General Definitions § 596.312 United States. The term United States means the United States, including its...

  16. Comparitive study of fluorescence lifetime quenching of rhodamine 6G by MoS2 and Au-MoS2

    Science.gov (United States)

    Shakya, Jyoti; Kasana, Parath; Mohanty, T.

    2018-04-01

    Time resolved fluorescence study of Rhodamine 6G (R6G) in the presence of Molybdenum disulfide (MoS2) nanosheets and gold doped MoS2 (Au-MoS2) have been carried out and discussed. We have analyzed the fluorescence decay curves of R6G and it is observed that Au-MoS2 is a better fluorescence lifetime quencher as compare to MoS2 nanosheets. Also, the energy transfer efficiency and energy transfer rate from R6G to MoS2 and Au-MoS2 has been calculated and found higher for Au-MoS2.

  17. 26 CFR 1.312-4 - Examples of adjustments provided in section 312(c).

    Science.gov (United States)

    2010-04-01

    ... 26 Internal Revenue 4 2010-04-01 2010-04-01 false Examples of adjustments provided in section 312... (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES Effects on Corporation § 1.312-4 Examples of adjustments... examples: Example 1. On December 2, 1954, Corporation X distributed to its sole shareholder, A, an...

  18. Characterization of the Fermi surface of BEDT-TTF4[Hg2Cl6].PhCl by electronic band structure calculations

    International Nuclear Information System (INIS)

    Veiros, L.F.; Canadell, E.

    1994-01-01

    Tight-binding band structure calculations for the room temperature structure of BEDT-TTF 4 [Hg 2 Cl 6 ]-PhCl show the existence of closed electron and hole Fermi surfaces, in agreement with the 2D metallic conductivity of this salt. It is shown that these closed Fermi surfaces result from the hybridization of two hidden 1D Fermi surfaces. However, our study also shows that a transition associated with either a usual or a hidden nesting type mechanism is unlikely. This explains why this salt retains its metallic properties without any resistivity anomaly down to 1.3 K. Our study suggests that BEDT-TTF 4 [Hg 2 Cl 6 ]-PhCl is somewhat anisotropic 2D semimetal and should exhibit Shubnikov-de Haas oscillations corresponding to a cross-sectional area of approximately 13% of the first Brillouin zone. (orig.)

  19. Quasi-one-dimensional magnetic behaviour of the Ising system CsFeCl3.2aq

    NARCIS (Netherlands)

    Kopinga, K.; Steiner, M.; Jonge, de W.J.M.

    1985-01-01

    The magnetic behaviour of the quasi-one-dimensional system CsFeCl3.2aq(aq=H2O, D2O) has been investigated by heat capacity measurements, quasi-elastic neutron scattering and spin-cluster resonance. the experiments demonstrate that below 25K the compound is a very good realisation of an (S=1/2) Ising

  20. Mild and Efficient Deoxygenation of Amine-N-Oxides with FeCl6H2O-Indium System under Ultrasonication

    International Nuclear Information System (INIS)

    Yoo, Byung Woo; Hwang, Sun Kyun; Kim, Dong Yoon; Choi, Jin Woo; Kang, Sang Ook; Yoo, Byoung Seung; Choi, Kyung Il; Kim, Joong Hyup

    2004-01-01

    We believe that the mild and efficient method described here will present an attractive alternative to the existing methods available for the reduction of amine-N-oxides to the corresponding amines. Further investigations of FeCl 3 ·6H 2 O/In system as reducing agent in organic synthesis are currently in progress. The deoxygenation of amine-N-oxides to amines in the presence of other functional groups is an important transformation in the synthesis of nitrogenous aromatic heterocycles. Many reagents have been employed for the deoxygenation of amine-N-oxides, including agents such as: low-valent titanium, phosphorous and sulphur compounds, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI 2 , indium/NH 4 Cl. Recently we reported that Cp 2 TiCl 2 /In system could be used for the deoxygenation of various amine-N-oxides

  1. Studying the hopping parameters of half-Heusler NaAuS using maximally localized Wannier function

    Science.gov (United States)

    Sihi, Antik; Lal, Sohan; Pandey, Sudhir K.

    2018-04-01

    Here, the electronic behavior of half-Heusler NaAuS is studied using PBEsol exchange correlation functional by plotting the band structure curve. These bands are reproduced using maximally localized Wannier function using WANNIER90. Tight-binding bands are nicely matched with density functional theory bands. By fitting the tight-binding model, hopping parameter for NaAuS is obtained by including Na 2s, 2p, Au 6s, 5p, 5d and S 3s, 3p orbitals within the energy interval of -5 to 16 eV around the Fermi level. In present study, hopping integrals for NaAuS are computed for the first primitive unit cell atoms as well as the first nearest neighbor primitive unit cell. The most dominating hopping integrals are found for Na (3s) - S (3s), Na (2px) - S (2px), Au (6s) - S (3px), Au (6s) - S (3py) and Au (6s) - S (3pz) orbitals. The hopping integrals for the first nearest neighbor primitive unit cell are also discussed in this manuscript. In future, these hopping integrals are very important to find the topological invariant for NaAuS compound.

  2. Comprehensive cluster-theory analysis of the magnetic structures and excitations in CoCl2·2H2O

    DEFF Research Database (Denmark)

    Jensen, Jens; Larsen, Jacob; Hansen, Ursula B.

    2018-01-01

    The magnetic properties of CoCl2·2H2O are analyzed in the mean-field/random-phase approximation using a basis of clusters with four spins along the c-axis chains of Co ions. The model gives a unifying account of the bulk properties, the spin waves, and the higher-order cluster-spin excitations...... at a transverse field of 160 kOe and is found to agree closely with their observations....

  3. Successful synthesis and thermal stability of immiscible metal Au-Rh, Au-Ir andAu-Ir-Rh nanoalloys

    Science.gov (United States)

    Shubin, Yury; Plyusnin, Pavel; Sharafutdinov, Marat; Makotchenko, Evgenia; Korenev, Sergey

    2017-05-01

    We successfully prepared face-centred cubic nanoalloys in systems of Au-Ir, Au-Rh and Au-Ir-Rh, with large bulk miscibility gaps, in one-run reactions under thermal decomposition of specially synthesised single-source precursors, namely, [AuEn2][Ir(NO2)6], [AuEn2][Ir(NO2)6] х [Rh(NO2)6]1-х and [AuEn2][Rh(NO2)6]. The precursors employed contain all desired metals ‘mixed’ at the atomic level, thus providing significant advantages for obtaining alloys. The observations using high-resolution transmission electron microscopy show that the nanoalloy structures are composed of well-dispersed aggregates of crystalline domains with a mean size of 5 ± 3 nm. Еnergy dispersive x-ray spectroscopy and x-ray powder diffraction (XRD) measurements confirm the formation of AuIr, AuRh, AuIr0.75Rh0.25, AuIr0.50Rh0.50 and AuIr0.25Rh0.75 metastable solid solutions. In situ high-temperature synchrotron XRD (HTXRD) was used to study the formation mechanism of nanoalloys. The observed transformations are described by the ‘conversion chemistry’ mechanism characterised by the primary development of particles comprising atoms of only one type, followed by a chemical reaction resulting in the final formation of a nanoalloy. The obtained metastable nanoalloys exhibit essential thermal stability. Exposure to 180 °C for 30 h does not cause any dealloying process.

  4. Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

    KAUST Repository

    Dehury, Niranjan

    2016-07-18

    Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

  5. Resonance production and exotic clusters in Au+Au, d+Au and p+p collisions at √(s) = 200 AGeV

    International Nuclear Information System (INIS)

    Besliu, Calin; Jipa, Alexandru; Lungescu, Andrea; Zgura, Sorin

    2004-01-01

    The resonance production in Au+Au, d+Au and p+p collisions at √(s) = 200 AGeV are presented. The resonances are used as a sensitive tool to examine the collision dynamics in the hadronic medium through their decay and regeneration. The modification of resonance mass, width, and shape due to phase space and dynamical effects are also discussed. The measurement of resonances provides an important tool for studying the dynamics in relativistic heavy-ion collisions by probing the time evolution of the source from chemical to kinetic freeze-out and the hadronic interactions at later stages

  6. [1,4-Bis(diphenylphosphanylbutane-κ2P,P′]chlorido(η5-indenylruthenium(II

    Directory of Open Access Journals (Sweden)

    Hui-Ling Sung

    2011-05-01

    Full Text Available Facile ligand substitution is observed when the ruthenium chloride complex [Ru(η5-C9H7Cl(PPh32] is treated with 1,4-bis(diphenylphosphanylbutane in refluxing toluene yielding the title compound, [Ru(C9H7Cl(C28H28P2]. The RuII atom has a typical piano-stool coordination, defined by the indenyl ligand, one Cl atom and two phosphanyl P atoms. The Ru—P bond lengths are 2.2502 (9 and 2.2968 (8 Å.

  7. Role of P27 -P55 operon from Mycobacterium tuberculosis in the resistance to toxic compounds

    Directory of Open Access Journals (Sweden)

    Cataldi Angel A

    2011-07-01

    Full Text Available Abstract Background The P27-P55 (lprG-Rv1410c operon is crucial for the survival of Mycobacterium tuberculosis, the causative agent of human tuberculosis, during infection in mice. P55 encodes an efflux pump that has been shown to provide Mycobacterium smegmatis and Mycobacterium bovis BCG with resistance to several drugs, while P27 encodes a mannosylated glycoprotein previously described as an antigen that modulates the immune response against mycobacteria. The objective of this study was to determine the individual contribution of the proteins encoded in the P27-P55 operon to the resistance to toxic compounds and to the cell wall integrity of M. tuberculosis. Method In order to test the susceptibility of a mutant of M. tuberculosis H37Rv in the P27-P55 operon to malachite green, sodium dodecyl sulfate, ethidium bromide, and first-line antituberculosis drugs, this strain together with the wild type strain and a set of complemented strains were cultivated in the presence and in the absence of these drugs. In addition, the malachite green decolorization rate of each strain was obtained from decolorization curves of malachite green in PBS containing bacterial suspensions. Results The mutant strain decolorized malachite green faster than the wild type strain and was hypersensitive to both malachite green and ethidium bromide, and more susceptible to the first-line antituberculosis drugs: isoniazid and ethambutol. The pump inhibitor reserpine reversed M. tuberculosis resistance to ethidium bromide. These results suggest that P27-P55 functions through an efflux-pump like mechanism. In addition, deletion of the P27-P55 operon made M. tuberculosis susceptible to sodium dodecyl sulfate, suggesting that the lack of both proteins causes alterations in the cell wall permeability of the bacterium. Importantly, both P27 and P55 are required to restore the wild type phenotypes in the mutant. Conclusions The results clearly indicate that P27 and P55 are

  8. Influence of hydrofluoric acid treatment on electroless deposition of Au clusters

    Directory of Open Access Journals (Sweden)

    Rachela G. Milazzo

    2017-01-01

    Full Text Available The morphology of gold nanoparticles (AuNPs deposited on a (100 silicon wafer by simple immersion in a solution containing a metal salt and hydrofluoric acid (HF is altered by HF treatment both before and after deposition. The gold clusters are characterized by the presence of flat regions and quasispherical particles consistent with the layer-by-layer or island growth modes, respectively. The cleaning procedure, including HF immersion prior to deposition, affects the predominantly occurring gold structures. Flat regions, which are of a few tens of nanometers long, are present after immersion for 10 s. The three-dimensional (3D clusters are formed after a cleaning procedure of 4 min, which results in a large amount of spherical particles with a diameter of ≈15 nm and in a small percentage of residual square layers of a few nanometers in length. The samples were also treated with HF after the deposition and we found out a general thickening of flat regions, as revealed by TEM and AFM analysis. This result is in contrast to the coalescence observed in similar experiments performed with Ag. It is suggested that the HF dissolves the silicon oxide layer formed on top of the thin flat clusters and promotes the partial atomic rearrangement of the layered gold atoms, driven by a reduction of the surface energy. The X-ray diffraction investigation indicated changes in the crystalline orientation of the flat regions, which partially lose their initially heteroepitaxial relationship with the substrate. A postdeposition HF treatment for almost 70 s has nearly the same effect of long duration, high temperature annealing. The process presented herein could be beneficial to change the spectral response of nanoparticle arrays and to improve the conversion efficiency of hybrid photovoltaic devices.

  9. Reacción de ligandos azufrados con el complejo au2pt (ch2p(Sph24,cl2

    Directory of Open Access Journals (Sweden)

    Guillermo Garzón

    2010-07-01

    Full Text Available Se describe la reacción de intercambio del cloro en el complejo au2pt (ch2p(Sph24,cl2 por los ligandos SCH2Ph-,S2CN(CH2CH3,2- y SCN-. Los nuevos derivados azufrados se caracterizan por análisis químico, espectroscopia infrarroja, electrónica y resonancia magnética nuclear protónica. Los ligandos se coordinan por el azufre a los dos átomos sw oro metálico en forma simétrica. El análisis elemental concuerda con las estequiomctrías y estructuras propuestas.

  10. Hydrothermal syntheses, structural, Raman, and luminescence studies of Cm[M(CN)2]3.3H2O and Pr[M(CN)2]3.3H2O (M=Ag, Au)

    International Nuclear Information System (INIS)

    Assefa, Zerihun; Haire, Richard G.; Sykora, Richard E.

    2008-01-01

    We have prepared Cm[Au(CN) 2 ] 3 .3H 2 O and Cm[Ag(CN) 2 ] 3 .3H 2 O as a part of our continuing investigations into the chemistry of the 5f-elements' dicyanometallates. Single crystals of Cm[Au(CN) 2 ] 3 .3H 2 O were obtained from the reaction of CmCl 3 and KAu(CN) 2 under mild hydrothermal conditions. Due to similarities in size, the related praseodymium compounds were also synthesized and characterized for comparison with the actinide systems. The compounds crystallize in the hexagonal space group P6 3 /mcm, where the curium and the transition metals interconnect through cyanide bridging. Crystallographic data (Mo Kα, λ=0.71073 A): Cm[Au(CN) 2 ] 3 .3H 2 O (1), a=6.6614(5) A, c=18.3135(13) A, V=703.77(9), Z=2; Pr[Au(CN) 2 ] 3 .3H 2 O (3), a=6.6662(8) A, c=18.497(3) A, V=711.83(17), Z=2; Pr[Ag(CN) 2 ] 3 .3H 2 O (4), a=6.7186(8) A, c=18.678(2) A, V=730.18(14), Z=2. The Cm 3+ and/or Pr 3+ ions are coordinated to six N-bound CN - groups resulting in a trigonal prismatic arrangement. Three oxygen atoms of coordinated water molecules tricap the trigonal prismatic arrangement providing a coordination number of nine for the f-elements. The curium ions in both compounds exhibit a strong red emission corresponding to the 6 D 7/2 → 8 S 7/2 transition. This transition is observed at 16,780 cm -1 , with shoulders at 17,080 and 16,840 cm -1 for the Ag complex, while the emission is red shifted by ∼100 cm -1 in the corresponding gold complex. The Pr systems also provide well-resolved emissions upon f-f excitation. - Graphical abstract: Coordination polymeric compounds between a trans-plutonium element, curium and transition metal ions, gold(I) and silver(I), were prepared using the hydrothermal synthetic procedure. The curium ion and the transition metals are interconnected through cyanide bridging. The Cm ion has a tricapped trigonal prismatic coordination environment with coordination number of nine. Detail photoluminescence studies of the complexes are also reported

  11. TiO2 Films Modified with Au Nanoclusters as Self-Cleaning Surfaces under Visible Light

    Directory of Open Access Journals (Sweden)

    Ting-Wei Liao

    2018-01-01

    Full Text Available In this study, we applied cluster beam deposition (CBD as a new approach for fabricating efficient plasmon-based photocatalytic materials. Au nanoclusters (AuNCs produced in the gas phase were deposited on TiO2 P25-coated silicon wafers with coverage ranging from 2 to 8 atomic monolayer (ML equivalents. Scanning Electron Microscopy (SEM images of the AuNCs modified TiO2 P25 films show that the surface is uniformly covered by the AuNCs that remain isolated at low coverage (2 ML, 4 ML and aggregate at higher coverage (8 ML. A clear relationship between AuNCs coverage and photocatalytic activity towards stearic acid photo-oxidation was measured, both under ultraviolet and green light illumination. TiO2 P25 covered with 4 ML AuNCs showed the best stearic acid photo-oxidation performance under green light illumination (Formal Quantum Efficiency 1.6 × 10−6 over a period of 93 h. These results demonstrate the large potential of gas-phase AuNCs beam deposition technology for the fabrication of visible light active plasmonic photocatalysts.

  12. Monolayer-Enriched Production of Au-Decorated WS2 Nanosheets via Defect Engineering

    Energy Technology Data Exchange (ETDEWEB)

    Dunklin, Jeremy R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lafargue, Paul [Ruprecht-Karls University Heidelberg; Higgins, Thomas M. [Ruprecht-Karls University Heidelberg; Forcherio, Gregory T. [U.S. Army Research Laboratory; Benamara, Mourad [University of Arkansas; McEvoy, Niall [Trinity College Dublin; Roper, D. Keith [University of Arkansas; Coleman, Jonathan N. [Trinity College Dublin; Vaynzof, Yana [Ruprecht-Karls University Heidelberg; Backes, Claudia [Ruprecht-Karls University Heidelberg

    2018-04-06

    Layered transition metal dichalcogenides (TMDs) represent a diverse, emerging source of two-dimensional (2D) nanostructures with broad application in optoelectronics and energy. Chemical functionalization has evolved into a powerful tool to tailor properties of these 2D TMDs; however, functionalization strategies have been largely limited to the metallic 1T-polytype. The work herein illustrates that 2H-semiconducting liquid-exfoliated tungsten disulfide (WS2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl3 is preferentially reduced on multi-layer WS2 and resulting large Au aggregates are easily separated from the colloidal dispersion by simple centrifugation. This process may be exploited to enrich the dispersions in laterally large, monolayer nanosheets. It is proposed that thiol groups at edges and defects sides reduce the AuCl3 to Au0 and are in turn oxidized to disulfides. Optical emission, i.e. photoluminescence, of the monolayers remained pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved. Taken together, these improvements in functionalization, fabrication, and catalytic activity represent an important advance in the study of these emerging 2D nanostructures.

  13. FTIR spectroscopy of UF6 clustering in a supersonic Laval nozzle

    International Nuclear Information System (INIS)

    Tanimura, Shinobu; Okada, Yoshiki; Takeuchi, Kazuo

    1996-01-01

    The clustering of UF 6 seeded in Ar was observed in a continuous supersonic Laval nozzle flow. The onset conditions for UF 6 clustering were investigated by measuring the FTIR spectra of UF 6 monomer and clusters in the nozzle. The onset conditions for the clustering, temperature, density of UF 6 (or partial pressure), and cooling rate, were determined. The onset temperature determined here was higher by 40-50 K than that determined by a light-scattering method. The frequency shift of the main peak of the UF 6 clusters from the monomer peak was about -17 cm -1 , which was smaller than the shift of the crystalline UF 6 by about 11 cm -1 . The increase in temperature caused by the heat of condensation and the change of the spectra of UF 6 clusters with the growth after the onset were also observed. It was shown that the clustering rate due to the collision between the monomer and cluster is much higher than that due to the collision between the monomers. 19 refs., 9 figs

  14. Magnetic cluster mean-field description of spin glasses in amorphous La-Gd-Au alloys

    International Nuclear Information System (INIS)

    Poon, S.J.; Durand, J.

    1978-03-01

    Bulk magnetic properties of splat-cooled amorphous alloys of composition La/sub 80-x/Gd/sub x/Au 20 (0 less than or equal to x less than or equal to 80) were studied. Zero-field susceptibility, high-field magnetization (up to 75 kOe) and saturated remanence were measured between 1.8 and 290 0 K. Data were analyzed using a cluster mean-field approximation for the spin-glass and mictomagnetic alloys (x less than or equal to 56). Mean-field theories can account for the experimental freezing-temperatures of dilute spin-glasses in which the Ruderman-Kittel-Kasuya-Yosida interaction is dominant. For the dilute alloys, the role of amorphousness on the magnetic interactions is discussed. By extending the mean-field approximation, the concentrated spin-glasses are represented by rigid ferromagnetic clusters as individual spin-entities interacting via random forces. Scaling laws for the magnetization M and saturation remanent magnetization M/sub rs/ are obtained and presented graphically for the x less than or equal to 32 alloys in which M/x = g(H/x*, T/x), M/sub rs/(T)/x = M/sub rs/(0)/x/ exp (-α*T/x/sup p/) where x* is the concentration of clusters, α* is a constant, and p is the freezing-temperature exponent given by T/sub M/ infinity x/sup p/. It is found that p = 1 and 1.3 for the regions 4 less than or equal to x less than or equal to 40 respectively. An attempt is also made to account for the freezing temperatures of concentrated spin glasses. The strength of the interaction among clusters is determined from high-field magnetization measurements using the Larkin-Smith method modified for clusters. It is shown that for the x < 24 alloys, the size of the clusters can be correlated to the structural short-range order in the amorphous state. More concentrated alloys are marked by the emergence of cluster percolation

  15. Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions

    Directory of Open Access Journals (Sweden)

    Wilson Silva do Nascimento

    2010-04-01

    Full Text Available Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3 or 2,3-diacetylene-1,4-naphthoquinone (4 it was possible to obtain triazole derivatives (naphthoquinonic. This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1. First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98% by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62% from compound 1, along with ethanolic solution (reflux and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b by 1,3-dipolar cycloaddition, involving compound (3 and terminal acetylenes (phenylacetylene, a and glycoside (b using Cu(OAc2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5 it was possible to synthesize (6, catalyzed by Pd(PPh32Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3 and alkynes (a, yield 23% and b, yield 30% were conducted using the solvent system, (1:1 terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65% and phenylacetylene was prepared using the solvent mixture (2:1 DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh32Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C. Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings.

  16. Massive open star clusters using the VVV survey IV. WR 62-2, a new very massive star in the core of the VVV CL041 cluster

    Czech Academy of Sciences Publication Activity Database

    Chene, A.-N.; Alegria, S.R.; Borissova, J.; O'Leary, E.; Martins, F.; Hervé, Anthony; Kuhn, M.; Kurtev, R.; Consuelo Amigo Fuentes, P.; Bonatto, C.; Minniti, D.

    2015-01-01

    Roč. 584, December (2015), A31/1-A31/8 ISSN 0004-6361 R&D Projects: GA ČR(CZ) GA14-02385S Institutional support: RVO:67985815 Keywords : open clusters and associations * VVV CL041 * massive star s Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics Impact factor: 4.378, year: 2014

  17. Positron lifetime in vacancy clusters. Application to the study of vacancy-impurity interactions

    International Nuclear Information System (INIS)

    Corbel, C.

    1986-02-01

    Positron lifetime measurements are used to study the vacancy recovery (77-650 K) in 20 K electron irradiated dilute gold or iron alloys in stainless steels. Positron lifetimes in clusters of various shapes and structures are calculated to precise the information obtained by measuring the positron lifetime in a vacancy cluster of unknown size and configuration. From the calculations, we have drawn the following conclusions: - the minimal size of an unknown cluster can be deduced from the measurement of the positron lifetime in the cluster; - a decrease of the positron lifetime when the structure of the cluster evolves, means either a decrease of the size of the cluster, or, the appearance of a relaxed configuration. - The positron lifetime is very useful to discriminate between a spatial planar or relaxed configuration and a tri-dimensional one. In AuGe, AuSb, AuTn alloys, vacancy clusters decorated by solute atoms appear at 250 K. Their configurations are different from those in pure Au. Mobile vacancy-solutes complexes are involved in the clustering process in AuGe, AuSb. The clusters are probably decorated by several solute atoms in AuGe and AuSb where the resistivity evidences a clustering of solute atoms. In AuFe, vacancy-single or multi-complexes stable up to 670 K prevent cluster formation. In FeTi, FeSb, FeAu, vacancy migration is hindered by the formation of vacancy-solute complexes up to 315 K (Ti), up to 670 K (Sb), up to 700 K (Au). In FeSi, FeCu, FeAg, tri-dimensional clusters grow less easily than Fe. This is likely due to the formation of several kinds of small decorated clusters with relaxed or planar configurations. They are peculiarly stable, surviving up to 700 K at least. In Si (resp. Ti) doped 59Fe25Ni16Cr, solute atoms retain the vacancies up to 300 K (resp. 320 K) [fr

  18. Measurement of the 115In(n,γ)116 m In reaction cross-section at the neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV

    Science.gov (United States)

    Lawriniang, Bioletty Mary; Badwar, Sylvia; Ghosh, Reetuparna; Jyrwa, Betylda; Vansola, Vibha; Naik, Haladhara; Goswami, Ashok; Naik, Yeshwant; Datrik, Chandra Shekhar; Gupta, Amit Kumar; Singh, Vijay Pal; Pol, Sudir Shibaji; Subramanyam, Nagaraju Balabenkata; Agarwal, Arun; Singh, Pitambar

    2015-08-01

    The 115In(n,γ)116 m In reaction cross section at neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV was determined by using an activation and off-line γ-ray spectrometric technique. The monoenergetic neutron energies of 1.12 - 4.12 MeV were generated from the 7Li(p,n) reaction by using proton beam with energies of 3 and 4 MeV from the folded tandem ion beam accelerator (FOTIA) at Bhabha Atomic Research Centre (BARC) and with energies of 5 and 6 MeV from the Pelletron facility at Tata Institute of Fundamental Research (TIFR), Mumbai. The 197Au(n,γ)198Au reaction cross-section was used as the neutron flux monitor.The 115In(n,γ)116 m In reaction cross section at neutron energies of 1.12, 2.12, 3.12 and 4.12 MeV was determined by using an activation and off-line γ-ray spectrometric technique. The monoenergetic neutron energies of 1.12 - 4.12 MeV were generated from the 7Li(p,n) reaction by using proton beam with energies of 3 and 4 MeV from the folded tandem ion beam accelerator (FOTIA) at Bhabha Atomic Research Centre (BARC) and with energies of 5 and 6 MeV from the Pelletron facility at Tata Institute of Fundamental Research (TIFR), Mumbai. The 197Au(n,γ)198 Au reaction cross-section was used as the neutron flux monitor. The 115In(n,γ)116 m In reaction cross-sections at neutron energies of 1.12 - 4.12 MeV were compared with the literature data and were found to be in good agreement with one set of data, but not with others. The 115In(n,γ)116 m In cross-section was also calculated theoretically by using the computer code TALYS 1.6 and was found to be slightly lower than the experimental data from the present work and the literature.)198Au reaction cross-section was used as the neutron flux monitor. The 115In(n,γ)116 m In reaction cross-sections at neutron energies of 1.12 - 4.12 MeV were compared with the literature data and were found to be in good agreement with one set of data, but not with others. The 115In(n,γ)116 m In cross-section was also calculated

  19. Polarizabilities and hyperpolarizabilities for the atoms Al, Si, P, S, Cl, and Ar: Coupled cluster calculations.

    Science.gov (United States)

    Lupinetti, Concetta; Thakkar, Ajit J

    2005-01-22

    Accurate static dipole polarizabilities and hyperpolarizabilities are calculated for the ground states of the Al, Si, P, S, Cl, and Ar atoms. The finite-field computations use energies obtained with various ab initio methods including Moller-Plesset perturbation theory and the coupled cluster approach. Excellent agreement with experiment is found for argon. The experimental alpha for Al is likely to be in error. Only limited comparisons are possible for the other atoms because hyperpolarizabilities have not been reported previously for most of these atoms. Our recommended values of the mean dipole polarizability (in the order Al-Ar) are alpha/e(2)a(0) (2)E(h) (-1)=57.74, 37.17, 24.93, 19.37, 14.57, and 11.085 with an error estimate of +/-0.5%. The recommended values of the mean second dipole hyperpolarizability (in the order Al-Ar) are gamma/e(4)a(0) (4)E(h) (-3)=2.02 x 10(5), 4.31 x 10(4), 1.14 x 10(4), 6.51 x 10(3), 2.73 x 10(3), and 1.18 x 10(3) with an error estimate of +/-2%. Our recommended polarizability anisotropy values are Deltaalpha/e(2)a(0) (2)E(h) (-1)=-25.60, 8.41, -3.63, and 1.71 for Al, Si, S, and Cl respectively, with an error estimate of +/-1%. The recommended hyperpolarizability anisotropies are Deltagamma/e(4)a(0) (4)E(h) (-3)=-3.88 x 10(5), 4.16 x 10(4), -7.00 x 10(3), and 1.65 x 10(3) for Al, Si, S, and Cl, respectively, with an error estimate of +/-4%. (c) 2005 American Institute of Physics.

  20. Single Nucleotide Polymorphism Detection Using Au-Decorated Single-Walled Carbon Nanotube Field Effect Transistors

    Directory of Open Access Journals (Sweden)

    Keum-Ju Lee

    2011-01-01

    Full Text Available We demonstrate that Au-cluster-decorated single-walled carbon nanotubes (SWNTs may be used to discriminate single nucleotide polymorphism (SNP. Nanoscale Au clusters were formed on the side walls of carbon nanotubes in a transistor geometry using electrochemical deposition. The effect of Au cluster decoration appeared as hole doping when electrical transport characteristics were examined. Thiolated single-stranded probe peptide nucleic acid (PNA was successfully immobilized on Au clusters decorating single-walled carbon nanotube field-effect transistors (SWNT-FETs, resulting in a conductance decrease that could be explained by a decrease in Au work function upon adsorption of thiolated PNA. Although a target single-stranded DNA (ssDNA with a single mismatch did not cause any change in electrical conductance, a clear decrease in conductance was observed with matched ssDNA, thereby showing the possibility of SNP (single nucleotide polymorphism detection using Au-cluster-decorated SWNT-FETs. However, a power to discriminate SNP target is lost in high ionic environment. We can conclude that observed SNP discrimination in low ionic environment is due to the hampered binding of SNP target on nanoscale surfaces in low ionic conditions.