Science.gov

Sample records for dinuclear metal centre

  1. Dinuclear transition metal complexes in carbon nanostructured materials synthesis

    NASA Astrophysics Data System (ADS)

    Ayuso, J. I.; Hernández, E.; Delgado, E.

    2013-06-01

    Carbon nanomaterials (CNMs) were prepared with two similar techniques using organometallic complexes as catalysts precursors. Chemical vapour deposition (CVD) and pyrolysis with chlorine gas approaches were employed in order to explore the effect of dinuclear transition metal compounds [Fe2(CO)6(μ-S2C6H2X2), (X=OH, Cl)] in synthesis of CNMs. Our to-date results have shown these complexes generate different carbonaceous materials when they are used in bulk, it was also observed that their performances in synthesis differ even though these compounds are analogous. With X=OH complex used in CVD process, metal nanoparticles of ca. 20-50 nm in size and embedded in carbon matrix were obtained. X=C1 complex has been used in pyrolysis experiments and showed an entire volatilisation or no reaction, depending on selected temperature. Furthermore, obtaining of a new tetranuclear iron cluster is presented in this work.

  2. Dihydrogen addition in a dinuclear rare-earth metal hydride complex supported by a metalated TREN ligand.

    PubMed

    Venugopal, Ajay; Fegler, Waldemar; Spaniol, Thomas P; Maron, Laurent; Okuda, Jun

    2011-11-09

    The dinuclear lutetium dihydride dication supported by metalated tripodal ligands undergoes facile hydrogenolysis with H(2) to form a trihydride dication. Molecular orbital analysis shows that the LUMO is a bonding Lu···Lu orbital that is poised to activate dihydrogen.

  3. Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

    PubMed

    Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

    2013-12-15

    The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

  4. Bent and planar structures of μ-η²:η²-N₂ dinuclear early transition metal complexes.

    PubMed

    Ma, Xuelu; Tang, Yanhui; Lei, Ming

    2014-08-14

    This work studied the bent and planar structures of M2N2 cores of a series of dinuclear early transition-metal complexes (M = Zr, Hf, Nb, Ta, Mo and W) containing a side-on bridging dinitrogen ligand using DFT method. The calculated results propose three key factors favoring a bent structure: (1) the availability of a single electron in the metal centers which leads to the bonding interaction between two metal atoms, (2) no remarkable steric effect around the metal centers, and (3) the cis conformation of the ligands in the dinitrogen dinuclear complexes. In addition, the bent and planar structures of M2N2 could be transformed into each other if the steric hindrance was slight.

  5. Unusual Metal-Metal Bonding in a Dinuclear Pt-Au Complex: Snapshot of a Transmetalation Process.

    PubMed

    Baya, Miguel; Belío, Úrsula; Fernández, Israel; Fuertes, Sara; Martín, Antonio

    2016-06-06

    The dinuclear Pt-Au complex [(CNC)(PPh3 )Pt Au(PPh3 )](ClO4 ) (2) (CNC=2,6-diphenylpyridinate) was prepared. Its crystal structure shows a rare metal-metal bonding situation, with very short Pt-Au and Au-Cipso (CNC) distances and dissimilar Pt-Cipso (CNC) bonds. Multinuclear NMR spectra of 2 show the persistence of the Pt-Au bond in solution and the occurrence of unusual fluxional behavior involving the [Pt(II) ] and [Au(I) ] metal fragments. The [Pt(II) ]⋅⋅⋅ [Au(I) ] interaction has been thoroughly studied by means of DFT calculations. The observed bonding situation in 2 can be regarded as a model for an intermediate in a transmetalation process.

  6. Electronic structure analysis of the dinuclear metal center in the bioremediator glycerophosphodiesterase (GpdQ) from Enterobacter aerogenes.

    PubMed

    Hadler, Kieran S; Mitić, Natasa; Yip, Sylvia Hsu-Chen; Gahan, Lawrence R; Ollis, David L; Schenk, Gerhard; Larrabee, James A

    2010-03-15

    The glycerophosphodiesterase (GpdQ) from Enterobacter aerogenes is a promiscuous, dinuclear metallohydrolase that has potential application in the remediation of organophosphate nerve agents and pesticides. GpdQ employs an unusual reaction mechanism in which the enzyme is predominantly mononuclear in the resting state, and substrate binding induces the formation of the catalytically competent dinuclear center (Hadler et al. J. Am. Chem. Soc. 2008, 130, 14129). Reactivity is further modulated by the coordination flexibility of Asn80, a ligand that binds to the second, loosely bound metal ion (Hadler et al. J. Am. Chem. Soc. 2009, 131, 11900). It is proposed that hydrolysis is initiated by a terminal, metal-bound hydroxide molecule which is activated at unusually low pH by electrostatic/hydrogen bonding interactions with a bridging hydroxide species. In this study, electronic structure analysis of the dinuclear center is employed to study the coordination environment of the dinuclear center at the resting and product-bound stage of catalysis. This is achieved through the use of variable temperature, variable field magnetic circular dichroism experiments involving the Co(II)-substituted wild type enzyme and its Asn80Asp variant. The data support the above model for the catalytic mechanism whereby the metal ion-bridging hydroxide molecule activates a terminally bound hydroxide nucleophile. Replacement of Asn80 by an aspartate residue does prevent coordination flexibility but also leads to cleavage of the mu-hydroxide bridge and reduced reactivity. This is the first study to investigate the electronic structure of an enzyme with a mu-1,1-carboxylate bridged dicobalt(II) center.

  7. ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous

  8. Dinuclear vs. mononuclear complexes: accelerated, metal-dependent ring-opening polymerization of lactide.

    PubMed

    Normand, M; Roisnel, T; Carpentier, J-F; Kirillov, E

    2013-12-25

    Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been synthesized and used in the polymerization of lactide. Kinetic studies demonstrate that the dialuminum precursor provides a more favorable reaction pathway in terms of activation free energy than that of directly related monoaluminum systems. No similar trend is observed with the corresponding diindium-monoindium systems, which is attributed to a dissimilar ROP mechanism.

  9. Evidence for a conserved binding motif of the dinuclear metal site in mammalian and plant purple acid phosphatases: 1H NMR studies of the di-iron derivative of the Fe(III)Zn(II) enzyme from kidney bean.

    PubMed

    Battistuzzi, G; Dietrich, M; Löcke, R; Witzel, H

    1997-05-01

    The di-iron core of mammalian purple acid phosphatases has been reproduced in the plant enzyme from kidney bean (Mr 111000) upon insertion of an Fe(II) ion in place of the native zinc(II) in the dinuclear Fe(III)Zn(II) core. The shortening of the electronic relaxation time of the metal centre allows detection of hyperfine-shifted 1H NMR resonances, although severe broadening due to Curie relaxation prevents independent signal assignment. Nevertheless, comparison of the spectral features of the structurally characterized plant enzyme with those of the mammalian species, which were previously extensively assigned, is consistent with a close similarity of the metal-binding sites, also suggested by previous sequence-alignment studies. Some differences appear to be mainly localized at the M(II) site. Spectral comparison was also carried out on the Fe(III)Co(II) derivatives.

  10. Multifrequency EPR Spectroscopy: A Toolkit for the Characterization of Mono- and Di-nuclear Metal Ion Centers in Complex Biological Systems

    NASA Astrophysics Data System (ADS)

    Hanson, Graeme R.

    Metalloenzymes are ubiquitous in nature containing complex metal ion cofactors intimately involved in the enzymes' biological function. The application of multifrequency continuous wave and orientation selective pulsed EPR in conjunction with computer simulation and density functional theory calculations has proven to be a powerful toolkit for the geometric and electronic structural characterization of these metal ion cofactors in the resting enzyme, enzyme-substrate and -product complexes, which in turn provides a detailed understanding of the enzymes' catalytic mechanism. In this chapter, a brief description of the multifrequency EPR toolkit used to structurally (geometric and electronic) characterize metal ion binding sites in complex biological systems and its application in the structural characterization of (i) molybdenum containing enzymes and model complexes, (ii) mono- and di-nuclear copper(II) cyclic peptide complexes (marine and synthetic analogues) and (iii) dinuclear metal ion centers in purple acid phosphatases will be presented.

  11. Achieving C-N bond cleavage in dinuclear metal cyanide complexes.

    PubMed

    Cavigliasso, Germán; Christian, Gemma J; Stranger, Robert; Yates, Brian F

    2011-07-28

    Cleavage of cyanide is more difficult to achieve compared to dinitrogen and carbon monoxide, even though these species contain triple bonds of greater strength. In this work, we have used computational methods to investigate thermodynamic and mechanistic aspects of the C-N bond cleavage process in [L(3)M-CN-M'L(3)] systems consisting of a central cyanide unit bound in an end-on fashion to two terminal metal tris-amide complexes. In these systems, [M] is a d(3) transition metal from the 3d, 4d, 5d, or 6d series and groups 4 through 7, and [L] is either [NH(2)], [NMe(2)], [N(i)PrPh], or [N(t)BuAr]. A comparison of various models for the experimentally relevant [L(3)Mo-CN-MoL(3)] system has shown that while the C-N cleavage step appears to be an energetically favourable process, a large barrier exists for the dissociation of [L(3)Mo-CN-MoL(3)]((-)) into [L(3)Mo-C]((-)) and [N-MoL(3)], which possibly explains why C-N bond scission is not observed experimentally. The general structural, bonding, and thermochemical trends across the transition metal series investigated, indicate that the systems exhibiting the greatest degree of C-N activation, and most favourable energetics for C-N cleavage, also possess the most favourable electronic properties, namely, a close match between the relevant π-like orbitals on the metal-based and cyanide fragments. The negative charge on the cyanide fragment leads to significant destabilization of the π* level which needs to be populated through back-donation from the metal centres in order for C-N bond scission to be achieved. Therefore, metal-based systems with high-lying d(π) orbitals are best suited to C-N cleavage. In terms of chemical periodicity, these systems can be identified as the heavier members within a group and the earlier members within a period. As a consequence, Mo complexes are not well suited to cleaving the C-N bond, whereas the Ta analogues are the most favourable systems and should, in principle, be capable of

  12. Dinuclear complexes formed by hydrogen bonds: synthesis, structure and magnetic and electrochemical properties.

    PubMed

    Williams, Alan Francis; Granelli, Matteo; Downward, Alan M; Huber, Robin; Guenée, Laure; Besnard, Céline; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia; Thompson, Laurence K

    2017-03-20

    The synthesis is reported of a series of homo- and hetero-dinuclear octahedral complexes of the ligand 1, 1,2-bis(1-methyl-benzimidazol-2-yl) ethanol, where the two metal centres are linked by hydrogen bonds between coordinated alcohols and coordinated alkoxides. Homonuclear divalent M(II)M(II), mixed valent M(II)M(III) and heteronuclear M(II)M'(III) species are prepared. The complexes have been characterised by X-ray crystallography and show unusually short O…O distances for the hydrogen bonds. Magnetic measurements show the hydrogen bond bridges can lead to ferromagnetic or antiferromagnetic coupling. The electrochemistry of the dinuclear species is significantly different from the mononuclear systems: the latter show irreversible waves in cyclic voltammograms as a result of the need to couple proton and electron transfer. The dinuclear species, in contrast, show reversible waves which are attributed to rapid intramolecular proton transfer facilitated by the hydrogen bonded structure.

  13. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    PubMed

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates.

  14. Mechanistic role of each metal ion in Streptomyces dinuclear aminopeptidase: PEPTIDE hydrolysis and 7x10(10)-fold rate enhancement of phosphodiester hydrolysis.

    PubMed

    Ercan, Altan; Tay, William M; Grossman, Steven H; Ming, Li-June

    2010-01-01

    The dinuclear aminopeptidase from Streptomyces griseus (SgAP) and its metal derivatives catalyze the hydrolysis of the phosphoester bis(p-nitrophenyl) phosphate (BNPP) and the phosphonate ester p-nitrophenyl phenylphosphonate with extraordinary rate enhancements at pH 7.0 and 25 degrees C [A. Ercan, H. I. Park, L.-J. Ming, Biochemistry 45, (2006) 13779-13793.], reaching 6.7 billion-fold in terms of the first-order rate constant of the di-Co(II) derivative with respect to the autohydrolytic rates. Since phosphoesters are transition state-like inhibitors in peptide hydrolysis, their hydrolysis by SgAP is quite novel. Herein, we report the investigation of this proficient alternative catalysis of SgAP and the role of each metal ion in the dinuclear site toward peptide and BNPP hydrolysis. Mn(II) selectively binds to one of the dinuclear metal sites (M1), affording MnE-SgAP with an empty (E) second site for the binding of another metal (M2), including Mn(II), Co(II), Ni(II), Zn(II), and Cd(II). Peptide hydrolysis is controlled by M2, wherein the k(cat) values for the derivatives MnM2-SgAP are different yet similar between MnCo- and CoCo-SgAP and pairs of other metal derivatives. On the other hand, BNPP hydrolysis is affected by metals in both sites. Thus, the two hydrolytic catalyses must follow different mechanisms. Based on crystal structures, docking, and the results presented herein, the M1 site is close to the hydrophobic specific site and the M2 site is next to Tyr246 that is H-bonded to a coordinated nucleophilic water molecule in peptide hydrolysis; whereas a coordinated water molecule on M1 becomes available as the nucleophile in phosphodiester hydrolysis.

  15. Femtosecond Time-Resolved Infrared Spectra of Organometallic Complexes Bound to a Dinuclear Metal Center

    NASA Astrophysics Data System (ADS)

    Brown-Xu, Samantha E.; Durr, Christopher B.

    2012-06-01

    Compounds of the form M2L2L'2, where M2 is a quadruply bonded metal center (M = Mo or W) and L and L' are conjugated organic ligands, are known to show interesting photophysical properties and exhibit intense metal-to-ligand charge transfer (MLCT) transitions throughout the visible spectrum. Recently, we have modified one of the ligands to incorporate a transition metal carbonyl complex bound to an organic moiety. Following excitation into the MLCT band, the vibrational modes of the organometallic ligand can be observed by fs time-resolved infrared (TRIR) spectroscopy. This allows for a visualization of where the electron density resides in the excited states, which provides useful information for designing new materials that could later be incorporated into solar devices.

  16. Emission and fs/ns-TRANSIENT Absorption of Organometallic Complexes Bound to a Dinuclear Metal Center

    NASA Astrophysics Data System (ADS)

    Durr, Christopher B.; Brown-Xu, Samantha E.; Chisholm, Malcolm H.

    2012-06-01

    Compounds containing a MM quadruple bond (M = Mo or W) of the form M2L2L'2, where L and L' are conjugated organic ligands, show interesting photophysical properties along with a metal-to-ligand charge transfer (MLCT) band that is tunable throughout the UV-Vis-NIR spectra. Recently, our attention has shifted towards ligands that incorporate a secondary transition metal complex bound to an organic moiety. Along with allowing for a second tunable MLCT band for better coverage of the solar spectrum, these hybrid molecules show unique spectroscopic properties that were explored using fs/ns-transient absorption and UV-Vis/NIR emission. These techniques allow for the elucidation of the electronic character of the excited states as well as their lifetimes. This knowledge will be put to use in the design of new materials that could later be incorporated into next generation photovoltaic devices.

  17. Bimetallic Reductive Elimination from Dinuclear Pd(III) Complexes

    PubMed Central

    Powers, David C.; Benitez, Diego; Tkatchouk, Ekaterina; Goddard, William A.

    2010-01-01

    In 2009, we reported C–halogen reductive elimination reactions from dinuclear Pd(III) complexes and implicated dinuclear intermediates in Pd(OAc)2-catalyzed C–H oxidation chemistry. Herein, we report results of a thorough experimental and theoretical investigation of the mechanism of reductive elimination from such dinuclear Pd(III) complexes, which establish the role of each metal during reductive elimination. Our results implicate reductive elimination from a complex in which the dinuclear core is intact and suggest that redox synergy between both metals is responsible for the facile reductive elimination reactions observed. PMID:20858006

  18. Mechanismic investigation on the cleavage of phosphate monoester catalyzed by unsymmetrical macrocyclic dinuclear complexes: the selection of metal centers and the intrinsic flexibility of the ligand.

    PubMed

    Zhang, Xuepeng; Zhu, Yajie; Zheng, Xiaowei; Phillips, David Lee; Zhao, Cunyuan

    2014-04-07

    The hydrolysis mechanisms of phosphor-monoester monoanions NPP(-) (p-nitrophenyl phosphate) catalyzed by unsymmetrical bivalent dinuclear complexes are explored using DFT calculations in this report. Four basic catalyst-substrate binding modes are proposed, and two optional compartments for the location of the nucleophile-coordinated metal center are also considered. Five plausible mechanisms are examined in this computational study. Mechanisms 1, 2, and 3 employ an unsymmetrical dizinc complex. All three mechanisms are based on concerted SN2 addition-substitution pathways. Mechanism 1, which involves more electronegative oxygen atoms attached to the imine nitrogen atoms in the nucleophile-coordinated compartment, was found to be more competitive compared to the other two mechanisms. Mechanisms 4 and 5 are based on consideration of the substitution of the bivalent metal centers and the intrinsic flexibility of the ligand. Both mechanisms 4 and 5 are based on stepwise SN2-type reactions. Magnesium ions with hard base properties and more available coordination sites were found to be good candidates as a substitute in the M(II) dinuclear phosphatases. The reaction energy barriers for the more distorted complexes are lower than those of the less distorted complexes. The proper intermediate distance and a functional second coordination sphere lead to significant catalytic power in the reactions studied. More importantly, the mechanistic differences between the concerted and the stepwise pathways suggest that a better nucleophile with more available coordination sites (from either the metal centers or a functional second coordination sphere) favors concerted mechanisms for the reactions of interest. The results reported in the paper are consistent with and provide a reasonable interpretation for experimental observations in the literature. More importantly, our present results provide some practical suggestions for the selection of the metal centers and how to approach

  19. Dinuclear metal(ii)-acetato complexes based on bicompartmental 4-chlorophenolate: syntheses, structures, magnetic properties, DNA interactions and phosphodiester hydrolysis.

    PubMed

    Massoud, Salah S; Ledet, Catherine C; Junk, Thomas; Bosch, Simone; Comba, Peter; Herchel, Radovan; Hošek, Jan; Trávníček, Zdeněk; Fischer, Roland C; Mautner, Franz A

    2016-08-09

    A series of dinuclear metal(ii)-acetato complexes: [Ni2(μ-L(Cl)O)(μ2-OAc)2](PF6)·3H2O (1), [Ni2(μ-L(Cl)O)(μ2-OAc)2](ClO4)·CH3COCH3 (2), [Cu2(μ-L(Cl)O)(μ2-OAc)(ClO4)](ClO4) (3), [Cu2(μ-L(Cl)O)(OAc)2](PF6)·H2O (4), [Zn2(μ-L(Cl)O)(μ2-OAc)2](PF6) (5) and [Mn2(L(Cl)-O)(μ2-OAc)2](ClO4)·H2O (6), where L(Cl)O(-) = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenolate, were synthesized. The complexes were structurally characterized by spectroscopic techniques and single crystal X-ray crystallography. Six-coordinate geometries with doubly bridged acetato ligands were found in Ni(ii), Zn(ii) and Mn(ii) complexes 1, 2, 5 and 6, whereas with Cu(ii) complexes a five-coordinate species was obtained with 4, and mixed five- and six-coordinate geometries with a doubly bridged dimetal core were observed in 3. The magnetic properties of complexes 1-4 and 6 were studied at variable temperatures and revealed weak to very weak antiferromagnetic interactions in 1, 2, 4 and 6 (J = -0.55 to -9.4 cm(-1)) and ferromagnetic coupling in 3 (J = 15.4 cm(-1)). These results are consistent with DFT calculations performed at the B3LYP/def2-TZVP(-f) level of theory. Under physiological conditions, the interaction of the dinculear complexes 1-5 with supercoiled plasmid ds-DNA did not show any pronounced nuclease activity, but Ni(ii) complexes 1 and 2 revealed a strong ability to unwind the supercoiled conformation of ds-DNA. The mechanistic studies performed on the interaction of the Ni(ii) complexes with DNA demonstrated the important impact of the nickel(ii) ion in the unwinding process. In combination with the DNA study, the phosphatase activity of complexes 1, 3, and 5 was examined by the phosphodiester hydrolysis of bis(2,4-dinitrophenol)phosphate (BDNPP) in the pH range of 5.5-10.5 at 25 °C. The Michaelis-Menten kinetics performed at pH 7 and 10.7 showed that catalytic efficiencies kcat/KM (kcat = catalytic rate constant, KM = substrate binding constant) decrease in the order

  20. Dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in μ-η(2) :η(1) :η(1) hapticities and their high catalytic activity for isoprene 1,4-cis-polymerization.

    PubMed

    Zhang, Guangchao; Wei, Yun; Guo, Liping; Zhu, Xiancui; Wang, Shaowu; Zhou, Shuangliu; Mu, Xiaolong

    2015-02-02

    Two series of new dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in novel μ-η(2) :η(1) :η(1) hapticities are synthesized and characterized. Treatment of [RE(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of 3-(tBuN=CH)C8 H5 NH (L1 ) in THF gives the dinuclear rare-earth metal alkyl complexes trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH(CH2 SiMe3 )}Ind)RE(thf)(CH2 SiMe3 )]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino C=N group is transferred to the amido group by alkyl CH2 SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ-η(2) :η(1) :η(1) bonding modes, forming the dinuclear rare-earth metal alkyl complexes. When L1 is reduced to 3-(tBuNHCH2 )C8 H5 NH (L2 ), the reaction of [Yb(CH2 SiMe3 )3 (thf)2 ] with 1 equivalent of L2 in THF, interestingly, generated the trans-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (major) and cis-[(μ-η(2) :η(1) :η(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (minor) complexes. The catalytic activities of these dinuclear rare-earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio- and stereoselectivities for isoprene 1,4-cis-polymerization.

  1. Synthesis, characterization and properties of tetra((1-hydroxyimino-methylnaphthalen-2-yloxy)methyl)ethene and its homo-dinuclear metal complexes: a combined experimental and theoretical investigation.

    PubMed

    Serbest, Kerim; Karaoğlu, Kaan; Erman, Murat; Er, Mustafa; Değirmencioğlu, Ismail

    2010-10-15

    Tetra((1-hydroxyiminomethylnaphthalen-2-yloxy)methyl)ethene (THIMNYOME), H(4)L, was synthesized by the agents of 2-hydroxy-1-naphtaldehyde, tetra(bromomethyl)ethene and hydroxylamine hydrochloride in two steps. Characterization of THIMNYOME and its dinuclear complexes was made by elemental analyses, IR, (1)H- and (13)C NMR, UV-vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. In the light of these results, it was suggested that the ligand coordinate to each metal atom by the two ether oxygen, two nitrogen atoms of oxime imine (CN) and an axial oxygen of perchlorate to form pseudo square-pyramidal complexes with Ni(II), Cu(II) and Zn(II). Molar conductivity measurements reveal that all the complexes are non-electrolytes. In addition, the full geometric optimization of the tetraoxime ligand (4) has been made by the B3LYP/6-31G(d) level in order to establish a stable conformation. Additionally, all the complex structures have been studied in the B3LYP/LANL2DZ level. NBO charge distribution and the characteristics of frontier molecular orbitals of these complexes have also been investigated in order to see the electrons movement between ligand and metal atom in the same level.

  2. Mechanical properties for irradiated face-centred cubic nanocrystalline metals.

    PubMed

    Xiao, X Z; Song, D K; Chu, H J; Xue, J M; Duan, H L

    2015-05-08

    In this paper, a self-consistent plasticity theory is proposed to model the mechanical behaviours of irradiated face-centred cubic nanocrystalline metals. At the grain level, a tensorial crystal model with both irradiation and grain size effects is applied for the grain interior (GI), whereas both grain boundary (GB) sliding with irradiation effect and GB diffusion are considered in modelling the behaviours of GBs. The elastic-viscoplastic self-consistent method with considering grain size distribution is developed to transit the microscopic behaviour of individual grains to the macroscopic properties of nanocrystals (NCs). The proposed theory is applied to model the mechanical properties of irradiated NC copper, and the feasibility and efficiency have been validated by comparing with experimental data. Numerical results show that: (i) irradiation-induced defects can lead to irradiation hardening in the GIs, but the hardening effect decreases with the grain size due to the increasing absorption of defects by GBs. Meanwhile, the absorbed defects would make the GBs softer than the unirradiated case. (ii) There exists a critical grain size for irradiated NC metals, which separates the grain size into the irradiation hardening dominant region (above the critical size) and irradiation softening dominant region (below the critical size). (iii) The distribution of grain size has a significant influence on the mechanical behaviours of both irradiated and unirradiated NCs. The proposed model can offer a valid theoretical foundation to study the irradiation effect on NC materials.

  3. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

    PubMed

    Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

    2015-06-25

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions.

  4. Synthesis, structure and DFT study of dinuclear iron, cobalt and nickel complexes with cyclopentadienyl-metal moieties.

    PubMed

    Liu, Nazhen; Li, Xiaoyan; Xu, Xiaofeng; Wang, Zhiping; Sun, Hongjian

    2011-07-14

    Reactions of 1,1'-bis(dipheny1phosphino)cobaltocene with Co(PMe(3))(4), Ni(PMe(3))(4), Fe(PMe(3))(4), Ni(COD)(2), FeMe(2)(PMe(3))(4) or NiMe(2)(PMe(3))(3) afford a series of novel dinuclear complexes [((Me(3)P)[lower bond 1 start]Co(η(5)-C(5)H(4)[upper bond 1 start]PPh(2)))((Me(3)P)M[upper bond 1 end](η(5)-C(5)H(4)P[lower bond 1 end]Ph(2)))] (M = Co(1), Ni(2) and Fe(3)) [Co(η(5)-C(5)H(4)[upper bond 1 start]PPh(2))(2)Ni[upper bond 1 end](COD)](4), [Co(η(5)-C(5)H(4)[upper bond 1 start]PPh(2))(2)Ni[upper bond 1 end](PMe(3))(2)] (5) and [((Me(3)P)[lower bond 1 start]Co(Me)(η(5)-C(5)H(4)[upper bond 1 start]PPh(2)))((Me(3)P)Fe[upper bond 1 end](Me)(η(5)-C(5)H(4)P[lower bond 1 end]Ph(2)))] (6). Reactions of 1,1'-bis(dipheny1phosphino)ferrocene with Ni(PMe(3))(4), NiMe(2)(PMe(3))(3), or Co(PMe(3))(4) gives rise to complexes [Fe(η(5)-C(5)H(4)[upper bond 1 start]PPh(2))(2)M[upper bond 1 end](PMe(3))(2)] (M = Ni (7), Co (8)). The complexes 1-8 were spectroscopically investigated and studied by X-ray single crystal diffraction. The possible reaction mechanisms and structural characteristics are discussed. Density functional theory (DFT) calculations strongly support the deductions.

  5. Synthesis, structure and magnetic properties of mono-, dinuclear and polymeric compounds of transition metals with 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole

    NASA Astrophysics Data System (ADS)

    Martín-Ramos, Pablo; Silva, Manuela Ramos; de A. e Silva, Joana; Martins, Nuno D.; Yuste-Vivas, Consuelo; Pereira da Silva, Pedro S.; Sobral, Abílio J. F. N.; Pereira, Laura C. J.

    2016-03-01

    Five new complexes were obtained from solution of transition metal salts (M=Co(II), Cu(II)) with 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (abpt) in different molar ratios. X-ray structural elucidation revealed low-dimensional compounds with the metal ions assembled in monomers, dimers or chains. Two similar polymorphs were obtained for the monomer synthesized from Cu(II) chloride. Temperature-dependent magnetic susceptibility measurements were conducted for the non-monomeric compounds, and efficient super-exchange interaction was found for the mostly planar dinuclear Co(II) complex.

  6. Thermostability of proteins: role of metal binding and pH on the stability of the dinuclear CuA site of Thermus thermophilus.

    PubMed

    Sujak, Agnieszka; Sanghamitra, Nusrat J M; Maneg, Oliver; Ludwig, Bernd; Mazumdar, Shyamalava

    2007-10-15

    The dinuclear copper center (TtCuA) forming the electron entry site in the subunit II of the cytochrome c oxidase in Thermus thermophilus shows high stability toward thermal as well as denaturant-induced unfolding of the protein at ambient pH. We have studied the effect of pH on the stability of the holo-protein as well as of the apo-protein by UV-visible absorption, far-UV, and visible circular dichroism spectroscopy. The results show that the holo-protein both in the native mixed-valence state as well as in the reduced state of the metal ions and the apo-protein of TtCuA were extremely stable toward unfolding by guanidine hydrochloride at ambient pH. The thermal unfolding studies at different values of pH suggested that decreasing pH had almost no effect on the thermal stability of the protein in the absence of the denaturant. However, the stability of the proteins in presence of the denaturant was considerably decreased on lowering the pH. Moreover, the stability of the holo-protein in the reduced state of the metal ion was found to be lower than that in the mixed-valence state at the same pH. The denaturant-induced unfolding of the protein at different values of pH was analyzed using a two-state unfolding model. The values of the free energy of unfolding were found to increase with pH. The holo-protein showed that the variation of the unfolding free energy was associated with a pKa of approximately 5.5. This is consistent with the model that the protonation of a histidine residue may be responsible for the decrease in the stability of the holo-protein at low pH. The results were interpreted in the light of the reported crystal structure of the protein.

  7. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre.

    PubMed

    Humbert, Nicolas; Mazet, Clément

    2016-08-23

    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated.

  8. Metal centre effects on HNO binding in porphyrins and the electronic origin: metal's electronic configuration, position in the periodic table, and oxidation state.

    PubMed

    Yang, Liu; Fang, Weihai; Zhang, Yong

    2012-04-21

    HNO binds to many different metals in organometallic and bioinorganic chemistry. To help understand experimentally observed metal centre effects, a quantum chemical investigation was performed, revealing clear general binding trends with respect to metal centre characteristics and the electronic origin for the first time.

  9. KMOS view of the Galactic Centre - II. Metallicity distribution of late-type stars

    NASA Astrophysics Data System (ADS)

    Feldmeier-Krause, A.; Kerzendorf, W.; Neumayer, N.; Schödel, R.; Nogueras-Lara, F.; Do, T.; de Zeeuw, P. T.; Kuntschner, H.

    2017-01-01

    Knowing the metallicity distribution of stars in the Galactic Centre has important implications for the formation history of the Milky Way nuclear star cluster. However, this distribution is not well known, and is currently based on a small sample of fewer than 100 stars. We obtained near-infrared K-band spectra of more than 700 late-type stars in the central 4 pc2 of the Milky Way nuclear star cluster with the integral-field spectrograph KMOS (VLT). We analyse the medium-resolution spectra using a full-spectral fitting method employing the Göttingen spectral library of synthetic PHOENIX spectra. The derived stellar metallicities range from metal-rich [M/H] > +0.3 dex to metal-poor [M/H] <-1.0 dex, with a fraction of 5.2^{+6.0}_{-3.1} per cent metal-poor ([M/H] ≤ -0.5 dex) stars. The metal-poor stars are distributed over the entire observed field. The origin of metal-poor stars remains unclear. They could originate from infalling globular clusters. For the metal-rich stellar population ([M/H] > 0 dex), a globular cluster origin can be ruled out. As there is only a very low fraction of metal-poor stars in the central 4 pc2 of the Galactic Centre, we believe that our data can discard a scenario in which the Milky Way nuclear star cluster is purely formed from infalling globular clusters.

  10. Self-assembly of transition-metal-based macrocycles linked by photoisomerizable ligands: examples of photoinduced conversion of tetranuclear-dinuclear squares.

    PubMed

    Sun, Shih-Sheng; Anspach, Jason A; Lees, Alistair J

    2002-04-08

    A series of hetero- and homometallic square complexes bridged by a photoactive 4,4'-azopyridine (AZP) or 1,2-bis(4-pyridyl)ethylene (BPE) ligand, cyclobis[[cis-(dppf)M](mu-L)(2)(fac-Re(CO)(3)Br)](OTf)(4) (M = Pd, L = trans-AZP (5); M = Pt, L = trans-AZP (7); M = Pd, L = trans-BPE (8); M = Pt, L = trans-BPE (10)), cyclo[[cis-(dppf)M](mu-L)(2)(fac-Re(CO)(3)Br)](OTf)(2) (M = Pd, L = cis-AZP (6); M = Pd, L = cis-BPE (9)), [cis-(dppf)Pd(mu-trans-AZP)](4)(OTf)(8) (11), and [cis-(dppf)Pd(mu-cis-AZP)](2)(OTf)(4) (12), where dppf is 1,1'-bis(diphenylphosphino)ferrocene and OTf is trifluoromethanesulfonate anion, were prepared by thermodynamically driven self-assembly processes. The photophysical and photochemical properties of these complexes have been investigated, and all of them show a lack of luminescence in room temperature solution. Upon irradiation at 313 or 366 nm, Pd(II)-Re(I)-containing tetranuclear squares 5, 8, and 11 undergo photoisomerization and convert to their corresponding dinuclear complexes 6, 9, and 12, whereas Pt(II)-Re(I)-based squares 7 and 10 show only slow square disassembling processes. The tetranuclear squares can be fully recovered by heating the photoisomerized solution for several hours.

  11. A new 3D metal-organic framework (MOF) Zn(DNBPDC)2(BPY) with a dinuclear zinc (II) clusters as SBU

    NASA Astrophysics Data System (ADS)

    Li, Song; Qin, Xiangdong; Deng, Linxin; Liu, Hui

    2017-04-01

    A new 3D framework compound 1 Zn(DNBPDC)2(BPY) (DBDBC =2,2‧-dinitro-[1,1‧-biphenyl]-4,4‧-dicarboxylic acid, BPY = 4,4‧-Bipyridine) with a dinuclear zinc (II) clusters as SBU have been synthesized and structurally characterized. This compound crystallizes in Tetragonal, space group I41/acd, with a = 21.2959(10)Å, b = 21.2959(10) Å, c = 27.969(3) Å, α = 90.00°, β = 90.00 (10)°, γ = 90.00°, V =12684.4(16) Å3, Z = 16, Dc = 1.424 mg/cm3, μ = 0.806 mm-1, F(000) = 3792. From the thermogravimetric analysis, the compound can be stabilized up to 380 °C and the skeleton collapsed occurred in about 350-550 °C. The luminescence property test shows that the compound exhibit strong emission at 485 nm. The nitrogen adsorption capacity was 10 cc/g when the compound was activated under the temperature of 77 K and reach to atmospheric pressure.

  12. Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

    PubMed

    Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C; Housecroft, Catherine E; Neuburger, Markus; Zampese, Jennifer A

    2014-08-28

    The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)- in high yield. The single crystal structure of (R)- reveals a tetranuclear copper(ii) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)- and (S,R)- have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)- selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)- exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)- and (S,R)- in controlling the reactivity towards aerobic oxidation reactions is discussed.

  13. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism

    NASA Astrophysics Data System (ADS)

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-02-01

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a PtII-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis-trans isomerization at the PtII centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one PtII ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems.

  14. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism

    PubMed Central

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-01-01

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a PtII-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis–trans isomerization at the PtII centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one PtII ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems. PMID:28176770

  15. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism.

    PubMed

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-02-08

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a Pt(II)-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis-trans isomerization at the Pt(II) centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one Pt(II) ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems.

  16. Influence of complex impurity centres on radiation damage in wide-gap metal oxides

    NASA Astrophysics Data System (ADS)

    Lushchik, A.; Lushchik, Ch.; Popov, A. I.; Schwartz, K.; Shablonin, E.; Vasil'chenko, E.

    2016-05-01

    Different mechanisms of radiation damage of wide-gap metal oxides as well as a dual influence of impurity ions on the efficiency of radiation damage have been considered on the example of binary ionic MgO and complex ionic-covalent Lu3Al5O12 single crystals. Particular emphasis has been placed on irradiation with ∼2 GeV heavy ions (197Au, 209Bi, 238U, fluence of 1012 ions/cm2) providing extremely high density of electronic excitations within ion tracks. Besides knock-out mechanism for Frenkel pair formation, the additional mechanism through the collapse of mobile discrete breathers at certain lattice places (e.g., complex impurity centres) leads to the creation of complex defects that involve a large number of host atoms. The experimental manifestations of the radiation creation of intrinsic and impurity antisite defects (Lu|Al or Ce|Al - a heavy ion in a wrong cation site) have been detected in LuAG and LuAG:Ce3+ single crystals. Light doping of LuAG causes a small enhancement of radiation resistance, while pair impurity centres (for instance, Ce|Lu-Ce|Al or Cr3+-Cr3+ in MgO) are formed with a rise of impurity concentration. These complex impurity centres as well as radiation-induced intrinsic antisite defects (Lu|Al strongly interacting with Lu in a regular site) tentatively serve as the places for breathers collapse, thus decreasing the material resistance against dense irradiation.

  17. A metal-organic cage incorporating multiple light harvesting and catalytic centres for photochemical hydrogen production

    PubMed Central

    Chen, Sha; Li, Kang; Zhao, Fang; Zhang, Lei; Pan, Mei; Fan, Yan-Zhong; Guo, Jing; Shi, Jianying; Su, Cheng-Yong

    2016-01-01

    Photocatalytic water splitting is a natural but challenging chemical way of harnessing renewable solar power to generate clean hydrogen energy. Here we report a potential hydrogen-evolving photochemical molecular device based on a self-assembled ruthenium–palladium heterometallic coordination cage, incorporating multiple photo- and catalytic metal centres. The photophysical properties are investigated by absorption/emission spectroscopy, electrochemical measurements and preliminary DFT calculations and the stepwise electron transfer processes from ruthenium-photocentres to catalytic palladium-centres is probed by ultrafast transient absorption spectroscopy. The photocatalytic hydrogen production assessments reveal an initial reaction rate of 380 μmol h−1 and a turnover number of 635 after 48 h. The efficient hydrogen production may derive from the directional electron transfers through multiple channels owing to proper organization of the photo- and catalytic multi-units within the octahedral cage, which may open a new door to design photochemical molecular devices with well-organized metallosupramolecules for homogenous photocatalytic applications. PMID:27827376

  18. A metal-organic cage incorporating multiple light harvesting and catalytic centres for photochemical hydrogen production

    NASA Astrophysics Data System (ADS)

    Chen, Sha; Li, Kang; Zhao, Fang; Zhang, Lei; Pan, Mei; Fan, Yan-Zhong; Guo, Jing; Shi, Jianying; Su, Cheng-Yong

    2016-11-01

    Photocatalytic water splitting is a natural but challenging chemical way of harnessing renewable solar power to generate clean hydrogen energy. Here we report a potential hydrogen-evolving photochemical molecular device based on a self-assembled ruthenium-palladium heterometallic coordination cage, incorporating multiple photo- and catalytic metal centres. The photophysical properties are investigated by absorption/emission spectroscopy, electrochemical measurements and preliminary DFT calculations and the stepwise electron transfer processes from ruthenium-photocentres to catalytic palladium-centres is probed by ultrafast transient absorption spectroscopy. The photocatalytic hydrogen production assessments reveal an initial reaction rate of 380 μmol h-1 and a turnover number of 635 after 48 h. The efficient hydrogen production may derive from the directional electron transfers through multiple channels owing to proper organization of the photo- and catalytic multi-units within the octahedral cage, which may open a new door to design photochemical molecular devices with well-organized metallosupramolecules for homogenous photocatalytic applications.

  19. Cleavage of hydrogen by activation at a single non-metal centre - towards new hydrogen storage materials.

    PubMed

    Grabowski, Sławomir J

    2015-05-28

    Molecular surfaces of non-metal species are often characterized by both positive and negative regions of electrostatic potential (EP) at a non-metal centre. This centre may activate molecular hydrogen which further leads to the addition reaction. The positive EP regions at the non-metal centres correspond to σ-holes; the latter sites are enhanced by electronegative substituents. This is why the following simple moieties; PFH2, SFH, AsFH2, SeFH, BrF3, PF(CH3)2 and AsF(CH3)2, were chosen here to analyze the H2 activation and its subsequent splitting at the P, As, S, Se and Br centres. Also the reverse H-H bond reforming process is analyzed. MP2/aug-cc-pVTZ calculations were performed for systems corresponding to different stages of these processes. The sulphur centre in the SFH moiety is analyzed in detail since the potential barrier height for the addition reaction for this species is the lowest of the moieties analyzed here. The results of calculations show that the SFH + H2 → SFH3 reaction in the gas phase is endothermic but it is exothermic in polar solvents.

  20. Robust silver-mediated imidazolo-dC base pairs in metal DNA: dinuclear silver bridges with exceptional stability in double helices with parallel and antiparallel strand orientation.

    PubMed

    Jana, Sunit Kumar; Guo, Xiurong; Mei, Hui; Seela, Frank

    2015-12-18

    A new unprecedented metal-mediated base pair was designed that stabilizes reverse Watson-Crick DNA (parallel strand orientation, ps) as well as canonical Watson-Crick DNA (antiparallel strand orientation, aps). This base pair contains two imidazolo-dC units decorated with furan residues. Tm measurements and spectroscopic studies reveal that each silver-mediated furano-imidazolo-dC forms exceptionally stable duplexes with ps and aps chain orientation. This stability increase by a silver-mediated base pair is the highest reported so far for ps and aps DNA helices.

  1. Synthesis, structure and reactivity of dinuclear rare earth metal bis(o-aminobenzyl) complexes bearing a 1,4-phenylenediamidinate co-ligand.

    PubMed

    Li, Meng; Hong, Jianquan; Chen, Zhenxia; Zhou, Xigeng; Zhang, Lixin

    2013-06-21

    A series of phenylenediamidinate rare earth metal complexes 1,4-C6H4[C(NR)2Ln(o-CH2C6H4NMe2)2]2 (R = 2,6-(i)Pr2-C6H3, Ln = Y (2a), Lu (2b), Sc (2c)) were synthesized by deprotonation of 1,4-C6H4[C(NR)(NHR)]2 (1) with two equivalents of n-BuLi followed by reacting with two equivalents of anhydrous LnCl3 and subsequently four equivalents of Li(o-CH2C6H4NMe2), or by protolysis of [Ln(o-CH2C6H4NMe2)3] with 0.5 equivalent of 1 in THF or toluene. Treatment of complexes 2a and 2b with four equivalents of phenyl isocyanate and phenyl isothiocyanate gave the corresponding insertion products 1,4-C6H4[C(NR)2Ln{OC(CH2C6H4NMe2-o)NPh}2(THF)]2 (Ln = Y (3a), Lu (3b)) and 1,4-C6H4[C(NR)2Ln{SC(CH2C6H4NMe2-o)NPh}2]2 (Ln = Y (4a), Lu (4b)), respectively. The structures of 1, 3b, and 4a were established by X-ray diffraction studies. Complexes 2 show high activity for rac-lactide and ε-caprolactone polymerization; for the former a synergistic effect between two metal centers is observed.

  2. Structure of a conserved hypothetical protein SA1388 from S. aureus reveals a capped hexameric toroid with two PII domain lids and a dinuclear metal center

    SciTech Connect

    Saikatendu, Kumar Singh; Zhang, Xuejun; Kinch, Lisa; Leybourne, Matthew; Grishin, Nick V.; Zhang, Hong

    2009-01-26

    The protein encoded by the SA1388 gene from Staphylococcus aureus was chosen for structure determination to elucidate its domain organization and confirm our earlier remote homology based prediction that it housed a nitrogen regulatory PII protein-like domain. SA1388 was predicted to contain a central PII-like domain and two flanking regions, which together belong to the NIF3-like protein family. Proteins like SA1388 remain a poorly studied group and their structural characterization could guide future investigations aimed at understanding their function. The structure of SA1388 has been solved to 2.0{angstrom} resolution by single wavelength anomalous dispersion phasing method using selenium anomalous signals. It reveals a canonical NIF3-like fold containing two domains with a PII-like domain inserted in the middle of the polypeptide. The N and C terminal halves of the NIF3-like domains are involved in dimerization, while the PII domain forms trimeric contacts with symmetry related monomers. Overall, the NIF3-like domains of SA1388 are organized as a hexameric toroid similar to its homologs, E. coli ybgI and the hypothetical protein SP1609 from Streptococcus pneumoniae. The openings on either side of the toroid are partially covered by trimeric 'lids' formed by the PII domains. The junction of the two NIF3 domains has two zinc ions bound at what appears to be a histidine rich active site. A well-defined electron density corresponding to an endogenously bound ligand of unknown identity is observed in close proximity to the metal site. SA1388 is the third member of the NIF3-like family of proteins to be structurally characterized, the other two also being hypothetical proteins of unknown function. The structure of SA1388 confirms our earlier prediction that the inserted domain that separates the two NIF3 domains adopts a PII-like fold and reveals an overall capped toroidal arrangement for the protein hexamer. The six PII-like domains form two trimeric 'lids' that

  3. Design of dinuclear manganese cofactors for bacterial reaction centers.

    PubMed

    Olson, Tien L; Espiritu, Eduardo; Edwardraja, Selvakumar; Simmons, Chad R; Williams, JoAnn C; Ghirlanda, Giovanna; Allen, James P

    2016-05-01

    A compelling target for the design of electron transfer proteins with novel cofactors is to create a model for the oxygen-evolving complex, a Mn4Ca cluster, of photosystem II. A mononuclear Mn cofactor can be added to the bacterial reaction center, but the addition of multiple metal centers is constrained by the native protein architecture. Alternatively, metal centers can be incorporated into artificial proteins. Designs for the addition of dinuclear metal centers to four-helix bundles resulted in three artificial proteins with ligands for one, two, or three dinuclear metal centers able to bind Mn. The three-dimensional structure determined by X-ray crystallography of one of the Mn-proteins confirmed the design features and revealed details concerning coordination of the Mn center. Electron transfer between these artificial Mn-proteins and bacterial reaction centers was investigated using optical spectroscopy. After formation of a light-induced, charge-separated state, the experiments showed that the Mn-proteins can donate an electron to the oxidized bacteriochlorophyll dimer of modified reaction centers, with the Mn-proteins having additional metal centers being more effective at this electron transfer reaction. Modeling of the structure of the Mn-protein docked to the reaction center showed that the artificial protein likely binds on the periplasmic surface similarly to cytochrome c2, the natural secondary donor. Combining reaction centers with exogenous artificial proteins provides the opportunity to create ligands and investigate the influence of inhomogeneous protein environments on multinuclear redox-active metal centers. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson.

  4. Chemical abundances of M giants in the Galactic centre: A single metal-rich population with low [α/Fe

    NASA Astrophysics Data System (ADS)

    Ryde, N.; Schultheis, M.

    2015-01-01

    Context. The formation and evolution of the Milky Way bulge is still largely an unanswered question. Some of the most essential observations needed for its modelling are the metallicity distribution and the trends of the α elements, as measured in stars. While bulge regions beyond R ≳ 50 pc of the centre have been targeted in several surveys, the central part has escaped a detailed study due to the extreme extinction and crowding. The abundance gradients from the centre are, however, of large diagnostic value. Aims: We aim at investigating the Galactic centre environment by probing M giants in the field by avoiding supergiants and cluster members. Methods: For nine field M-giants in the Galactic centre region, we have obtained high- and low-resolution spectra observed simultaneously with CRIRES and ISAAC on UT1 and UT3 of the VLT. The low-resolution spectra provide a means of determining the effective temperatures, and the high-resolution spectra provide detailed abundances of Fe, Mg, Si, and Ca. Results: We find a metal-rich population at [ Fe / H ] = + 0.11 ± 0.15 and a lack of the metal-poor population, which is found further out in the bulge, corroborating earlier studies. Our [α/Fe] element trends, however, show low values, by following the outer bulge trends. A possible exception of the [Ca/Fe] trend is found and needs further investigation. Conclusions: The results of the analysed field M-giants in the Galactic centre region exclude a scenario with rapid formation, in which SNIIe played a dominated role in the chemical enrichment of the gas. The high metallicities with low α-enhancement seems to indicate a bar-like population that is, perhaps, related to the nuclear bar. Based on observations collected at the European Southern Observatory, Chile, program number 089.B-0312(A)/VM/CRIRES and 089.B-0312(B)/VM/ISAAC.Figures 8 and 9 are available in electronic form at http://www.aanda.org

  5. Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

    PubMed

    Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

    2004-11-15

    The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

  6. Structural alteration of the metal-organic pyrogallol[4]arene nano-capsule motif by incorporation of large metal centres.

    PubMed

    Jin, Ping; Kumari, Harshita; Kennedy, Stuart; Barnes, Charles L; Teat, Simon J; Dalgarno, Scott J; Atwood, Jerry L

    2014-05-04

    Addition of cadmium(II) nitrate to gallium-coordinated metal-organic C-alkylpyrogallol[4]arene nano-capsules affords a variation of the near spherical hexamer motif, structural changes in which are induced by the markedly different nature of the secondary incorporated metal.

  7. Synthesis of a novel heptacoordinated Fe(III) dinuclear complex: experimental and theoretical study of the magnetic properties.

    PubMed

    Craig, Gavin A; Barrios, Leoní A; Sánchez Costa, José; Roubeau, Olivier; Ruiz, Eliseo; Teat, Simon J; Wilson, Chick C; Thomas, Lynne; Aromí, Guillem

    2010-05-28

    A new functionalized bis-pyrazol-pyridine ligand has been prepared by reaction with hydrazine of the corresponding bis-β-diketone precursor, also unprecedented. The aerobic reaction of this ligand with ferrous thiocyanate in the presence of ascorbic or oxalic acid affords the dinuclear complex of seven-coordinate Fe(III), [Fe₂(H₄L2)₂(ox)(NCS)₄] (1), as revealed by single crystal X-ray diffraction. This may represent an entry into a new family of [Fe₂] compounds with heptacoordinate metal centres. The capacity of this unusual chromophore to undergo magnetic super-exchange was investigated by means of bulk magnetization and DFT calculations. Both approaches confirmed the presence of antiferromagnetic interactions within the molecule. The theoretical investigation has served to describe the magnetic orbitals of Fe(III) in this unusual coordination geometry, as well as the exchange mechanism. A brief review of the scarce number of iron heptacoordinate complexes reported in the literature is also included and discussed.

  8. Validation of primary metal-on-metal hip arthroplasties on the National Joint Registry for England, Wales and Northern Ireland using data from the London Implant Retrieval Centre

    PubMed Central

    Sabah, S. A.; Henckel, J.; Cook, E.; Whittaker, R.; Hothi, H.; Pappas, Y.; Blunn, G.; Skinner, J. A.; Hart, A. J.

    2015-01-01

    Arthroplasty registries are important for the surveillance of joint replacements and the evaluation of outcome. Independent validation of registry data ensures high quality. The ability for orthopaedic implant retrieval centres to validate registry data is not known. We analysed data from the National Joint Registry for England, Wales and Northern Ireland (NJR) for primary metal-on-metal hip arthroplasties performed between 2003 and 2013. Records were linked to the London Implant Retrieval Centre (RC) for validation. A total of 67 045 procedures on the NJR and 782 revised pairs of components from the RC were included. We were able to link 476 procedures (60.9%) recorded with the RC to the NJR successfully. However, 306 procedures (39.1%) could not be linked. The outcome recorded by the NJR (as either revised, unrevised or death) for a primary procedure was incorrect in 79 linked cases (16.6%). The rate of registry-retrieval linkage and correct assignment of outcome code improved over time. The rates of error for component reference numbers on the NJR were as follows: femoral head category number 14/229 (5.0%); femoral head batch number 13/232 (5.3%); acetabular component category number 2/293 (0.7%) and acetabular component batch number 24/347 (6.5%). Registry-retrieval linkage provided a novel means for the validation of data, particularly for component fields. This study suggests that NJR reports may underestimate rates of revision for many types of metal-on-metal hip replacement. This is topical given the increasing scope for NJR data. We recommend a system for continuous independent evaluation of the quality and validity of NJR data. Cite this article: Bone Joint J 2015;97-B:10–18. PMID:25568407

  9. Unprecedented dinuclear silver(I)-mediated base pair involving the DNA lesion 1,N(6)-ethenoadenine.

    PubMed

    Mandal, Soham; Hepp, Alexander; Müller, Jens

    2015-02-28

    The DNA lesion 1,N(6)-ethenoadenine (εA) has been investigated with respect to its metal-binding properties. A synthetic DNA duplex comprising an εA : εA mispair readily forms doubly silver(I)-mediated base pairs εA-Ag(I)2-εA, representing the first example for a dinuclear metal-mediated homo base pair of a purine derivative. It also constitutes the first example for a Hoogsteen-type metal-mediated homo base pair within a B-DNA duplex.

  10. Crystal structure of a mixed-ligand dinuclear Ba-Zn complex with 2-meth-oxy-ethanol having tri-phenyl-acetate and chloride bridges.

    PubMed

    Utko, Józef; Sobocińska, Maria; Dobrzyńska, Danuta; Lis, Tadeusz

    2015-07-01

    The dinuclear barium-zinc complex, μ-chlorido-1:2κ(2) Cl:Cl-chlorido-2κCl-bis-(2-meth-oxy-ethanol-1κO)bis-(2-meth-oxy-ethanol-1κ(2) O,O')bis-(μ-tri-phenyl-acetato-1:2κ(2) O:O')bariumzinc, [BaZn(C20H15O2)2Cl2(C3H8O2)4], has been synthesized by the reaction of barium tri-phenyl-acetate, anhydrous zinc chloride and 2-meth-oxy-ethanol in the presence of toluene. The barium and zinc metal cations in the dinuclear complex are linked via one chloride anion and carboxyl-ate O atoms of the tri-phenyl-acetate ligands, giving a Ba⋯Zn separation of 3.9335 (11) Å. The irregular nine-coordinate BaO8Cl coordination centres comprise eight O-atom donors, six of them from 2-meth-oxy-ethanol ligands (four from two bidentate O,O'-chelate inter-actions and two from monodentate inter-actions), two from bridging tri-phenyl-acetate ligands and one from a bridging Cl donor. The distorted tetra-hedral coordination sphere of zinc comprises two O-atom donors from the tri-phenyl-acetate ligands and two Cl donors (one bridging and one terminal). In the crystal, O-H⋯Cl, O-H⋯O and C-H⋯Cl inter-molecular inter-actions form a layered structure, lying parallel to (001).

  11. Metal levels in seston and marine fish flesh near industrial and metropolitan centres in South Australia.

    PubMed

    Edwards, J W; Edyvane, K S; Boxall, V A; Hamann, M; Soole, K L

    2001-05-01

    Port Pirie is the site of the largest lead smelter in the world, depositing 250 t of zinc, and 100 t of lead annually into Spencer Gulf. Barker Inlet is adjacent to metropolitan Adelaide, and receives unknown quantities of urban and industrial discharges. Both areas are sites of major commercial and recreational fisheries, contained within delicately balanced marine wetland ecosystems, comprising large areas of mangrove and seagrass habitats. Aldrichetta forsteri and Sillago schomburgkii are major species within these fisheries and as estuarine-dependent species were chosen for this study as indicator species for the detection and monitoring of pollutant impacts in the nearshore marine ecosystems of South Australia. Seston sediment collectors were deployed at each site and analysed seasonally for the presence of cadmium, lead and copper. Flesh samples from A. forsteri and S. schomburgkii were examined seasonally for the presence of cadmium, lead and copper and the results correlated with levels found in the seston sediment at each site. Metal concentrations were also correlated with a biomarker of genotoxicity measured in the same animals (micronuclei in erythrocytes) that were reported previously. Seston levels of cadmium, lead and copper were highest at Port Pirie, followed by Barker Inlet and were lowest at Wills Creek, with cadmium undetectable at the latter site. Metals in seston varied considerably with season, with generally higher levels in winter samples. In fish flesh, metal levels followed broadly similar trends as for seston. Spearman rank correlations between metals in seston and in flesh were strongly positive. There was also a significant correlation between flesh concentrations of each metal and the frequency of micronuclei in erythrocytes. This study has shown that seston concentration of pollutant metals are high in areas of industrial activity, and that these levels are also reflected in metal content of fish flesh. Mean flesh levels of cadmium

  12. Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

    2015-08-01

    Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s-1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

  13. Geometries of low spin states of multi-centre transition metal complexes through extended broken symmetry variational Monte Carlo

    NASA Astrophysics Data System (ADS)

    Barborini, Matteo; Guidoni, Leonardo

    2016-09-01

    The correct description of the ground state electronic and geometrical properties of multi-centre transition metal complexes necessitates of a high-level description of both dynamical and static correlation effects. In di-metallic complexes, the ground state low spin properties can be computed starting from single-determinants High-Spin (HS) and Broken Symmetry (BS) states by reconstructing an approximated low spin potential energy surface through the extended broken symmetry approach, based on the Heisenberg Hamiltonian. In the present work, we first apply this approach within the variational Monte Carlo method to tackle the geometry optimization of a Fe2S2(SH)42- model complex. To describe the HS and BS wavefunctions, we use a fully optimized unrestricted single determinant with a correlated Jastrow factor able to recover a large amount of dynamical correlation. We compared our results with those obtained by density functional theory and other multiconfigurational approaches, discussing the role of the nodal surface on the structural parameters.

  14. Geometries of low spin states of multi-centre transition metal complexes through extended broken symmetry variational Monte Carlo.

    PubMed

    Barborini, Matteo; Guidoni, Leonardo

    2016-09-28

    The correct description of the ground state electronic and geometrical properties of multi-centre transition metal complexes necessitates of a high-level description of both dynamical and static correlation effects. In di-metallic complexes, the ground state low spin properties can be computed starting from single-determinants High-Spin (HS) and Broken Symmetry (BS) states by reconstructing an approximated low spin potential energy surface through the extended broken symmetry approach, based on the Heisenberg Hamiltonian. In the present work, we first apply this approach within the variational Monte Carlo method to tackle the geometry optimization of a Fe2S2(SH)4(2-) model complex. To describe the HS and BS wavefunctions, we use a fully optimized unrestricted single determinant with a correlated Jastrow factor able to recover a large amount of dynamical correlation. We compared our results with those obtained by density functional theory and other multiconfigurational approaches, discussing the role of the nodal surface on the structural parameters.

  15. Theory of magnetoresistance due to lattice dislocations in face-centred cubic metals

    NASA Astrophysics Data System (ADS)

    Bian, Q.; Niewczas, M.

    2016-06-01

    A theoretical model to describe the low temperature magneto-resistivity of high purity copper single and polycrystals containing different density and distribution of dislocations has been developed. In the model, magnetoresistivity tensor is evaluated numerically using the effective medium approximation. The anisotropy of dislocation-induced relaxation time is considered by incorporating two independent energy bands with different relaxation times and the spherical and cylindrical Fermi surfaces representing open, extended and closed electron orbits. The effect of dislocation microstructure is introduced by means of two adjustable parameters corresponding to the length and direction of electron orbits in the momentum space, which permits prediction of magnetoresistance of FCC metals containing different density and distribution of dislocations. The results reveal that dislocation microstructure influences the character of the field-dependent magnetoresistivity. In the orientation of the open orbits, the quadratic variation in magnetoresistivity changes to quasi-linear as the density of dislocations increases. In the closed orbit orientation, dislocations delay the onset of magnetoresistivity saturation. The results indicate that in the open orbit orientations of the crystals, the anisotropic relaxation time due to small-angle dislocation scattering induces the upward deviation from Kohler's rule. In the closed orbit orientations Kohler's rule holds, independent of the density of dislocations. The results obtained with the model show good agreement with the experimental measurements of transverse magnetoresistivity in deformed single and polycrystal samples of copper at 2 K.

  16. Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.

    PubMed

    Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

    2015-04-01

    Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.

  17. Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands.

    PubMed

    Hochreuther, Stephanie; Puchta, Ralph; van Eldik, Rudi

    2011-12-19

    A series of novel dinuclear platinum(II) complexes were synthesized containing a mixed nitrogen-sulfur donor bidentate chelate system in which the two platinum centers are connected by an aliphatic chain of variable length. The bidentate chelating ligands were selected to stabilize the complex toward decomposition. The pK(a) values and reactivity of the four synthesized complexes, namely, [Pt(2)(S(1),S(4)-bis(2-pyridylmethyl)-1,4-butanedithioether)(OH(2))(4)](4+) (4NSpy), [Pt(2)(S(1),S(6)-bis(2-pyridylmethyl)-1,6-hexanedithioether)(OH(2))(4)](4+) (6NSpy), [Pt(2)(S(1),S(8)-bis(2-pyridylmethyl)-1,8-octanedithioether)(OH(2))(4)](4+) (8NSpy), and [Pt(2)(S(1),S(10)-bis(2-pyridylmethyl)-1,10-decanedithioether)(OH(2))(4)](4+) (10NSpy), were investigated. This system is of special interest because only little is known about the substitution behavior of dinuclear platinum complexes that contain a bidentate chelate that forms part of the aliphatic bridging ligand. Moreover, the ligands as well as the dinuclear complexes were examined in terms of their cytotoxic activity, and the 10NSpy complex was found to be active. Spectrophotometric acid-base titrations were performed to determine the pK(a) values of all the coordinated water molecules. The substitution of coordinated water by thiourea was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV-vis spectroscopy. The results for the dinuclear complexes were compared to those for the corresponding mononuclear reference complex [Pt(methylthiomethylpyridine)(OH(2))(2)](2+) (Pt(mtp)), by which the effect of the increasing aliphatic chain length of the bridged complexes could be investigated. The results indicate that there is a clear interaction between the two platinum centers, which becomes weaker as the chain length between the metal centers increases. Furthermore, differences and similarities of the N,S-system were compared to

  18. Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

    PubMed Central

    Benkhäuser, Christian

    2015-01-01

    Summary A Tröger's base-derived racemic bis(1,10-phenanthroline) ligand (rac)-1 and a bis(2,2'-bipyridine) ligand with a central 1,3-diethynylbenzene unit 2 were synthesized. Each of these ligands acts as a multivalent entity for the binding of two copper(I) ions. Upon coordination to the metal ions these two ligands undergo selective self-assembly into heteroleptic dinuclear metallosupramolecular kites in a high-fidelity social self-sorting manner as evidenced by NMR spectroscopy and mass spectrometry. PMID:26124873

  19. Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

    PubMed

    Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

    2010-02-01

    Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

  20. Dinuclear copper complexes with imidazole derivative ligands: a theoretical study related to catechol oxidase activity.

    PubMed

    Martínez, Ana; Membrillo, Ingrid; Ugalde-Saldívar, Victor M; Gasque, Laura

    2012-07-19

    Catechol oxidase is a very important and interesting metalloprotein. In spite of the efforts to understand the reaction mechanism of this protein, there are important questions that remain unanswered concerning the catalytic mechanism of this enzyme. In this article, dinuclear copper compounds are used as biomimetic models of catechol oxidase to study plausible reaction paths. These dinuclear copper(II) complexes have distant metal centers (of 7.5 Å approximately) and superior catalytic activity to that of many dicopper complexes with shorter Cu-Cu distances. One mononuclear copper(II) complex is also analyzed in this investigation in order to see the influence of the two metal centers in the catalytic activity. Density functional theory calculations were performed to obtain optimized structures, vertical ionization energies, vertical electron affinities, the electrodonating power (ω(-)), the electroaccepting power (ω(+)) and the energy difference of several reaction paths. The K(M) experimental results that were previously reported compare well with the electroaccepting power (ω(+)) of the copper compounds that are included in this article, indicating that this index is useful for the interpretation of the electron transfer capacity and therefore the catalytic activity. The catechol moiety coordinates to only one Cu ion, but two metal atoms are needed in order to have a good electron acceptor capacity of the biomimetic models.

  1. Synthesis, structural characterization, cytotoxic properties and DNA binding of a dinuclear copper(II) complex.

    PubMed

    Ferreira, B J M Leite; Brandão, P; Meireles, M; Martel, Fátima; Correia-Branco, Ana; Fernandes, Diana M; Santos, T M; Félix, V

    2016-08-01

    In this study a novel dinuclear copper(II) complex with adenine and phenanthroline has been synthesized and its structure determined by single crystal X-ray diffraction. In the dinuclear complex [Cu₂(μ-adenine)₂(phen)₂(H2O)2](NO3)4·0.5H2O (phen=1,10-phenanthroline) (1) the two Cu(II) centres exhibit a distorted square pyramidal coordination geometry linked by two nitrogen donors from adenine bridges leading to a Cu-Cu distance of 3.242(3)Å. Intramolecular and intermolecular π⋯π interactions as well as an H-bonding network were observed. The antitumor capacity of the complex has been tested in vitro against human cancer cell lines, cervical carcinoma (HeLa) and colorectal adenocarcinoma (Caco-2), by metabolic tests, using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide as reagent. The complex 1 has remarkable low IC50 values of 0.87±0.06μM (HeLa) and 0.44±0.06μM (Caco-2), when compared with values for cisplatin against the same cell lines. The interaction of complex 1 with calf thymus DNA (CT DNA) was further investigated by absorption and fluorescence spectroscopic methods. A binding constant of 5.09×10(5)M(-1) was obtained from UV-vis absorption studies.

  2. Pyrazole bridged dinuclear Cu(II) and Zn(II) complexes as phosphatase models: Synthesis and activity

    NASA Astrophysics Data System (ADS)

    Naik, Krishna; Nevrekar, Anupama; Kokare, Dhoolesh Gangaram; Kotian, Avinash; Kamat, Vinayak; Revankar, Vidyanand K.

    2016-12-01

    Present work describes synthesis of dibridged dinuclear [Cu2L2(μ2-NN pyr)(NO3)2(H2O)2] and [Zn2L(μ-OH)(μ-NNpyr)(H2O)2] complexes derived from a pyrazole based ligand bis(2-hydroxy-3-methoxybenzylidene)-1H-pyrazole-3,5-dicarbohydrazide. The ligand shows dimeric chelate behaviour towards copper against monomeric for zinc counterpart. Spectroscopic evidences affirm octahedral environment around the metal ions in solution state and non-electrolytic nature of the complexes. Both the complexes are active catalysts towards phosphomonoester hydrolysis with first order kcat values in the range of 2 × 10-3s-1. Zinc complex exhibited promising catalytic efficiency for the hydrolysis. The dinuclear complexes hydrolyse via Lewis acid activation, whereby the phosphate esters are preferentially bound in a bidentate bridging fashion and subsequent nucleophilic attack to release phosphate group.

  3. Formation, characterization and computational studies of mono- and dinuclear rhenium(I) chromone compounds

    NASA Astrophysics Data System (ADS)

    Ebinumoliseh, Ifeoma; Booysen, Irvin Noel; Akerman, Matthew Piers; Xulu, Bheki

    2016-11-01

    Herein, we report the formation and characterization of a novel dinuclear rhenium(I) compound, fac-(Re(CO)3Br)2(μ-chret) (1) [chret = N, N'-bis(2-amino-3-imino)methylenechromone-1,2-ethane] and a mononuclear metal complex, fac-[Re(CO)3(bzch)Br] (2) [bzch = 2-benzimidazole-4H-chromen-4-one]. The metal complexes were characterized by 1H NMR-, IR-, UV-Vis, melting point and conductivity measurements. The solid-state structures for 1 and 2 were confirmed via single crystal X-ray analysis. X-ray studies of 2 revealed the transformation of the chb diimine into the bzch chelator (in 2). The simulated IR spectra for the respective metal complexes provided insight in the interpretation of their corresponding experimental spectra.

  4. Collective dynamics of a dinuclear system

    NASA Astrophysics Data System (ADS)

    Mshelia, E. D.; Scheid, W.

    . There are theoretical and experimental evidences that show that the cluster model, consisting of a dinuclear system, is capable of explaining several features of deformed heavy nuclei. Examples are the fusion to super-heavy nuclei and the nuclear-structure effects arising from parity splitting in alternating rotational parity bands, especially of the actinide nuclei. The model developed by Shneidman et al. has been able to explain the parity splitting in the actinides using the cluster model in which oscillations in mass asymmetry and relative motion were considered. On the other hand, Hess and Greiner developed a model for nuclear molecules in which the degrees of freedom of butterfly, belly-dancer-type motions, γ - and β -vibrations of individual nuclei were incorporated. The purpose of this work is to extend the model of Shneidman et al. to include some of the degrees of freedom in the work of Hess et al. and, in addition, to consider nuclear molecular rotations and the coupling of these degrees of freedom among themselves, arising from mass asymmetry.

  5. New discrete and polymeric supramolecular architectures derived from dinuclear (bis-beta-diketonato)copper(II) metallocycles.

    PubMed

    Clegg, Jack K; Gloe, Karsten; Hayter, Michael J; Kataeva, Olga; Lindoy, Leonard F; Moubaraki, Boujemaa; McMurtrie, John C; Murray, Keith S; Schilter, David

    2006-09-07

    New examples of adducts between di- (and, in one instance, tetra-) functional nitrogen ligands and planar 'platform-like' dinuclear copper(II) complexes, [Cu2L2], incorporating the 1,3-aryl linked bis-beta-diketonato bridging ligand 1,1'-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L) have been synthesised. The X-ray structures of six adduct species are reported. The interaction of [Cu2(L)2] with the ditopic ligand aminopyrazine (apyz) yielded the sandwich-like tetranuclear species [(Cu2L2(apyz))2]. A variable-temperature magnetochemical investigation of this product indicated weak antiferromagnetic coupling between the (five-coordinate) copper centres, mediated by the 2-aminopyrazine linkers. An analogous structure, [(Cu2L2(dabco))2] (dabco=1,4-diazabicyclo[2.2.2]octane), was generated when dabco was substituted for aminopyrazine while use of 4,4'-dipyridyl sulfide (dps) and 4,4'-(1,3-xylylene)-bis(3,5-dimethylpyrazole) (xbp) as the ditopic 'spacer' ligands resulted in polymeric species of type [Cu2L2(dps)]n and [Cu2L2(xbp)]n, respectively. These latter species exist as one-dimensional chain structures in which copper(II) centres on different dinuclear platforms are linked in a 'zigzag' fashion. In contrast, with 2,2'-dipyridylamine (dpa) a discrete complex of type [Cu2L2(dpa)2] formed in which one potential pyridyl donor from each 2,2'-dipyridylamine ligand remains uncoordinated. The use of the potentially quadruply-bridging hexamethylenetetramine (hmt) ligand as the linker unit was found to give rise to an unusual two-dimensional polymeric motif of type [(Cu2(L2)2)3(hmt)2]n. The product takes the form of a (6,3) network, incorporating triply bridging hexamethylenetetramine units.

  6. Conserved histidine residues at the ferroxidase centre of the Campylobacter jejuni Dps protein are not strictly required for metal binding and oxidation.

    PubMed

    Sanchuki, Heloisa B S; Valdameri, Glaucio; Moure, Vivian R; Rodriguez, Jorge A; Pedrosa, Fábio O; Souza, Emanuel M; Korolik, Victoria; Ribeiro, Ronny Rocha; Huergo, Luciano F

    2016-01-01

    Iron is an essential micronutrient for living organisms as it is involved in a broad variety of important biological processes. However, free iron inside the cell could be potentially toxic, generating hydroxyl radicals through the Fenton reaction. Dps (DNA-binding protein from starved cells) belongs to a subfamily of ferritins and can store iron atoms inside the dodecamer. The presence of a ferroxidase centre, composed of highly conserved residues, is a signature of this protein family. In this study, we analysed the role of two conserved histidine residues (H25 and H37) located at the ferroxidase centre of the Campylobacter jejuni Dps protein by replacing them with glycine residues. The C. jejuni H25G/H37G substituted variant showed reduced iron binding and ferroxidase activities in comparison with wt Dps, while DNA-binding activity remained unaffected. We also found that both CjDps wt and CjDps H25G/H37G were able to bind manganese atoms. These results indicate that the H25 and H37 residues at the ferroxidase centre of C. jejuni Dps are not strictly required for metal binding and oxidation.

  7. Mono- and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms.

    PubMed

    Ye, Rui-Rong; Tan, Cai-Ping; Chen, Mu-He; Hao, Liang; Ji, Liang-Nian; Mao, Zong-Wan

    2016-06-01

    Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes (Re1 and Re2), along with their corresponding dinuclear complexes (Re3 and Re4), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1-Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase-independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase-independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes.

  8. Nanodiamond-based nanostructures for coupling nitrogen-vacancy centres to metal nanoparticles and semiconductor quantum dots

    NASA Astrophysics Data System (ADS)

    Gong, Jianxiao; Steinsultz, Nat; Ouyang, Min

    2016-06-01

    The ability to control the interaction between nitrogen-vacancy centres in diamond and photonic and/or broadband plasmonic nanostructures is crucial for the development of solid-state quantum devices with optimum performance. However, existing methods typically employ top-down fabrication, which restrict scalable and feasible manipulation of nitrogen-vacancy centres. Here, we develop a general bottom-up approach to fabricate an emerging class of freestanding nanodiamond-based hybrid nanostructures with external functional units of either plasmonic nanoparticles or excitonic quantum dots. Precise control of the structural parameters (including size, composition, coverage and spacing of the external functional units) is achieved, representing a pre-requisite for exploring the underlying physics. Fine tuning of the emission characteristics through structural regulation is demonstrated by performing single-particle optical studies. This study opens a rich toolbox to tailor properties of quantum emitters, which can facilitate design guidelines for devices based on nitrogen-vacancy centres that use these freestanding hybrid nanostructures as building blocks.

  9. Nanodiamond-based nanostructures for coupling nitrogen-vacancy centres to metal nanoparticles and semiconductor quantum dots

    SciTech Connect

    Gong, Jianxiao; Steinsultz, Nat; Ouyang, Min

    2016-06-08

    The ability to control the interaction between nitrogen-vacancy centres in diamond and photonic and/or broadband plasmonic nanostructures is crucial for the development of solid-state quantum devices with optimum performance. However, existing methods typically employ top-down fabrication, which restrict scalable and feasible manipulation of nitrogen-vacancy centres. Here, we develop a general bottom-up approach to fabricate an emerging class of freestanding nanodiamond-based hybrid nanostructures with external functional units of either plasmonic nanoparticles or excitonic quantum dots. Precise control of the structural parameters ( including size, composition, coverage and spacing of the external functional units) is achieved, representing a pre-requisite for exploring the underlying physics. Fine tuning of the emission characteristics through structural regulation is demonstrated by performing single-particle optical studies. Lastly, this study opens a rich toolbox to tailor properties of quantum emitters, which can facilitate design guidelines for devices based on nitrogen vacancy centres that use these freestanding hybrid nanostructures as building blocks.

  10. Nanodiamond-based nanostructures for coupling nitrogen-vacancy centres to metal nanoparticles and semiconductor quantum dots

    DOE PAGES

    Gong, Jianxiao; Steinsultz, Nat; Ouyang, Min

    2016-06-08

    The ability to control the interaction between nitrogen-vacancy centres in diamond and photonic and/or broadband plasmonic nanostructures is crucial for the development of solid-state quantum devices with optimum performance. However, existing methods typically employ top-down fabrication, which restrict scalable and feasible manipulation of nitrogen-vacancy centres. Here, we develop a general bottom-up approach to fabricate an emerging class of freestanding nanodiamond-based hybrid nanostructures with external functional units of either plasmonic nanoparticles or excitonic quantum dots. Precise control of the structural parameters ( including size, composition, coverage and spacing of the external functional units) is achieved, representing a pre-requisite for exploring themore » underlying physics. Fine tuning of the emission characteristics through structural regulation is demonstrated by performing single-particle optical studies. Lastly, this study opens a rich toolbox to tailor properties of quantum emitters, which can facilitate design guidelines for devices based on nitrogen vacancy centres that use these freestanding hybrid nanostructures as building blocks.« less

  11. Nanodiamond-based nanostructures for coupling nitrogen-vacancy centres to metal nanoparticles and semiconductor quantum dots

    PubMed Central

    Gong, Jianxiao; Steinsultz, Nat; Ouyang, Min

    2016-01-01

    The ability to control the interaction between nitrogen-vacancy centres in diamond and photonic and/or broadband plasmonic nanostructures is crucial for the development of solid-state quantum devices with optimum performance. However, existing methods typically employ top-down fabrication, which restrict scalable and feasible manipulation of nitrogen-vacancy centres. Here, we develop a general bottom-up approach to fabricate an emerging class of freestanding nanodiamond-based hybrid nanostructures with external functional units of either plasmonic nanoparticles or excitonic quantum dots. Precise control of the structural parameters (including size, composition, coverage and spacing of the external functional units) is achieved, representing a pre-requisite for exploring the underlying physics. Fine tuning of the emission characteristics through structural regulation is demonstrated by performing single-particle optical studies. This study opens a rich toolbox to tailor properties of quantum emitters, which can facilitate design guidelines for devices based on nitrogen-vacancy centres that use these freestanding hybrid nanostructures as building blocks. PMID:27273426

  12. Nuclear structure in the dinuclear model with rotating clusters

    SciTech Connect

    Adamian, G. G.; Antonenko, N. V.; Jolos, R. V.; Palchikov, Yu. V.; Shneidman, T. M.; Scheid, W.

    2007-08-15

    The dinuclear-system model can be applied to nuclear structure. Here, we study deformed clusters which rotate with respect to the internuclear distance and exchange nucleons. The model can be used to explain the band structure of nuclear spectra, especially the parity splitting observed in actinides, e.g., in {sup 238}U.

  13. Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

    PubMed Central

    2013-01-01

    Background Various dinuclear copper (II) complexes with octahedral geometry have been reported. The majority of these complexes contain N containing aromatic rings as axial ligands. There are also a few cases where the solvent used in the reaction occupies the axial position of the dinuclear copper (II) complex. This may occur by planned synthesis or some times by serendipity. Here we report some four copper (II) complexes containing solvent and or N containing heterocyclic ring as the axial ligand. Results Four compounds, each containing dinuclear Copper (II) units (with the most robust, frequently occurring paddle wheel structures) were synthesized and characterised by single crystal X-ray diffraction and by IR spectroscopy. The compounds 1 & 2 have the general formula Cu2(RCOO) 4(L)2 [(for (1) RCOO= 4-Chloro Benzoate, L= Isopropanol; for 2 RCOO= Benzoate, L= 2-Amino-4,6-dimethyl pyrimidine )] while 3 & 4 have the general formula, Cu2(RCOO) 4(S)2 Cu2(RCOO) 4(L)2 [RCOO=5-Chloro-thiophene-2-carboxylate L= 2-Amino-4,6-dimethyl pyrimidine, for 3 S= ethanol; for 4 S= methanol ]. A wide range of hydrogen bonds (of the O-H…O, N-H…O and N-H…N type) and π-π stacking interactions are present in the crystal structures. Conclusions All compounds contain the dinuclear units, in which two Cu (II) ions are bridged by four syn, syn-η1:η1:μ carboxylates, showing a paddle-wheel cage type with a distorted octahedral geometry. The compounds 1 &2 contain a single dimeric unit while 3 &4 contain two dimeric units. The structures 3 and 4 are very interesting co-crystals of two paddle wheel molecules. Also it is interesting to note that the compounds 3 &4 are isostructural with similar cell parameters. Both the compounds 3 &4 differ in the solvent molecule coordinated to copper in one of the dimeric units. In all the four compounds, each of the copper dimers has an inversion centre. Every copper has a distorted octahedral centre, formed by four oxygen atoms (from different

  14. A heterotrimetallic Ir(III), Au(III) and Pt(II) complex incorporating cyclometallating bi- and tridentate ligands: simultaneous emission from different luminescent metal centres leads to broad-band light emission.

    PubMed

    Muñoz-Rodríguez, Rebeca; Buñuel, Elena; Fuentes, Noelia; Williams, J A Gareth; Cárdenas, Diego J

    2015-05-14

    Di- and tri-nuclear metal complexes incorporating gold(III), iridium(III) and platinum(II) units linked via a 1,3,5-triethynylbenzene core are reported, together with the corresponding mononuclear complexes as models. The gold(III) and platinum(II) units comprise tridentate, cyclometallating, C^N^C and N^N^C-coordinating ligands, respectively, with the Ar-C≡C- directly bound to the metal at the fourth coordination site. The iridium moiety is an Ir(ppy)2(acac) unit bound to the triethynylbenzene through a phenyl substituent at the 3-position of the acac ligand. The multinuclear compounds are prepared, using a modular synthetic strategy, from the monometallic complexes. All of the compounds are luminescent in solution at room temperature, and their photophysical properties were studied. The triplet excited state energies of the mononuclear complexes lie in the order Au > Ir > Pt. Consistent with this order, energy transfer from Au to Ir and from Au to Pt is observed, leading to quenching of the Au emission in the gold-containing multinuclear complexes. Energy transfer from Ir to Pt occurs at a rate that only partially quenches the Ir-based emission. As a result, the dinuclear Ir-Pt and trinuclear Au-Ir-Pt complexes display broad emission across most of the visible region of the spectrum.

  15. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    SciTech Connect

    Qin, Ling; Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  16. Chalcogenide centred gold complexes.

    PubMed

    Gimeno, M Concepción; Laguna, Antonio

    2008-09-01

    Chalcogenide-centred gold complexes are an important class of compounds in which a central chalcogen is surrounded by several gold atoms or gold and other metals. They have special characteristics such as unusual geometries, electron deficiency and properties such as luminescence or non-linear optical properties. The best known species are the trinuclear [E(AuPR3)3]+, 'oxonium' type species, that have high synthetic applicability, not only in other chalcogen-centred species, but in many other organometallic derivatives. The aurophilic interactions play an important role in the stability, preference for a particular geometry and luminescence properties in this type of derivatives (critical review, 117 references).

  17. Retrospective cohort study of the performance of the Pinnacle metal on metal (MoM) total hip replacement: a single-centre investigation in combination with the findings of a national retrieval centre

    PubMed Central

    Langton, David John; Sidaginamale, Raghavendra Prasad; Avery, Peter; Waller, Sue; Tank, Ghanshyabhai; Lord, James; Joyce, Thomas; Cooke, Nick; Logishetty, Raj; Nargol, Antoni Viraf Francis

    2016-01-01

    Objectives To determine risk factors for revision in patients implanted with a commonly used metal on metal (MoM) hip replacement. Design Retrospective cohort study in combination with a prospective national retrieval study (Northern Retrieval Registry (NRR)). Setting Combined orthopaedic unit in combination with the NRR. Participants All patients implanted with a DePuy Pinnacle MoM hip prostheses by the 2 senior authors were invited to attend for a review which included clinical examination, blood metal ion measurements, radiographs and targeted imaging. Explanted components underwent wear analysis using validated methodology and these results were compared with those obtained from the NRR. Results 489 MoM Pinnacle hips were implanted into 434 patients (243 females and 191 males). Of these, 352 patients attended the MoM recall clinics. 64 patients had died during the study period. For the purposes of survival analysis, non-attendees were assumed to have well-functioning prostheses. The mean follow-up of the cohort as a whole was 89 months. 71 hips were revised. Prosthetic survival for the whole cohort was 83.6% (79.9–87.3) at 9 years. The majority of explanted devices exhibited signs of taper junction failure. Risk factors for revision were bilateral MoM prostheses, smaller Pinnacle liners, and implantation in 2006 and later years. A significant number of devices were found to be manufactured out of their specifications. This was confirmed with analysis of the wider data set from the NRR. Conclusions This device was found to have an unacceptably high revision rate. Bilateral prostheses, those implanted into female patients and devices implanted in later years were found to be at greater risk. A significant number of explanted components were found to be manufactured with bearing diameters outside of the manufacturer's stated tolerances. Our findings highlight the clinical importance of hitherto unrecognised variations in device production. PMID:27130159

  18. Validation of primary metal-on-metal hip arthroplasties on the National Joint Registry for England, Wales and Northern Ireland using data from the London Implant Retrieval Centre: a study using the NJR dataset.

    PubMed

    Sabah, S A; Henckel, J; Cook, E; Whittaker, R; Hothi, H; Pappas, Y; Blunn, G; Skinner, J A; Hart, A J

    2015-01-01

    Arthroplasty registries are important for the surveillance of joint replacements and the evaluation of outcome. Independent validation of registry data ensures high quality. The ability for orthopaedic implant retrieval centres to validate registry data is not known. We analysed data from the National Joint Registry for England, Wales and Northern Ireland (NJR) for primary metal-on-metal hip arthroplasties performed between 2003 and 2013. Records were linked to the London Implant Retrieval Centre (RC) for validation. A total of 67,045 procedures on the NJR and 782 revised pairs of components from the RC were included. We were able to link 476 procedures (60.9%) recorded with the RC to the NJR successfully. However, 306 procedures (39.1%) could not be linked. The outcome recorded by the NJR (as either revised, unrevised or death) for a primary procedure was incorrect in 79 linked cases (16.6%). The rate of registry-retrieval linkage and correct assignment of outcome code improved over time. The rates of error for component reference numbers on the NJR were as follows: femoral head category number 14/229 (5.0%); femoral head batch number 13/232 (5.3%); acetabular component category number 2/293 (0.7%) and acetabular component batch number 24/347 (6.5%). Registry-retrieval linkage provided a novel means for the validation of data, particularly for component fields. This study suggests that NJR reports may underestimate rates of revision for many types of metal-on-metal hip replacement. This is topical given the increasing scope for NJR data. We recommend a system for continuous independent evaluation of the quality and validity of NJR data.

  19. Towards accurate structural characterization of metal centres in protein crystals: the structures of Ni and Cu T{sub 6} bovine insulin derivatives

    SciTech Connect

    Frankaer, Christian Grundahl; Mossin, Susanne; Ståhl, Kenny; Harris, Pernille

    2014-01-01

    The level of structural detail around the metal sites in Ni{sup 2+} and Cu{sup 2+} T{sub 6} insulin derivatives was significantly improved by using a combination of single-crystal X-ray crystallography and X-ray absorption spectroscopy. Photoreduction and subsequent radiation damage of the Cu{sup 2+} sites in Cu insulin was followed by XANES spectroscopy. Using synchrotron radiation (SR), the crystal structures of T{sub 6} bovine insulin complexed with Ni{sup 2+} and Cu{sup 2+} were solved to 1.50 and 1.45 Å resolution, respectively. The level of detail around the metal centres in these structures was highly limited, and the coordination of water in Cu site II of the copper insulin derivative was deteriorated as a consequence of radiation damage. To provide more detail, X-ray absorption spectroscopy (XAS) was used to improve the information level about metal coordination in each derivative. The nickel derivative contains hexacoordinated Ni{sup 2+} with trigonal symmetry, whereas the copper derivative contains tetragonally distorted hexacoordinated Cu{sup 2+} as a result of the Jahn–Teller effect, with a significantly longer coordination distance for one of the three water molecules in the coordination sphere. That the copper centre is of type II was further confirmed by electron paramagnetic resonance (EPR). The coordination distances were refined from EXAFS with standard deviations within 0.01 Å. The insulin derivative containing Cu{sup 2+} is sensitive towards photoreduction when exposed to SR. During the reduction of Cu{sup 2+} to Cu{sup +}, the coordination geometry of copper changes towards lower coordination numbers. Primary damage, i.e. photoreduction, was followed directly by XANES as a function of radiation dose, while secondary damage in the form of structural changes around the Cu atoms after exposure to different radiation doses was studied by crystallography using a laboratory diffractometer. Protection against photoreduction and subsequent

  20. Reactions of Dinuclear Platinum(II) Complexes with Peptides.

    PubMed

    Rajković, Snežana; Živković, Marija D; Djuran, Miloš I

    2016-01-01

    The present review article highlights recent findings in the reactions between different dinuclear Pt(II) complexes with peptides containing cysteine, methionine and histidine residues. The reactions of {trans-[Pt(NH3)2Cl]2(μ-X)}(2+) and {trans-[Pt(NH3)2(H2O)]2(μ-X)}(4+) type complexes with different bridging ligands (X) (X = pyrazine, 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane) with the tripeptide glutathione proceeded in two steps. In the first step, one water or chlorido ligand of the dinuclear Pt(II) complex was substituted by the sulfhydryl group of GSH, while in the second step, the remaining water or chlorido ligand from the dinuclear Pt(II)-peptide complex was replaced by the second molecule of glutathione, finally leading to the formation of the {trans-[Pt(NH3)2(GS)]2(μ-X)}(2+) complex. It was shown that the bridging ligand had an important influence on the reactivity of these complexes with glutathione. No hydrolytic cleavage of any amide bond was observed in the reactions between these complexes and glutathione. However, in reactions performed in acidic media (2.0 < pH < 2.5) between dinuclear Pt(II) complexes with the general formulae {[Pt(L)(H2O)]2(μ-diazine)}(4+) (L is different bidentate coordinated diamine ligands and diazine is a pyrazine- or pyridazine-bridging ligand) and Nacetylated peptides containing L-methionine and L-histidine amino acids in the side chains (Ac-L-Met-Gly, Ac-L-His-Gly and Ac-L-Met-Gly-L-His-GlyNH2), regioselective cleavage of these peptides occurred. The mechanism of these hydrolytic reactions was discussed in relation to the structure of the diazine-bridged Pt(II) complex and the investigated peptides. A systematic summary of these results could contribute to the future design of new dinuclear Pt(II) complexes as potential reagents for regioselective cleavage of peptides and proteins.

  1. Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes

    PubMed Central

    Roux, Yoann; Ricoux, Rémy; Avenier, Frédéric; Mahy, Jean-Pierre

    2015-01-01

    Development of artificial systems, capable of delivering electrons to metal-based catalysts for the reductive activation of dioxygen, has been proven very difficult for decades, constituting a major scientific lock for the elaboration of environmentally friendly oxidation processes. Here we demonstrate that the incorporation of a flavin mononucleotide (FMN) in a water-soluble polymer, bearing a locally hydrophobic microenvironment, allows the efficient reduction of the FMN by NADH. This supramolecular entity is then capable of catalysing a very fast single-electron reduction of manganese(III) porphyrin by splitting the electron pair issued from NADH. This is fully reminiscent of the activity of natural reductases such as the cytochrome P450 reductases with kinetic parameters, which are three orders of magnitude faster compared with other artificial systems. Finally, we show as a proof of concept that the reduced manganese porphyrin activates dioxygen and catalyses the oxidation of organic substrates in water. PMID:26419885

  2. Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

    PubMed

    Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

    2015-05-01

    A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

  3. Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes

    SciTech Connect

    Harris, Travis V.; Morokuma, Keiji; Kurashige, Yuki; Yanai, Takeshi

    2014-02-07

    The applicability of ab initio multireference wavefunction-based methods to the study of magnetic complexes has been restricted by the quickly rising active-space requirements of oligonuclear systems and dinuclear complexes with S > 1 spin centers. Ab initio density matrix renormalization group (DMRG) methods built upon an efficient parameterization of the correlation network enable the use of much larger active spaces, and therefore may offer a way forward. Here, we apply DMRG-CASSCF to the dinuclear complexes [Fe{sub 2}OCl{sub 6}]{sup 2−} and [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+}. After developing the methodology through systematic basis set and DMRG M testing, we explore the effects of extended active spaces that are beyond the limit of conventional methods. We find that DMRG-CASSCF with active spaces including the metal d orbitals, occupied bridging-ligand orbitals, and their virtual double shells already capture a major portion of the dynamic correlation effects, accurately reproducing the experimental magnetic coupling constant (J) of [Fe{sub 2}OCl{sub 6}]{sup 2−} with (16e,26o), and considerably improving the smaller active space results for [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+} with (12e,32o). For comparison, we perform conventional MRCI+Q calculations and find the J values to be consistent with those from DMRG-CASSCF. In contrast to previous studies, the higher spin states of the two systems show similar deviations from the Heisenberg spectrum, regardless of the computational method.

  4. Solid state and solution characterization of a new dinuclear nickel (II) complex: The search for synthetic models for urease

    NASA Astrophysics Data System (ADS)

    Horn, Adolfo; Fim, Luciana; Bortoluzzi, Adailton J.; Szpoganicz, Bruno; Silva, Marlon de S.; Novak, Miguel A.; Neto, Mario Benassi; Eberlin, Lívia Schiavinato; Catharino, Rodrigo Ramos; Eberlin, Marcos Nogueira; Fernandes, Christiane

    2006-09-01

    The X-ray molecular structure and, magnetic, and spectroscopic properties, as well as the analysis of the structural behavior in solution of a novel nickel (II) complex [Ni 2(HBPClNOL) 2(OAc)](ClO 4) 1 are reported. Complex 1 was prepared by the reaction between the ligand H 2BPClNOL ( N-(2-hydroxybenzyl)- N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)]propylamine), [Ni(H 2O) 6](ClO 4) 2 and sodium acetate. Magnetic measurements indicate the presence of a weak antiferromagnetic coupling between the Ni(II) ions in 1, resulting in J = -4.23 cm -1. Mass spectrometric characterization of the complex 1 was also performed via ESI-MS and ESI-MS/MS experiments and reveals that there are at least three different cations in solution, one mononuclear [Ni(H 2BPClNOL)(OAc)] + and two dinuclear [Ni 2(HBPClNOL) 2(OAc)] + and [Ni 2(HBPClNOL) 2(ClO 4)] + cations, as well as likely a fourth one [Ni(HBPClNOL)] +. Potentiometric titration experiments confirm that under acid conditions, the dinuclear unit is broken. However, under neutral/basic pH values the dinuclear unit is stable and shows the presence of two water molecules coordinated to the nickel ions, resulting in the cation [Ni 2(HBPClNOL) 2(H 2O) 2] 2+. This cation shows two protonation/deprotonation equilibriums with p Ka values of 9.68 and at 10.29, which are related to the aquo/hydroxo equilibrium associated with the water molecules coordinated to the metal ions.

  5. Reactivity of dinuclear copper(II) complexes towards melanoma cells: Correlation with its stability, tyrosinase mimicking and nuclease activity.

    PubMed

    Nunes, Cléia Justino; Borges, Beatriz Essenfelder; Nakao, Lia Sumie; Peyroux, Eugénie; Hardré, Renaud; Faure, Bruno; Réglier, Marius; Giorgi, Michel; Prieto, Marcela Bach; Oliveira, Carla Columbano; Da Costa Ferreira, Ana M

    2015-08-01

    In this work, the influence of two new dinuclear copper(II) complexes in the viability of melanoma cells (B16F10 and TM1MNG3) was investigated, with the aim of verifying possible correlations between their cytotoxicity and their structure. One of the complexes had a polydentate dinucleating amine-imine ligand (complex 2), and the other a tridentate imine and a diamine-bridging ligand (complex 4). The analogous mononuclear copper(II) species (complexes 1 and 3, respectively) were also prepared for comparative studies. Crystal structure determination of complex 2 indicated a square-based pyramidal geometry around each copper, coordinated to three N atoms from the ligand and the remaining sites being occupied by either solvent molecules or counter-ions. Complex 4 has a tetragonal geometry. Interactions of these complexes with human albumin protein (HSA) allowed an estimation of their relative stabilities. Complementary studies of their reactivity towards DNA indicated that all of them are able of causing significant oxidative damage, with single and double strand cleavages, in the presence of hydrogen peroxide. However, nuclease activity of the dinuclear species was very similar and much higher than that of the corresponding mononuclear compounds. Although complex 2, with a more flexible structure, exhibits a much higher tyrosinase activity than complex 4, having a more rigid environment around the metal ion, both complexes showed comparable cytotoxicity towards melanoma cells. Corresponding mononuclear complexes showed to be remarkably less reactive as tyrosinase mimics as well as cytotoxic agents. Moreover, the dinuclear complexes showed higher cytotoxicity towards more melanogenic cells. The obtained results indicated that the structure of these species is decisive for its activity towards the malignant tumor cells tested.

  6. New dinuclear nickel(II) and iron(II) complexes with a macrocyclic ligand containing a N6S2 donor-set: synthesis, structural, MALDI-TOF-MS, magnetic and spectroscopic studies.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Macías, Alejandro; Valencia, Laura; Ribas, Joan; Capelo, José Luis; Lodeiro, Carlos

    2010-09-07

    A series of dinuclear Ni(II) and Fe(II) complexes with a Py(2)N(4)S(2) coordinating octadentate macrocyclic ligand L prepared by direct reactions have been studied. The overall geometry and bonding mode have been deduced on the basis of elemental analysis data, infrared, MALDI-TOF-MS, UV-vis spectroscopy, X-ray diffraction, conductivity and magnetic susceptibility measurements. In general both M(2+) centres are sited into the macrocyclic cavity coordinated to a pyridinic nitrogen atom, one sulfur atom, two secondary amine groups from the macrocyclic backbone and completing the coordination spheres with two solvent or anionic molecules in a distorted octahedral geometry, except in the case of [Ni(2)L(mu-Cl)(H(2)O)(2)](BF(4))(3).2H(2)O, where the metal ions are sited in the macrocyclic cavity coordinated to a pyridinic nitrogen atom, one sulfur atom, two secondary amine groups from the macrocyclic backbone, one water molecule and one chloride ion acting as a bridge between the two centres in a distorted octahedral geometry. The magnetic properties of the nickel(II) complexes, [Ni(2)L(CH(3)CN)(4)](BF(4))(4).3.5CH(3)CN (11) and [Ni(2)L(mu-Cl)(H(2)O)(2)](BF(4))(3).2H(2)O (12) has been recorded in the solid state and indicates an unexpected ferromagnetic exchange in both cases, especially in compound 11 because no similar systems are previously reported in the literature presenting this magnetic behaviour. Further complexes with similar ligands are in progress to corroborate this unexpected ferromagnetic behaviour.

  7. Testing bridge-mediated differences in dinuclear valence tautomeric behavior.

    PubMed

    Bin-Salamon, Sofi; Brewer, Scott H; Depperman, Ezra C; Franzen, Stefan; Kampf, Jeff W; Kirk, Martin L; Kumar, R Krishna; Lappi, Simon; Peariso, Katrina; Preuss, Kathryn E; Shultz, David A

    2006-05-29

    Two structurally characterized dinuclear valence tautomers are described. Cobalt ions are bridged by p- and m-phenylene units connected to 2,2'-bipyridines. X-ray crystal structures show that the molecules are in the [(Co(III))(Co(III))] forms at ca. 125 K, while spectroscopic studies show that both molecules can achieve the [(Co(II))(Co(II))] form above 400 K and confirm the [(Co(III))(Co(III))] form below 10 K. Magnetic susceptibility studies are also included. Our results highlight the necessity of studying both crystalline and amorphous samples to distinguish the effects of intrinsic electronic structure and intermolecular forces on valence tautomeric behavior.

  8. Rational design of a cytotoxic dinuclear Cu2 complex that binds by molecular recognition at two neighboring phosphates of the DNA backbone.

    PubMed

    Jany, Thomas; Moreth, Alexander; Gruschka, Claudia; Sischka, Andy; Spiering, Andre; Dieding, Mareike; Wang, Ying; Samo, Susan Haji; Stammler, Anja; Bögge, Hartmut; Fischer von Mollard, Gabriele; Anselmetti, Dario; Glaser, Thorsten

    2015-03-16

    The mechanism of the cytotoxic function of cisplatin and related anticancer drugs is based on their binding to the nucleobases of DNA. The development of new classes of anticancer drugs requires establishing other binding modes. Therefore, we performed a rational design for complexes that target two neighboring phosphates of the DNA backbone by molecular recognition resulting in a family of dinuclear complexes based on 2,7-disubstituted 1,8-naphthalenediol. This rigid backbone preorganizes the two metal ions for molecular recognition at the distance of two neighboring phosphates in DNA of 6-7 Å. Additionally, bulky chelating pendant arms in the 2,7-position impede nucleobase complexation by steric hindrance. We successfully synthesized the Cu(II)2 complex of the designed family of dinuclear complexes and studied its binding to dsDNA by independent ensemble and single-molecule methods like gel electrophoresis, precipitation, and titration experiments followed by UV-vis spectroscopy, atomic force microscopy (AFM), as well as optical tweezers (OT) and magnetic tweezers (MT) DNA stretching. The observed irreversible binding of our dinuclear Cu(II)2 complex to dsDNA leads to a blocking of DNA synthesis as studied by polymerase chain reactions and cytotoxicity for human cancer cells.

  9. Synthesis and cytotoxicity of dinuclear complexes containing ruthenium(II) bipyridyl units linked by a bis(pyridylimine) ligand.

    PubMed

    McDonnell, Ursula; Kerchoffs, Jessica M C A; Castineiras, Rosa P M; Hicks, Matthew R; Hotze, Anna C G; Hannon, Michael J; Rodger, Alison

    2008-02-07

    Enantiopure dinuclear ruthenium polypyridyl complexes of the form [Ru(2)(LL)(4)L(1)](PF(6))(4) (LL = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen); L(1)= C(25)H(20)N(4) a bis(pyridylimine) ligand containing a diphenylmethane spacer) have been synthesized using the chiral building blocks cis-[Ru(bpy)(2)(py)(2)](2+) and cis-[Ru(phen)(2)(py)(2)](2+). These dinuclear ruthenium complexes have been characterised using NMR, mass spectrometry, UV-visible absorbance, circular dichroism and linear dichroism. The compounds exhibit good photo and thermal stability. The extinction coefficient for the bpy complex at 478 nm is epsilon(478) = 15,700 mol(-1) cm(-1) dm(3) and for the phen complex is epsilon(478) = 24,900 mol(-1) cm(-1) dm(3). Both complexes have their longest wavelength (metal to ligand charge transfer) transition predominantly x/y (short axis)-polarised while the transitions at shorter wavelength are a mixture of x/y and z-polarisations, similar to both the copper helicate and iron triple helicate studied previously. Cytotoxicity studies reveal that the compounds are dramatically less active against cancer cell lines than the recently reported supramolecular cylinders prepared from the same bis(pyridylimine) ligand.

  10. Dinuclear Zinc Salen Catalysts for the Ring Opening Copolymerization of Epoxides and Carbon Dioxide or Anhydrides.

    PubMed

    Thevenon, Arnaud; Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

    2015-12-21

    A series of four dizinc complexes coordinated by salen or salan ligands, derived from ortho-vanillin and bearing (±)-trans-1,2-diaminocyclohexane (L1) or 2,2-dimethyl-1,3-propanediamine (L2) backbones, is reported. The complexes are characterized using a combination of X-ray crystallography, multinuclear NMR, DOSY, and MALDI-TOF spectroscopies, and elemental analysis. The stability of the dinuclear complexes depends on the ligand structure, with the most stable complexes having imine substituents. The complexes are tested as catalysts for the ring-opening copolymerization (ROCOP) of CO2/cyclohexene oxide (CHO) and phthalic anhydride (PA)/CHO. All complexes are active, and the structure/activity relationships reveal that the complex having both L2 and imine substituents displays the highest activity. In the ROCOP of CO2/CHO its activity is equivalent to other metal salen catalysts (TOF = 44 h(-1) at a catalyst loading of 0.1 mol %, 30 bar of CO2, and 80 °C), while for the ROCOP of PA/CHO, its activity is slightly higher than other metal salen catalysts (TOF = 198 h(-1) at a catalyst loading of 1 mol % and 100 °C). Poly(ester-block-carbonate) polymers are also afforded using the most active catalyst by the one-pot terpolymerization of PA/CHO/CO2.

  11. Homo-and heterodinuclear complexes of the tris(catecholamide) derivative of a tetraazamacrocycle with Fe3+, Cu2+ and Zn2+ metal ions.

    PubMed

    Guerra, Krassimira P; Delgado, Rita

    2008-01-28

    The new ditopic catecholamide 3,7,11-tris-{N-[3,4-(dihydroxybenzoyl)-aminopropyl]} derivative of a 14-membered tetraazamacrocycle containing pyridine (H(6)L(1)) has been synthesized. The protonation constants of (L(1))(6-) and the stability constants of its mono-, homo- and hetero-dinuclear complexes with Fe(3+), Cu(2+) and Zn(2+) metal ions were determined at 298.2 K and ionic strength 0.10 mol dm(-3) in KNO(3). The large overall basicity of the ligand was ascribed to the very high protonation constants of the catecholate groups, and its acid-base behaviour was correlated with the presence of tertiary nitrogen atoms and secondary amide functions. The UV-vis spectrum of the red solution of [FeL(1)](3-) complex exhibits the LMCT band of catecholate to iron(III), and its EPR spectrum revealed a typical isotropic signal of a rhombic distorted ferric centre in a high-spin state and E/D approximately 0.31, both characteristic of a tris-catecholate octahedral environment. The ligand forms with copper(II) and zinc(II) ions mono- and dinuclear protonated complexes and their stability constants were determined, except for the [ML(1)](4-) complexes as the last proton is released at very high pH. Electronic spectroscopic studies of the copper complexes revealed the involvement of catecholate groups in the coordination to the metal centre in the mono- and dinuclear copper(II) complexes. This information together with the determined stability constants indicated that the copper(II) ion can be involved in both types of coordination site of the ligand with comparable binding affinity. The EPR spectrum of [Cu(2)L(1)](2-) showed a well resolved seven-line hyperfine pattern of copper(II) dinuclear species typical of a paramagnetic triplet spin state with weak coupling between the two metal centres. Thermodynamically stable heterodinuclear complexes, [CuFeH(h)L(1)](h-1) (h = 0-3) and [CuZnH(h)L(1)](h-2) (h = 0-4), were formed as expected from a ditopic ligand having two dissimilar

  12. Zn(II) coordination to polyamine macrocycles containing dipyridine units. New insights into the activity of dinuclear Zn(II) complexes in phosphate ester hydrolysis.

    PubMed

    Bazzicalupi, Carla; Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Valtancoli, Barbara

    2004-10-04

    Zn(II) binding by the dipyridine-containing macrocycles L1-L3 has been analyzed by means of potentiometric measurements in aqueous solutions. These ligands contain one (L1, L2) or two (L3) 2,2'-dipyridine units as an integral part of a polyamine macrocyclic framework having different dimensions and numbers of nitrogen donors. Depending on the number of donors, L1-L3 can form stable mono- and/or dinuclear Zn(II) complexes in a wide pH range. Facile deprotonation of Zn(II)-coordinated water molecules gives mono- and dihydroxo-complexes from neutral to alkaline pH values. The ability of these complexes as nucleophilic agents in hydrolytic processes has been tested by using bis(p-nitrophenyl) phosphate (BNPP) as a substrate. In the dinuclear complexes the two metals play a cooperative role in BNPP cleavage. In the case of the L2 dinuclear complex [Zn(2)L2(OH)(2)](2+), the two metals act cooperatively through a hydrolytic process involving a bridging interaction of the substrate with the two Zn(II) ions and a simultaneous nucleophilic attack of a Zn-OH function at phosphorus; in the case of the dizinc complex with the largest macrocycle L3, only the monohydroxo complex [Zn(2)L3(OH)](3+) promotes BNPP hydrolysis. BNPP interacts with a single metal, while the hydroxide anion may operate a nucleophilic attack. Both complexes display high rate enhancements in BNPP cleavage with respect to previously reported dizinc complexes, due to hydrophobic and pi-stacking interactions between the nitrophenyl groups of BNPP and the dipyridine units of the complexes.

  13. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    PubMed Central

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-01-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2− ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4·2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography. PMID:27869124

  14. Bisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation

    NASA Astrophysics Data System (ADS)

    Zong, Lili; Wang, Chao; Moeljadi, Adhitya Mangala Putra; Ye, Xinyi; Ganguly, Rakesh; Li, Yongxin; Hirao, Hajime; Tan, Choon-Hong

    2016-11-01

    Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2- ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst is isolatable, stable and useful for the oxidation of a range of dialkyl sulfides. The practical utility was illustrated using a gram-scale synthesis of armodafinil, a commercial drug, with the catalyst generated in situ from 0.25 mol% of bisguanidinium and 2.5 mol% of Na2MoO4.2H2O. Structural characterization of this ion pair catalyst has been successfully achieved using single-crystal X-ray crystallography.

  15. Preparation, structure, and luminescence of dinuclear lanthanide complexes of a novel imine-amine phenolate macrocycle

    SciTech Connect

    Matthews, K.D.; Kahwa, I.A. ); Williams, D.J. )

    1994-03-30

    Metal-free condensation of 2,6-diformyl-p-cresol with 3,6-dioxa-1,8-octanediamine followed by reduction with sodium tetrahydroborate and addition of lanthanide(III) nitrate salts, in that order, yield (slowly) crystalline dinuclear complexes of a novel imine-amine phenolate macrocycle 2. The decacoordination geometry of the identical Pr[sup 3+] ions in a C[sub 2v] 4A,6B-extended dodecahedron made up of two bidentate NO[sub 3]-ions, two phenolate and two either oxygens, and one imine and one amine nitrogens. Dinuclear lanthanide complexes of 2 appear to be more stable than those of the totally reduced chelate 2 in alcoholic media. The Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]-OH and (La[sub 0.97]Tb[sub 0.03])[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH compounds exhibit strong Tb[sup 3+] ([sup 5]D[sub 4] [yields] [sup 7]F[sub J]) emission sensitized by the single state of 2 at both 77 and 295 K. No Tb[sup 3+]-Tb[sup 3+] self-quenching or N-H trapping effects are observed at 77 K (decay rate is 598 s[sup [minus]1]); the coordination cavities of 2 are therefore potentially good hosts for Tb[sup 3+] in luminescent diagnostic agents. At room temperature the complex decay kinetics of Tb[sup 3+] in Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH are similar to those of Tb[sub 2]1(NO[sub 3])[sub 4][center dot]H[sub 2]O. But for the dilute complex, (La[sub 0.97]-Tb[sub 0.03])[sub 2]2(NO[sub 3])[sub 4][center dot]1.35CH[sub 3]OH, unusual thermal equilibration of the ligand triplet and Tb[sup 3+] [sup 5]D[sub 4] states occurs at room temperature; the ligand-to-Tb[sup 3+] energy-transfer rate is [approx]4.36 x 10[sup 4] s[sup [minus]1], while Tb[sup 3+]-to-ligand back-energy-transfer is [approx]7.1 x 10[sup 4] s[sup [minus]1].

  16. Synthesis and crystal structure of a dinuclear yttrium(III)- (lanthanide(III)-) copper(II) complex with an unusual 2-methyl-2,4,6-tris(trifluoromethyl)-1,3-dioxane-4,6-diolato ligand

    SciTech Connect

    Wang, S.; Pang, Z.; Smith, K.D.L. )

    1993-11-10

    A dinuclear Ln[sup III]-Cu[sup II] complex with an unusual 2-methyl-2,4,6-tris(trifluoromethyl)-1,3-dioxane-4,6-diolato ligand has been synthesized and characterized structurally. The 1,3-dioxane-4,6-diolato ligand is the product of cycloaddition of 1,1,1-trifluoro-2,2-propanediol to a hexafluoroacetylacetonato ligand promoted by the metal complex.

  17. A Highly Effective Strategy for Encapsulating Potassium Cations in Small Crown Ether Rings on a Dinuclear Palladium Complex.

    PubMed

    Lucio-Martínez, Fátima; Bermúdez, Brais; Ortigueira, Juan M; Adams, Harry; Fernández, Alberto; Pereira, M Teresa; Vila, José M

    2017-03-16

    The potential of 15-crown-5 ethers to link large cations, such as potassium, is limited by the quasi-parallel arrangement of two oxygen donor moieties upon appropriate orientation of the corresponding ether-ring-containing molecules. Substrates bearing the two crown ethers that are capable of achieving such coordination are hitherto unknown. The synthesis and isolation of a tailor-made dinuclear palladacycle bearing 15-crown-5 ether rings on the metallated phenyls offers such a possibility, providing the adequate environment for the formation of the sandwiched [K(metallacycle-15-crown-5)2 ] moiety. This synthetic strategy also culminates in the isolation of the first palladacycle able to entrap a potassium cation through bonding to two 15-crown-5 ether rings in a single molecule.

  18. Dinuclear cobalt(II) and copper(II) complexes with a Py2N4S2 macrocyclic ligand.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Lezama, Luis; Macías, Alejandro; Pérez-Lourido, Paulo; Valencia, Laura

    2011-06-20

    The interaction between Co(II) and Cu(II) ions with a Py(2)N(4)S(2)-coordinating octadentate macrocyclic ligand (L) to afford dinuclear compounds has been investigated. The complexes were characterized by microanalysis, conductivity measurements, IR spectroscopy and liquid secondary ion mass spectrometry. The crystal structure of the compounds [H(4)L](NO(3))(4), [Cu(2)LCl(2)](NO(3))(2) (5), [Cu(2)L(NO(3))(2)](NO(3))(2) (6), and [Cu(2)L(μ-OH)](ClO(4))(3)·H(2)O (7) was also determined by single-crystal X-ray diffraction. The [H(4)L](4+) cation crystal structure presents two different conformations, planar and step, with intermolecular face-to-face π,π-stacking interactions between the pyridinic rings. Complexes 5 and 6 show the metal ions in a slightly distorted square-pyramidal coordination geometry. In the case of complex 7, the crystal structure presents the two metal ions joined by a μ-hydroxo bridge and the Cu(II) centers in a slightly distorted square plane or a tetragonally distorted octahedral geometry, taking into account weak interactions in axial positions. Electron paramagnetic resonance spectroscopy is in accordance with the dinuclear nature of the complexes, with an octahedral environment for the cobalt(II) compounds and square-pyramidal or tetragonally elongated octahedral geometries for the copper(II) compounds. The magnetic behavior is consistent with the existence of antiferromagnetic interactions between the ions for cobalt(II) and copper(II) complexes, while for the Co(II) ones, this behavior could also be explained by spin-orbit coupling.

  19. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    PubMed

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  20. Stereospecific formation of dinuclear vanadium(V) tartrato complexes.

    PubMed

    Gáliková, Jana; Schwendt, Peter; Tatiersky, Jozef; Tracey, Alan S; Zák, Zdirad

    2009-09-07

    The first dinuclear nonperoxido tartrato complexes of vanadium(V), (NMe(4))(2)[V(2)O(4)((2R,3R)-H(2)tart)(2)] x 6 H(2)O (1), (NMe(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (2), (NEt(4))(2)[V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)] (3) (tart = tartrato(4-) = C(4)H(2)O(6)(4-)) have been prepared from water-ethanol medium and characterized by X-ray structure analysis and spectral methods. The formation of the complexes has been found to be stereospecific; the composition and structure of anions containing one or both enantiomers of the ligand are profoundly different. The structure of anions in 1-3 also differs significantly from the structure of other dinuclear vanadium(V) alpha-hydroxycarboxylato complexes, but, interestingly, the geometry of the [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) ion resembles the structure of the [(VO)(2)((2R,3R)-tart)((2S,3S)-tart)](4-) ion which has a vanadium(IV) center. Using Raman and (51)V NMR spectroscopy the solvent dependent mutual transformations of [V(4)O(8)((2R,3R)-tart)(2)](4-) (V(4)L(2)-RR), [V(4)O(8)((2S,3S)-tart)(2)](4-) (V(4)L(2)-SS), [V(2)O(4)((2R,3R)-H(2)tart)(2)](2-) (V(2)L(2)-RR), [V(2)O(4)((2S,3S)-H(2)tart)(2)](2-) (V(2)L(2)-SS), and [V(2)O(2)((2R,3R)-tart)((2S,3S)-tart)](2-) (V(2)L(2)-rac) have been established. In aqueous solution the following reactions take place; 2 V(2)L(2)-rac --> V(2)L(2)-RR + V(2)L(2)-SS followed by partial decomposition, V(2)L(2)-RR --> V(4)L(2)-RR + 2 L (V(2)L(2)-SS --> V(4)L(2)-SS + 2 L). On the other hand V(2)L(2)-rac is stable in CH(3)CN solution while V(2)L(2)-RR (V(2)L(2)-SS) decomposes into several species.

  1. Structural, MALDI-TOF-MS, magnetic and spectroscopic studies of new dinuclear copper(II), cobalt(II) and zinc(II) complexes containing a biomimicking μ-OH bridge.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Macías, Alejandro; Valencia, Laura; Neuman, Nicolás I; Rizzi, Alberto C; Brondino, Carlos D; González, Pablo J; Capelo, José Luis; Lodeiro, Carlos

    2010-12-28

    The Py(2)N(4)S(2) octadentate coordinating ligand afforded dinuclear cobalt, copper and zinc complexes and the corresponding mixed metal compounds. The overall geometry and bonding modes have been deduced on the basis of elemental analysis data, MALDI-TOF-MS, IR, UV-vis and EPR spectroscopies, single-crystal X-Ray diffraction, conductivity and magnetic susceptibility measurements. In the copper and zinc complexes, a μ-hydroxo bridge links the two metal ions. In both cases, the coordination geometry is distorted octahedral. Magnetic and EPR data reveal weakly antiferromagnetic high spin Co(II) ions, compatible with a dinuclear structure. The magnetic characterization of the dinuclear Cu(II) compound indicates a ferromagnetically coupled dimer with weak antiferromagnetic intermolecular interactions. The intra-dimer ferromagnetic behaviour was unexpected for a Cu(II) dimer with such μ-hydroxo bridging topology. We discuss the influence on the magnetic properties of non-covalent interactions between the bridging moiety and the lattice free water molecules.

  2. Luminescent supramolecular soft nanostructures from amphiphilic dinuclear Re(i) complexes

    NASA Astrophysics Data System (ADS)

    Cebrián, Cristina; Natali, Mirco; Villa, Davide; Panigati, Monica; Mauro, Matteo; D'Alfonso, Giuseppe; de Cola, Luisa

    2015-07-01

    Luminescent metallo-surfactants based on highly emissive dinuclear Re(i) complexes have been synthesized combining the peculiar photophysical behaviour of this class of neutral hydrophobic complexes with new properties imparted by hydrophilic chains anchored on the coordinated chromophoric ligand. In solution, the resulting neutral amphiphiles tend to self-assembly in soft structures. The aggregation properties have been thoroughly investigated in dioxane-water mixtures, where all the complexes assembly in globular-like supramolecular architectures with well-defined size (hydrodynamic diameter = 200-400 nm). The morphology of these nano-objects has been completely characterized with Dynamic Light Scattering (DLS) analysis, Scanning Transmission Electron Microscopy (STEM) and cryo-TEM to determine the size, polydispersity, and stability of the nanoparticles in relationship with the structure of the metallo-surfactants. The photophysical properties of both the isolated metal complexes and their aggregates have been investigated by means of UV-Vis absorption, steady-state and time-resolved emission spectroscopy. Noteworthy, the self-assembly properties of the reported luminescent rhenium metallo-amphiphiles can be modulated by solvent polarity. Even more importantly, such aggregation process yielded a small hypsochromic shift of the emission energy accompanied by a sizeable elongation of the excited-state lifetime and an enhancement of the photoluminescence quantum yield, reaching a remarkably high value of 0.20 despite the air-equilibrated aqueous condition. The presented findings endorse novel possibilities for the efficient use of soft-nanostructures based on metallo-amphiphiles in dual (electron and optical microscopy) bio-imaging applications and theranostics where the non-covalent nature of the intermolecular interactions would offer the powerful and unique possibility to reversibly assemble and disassemble imaging agents.Luminescent metallo-surfactants based on

  3. Dinuclear zinc(II) complexes with hydrogen bond donors as structural and functional phosphatase models.

    PubMed

    Bosch, Simone; Comba, Peter; Gahan, Lawrence R; Schenk, Gerhard

    2014-09-02

    It is becoming increasingly apparent that the secondary coordination sphere can have a crucial role in determining the functional properties of biomimetic metal complexes. We have therefore designed and prepared a variety of ligands as metallo-hydrolase mimics, where hydrogen bonding in the second coordination sphere is able to influence the structure of the primary coordination sphere and the substrate binding. The assessment of a structure-function relationship is based on derivates of 2,6-bis{[bis(pyridin-2-ylmethyl)amino]methyl}-4-methylphenol (HBPMP = HL(1)) and 2-{[bis(pyridin-2-ylmethyl)amino]methyl}-6-{[(2-hydroxybenzyl)(pyridin-2-ylmethyl)amino]methyl}-4-methylphenol (H2BPBPMP = H2L(5)), well-known phenolate-based ligands for metallo-hydrolase mimics. The model systems provide similar primary coordination spheres but site-specific modifications in the secondary coordination sphere. Pivaloylamide and amine moieties were chosen to mimic the secondary coordination sphere of the phosphatase models, and the four new ligands H3L(2), H3L(3), HL(4), and H4L(6) vary in the type and geometric position of the H-bond donors and acceptors, responsible for the positioning of the substrate and release of the product molecules. Five dinuclear Zn(II) complexes were prepared and structurally characterized in the solid, and four also in solution. The investigation of the phosphatase activity of four model complexes illustrates the impact of the H-bonding network: the Michaelis-Menten constants (catalyst-substrate binding) for all complexes that support hydrogen bonding are smaller than for the reference complex, and this generally leads to higher catalytic efficiency and higher turnover numbers.

  4. A series of dinuclear lanthanide complexes with slow magnetic relaxation for Dy2 and Ho2.

    PubMed

    Zhang, Jin; Zhang, Haifeng; Chen, Yanmei; Zhang, Xiangfei; Li, Yahong; Liu, Wei; Dong, Yaping

    2016-10-18

    The employment of a new Schiff base ligand, 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}naphthalen-1-ol (H2L), in 4f-metal chemistry has led to the formation of seven new isostructural lanthanide(iii) complexes. More specifically the 1 : 1 reaction of Ln(NO3)3·6H2O and H2L in ethanol in the presence of 3 equivalents of pyridine yielded seven dinuclear complexes of compositions [Ln2L2(NO3)2(C2H5OH)2]·0.5py (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Yb (7); py = pyridine). The structures of the isomorphous complexes 1-7 were determined by single-crystal X-ray crystallography. X-ray crystallography data reveal that each compound is neutral, and contains two doubly-deprotonated ligands, two chelated nitrates and two coordinated ethanol molecules. The two Ln(III) atoms in 1-7 are doubly bridged by the two phenolato oxygen atoms of two L(2-) ligands. Each of the two lanthanide ions is eight-coordinated and possesses distorted dodecahedron geometry. Dc magnetic susceptibility studies in the 2-300 K range reveal probably a weak antiferromagnetic interaction for 2, 3 and 6, and a ferromagnetic interaction at low temperature for 4 and 5. Complexes 4 and 5 show slow magnetic relaxation behavior. The Ueff for 4 of 66.7 K is a relatively high value among the reported Dy2 SMMs. Complex 5 is a very rare example of a Ho2 compound which exhibits slow magnetic relaxation.

  5. Phosphate ester hydrolysis and DNA binding capacity of two new dinuclear Ni(II) complexes

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Xiao, W.; Mao, J. W.; Zhou, H.; Pan, Z. Q.

    2013-03-01

    Two new dinuclear Ni(II) complexes, [Ni2L1(OAc)2]ClO4 (1) and [Ni2L2(OAc)2] Br·0.5H2O (2) (where HL is the condensation product of 2,6-diformyl-4-X-phenol (X = CH3, Br) and N1-(2-aminoethyl)-N2-(4-nitrobenzyl)ethane-1,2-diamine), were synthesized and characterized. The coordination polyhedron of each metal ion in the complexes can be approximately described as a distorted octahedron. The Ni-Ni distances in 1 and 2 are 3.306 Å and 3.369 Å, respectively. The phosphate hydrolysis promoted by the complexes was examined using 4-nitrophenyl phosphate disodium salt hexahydrate (pNPP) as the substrate. The catalytic rate constants (kcat) are 1.29 × 10-5 s-1 for 1 and 0.47 × 10-5 s-1 for 2 at 25 °C in physiological pH condition. The binding activities of the complexes toward calf thymus (CT-DNA) were analyzed by spectroscopic and voltammetric methods, and the corresponding binding constants are 7.75 × 105 and 6.51 × 104 M-1 for 1 and 8.59 × 105 and 9.18 × 104 M-1 for 2, respectively. The linear Stern-Volmer quenching constants obtained in the fluorescent spectroscopic study of 1 and 2 are 0.7 × 103 and 1.5 × 103 M-1, respectively.

  6. Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex

    PubMed Central

    Pedziwiatr, Jakub; Ghiviriga, Ion; Veige, Adam S.

    2017-01-01

    This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-bis­[(diethyl ether)lithium], [Li2Br2(C24H33N3)(C4H10O)2] (1) and a dinuclear metal complex, namely di-μ-bromido-2:3κ4 Br:Br-bis­{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-1κ3 N,N′,N′′;4κ3 N,N′,N′′-tetra-μ-iso­propano­lato-1:2κ4 O:O;3:4κ4 O:O-diiso­propano­lato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N3)2(C3H7O)6] or {[NHNNH]Ti(OiPr)3(LiBr)2}2 (2). Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O) fragment bonded to them, with the Li atom adopting a distorted tetra­hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octa­hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra­hedral coordination as in 1). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure

  7. Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex.

    PubMed

    Pedziwiatr, Jakub; Ghiviriga, Ion; Abboud, Khalil A; Veige, Adam S

    2017-02-01

    This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di-methylpropanimido-yl)-N-[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-bis-[(diethyl ether)lithium], [Li2Br2(C24H33N3)(C4H10O)2] (1) and a dinuclear metal complex, namely di-μ-bromido-2:3κ(4)Br:Br-bis-{2-(2,2-di-methylpropanimido-yl)-N-[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-1κ(3)N,N',N'';4κ(3)N,N',N''-tetra-μ-iso-propano-lato-1:2κ(4)O:O;3:4κ(4)O:O-diiso-propano-lato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N3)2(C3H7O)6] or {[NHNNH]Ti(O (i) Pr)3(LiBr)2}2 (2). Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O) fragment bonded to them, with the Li atom adopting a distorted tetra-hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a Ti(IV) metal atom in an octa-hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra-hedral coordination as in 1). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N

  8. Dinuclear cadmium(II), zinc(II), and manganese(II), trinuclear nickel(II), and pentanuclear copper(II) complexes with novel macrocyclic and acyclic Schiff-base ligands having enantiopure or racemic camphoric diamine components.

    PubMed

    Jiang, Jue-Chao; Chu, Zhao-Lian; Huang, Wei; Wang, Gang; You, Xiao-Zeng

    2010-07-05

    Four novel [3 + 3] Schiff-base macrocyclic ligands I-IV condensed from 2,6-diformyl-4-substituted phenols (R = CH(3) or Cl) and enantiopure or racemic camphoric diamines have been synthesized and characterized. Metal-ion complexations of these enantiopure and racemic [3 + 3] macrocyclic ligands with different cadmium(II), zinc(II), manganese(II), nickel(II), and copper(II) salts lead to the cleavage of Schiff-base C horizontal lineN double bonds and subsequent ring contraction of the macrocyclic ligands due to the size effects and the spatial restrictions of the coordination geometry of the central metals, the steric hindrance of ligands, and the counterions used. As a result, five [2 + 2] and one [1 + 2] dinuclear cadmium(II) complexes (1-6), two [2 + 2] dinuclear zinc(II) (7 and 8), and two [2 + 2] dinuclear manganese(II) (9 and 10) complexes together with one [1 + 1] trinuclear nickel(II) complex (11) and one [1 + 2] pentanuclear copper(II) complex (12), bearing enantiopure or racemic ligands, different substituent groups in the phenyl rings, and different anionic ligands (Cl(-), Br(-), OAc(-), and SCN(-)), have been obtained in which the chiral carbon atoms in the camphoric backbones are arranged in different ways (RRSS for the enantiopure ligands in 1, 2, 4, 5, and 7-10 and RSRS for the racemic ligands in 3, 6, 11, and 12). The steric hindrance effects of the methyl group bonded to one of the chiral carbon atoms of camphoric diamine units are believed to play important roles in the formation of the acyclic [1 + 1] trinuclear complex 11 and [1 + 2] dinuclear and pentanuclear complexes 6 and 12. In dinuclear cadmium(II), zinc(II), and manganese(II) complexes 1-10, the sequence of separations between the metal centers is consistent with that of the ionic radii shortened from cadmium(II) to manganese(II) to zinc(II) ions. Furthermore, UV-vis, circular dichroism, (1)H NMR, and fluorescence spectra have been used to characterize and compare the structural

  9. Structure and properties of Dinuclear [RuII([n]aneS4)] complexes of 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine.

    PubMed

    Newell, Mike; Ingram, James D; Easun, Timothy L; Vickers, Steven J; Adams, Harry; Ward, Michael D; Thomas, Jim A

    2006-01-23

    The synthesis of dinuclear [Ru(II)([n]aneS(4))] (where n = 12, 14) complexes of the bridging ligand 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine are reported. The X-ray structures of both of the new complexes are compared to a newly obtained structure for a dinuclear [Ru(II)([9]aneS(3))]-based analogue, whose synthesis has previously been reported. A comparison of the electrochemistry of the three complexes reveals that the first oxidation of the [Ru(II)([n]aneS(4))]-based systems is a ligand-based couple, indicating that the formation of the radical anion form of the bridging ligand is stabilized by metal center coordination. Spectroelectrochemistry studies on the mixed-valence form of the new complexes suggest that they are Robin and Day Class II systems. The electrochemical and electronic properties of these complexes is rationalized by a consideration of the pi-bonding properties of thiacrown ligands.

  10. Enzyme-like catalysis via ternary complex mechanism: alkoxy-bridged dinuclear cobalt complex mediates chemoselective O-esterification over N-amidation.

    PubMed

    Hayashi, Yukiko; Santoro, Stefano; Azuma, Yuki; Himo, Fahmi; Ohshima, Takashi; Mashima, Kazushi

    2013-04-24

    Hydroxy group-selective acylation in the presence of more nucleophilic amines was achieved using acetates of first-row late transition metals, such as Mn, Fe, Co, Cu, and Zn. Among them, cobalt(II) acetate was the best catalyst in terms of reactivity and selectivity. The combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (2a: R = CF3, 2b: R = CH3, 2c: R = (t)Bu) with nitrogen-containing ligands, such as 2,2'-bipyridine, provided an efficient catalytic system for transesterification, in which an alkoxide-bridged dinuclear complex, Co2(OCO(t)Bu)2(bpy)2(μ2-OCH2-C6H4-4-CH3)2 (10), was successfully isolated as a key intermediate. Kinetic studies and density functional theory calculations revealed Michaelis-Menten behavior of the complex 10 through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting the formation of alkoxides followed by coordination of the ester.

  11. Rigid rod-like dinuclear Ru(II)/Os(II) terpyridine-type complexes. Electrochemical behavior, absorption spectra, luminescence properties, and electronic energy transfer through phenylene bridges

    SciTech Connect

    Barigelletti, F.; Flamigni, L.; Balzani, V. ||

    1994-08-24

    The absorption spectra, the luminescence properties (at 293 and 77 K), and the electrochemical behavior of six dinuclear heterometallic compounds have been investigated. The compounds are made of Ru(tpy){sub 2}{sup 2+}- and Os(tpy){sub 2}{sup 2+}-type components (tpy = 2,2{prime}:6{prime},2 inches-terpyridine, which in some cases carries p-tolyl (Meph) or methylsulphone (MeO{sub 2}S) substituents in the 4{prime} position), connected by n phenylene (ph) spacers (n=0,1, and 2). In the resulting rigid rod-like structures of general formula (X{sub 1}tpy)Ru(tpy(ph){sub n}tpy)Os(tpyX{sub 2}){sup 4+} the metal-to-metal distance varies form 11 to 20 {Angstrom}. The absorption spectra of the two components are slightly perturbed in the dinuclear compounds, and metal-metal and ligand-ligand interactions are evidenced by the trends of the oxidation and reduction potentials. The luminescence of the Ru-based unit is quenched by the connected Os-based unit with practically unitary efficiency, regardless of the number of interposed phenylene spacers. Quenching is accompanied by quantitative sensitization of the Os-based luminescence. The rate of energy transfer at 293 K is larger than 10{sup 10} s{sup -1} in all cases. The Foerster (Coulombic) mechanism does not satisfactorily account for such a fast rate, particularly for the species with n=2. It is concluded that the observed energy-transfer processes take place most likely via a Dexter (electron exchange) mechanism. This is consistent with the strong electronic coupling of the Ru-based units in the compound with n=0, and with the relatively small insulating effect expected for the phenylene spacers. 37 refs., 7 figs., 3 tabs.

  12. Hydrogen peroxide and dioxygen activation by dinuclear copper complexes in aqueous solution: hydroxyl radical production initiated by internal electron transfer.

    PubMed

    Zhu, Qing; Lian, Yuxiang; Thyagarajan, Sunita; Rokita, Steven E; Karlin, Kenneth D; Blough, Neil V

    2008-05-21

    Dinuclear Cu(II) complexes, CuII2Nn (n = 4 or 5), were recently found to specifically cleave DNA in the presence of a reducing thiol and O2 or in the presence of H2O2 alone. However, CuII2N3 and a closely related mononuclear Cu(II) complex exhibited no selective reaction under either condition. Spectroscopic studies indicate an intermediate is generated from CuII2Nn (n = 4 or 5) and mononuclear Cu(II) solutions in the presence of H2O2 or from CuI2Nn (n = 4 or 5) in the presence of O2. This intermediate decays to generate OH radicals and ligand degradation products at room temperature. The lack of reactivity of the intermediate with a series of added electron donors suggests the intermediate discharges through a rate-limiting intramolecular electron transfer from the ligand to the metal peroxo center to produce an OH radical and a ligand-based radical. These results imply that DNA cleavage does not result from direct reaction with a metal-peroxo intermediate but instead arises from reaction with either OH radicals or ligand-based radicals.

  13. Phthalocyanine supported dinuclear Ln(III) complexes: the solvent-induced change of magnetic properties in dysprosium(iii) analogues.

    PubMed

    Ge, Jing-Yuan; Wang, Hai-Ying; Li, Jing; Xie, Jia-Ze; Song, You; Zuo, Jing-Lin

    2017-02-24

    Three dinuclear lanthanide complexes, [Ln2(thd)4Pc]·2C6H6 (Hthd = 2,2,6,6-tetramethylheptanedione, Ln = Sm (1), Tb (2), Dy (3)), have been synthesized based on phthalocyanine (Pc). They can be reversibly transformed into [Ln2(thd)4Pc] (Ln = Sm (1'), Tb (2'), Dy (3')) via desolvation and resolvation of the lattice benzene molecules. This change generates dramatic influences on the structural and magnetic properties of the dysprosium analogue. In complex 3, one crystallographically independent metal center is observed, and it exhibits a single relaxation process of magnetization with an energy barrier of 55.7 K. Upon desolvation, the resulting complex 3' contains two types of metal centers, and shows the field-induced single-molecule magnetic behavior with two thermally activated magnetic relaxation processes. The anisotropy barriers for 3' are as high as 63.3 K and 109.6 K, respectively. This work confirms that the solvated molecules can finely tune the magnetic relaxation mechanisms.

  14. Structural Investigation of Dinuclear Clusters Incorporated in Polyoxotungstates

    NASA Astrophysics Data System (ADS)

    Nagy, C.; Rusu, D.; Somesan, C.; Filip, S.; Rusu, M.; David, L.

    2011-10-01

    The new K10[M2Bi2W20O70]ṡH2O (M = Mn(II), Co(II), Ni(II), Cu(II)) sandwich-type complex have been investigated by spectroscopic (FT-IR, UV-VIS, ESR) methods. The main goal was to obtain information about the metal ions coordination to the trilacunary regions of Keggin polioxoanion ligands, the local symmetry around the metal ions and the presence of possible metal-metal couplings.

  15. Poster — Thur Eve — 11: Validation of the orthopedic metallic artifact reduction tool for CT simulations at the Ottawa Hospital Cancer Centre

    SciTech Connect

    Sutherland, J; Foottit, C

    2014-08-15

    Metallic implants in patients can produce image artifacts in kilovoltage CT simulation images which can introduce noise and inaccuracies in CT number, affecting anatomical segmentation and dose distributions. The commercial orthopedic metal artifact reduction algorithm (O-MAR) (Philips Healthcare System) was recently made available on CT simulation scanners at our institution. This study validated the clinical use of O-MAR by investigating its effects on CT number and dose distributions. O-MAR corrected and uncorrected images were acquired with a Philips Brilliance Big Bore CT simulator of a cylindrical solid water phantom that contained various plugs (including metal) of known density. CT number accuracy was investigated by determining the mean and standard deviation in regions of interest (ROI) within each plug for uncorrected and O-MAR corrected images and comparing with no-metal image values. Dose distributions were calculated using the Monaco treatment planning system. Seven open fields were equally spaced about the phantom around a ROI near the center of the phantom. These were compared to a “correct” dose distribution calculated by overriding electron densities a no-metal phantom image to produce an image containing metal but no artifacts. An overall improvement in CT number and dose distribution accuracy was achieved by applying the O-MAR correction. Mean CT numbers and standard deviations were found to be generally improved. Exceptions included lung equivalent media, which is consistent with vendor specified contraindications. Dose profiles were found to vary by ±4% between uncorrected or O-MAR corrected images with O-MAR producing doses closer to ground truth.

  16. A neutral dinuclear Ir(iii) complex for anti-counterfeiting and data encryption.

    PubMed

    Jiang, Yang; Li, Guangfu; Che, Weilong; Liu, Yingjie; Xu, Bin; Shan, Guogang; Zhu, Dongxia; Su, Zhongmin; Bryce, Martin R

    2017-03-09

    A neutral dinuclear Ir(iii) Schiff base complex PIBIP has been synthesized and shown to exhibit both piezochromic luminescence (PCL) and aggregation induced emission (AIE) behaviour. An efficient second-level anti-counterfeit trademark and a data encryption device were fabricated using PIBIP as the active material.

  17. Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes

    SciTech Connect

    Piguet, C.; Bernardinelli, G.; Williams, A.F. ); Buenzli, J.C.G. ); Hopfgartner, G. )

    1993-09-08

    The dinucleating ligand bis[1-methyl-2-(6[prime]-[1[double prime]-(3,5-dimethoxybenzyl)benzimidazol-2[double prime]-yl]pyrid-2[prime]-yl)benzimidazol-5-yl]methane (L) reacts with lanthanide perchlorates to give dinuclear 2:3 complexes [Ln[sub 2](L)[sub 3

  18. Interpretation of the mechanism of spontaneous fission of heavy nuclei in the framework of dinuclear system conception

    NASA Astrophysics Data System (ADS)

    Volkov, V. V.; Cherepanov, E. A.; Kalandarov, Sh. A.

    2016-11-01

    The new approach to the interpretation of the process of spontaneous fission of heavy nuclei is suggested. It is based on nuclear physics data which are obtained in heavy ion collisions. The process of spontaneous fission consists of three sequential stages: clusterization of the valent nucleons of a heavy nucleus into a light nucleus-cluster, which leads to the formation of a dinuclear system; evolution of the dinuclear system which proceeds by nucleon transfer from the heavy to light nucleus and decay of the dinuclear system from the equilibrium configuration into two fragments.

  19. Computational, electrochemical, and spectroscopic studies of two mononuclear cobaloximes: the influence of an axial pyridine and solvent on the redox behaviour and evidence for pyridine coordination to cobalt(i) and cobalt(ii) metal centres.

    PubMed

    Lawrence, Mark A W; Celestine, Michael J; Artis, Edward T; Joseph, Lorne S; Esquivel, Deisy L; Ledbetter, Abram J; Cropek, Donald M; Jarrett, William L; Bayse, Craig A; Brewer, Matthew I; Holder, Alvin A

    2016-06-21

    [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluoroboryldimethylglyoximato) was used to synthesize [Co(dmgBF2)2(H2O)(py)]·0.5(CH3)2CO (where py = pyridine) in acetone. The formulation of complex was confirmed by elemental analysis, high resolution MS, and various spectroscopic techniques. The complex [Co(dmgBF2)2(solv)(py)] (where solv = solvent) was readily formed in situ upon the addition of pyridine to complex . A spectrophotometric titration involving complex and pyridine proved the formation of such a species, with formation constants, log K = 5.5, 5.1, 5.0, 4.4, and 3.1 in 2-butanone, dichloromethane, acetone, 1,2-difluorobenzene/acetone (4 : 1, v/v), and acetonitrile, respectively, at 20 °C. In strongly coordinating solvents, such as acetonitrile, the lower magnitude of K along with cyclic voltammetry, NMR, and UV-visible spectroscopic measurements indicated extensive dissociation of the axial pyridine. In strongly coordinating solvents, [Co(dmgBF2)2(solv)(py)] can only be distinguished from [Co(dmgBF2)2(solv)2] upon addition of an excess of pyridine, however, in weakly coordinating solvents the distinctions were apparent without the need for excess pyridine. The coordination of pyridine to the cobalt(ii) centre diminished the peak current at the Epc value of the Co(I/0) redox couple, which was indicative of the relative position of the reaction equilibrium. Herein we report the first experimental and theoretical (59)Co NMR spectroscopic data for the formation of Co(i) species of reduced cobaloximes in the presence and absence of py (and its derivatives) in CD3CN. From spectroelectrochemical studies, it was found that pyridine coordination to a cobalt(i) metal centre is more favourable than coordination to a cobalt(ii) metal centre as evident by the larger formation constant, log K = 4.6 versus 3.1, respectively, in acetonitrile at 20 °C. The electrosynthesis of hydrogen by complexes and in various solvents demonstrated the dramatic effects of the axial

  20. Using the multi-object adaptive optics demonstrator RAVEN to observe metal-poor stars in and towards the Galactic Centre

    NASA Astrophysics Data System (ADS)

    Lamb, M.; Venn, K.; Andersen, D.; Oya, S.; Shetrone, M.; Fattahi, A.; Howes, L.; Asplund, M.; Lardière, O.; Akiyama, M.; Ono, Y.; Terada, H.; Hayano, Y.; Suzuki, G.; Blain, C.; Jackson, K.; Correia, C.; Youakim, K.; Bradley, C.

    2017-03-01

    The chemical abundances for five metal-poor stars in and towards the Galactic bulge have been determined from the H-band infrared spectroscopy taken with the RAVEN multi-object adaptive optics science demonstrator and the Infrared Camera and Spectrograph at the Subaru 8.2-m telescope. Three of these stars are in the Galactic bulge and have metallicities between -2.1 < [Fe/H] < -1.5, and high [α/Fe] ∼ +0.3, typical of Galactic disc and bulge stars in this metallicity range; [Al/Fe] and [N/Fe] are also high, whereas [C/Fe] < +0.3. An examination of their orbits suggests that two of these stars may be confined to the Galactic bulge and one is a halo trespasser, though proper motion values used to calculate orbits are quite uncertain. An additional two stars in the globular cluster M22 show [Fe/H] values consistent to within 1σ, although one of these two stars has [Fe/H] = -2.01 ± 0.09, which is on the low end for this cluster. The [α/Fe] and [Ni/Fe] values differ by 2σ, with the most metal-poor star showing significantly higher values for these elements. M22 is known to show element abundance variations, consistent with a multipopulation scenario though our results cannot discriminate this clearly given our abundance uncertainties. This is the first science demonstration of multi-object adaptive optics with high-resolution infrared spectroscopy, and we also discuss the feasibility of this technique for use in the upcoming era of 30-m class telescope facilities.

  1. Dinuclear osmium(II) probes for high-resolution visualisation of cellular DNA structure using electron microscopy.

    PubMed

    Wragg, Ashley; Gill, Martin R; Hill, Christopher J; Su, Xiaodi; Meijer, Anthony J H M; Smythe, Carl; Thomas, Jim A

    2014-12-04

    Two dinuclear osmium polypyridyl complexes function as convenient, easy to handle TEM contrast agents and facilitate the high-resolution visualisation of intracellular structure, particularly sub-nuclear detail.

  2. Mono- and dinuclear manganese(III) complexes showing efficient catechol oxidase activity: syntheses, characterization and spectroscopic studies.

    PubMed

    Banu, Kazi Sabnam; Chattopadhyay, Tanmay; Banerjee, Arpita; Mukherjee, Madhuparna; Bhattacharya, Santanu; Patra, Goutam Kumar; Zangrando, Ennio; Das, Debasis

    2009-10-28

    Four side-off compartmental ligands L1-L4 [L1 = N,N'-ethylenebis(3-formyl-5-methyl-salicylaldimine), L2 = N,N'-1-methylethylenebis(3-formyl-5-methylsalicylaldimine), L3 = N,N'-1,1-dimethylethylenebis(3-formyl-5-methylsalicylaldimine) and L4= N,N'-cyclohexenebis(3-formyl-5-methylsalicylaldimine)] having two binding sites, N2O2 and O4, have been chosen to synthesize mononuclear and dinuclear manganese(III) complexes with the aim to study their catecholase activity using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate in the presence of molecular oxygen. In all cases only mononuclear manganese complexes (1-4) were obtained, with manganese coordination taking place at the N2O2 binding site only, irrespective of the amount of manganese salt used. All these complexes have been characterized by routine physico-chemical techniques. Complex MnL2Cl.4H2O (2) has further been structurally characterized by X-ray single crystal structure analysis. Four dinuclear manganese complexes, 5-8, were obtained after condensing the two pending formyl groups on each ligand (L1-L4) with aniline followed by reaction with MnCl2 to put the second Mn atom onto another N2O2 site. The catalytic activity of all complexes 1-8 has been investigated following the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) with molecular oxygen in two different solvents, methanol and acetonitrile. The study reveals that the catalytic activity is influenced by the solvent and to a significant extent by the backbone of the diamine and the behavior seems to be related mainly to steric rather than electronic factors. Experimental data suggest that a correlation, the lower the E(1/2) value the higher the catalytic activity, can be drawn between E(1/2) and Vmax of the complexes in a particular solvent. The EPR measurements suggest that the catalytic property of the complexes is related to the metal center(s) participation rather than to a radical mechanism.

  3. Discrete and Polymeric, Mono- and Dinuclear Silver Complexes of a Macrocyclic Tetraoxime Ligand with AgI–AgI Interactions

    PubMed Central

    Tashiro, Shohei; Tanihira, Jun-ichiro; Yamada, Mihoko; Shionoya, Mitsuhiko

    2013-01-01

    Macrocyclic compounds that can bind cationic species efficiently and selectively with their cyclic cavities have great potential as excellent chemosensors for metal ions. Recently, we have developed a tetraoxime-type tetraazamacrocyclic ligand 1 formed through a facile one-pot cyclization reaction. Aiming to explore and bring out the potential of the tetraoxime macrocycle 1 as a chelating sensor, we report herein the preparation of several kinds of silver complexes of 1 and their unique coordination structures determined by single-crystal X-ray diffraction analyses. As a result, the formation of two kinds of discrete structures, monomeric complexes [Ag(1)X] (X = counter anions) and a dimeric complex [Ag2(1)2]X2, and two kinds of polymeric structures from a mononuclear complex, [Ag(1)]nXn, and from a dinuclear complex, [Ag2(1)X2]n, was demonstrated. In the resulting complexes, the structurally flexible macrocyclic ligand 1 was found to provide several different coordination modes. Notably, in some silver complexes of 1, AgI–AgI interactions were observed with different AgI–AgI distances which depend on the kind of counter anions and the chemical composition. PMID:23645105

  4. Self-assembly of dinuclear Pd(ii)/Pt(ii) metallacyclic receptors incorporating N-heterocyclic carbene complexes as corners.

    PubMed

    Marcos, Ismael; Domarco, Olaya; Peinador, Carlos; Fenández, Alberto; Fernández, Jesús J; Vázquez-García, Digna; García, Marcos D

    2017-03-07

    We report herein the self-assembly of a series of new square and rectangular-shaped dinuclear M2L2 metallacycles (M = Pd(ii)/Pt(ii)), receptors self-assembled in water from four different N-monoalkyl-4,4'-bipyridinium derivatives as ligands and square-planar Pd(ii) and Pt(ii) metal centers having the chelating N-heterocyclic carbene 1,1'-di(methyl)-3,3'-methylene-4-diimidazolin-2,2'-diylidene. The concentration-dependent Pd2L2 metallacycles were successfully obtained and characterized by means of NMR experiments in aqueous media. Due to the strong trans effect exerted by the carbene ligands, the synthesis of the Pt2L2 receptors was achieved as well by self-assembly of the components at room temperature in a few hours, in clear contraposition to the harsh reaction conditions usually required for the labilization of other kinetically inert Pt(ii)-N(pyridine) bonds. X-ray diffraction studies of suitable single crystals of two of the obtained receptors offered additional information on the structure of the obtained supramolecules, whose ability as receptors has been explored by the preparation and study of the corresponding inclusion complexes in water with 1,5-dihydroxynaphthalene as the model substrate.

  5. A novel dinuclear bismuth(III) coordination compound: bis(μ-pyridine-2,6-dicarboxylato)-κ4O2,N,O6:O6′;κ4O2:O2′,N,O6-bis[(azido-κN)(1,10-phenanthroline-κ2N,N')bismuth(III)] tetrahydrate.

    PubMed

    Zhang, Wei; Feng, Yu-Quan

    2014-06-01

    A novel dinuclear bismuth(III) coordination compound, [Bi2(C7H3NO4)2(N3)2(C12H8N2)2]·4H2O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi(III) centre is seven-coordinated by three O atoms and four N atoms. The coordination geometry of each Bi(III) atom is distorted pentagonal-bipyramidal (BiO3N4), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O-H···O hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. Two types of π-π stacking interactions are found, with centroid-to-centroid distances of 3.461 (4) and 3.641 (4) Å.

  6. Determination of electronic ground state properties of a dinuclear iron(II) spin crossover complex

    NASA Astrophysics Data System (ADS)

    Bauer, T. O.; Schmitz, M.; Graf, M.; Kelm, H.; Krüger, H.-J.; Schünemann, V.

    2016-12-01

    The dinuclear complex [(Fe(L-N4Me2))2(BiBzIm)](ClO4)2ṡ2EtCN (1) has been investigated by Mössbauer spectroscopy carried out in the temperature range from 5 to 150 K with externally applied magnetic fields of up to B = 5 T. By means of a consistent simulation of all experimental data sets within the Spin Hamiltonian formalism, the zero-field splitting D and the rhombicity parameter E/ D of the ferrous high-spin (HS) site in this complex was determined to be D = -15.0 ± 1.0 cm-1 and E/ D = 0.33 respectively. The sign of the quadrupole splitting of the HS site is positive which indicates that this iron site of the dinuclear complex 1 has an electronic ground state with the dxy orbital being twofold occupied.

  7. Dinuclear Calcium Complexes with Intramolecularly NH.O Hydrogen-Bonded Dicarboxylate Ligands.

    PubMed

    Ueyama, Norikazu; Takeda, Jiro; Yamada, Yusuke; Onoda, Akira; Okamura Ta, Taka-aki; Nakamura, Akira

    1999-02-08

    A novel dinuclear calcium complex, [Ca(2){(2-OCO-3-CH(3)C(6)H(3)NHCO)(2)C(CH(3))(2)}(2)(CH(3)OH)(6)] (1), was synthesized as a structural model of 8-coordinated Ca(II) ions in the double calcium-binding site of thermolysin. The complex has four NH.O hydrogen bonds between the amide NH and the carboxylate oxygen anion. Two types of bridging coordination of the carboxylate ligand to Ca(II) were found in 1. The amide NH forms a strong NH.O hydrogen bond with the anionic oxygen of the two carboxylate oxygens. A ligand-exchange reaction between the dinuclear calcium complex and eight equimolar amounts of 2,4,6-trimethylbenzoic acid or 2-CH(3)-6-t-BuCONHC(6)H(3)COOH indicates that the NH.O hydrogen bond prevents the dissociation of the Ca-O bond.

  8. Dinuclear Spin-Crossover Complexes Based on Tetradentate and Bridging Cyanocarbanion Ligands.

    PubMed

    Milin, Eric; Belaïd, Sabrina; Patinec, Véronique; Triki, Smail; Chastanet, Guillaume; Marchivie, Mathieu

    2016-09-06

    Spin-crossover (SCO) Fe(II) dinuclear complexes of formula [Fe2(tmpa)2(μ2-tcpd)2]·0.8(CH3OH) (1·MeOH) and [Fe2(andmpa)2(μ2-tcpd)2]·2CH3OH (2·MeOH) (tmpa = tris(2-pyridylmethyl)amine, andmpa = bis(2-pyridylmethyl)aminomethyl)aniline, (tcpd)(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of the two complexes (1·MeOH and 2·MeOH) and the desolvated complex 1 (from 1·MeOH) revealed a neutral centrosymmetrical dinuclear structure in which the (tcpd)(2-) cyanocarbanion acts as a double μ2-bridging ligand between two [FeL](2+) (L = tmpa (1), andmpa (2)) units involving two free coordination sites in the cis configuration. Examination of the shortest intermolecular contacts in 1·MeOH and 1 reveals no significant hydrogen bonding between the dinuclear units, while in 2·MeOH these units are held together by significant hydrogen bonds between one of the uncoordinated nitrile groups and the anilate function, giving rise to 1D supramolecular structure. The three dinuclear complexes 1, 2·MeOH, and 2 exhibit SCO behaviors which have been evidenced by the thermal evolutions of the χmT product and by the average values of the six Fe-N distances for 1 and 2·MeOH, that reveal a gradual conversion with transition temperatures (T1/2) at ca. 352 K (1), 196 K (2), and 180 K (2·MeOH). For the solvated 1·MeOH, the sharp SCO transition observed around 365 K was induced by the desolvatation process above 330 K during the magnetic measurements.

  9. Formation of hyperdeformed states by neutron emission from a dinuclear system

    SciTech Connect

    Zubov, A. S.; Antonenko, N. V.; Sargsyan, V. V.; Adamian, G. G.; Scheid, W.

    2010-02-15

    The hyperdeformed nuclei treated as dinuclear or quasimolecular configurations are suggested to be directly produced in heavy-ion reactions at bombarding energies near the Coulomb barrier. The excited dinuclear system formed in the entrance channel of the heavy-ion collision can be cooled down by neutron emission to be transformed into the hyperdeformed nuclear system. This transition from the excited dinuclear system to a hyperdeformed configuration is described within the statistical approach. The reactions {sup 48}Ca+{sup 124,128,130,132,134}Sn, {sup 48}Ca+{sup 136,138}Xe, {sup 48}Ca+{sup 137,138,140}Ba, {sup 40}Ca+{sup 83,84}Kr, {sup 48}Ca+{sup 83,84,86}Kr, {sup 40,48}Ca+{sup 40,48}Ca, {sup 58,60}Ni+{sup 58,60}Ni, and {sup 40}Ca+{sup 58}Ni are suggested for the population of hyperdeformed states. The production cross sections, quadrupole moments, and moments of inertia of hyperdeformed states formed in these reactions are calculated, and the optimal conditions for the experimental identification of such states are proposed.

  10. An unusual 3D interdigitated architecture assembled from Keggin polyoxometalates and dinuclear copper(II) complexes

    SciTech Connect

    Pang, Haijun; Yang, Ming; Kang, Lu; Ma, Huiyuan; Liu, Bo; Li, Shaobin; Liu, Heng

    2013-02-15

    A novel organic-inorganic hybrid compound, [Cu{sub 2}(bipy){sub 3}({mu}{sub 1}-H{sub 2}O){sub 2}({mu}{sub 2}-H{sub 2}O)({mu}{sub 2}-OH)(H{sub 2}BW{sub 12}O{sub 40})]{center_dot}4 H{sub 2}O (1) (bipy=4,4 Prime -bipy), has been synthesized in hydrothermal condition and characterized by elemental analysis, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 possesses poly-pendant layered motifs composed of 12-tungstoborates and dinuclear copper(II) complexes, in which the mono-coordinated bipy molecules are orderly appended to both sides of the layer, respectively. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture. The variable-temperature magnetic susceptibility of 1 showed that there existed weak antiferromagnetic interaction in 1. Toward the reduction of hydrogen peroxide, 1 has good electrocatalytic activity and remarkable stability. - A new compound has been obtained, which represents the first interdigitated architecture assembled by POMs and dinuclear copper(II) complexes. Highlights: Black-Right-Pointing-Pointer The first example of interdigitated architecture assembled by POMs and dinuclear copper(II) complexes is observed. Black-Right-Pointing-Pointer A zipper-like pattern is observed in the structure. Black-Right-Pointing-Pointer The IR, TG, XRPD, magnetism and electrochemical property of the title compound were studied.

  11. [Allergic contact dermatitis to metals over a 20-year period in the Centre of Portugal: evaluation of the effects of the European directives].

    PubMed

    Teixeira, Vera; Coutinho, Inês; Gonçalo, Margarida

    2014-01-01

    Introdução: Os metais são causa frequente de dermatite de contacto alérgica. Desde a introdução da Directiva Comunitária do Níquel (1994/27/CE; 2004/96/CE) e, mais recentemente, da Directiva do Cimento (2003/53/CE), nos países nórdicos tem havido uma diminuição da sensibilização aos metais. A aplicabilidade destas medidas e o seu impacto permanece por avaliar em Portugal. Material e Métodos: Foi realizado um estudo retrospectivo (1992-2011) na Consulta de Alergologia Cutânea com o principal objectivo de analisar a variação dos padrões de sensibilização aos metais (níquel [Ni], cobalto [Co] e crómio [Cr]) ao longo de 20 anos, em particular no que se refere ao género, grupo etário e relação com a actividade profissional. Resultados: Do total de 5 250 doentes estudados, em 1 626 (31%) observámos pelo menos um teste epicutâneo positivo a um metal (26,5% ao Ni; 10,0% ao Co e 7,0% ao Cr). A prevalência de sensibilização ao Ni era significativamente maior nas mulheres (34,4% versus 8,9%) e ao Cr nos homens (11,5% versus 5,0%). Não houve diminuição significativa da sensibilização ao Ni ao longo dos 20 anos, mas o contributo da faixa etária dos 16-30 anos no total de mulheres sensíveis a este metal decresceu de forma significativamente estatística ao longo dos anos (p < 0,001). A sensibilização ao Cr decresceu sobretudo nos homens (r = -0,535), muito particularmente nos casos relacionados com a construção civil (r = -0,639), enquanto a reatividade ao Cr relacionado com o uso de calçado se manteve estável. Discussão: A manutenção dos elevados níveis de sensibilização ao níquel denota ainda uma fraca implementação das Directivas comunitárias mas a redução da percentagem de mulheres jovens poderá significar já algum efeito positivo nesta faixa etária. Ao contrário, a Directiva referente à redução do Cr no cimento parece estar a ter os seus efeitos positivos. Há, contudo, necessidade de interferir com o conte

  12. Aqueous V(V)-peroxo-amino acid chemistry. Synthesis, structural and spectroscopic characterization of unusual ternary dinuclear tetraperoxo vanadium(V)-glycine complexes.

    PubMed

    Gabriel, C; Kaliva, M; Venetis, J; Baran, P; Rodriguez-Escudero, I; Voyiatzis, G; Zervou, M; Salifoglou, A

    2009-01-19

    Vanadium participation in cellular events entails in-depth comprehension of its soluble and bioavailable forms bearing physiological ligands in aqueous distributions of binary and ternary systems. Poised to understand the ternary V(V)-H(2)O(2)-amino acid interactions relevant to that metal ion's biological role, we have launched synthetic efforts involving the physiological ligands glycine and H(2)O(2). In a pH-specific fashion, V(2)O(5), glycine, and H(2)O(2) reacted and afforded the unusual complexes (H(3)O)(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x 5/4 H(2)O (1) and K(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x H(2)O (2). 1 crystallizes in the triclinic space group P1, with a = 7.805(4) A, b = 8.134(5) A, c = 12.010(7) A, alpha = 72.298(9) degrees, beta = 72.991(9) degrees, gamma = 64.111(9) degrees, V = 641.9(6) A(3), and Z = 2. 2 crystallizes in the triclinic space group P1, with a = 7.6766(9) A, b = 7.9534(9) A, c = 11.7494(13) A, alpha = 71.768(2) degrees, beta = 73.233(2) degrees, gamma = 65.660(2) degrees, V = 610.15(12) A(3), and Z = 2. Both complexes 1 and 2 were characterized by UV/visible, LC-MS, FT-IR, Raman, NMR spectroscopy, cyclic voltammetry, and X-ray crystallography. The structures of 1 and 2 reveal the presence of unusual ternary dinuclear vanadium-tetraperoxo-glycine complexes containing [(V(V)=O)(O(2))(2)](-) units interacting through long V-O bonds and an effective glycinate bridge. The latter ligand is present in the dianionic assembly as a bidentate moiety spanning both V(V) centers in a zwitterionic form. The collective physicochemical properties of the two ternary species 1 and 2 project the chemical role of the low molecular mass biosubstrate glycine in binding V(V)-diperoxo units, thereby stabilizing a dinuclear V(V)-tetraperoxo dianion. Structural comparisons of the anions in 1 and 2 with other known dinuclear V(V)-tetraperoxo binary anionic species provide insight

  13. The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(II) complexes: dual excited state deactivation and dual emission.

    PubMed

    Kreitner, Christoph; Heinze, Katja

    2016-04-07

    The synthesis and characterization of a series of weakly emissive mononuclear cyclometalated [Ru(dpb-R)(tpy)](+) complexes with functional groups R of varying electron-donating characters at the dpb ligand are described (dpbH = 1,3-di(2-pyridyl)benzene, tpy = 2,2';6',2''-terpyridine, 1(+): R = NHCOMe, 2(+): R = NH2, 3(+): R = COOEt, 4(+): R = COOH). Steady-state emission spectroscopy in the temperature range between 298 K and 77 K revealed a previously unrecognized excited state deactivation pathway via low-lying triplet ligand-to-ligand ((3)LL'CT) charge transfer states in addition to the well-known pathway via(3)MC states. Thermal activation barriers for depopulation of the emissive metal-to-ligand charge transfer ((3)MLCT) states via the (3)MC (metal-centered) and (3)LL'CT states were determined experimentally for complexes 1(+) and 3(+). The experimental results were further corroborated by calculating the respective (3)MLCT-(3)LL'CT and (3)MLCT-(3)MC transition states and their energies with density functional theoretical methods. The R substituent modifies the energy difference between the (3)MLCT and (3)LL'CT states and the corresponding activation barrier but leaves the analogous (3)MLCT/(3)MC energetics essentially untouched. Additionally, the dinuclear complex [(tpy)Ru(dpb-NHCO-dpb)Ru(tpy)](2+), 6(2+), containing a biscyclometalating bridge was devised. Despite the asymmetric nature induced by the amide bridge, the mixed-valent cation 6(3+) is ascribed to Robin-Day class II with a broad and intense intervalence charge-transfer (IVCT) absorption (λmax = 1165 nm). Upon optical excitation, the Ru(II)/Ru(II) complex 6(2+) exhibits dual emission in liquid solution from two independently emitting (3)MLCT states localized at the two remote [Ru(tpy)] fragments. No equilibration via Dexter energy transfer is possible due to their large distance and short excited state lifetimes.

  14. Excited state localization and internuclear interactions in asymmetric ruthenium(II) and osmium(II) bpy/tpy based dinuclear compounds.

    PubMed

    Halpin, Yvonne; Dini, Danilo; Ahmed, Hamid M Younis; Cassidy, Lynda; Browne, Wesley R; Vos, Johannes G

    2010-03-15

    The synthesis of two asymmetric dinuclear complexes with the formula [M(bpy)(2)(bpt)Ru(tpy)Cl](2+), where M = Ru (1a), Os(2a); bpy = 2,2'-bipyridyl; Hbpt = 3,5-bis(pyridin-2-yl)1,2,4-triazole and tpy = 2,2',6',2''-terpyridine, is reported. The compounds obtained are characterized by mass spectrometry, (1)H NMR, UV/vis/NIR absorption, luminescence, and resonance Raman spectroscopy. Deuterium isotope labeling facilitates assignment of the (1)H NMR and resonance Raman spectra. The interaction between the two metal centers, mediated by the bridging 1,2,4-triazolato moiety in the mixed valent state, is assigned as type II based on the observation of metal to metal charge transfer absorption bands at 7090 and 5990 cm(-1) for 1a and 2a, respectively. The extent of localization of the emissive excited state was determined by transient resonance Raman and emission spectroscopy. Both 1a and 2a show phosphorescence at the same wavelengths; however, whereas for compound 1a the emission is based on the Ru(tpy)Cl- center, for 2a the emissive state is localized on the Os(bpy)(2)- unit. This indicates that also in the excited state there is efficient interaction between the two metal centers.

  15. Total enantioselectivity in the DNA binding of the dinuclear ruthenium(II) complex [[Ru(Me2bpy)2]2(mu-bpm)]4+ [bpm = 2,2'-bipyrimidine; Me2bpy = 4,4'-dimethyl-2,2'-bipyridine].

    PubMed

    Smith, Jayden A; Collins, J Grant; Patterson, Bradley T; Keene, F Richard

    2004-05-07

    The binding of the three stereoisomers (DeltaDelta-, LambdaLambda- and DeltaLambda-) of the dinuclear ruthenium(II) complex [[Ru(Me2bpy)2]2(mu-bpm)]4+ [Me2bpy = 4,4'-dimethyl-2,2'-bipyridine; bpm = 2,2'-bipyrimidine] to a tridecanucleotide containing a single adenine bulge has been studied by 1H NMR spectroscopy. The addition of the DeltaDelta-isomer to d(CCGAGAATTCCGG)2 induced significant chemical shift changes for the base and sugar resonances of the residues at the bulge site (G3A4G5/C11C10), whereas small shifts were observed upon addition of the enantiomeric LambdaLambda-form. NOESY spectra of the tridecanucleotide bound with the DeltaDelta-isomer revealed intermolecular NOE's between the metal complex and the nucleotide residues at the bulge site, while only weak NOE's were observed to terminal residues to the LambdaLambda-form. Competitive binding studies were performed where both enantiomers were simultaneously added to the tridecanucleotide, and for all ratios of the two stereoisomers the DeltaDelta-isomer remained selectively bound at the bulge site with the LambdaLambda-enantiomer localised at the terminal regions of the tridecanucleotide. The meso-diastereoisomer (DeltaLambda) was found to bind to the tridecanucleotide with characteristics intermediate between the DeltaDelta- and LambdaLambda-enantiomers of the rac form. Two distinct sets of metal complex resonances were observed, with one set having essentially the same shift as the free metal complex, whilst the other set of resonances exhibited significant shifts. The NOE data indicated that the meso-diastereoisomer does not bind as selectively as the DeltaDelta-isomer, with NOE's observed to a greater number of nucleotide residues compared to the DeltaDelta-form. This study provides a rare example of total enantioselectivity in the binding of an inert transition metal complex to DNA, produced by the shape recognition of both ruthenium(II) centres.

  16. Synthesis and characterization of dinuclear rare-earth complexes supported by amine-bridged bis(phenolate) ligands and their catalytic activity for the ring-opening polymerization of l-lactide.

    PubMed

    Duan, Yu-Lai; He, Jia-Xuan; Wang, Wei; Zhou, Jing-Jing; Huang, Yong; Yang, Ying

    2016-06-28

    Reactions of amine-bridged bis(phenolate) protio-ligands N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)aminoacetic acid (L(1)-H3) and N,N-bis[3,5-bis(α,α'-dimethylbenzyl)-2-hydroxybenzyl]aminoacetic acid (L(2)-H3), with 1 equiv. M[N(SiMe3)2]3 (M = La, Nd, Sm, Gd, Y) in THF at room temperature yielded the neutral rare-earth complexes [M2(L)2(THF)4] (L = L(1), M = La (), Nd (), Sm (), Gd (), Y (); L = L(2), M = La (), Nd (), Sm (), Gd (), Y ()). All of these complexes were characterized by single-crystal X-ray diffraction, elemental analysis and in the case of yttrium and lanthanum complexes, (1)H NMR spectroscopy. The molecular structure of revealed dinuclear species in which the eight-coordinate lanthanum centers were bonded to two oxygen atoms of two THF molecules, to three oxygen atoms and one nitrogen atom of one L(1) ligand, and two oxygen atoms of the carboxyl group of another. Complexes were also dinuclear species containing seven-coordinate metal centers similar to , albeit with bonding to one rather than two carboxyl group oxygens of another ligand. Further treatment of with excess benzyl alcohol provided dinuclear complex [La2(L(1))2(BnOH)6] (), in which each lanthanum ion is eight-coordinate, bonded to three oxygen atoms and one nitrogen atom of one ligand, three oxygen atoms of three BnOH molecules, as well as one oxygen atom of bridging carboxyl group of the other ligand. In the presence of BnOH, complexes efficiently catalyzed the ring-opening polymerization of l-lactide in a controlled manner and gave polymers with relatively narrow molecular weight distributions. The kinetic and mechanistic studies associated with the ROP of l-lactide using /BnOH initiating system have been performed.

  17. Lidar Calibration Centre

    NASA Astrophysics Data System (ADS)

    Pappalardo, Gelsomina; Freudenthaler, Volker; Nicolae, Doina; Mona, Lucia; Belegante, Livio; D'Amico, Giuseppe

    2016-06-01

    This paper presents the newly established Lidar Calibration Centre, a distributed infrastructure in Europe, whose goal is to offer services for complete characterization and calibration of lidars and ceilometers. Mobile reference lidars, laboratories for testing and characterization of optics and electronics, facilities for inspection and debugging of instruments, as well as for training in good practices are open to users from the scientific community, operational services and private sector. The Lidar Calibration Centre offers support for trans-national access through the EC HORIZON2020 project ACTRIS-2.

  18. An Altered Transition State for the Reaction of an RNA Model Catalyzed by a Dinuclear Zinc(II) Catalyst

    PubMed Central

    Humphry, Tim; Iyer, Subashree; Iranzo, Olga; Morrow, Janet R.; Richard, John P.; Paneth, Piotr

    2009-01-01

    The cyclization of 2-hydroxypropyl-4-nitrophenyl phosphate (HpPNP) catalyzed by the dinuclear zinc complex of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2-hydroxypropane (1) proceeds by a transition state that is different from that of the uncatalyzed reaction. Kinetic isotope effects (KIEs) measured in the nucleophilic atom and in the leaving group show that the uncatalyzed cyclization has a transition state (TS) with little phosphorus-oxygen bond fission to the leaving group (18klg = 1.0064 ± 0.0009 and 15k = 1.0002 ± 0.0002), and that nucleophilic bond formation occurs in the rate-determining step (18knuc = 1.0326 ± 0.0008). In the catalyzed reaction, larger leaving group isotope effects (18klg = 1.0113 ± 0.0005 and 15k = 1.0015 ± 0.0005) and a smaller nucleophile isotope effect (18knuc = 1.0116 ± 0.0010) indicate a later TS with greater leaving group bond fission, and greater nucleophilic bond formation. These observed nucleophile KIEs are the combined effect of the equilibrium effect on deprotonation of the 2’-hydroxyl nucleophile and the KIE on the nucleophilic step. An EIE of 1.0245 for deprotonation of the hydroxyl group of HPpNP was obtained computationally. The different KIEs for the two reactions indicate that the effective catalysis by 1 is accompanied by selection for an altered transition state, presumably arising from the preferential stabilization by the catalyst of charge away from the nucleophile and toward the leaving group. These results demonstrate the potential for a catalyst using biologically relevant metal ions to select for an altered transition state for phosphoryl transfer. PMID:19053445

  19. Altered transition state for the reaction of an RNA model catalyzed by a dinuclear zinc(II) catalyst.

    PubMed

    Humphry, Tim; Iyer, Subashree; Iranzo, Olga; Morrow, Janet R; Richard, John P; Paneth, Piotr; Hengge, Alvan C

    2008-12-31

    The cyclization of 2-(hydroxypropyl)-4-nitrophenyl phosphate (HpPNP) catalyzed by the dinuclear zinc complex of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2-hydroxypropane (1) proceeds by a transition state that is different from that of the uncatalyzed reaction. Kinetic isotope effects (KIEs) measured in the nucleophilic atom and in the leaving group show that the uncatalyzed cyclization has a transition state (TS) with little phosphorus-oxygen bond fission to the leaving group ((18)k(lg) = 1.0064 +/- 0.0009 and (15)k = 1.0002 +/- 0.0002) and that nucleophilic bond formation occurs in the rate-determining step ((18)k(nuc) = 1.0326 +/- 0.0008). In the catalyzed reaction, larger leaving group isotope effects ((18)k(lg) = 1.0113 +/- 0.0005 and (15)k = 1.0015 +/- 0.0005) and a smaller nucleophile isotope effect ((18)k(nuc) = 1.0116 +/- 0.0010) indicate a later TS with greater leaving group bond fission and greater nucleophilic bond formation. These observed nucleophile KIEs are the combined effect of the equilibrium effect on deprotonation of the 2'-hydroxyl nucleophile and the KIE on the nucleophilic step. An EIE of 1.0245 for deprotonation of the hydroxyl group of HPpNP was obtained computationally. The different KIEs for the two reactions indicate that the effective catalysis by 1 is accompanied by selection for an altered transition state, presumably arising from the preferential stabilization by the catalyst of charge away from the nucleophile and toward the leaving group. These results demonstrate the potential for a catalyst using biologically relevant metal ions to select for an altered transition state for phosphoryl transfer.

  20. Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

    PubMed

    Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

    2016-06-06

    We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

  1. PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

    PubMed

    Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

    2009-07-01

    A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

  2. Dinuclear Pt(II)-bisphosphonate complexes: a scaffold for multinuclear or different oxidation state platinum drugs.

    PubMed

    Piccinonna, Sara; Margiotta, Nicola; Pacifico, Concetta; Lopalco, Antonio; Denora, Nunzio; Fedi, Serena; Corsini, Maddalena; Natile, Giovanni

    2012-08-28

    Geminal bisphosphonates (BPs), used in the clinic for the treatment of hypercalcaemia and skeletal metastases, have been also exploited for promoting the specific accumulation of platinum antitumor drugs in bone tissue. In this work, the platinum dinuclear complex [{Pt(en)}(2)(μ-AHBP-H(2))](+) (1) (the carbon atom bridging the two phosphorous atoms carrying a 2-ammonioethyl and a hydroxyl group, AHBP-H(2)) has been used as scaffold for the synthesis of a Pt(II) trinuclear complex, [{Pt(en)}(3)(μ-AHBP)](+) (2), and a Pt(IV) adamantane-shaped dinuclear complex featuring an oxo-bridge, [{Pt(IV)(en)Cl}(2)(μ-O)(μ-AHBP-H(2))](+) (3) (X-ray structure). Compound 2 undergoes a reversible, pH dependent, rearrangement with a neat switch point around pH = 5.4. Compound 3 undergoes a one-step electrochemical reduction at E(pc) = -0.84 V affording compound 1. Such a potential is far lower than that of glutathione (-0.24 V), nevertheless compound 3 can undergo chemical reduction to 1 by GSH, most probably through a different (inner-sphere) mechanism. In vitro cytotoxicity of the new compounds, tested against murine glioma (C6) and human cervix (HeLa) and hepatoma (HepG2) cell lines, has shown that, while the Pt(IV) dimer 3 is inactive up to a concentration of 50 μM, the two Pt(II) polynuclear compounds 1 and 2 have a cytotoxicity comparable to that of cisplatin with the trinuclear complex 2 generally more active than the dinuclear complex 1.

  3. Synthesis of superheavy elements and dinuclear-system concept of compound-nucleus formation

    SciTech Connect

    Antonenko, N.V.; Adamian, G.G.; Cherepanov, E.A.

    1996-12-31

    Dinuclear system concept is applied to the analysis of reactions used for the synthesis of elements with Z = 110, 112, 114, and 116. The inner fusion barriers obtained for these reactions are in good agreement with the experimental estimations resulted from the excitation energies of compound nuclei. A model is suggested for the calculation of the competition between complete fusion and quasifission in reactions with heavy nuclei. The fusion rate through the inner fusion barrier in mass asymmetry is found by using the multidimensional Kramers-type stationary solution of the Fokker-Planck equation. The influence of dissipative effects on the dynamics of nuclear fusion is considered.

  4. Synthesis of 3-Indolylglycine Derivatives via Dinuclear Zinc Catalytic Asymmetric Friedel-Crafts Alkylation Reaction.

    PubMed

    Wang, Xin-Wei; Hua, Yuan-Zhao; Wang, Min-Can

    2016-10-07

    A direct asymmetric Friedel-Crafts (F-C) alkylation reaction between a wide range of indoles and ethyl 2-(4-methoxyphenylimino)acetate catalyzed by Trost's dinuclear complex is reported. A series of 3-indolylglycine derivatives were synthesized in enantioselectivity of up to >99% enantiomeric excess (ee) using 10 mol% catalyst loading under mild conditions. This atom economic reaction could be run on a gram scale without impacting its enantioselectivity. The absolute stereochemistry of catalytic products was determined by correlation with a known configuration compound. A possible mechanism was proposed for the asymmetric induction.

  5. Synthesis and characterisation of bis-cyclen based dinuclear lanthanide complexes.

    PubMed

    Gunnlaugsson, Thorfinnur; Harte, Andrew J

    2006-04-21

    The design and synthesis of several bis-macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) ligands and their corresponding lanthanum or europium complexes is described; these dinuclear lanthanide systems were made by connecting two macrocyclic cyclen moieties through a rigid, covalent, p-xylylenediamide bridge or a flexible aliphatic hexane bridge. These ligands were subsequently functionalised with six acetamide pendant arms (CONR1R2: R1 = R2 = H or CH3, or R1 = H, R2 = CH3). The corresponding lanthanide bis-complexes were then formed by reaction with La(III) and Eu(III) triflates, yielding overall cationic (+VI charged) complexes.

  6. Winnipeg Centre Project.

    ERIC Educational Resources Information Center

    Manitoba Dept. of Education, Winnipeg.

    The Winnipeg Centre Project is a field-based, work-study program that attempts to create more appropriate education for the inner-city child. Sponsored by the Planning and Research Branch of the Department of Colleges and Universities Affairs and administered by Brandon University in consultation with the Winnipeg School Division, the project is…

  7. Maple Leaf Outdoor Centre.

    ERIC Educational Resources Information Center

    Maguire, Molly; Gunton, Ric

    2000-01-01

    Maple Leaf Outdoor Centre (Ontario) has added year-round outdoor education facilities and programs to help support its summer camp for disadvantaged children. Schools, youth centers, religious groups, and athletic teams conduct their own programs, collaborate with staff, or use staff-developed programs emphasizing adventure education and personal…

  8. Implementing Responsibility Centre Budgeting

    ERIC Educational Resources Information Center

    Vonasek, Joseph

    2011-01-01

    Recently, institutes of higher education (universities) have shown a renewed interest in organisational structures and operating methodologies that generate productivity and innovation; responsibility centre budgeting (RCB) is one such process. This paper describes the underlying principles constituting RCB, its origin and structural elements, and…

  9. Wycheproof Education Centre.

    ERIC Educational Resources Information Center

    Sweetnam and Godfrey, Melbourne (Australia).

    The Wycheproof township in New South Wales (Australia) is the regional center for a grain farming community. The Wycheproof Education Centre was formed by the merger of a separate primary and secondary school (on one site with existing buildings), into a single governing body that is educationally structured into junior, middle, and senior…

  10. Discovering a Discovery Centre

    ERIC Educational Resources Information Center

    McCullagh, John; Stewart, James; Greenwood, Julian

    2007-01-01

    There has recently been a growth in the popularity of "science centres" and this development provides an excellent opportunity to support the primary science curriculum. Their use is therefore well worth including within initial teacher education courses. Hence, undergraduate student teachers at Stranmillis University College Belfast may…

  11. The Iranian Documentation Centre.

    ERIC Educational Resources Information Center

    Harvey, John F.

    The purpose of the Iranian Documentation Centr (Irandoc) was to collect that portion of the world's literature which was pertinent to Iran's research interests, to organize that material, and to promote its use by Iranian researchers. Stated more succinctly, Irandoc's purpose was to obtain ready access to the world's scientific literature in order…

  12. A dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers.

    PubMed

    Albani, B A; Peña, B; Saha, S; White, J K; Schaeffer, A M; Dunbar, K R; Turro, C

    2015-11-28

    {[Ru(CH3CN)3]2(tppz)}(4+) (tppz = tetra-2-pyridylpyrazine) undergoes photoinduced CH3CN exchange with λirr ≥ 610 nm in H2O. In contrast, cis-{[Ru(tpy)(L)]2(bpm)}(4+) (tpy = 2,2':6',2''-terpyridine, bpm = 2,2'-bipyrimidine, L = CH3CN) is not reactive, but the complex with L = DMSO is photoactive. These complexes are potentially useful for the release of multiply caged drugs.

  13. Structure and spectral properties of dinuclear zinc complex containing semicarbazonate ligands

    NASA Astrophysics Data System (ADS)

    Jing-Lin, Wang; Jiao, Feng; Mei-Ping, Xu; Bin-Sheng, Yang

    2011-04-01

    The dinuclear Zn 2+ complex [Zn(HSSC)OAc] 2·2DMF (H 2SSC = salicylaldehyde semicarbazone; HOAc = acetic acid; DMF = N,N-dimethylfomamide) was prepared and structurally characterized by single crystal X-ray. The basic structural unit of the complex is a dinuclear complex [Zn(HSSC)OAc] 2 in which the semicarbazone ligand adopts the phenol-imine form. The deprotonated phenol group forms a one-atom bridge between the two zinc centers, and both of the zinc centers are five-coordinated. The local coordination environment of Zn 2+ can be approximately considered as square pyramidal. UV spectral studies show that the H 2SSC provides strong binding of Zn 2+ in a 1:1 ratio in solution. The conditional binding constant of the complex is lg KZn-L = 12.89 ± 0.76 in 0.05 M Tris-HCl buffer at pH 7.4. The H 2SSC exhibits an enhanced fluorescence effect by the addition of Zn 2+, and affords an excellent selectivity for Zn 2+ under physiological conditions.

  14. Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure.

    PubMed

    Li, Hong-Feng; Yan, Peng-Fei; Chen, Peng; Wang, Yan; Xu, Hui; Li, Guang-Ming

    2012-01-21

    A new bis-β-diketone, 3,3'-bis(4,4,4-trifluoro-1,3-dioxobutyl)biphenyl (BTB), has been designed and prepared for the synthesis of a series of dinuclear lanthanide complexes [Ln(2)(BTB)(3)(C(2)H(5)OH)(2)(H(2)O)(2)] [Ln = Eu (1), Gd (2)], [Ln(2)(BTB)(3)(DME)(2)] [Ln = Nd (3), Yb (4); DME = ethylene glycol dimethyl ether] and [Eu(2)(BTB)(3)(L)(2)] [L = 2,2-bipydine (5); 1,10-phenanthroline (6); 4,7-diphenyl-1,10-phenanthroline (7)]. Complexes 1-7 have been characterized by various spectroscopic techniques and their photophysical properties are investigated. X-ray crystallographical analysis reveals that complexes 1, 3 and 4 adopt triple-stranded dinuclear structures which are formed by three bis-bidentate ligands with two lanthanide ions. The complexes 1 and 3-7 display strong visible red or NIR luminescence upon irradiation at ligand band around 372 nm, depending on the choice of the lanthanide. The solid-state photoluminescence quantum yields and the lifetimes of Eu(3+) complexes are determined and described.

  15. μ2-Oxido bridged dinuclear vanadium(V) complex: Synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Ghorbani, Maryam; Khalaji, Aliakbar Dehno; Feizi, Nourollah; Akbari, Alireza; Eigner, Vaclav; Dusek, Michal

    2017-02-01

    μ2-Oxido bridged dinuclear vanadium(V) Schiff base complex with the general formula [VO2(L)]2·2CH3OH was synthesized and characterized. The X-ray results show the complex is dinuclear with two μ-O bridging ions, and the vanadium centers have an octahedral N2O4 coordination sphere. The tridentate Schiff base ligand L coordinated to vanadium(V) center as a monoanion in the basal plane. The basal plane is completed by one of the μ-O bridges. The other μ-O bridge coordinated to vanadium(V) center as apical direction. The two oxido bridged connected the two Vv centers together with the Vv-O-Vv angle of 101.21(6)°, the Vsbnd O distances of 1.70(6) and 2.31(7) Å and the V⋯V separation of 3.113(5) Å. Finally, the complex was calcinated at 600 °C for 3 h. The FT-IR spectrum of the product shows the formation of the V2O5 particles.

  16. SPOT4 Management Centre

    NASA Technical Reports Server (NTRS)

    Labrune, Yves; Labbe, X.; Roussel, A.; Vielcanet, P.

    1994-01-01

    In the context of the CNES SPOT4 program CISI is particularly responsible for the development of the SPOT4 Management Centre, part of the SPOT4 ground control system located at CNES Toulouse (France) designed to provide simultaneous control over two satellites. The main operational activities are timed to synchronize with satellite visibilities (ten usable passes per day). The automatic capability of this system is achieved through agenda services (sequence of operations as defined and planned by operator). Therefore, the SPOT4 Management Centre offers limited, efficient and secure human interventions for supervision and decision making. This paper emphasizes the main system characteristics as degree of automation, level of dependability and system parameterization.

  17. Elderly Care Centre

    NASA Astrophysics Data System (ADS)

    Wagiman, Aliani; Haja Bava Mohidin, Hazrina; Ismail, Alice Sabrina

    2016-02-01

    The demand for elderly centre has increased tremendously abreast with the world demographic change as the number of senior citizens rose in the 21st century. This has become one of the most crucial problems of today's era. As the world progress into modernity, more and more people are occupied with daily work causing the senior citizens to lose the care that they actually need. This paper seeks to elucidate the best possible design of an elderly care centre with new approach in order to provide the best service for them by analysing their needs and suitable activities that could elevate their quality of life. All these findings will then be incorporated into design solutions so as to enhance the living environment for the elderly especially in Malaysian context.

  18. Crystal structure of the membrane-exposed domain from a respiratory quinol oxidase complex with an engineered dinuclear copper center.

    PubMed

    Wilmanns, M; Lappalainen, P; Kelly, M; Sauer-Eriksson, E; Saraste, M

    1995-12-19

    Cytochrome oxidase is a membrane protein complex that catalyzes reduction of molecular oxygen to water and utilizes the free energy of this reaction to generate a transmembrane proton gradient during respiration. The electron entry site in subunit II is a mixed-valence dinuclear copper center in enzymes that oxidize cytochrome c. This center has been lost during the evolution of the quinoloxidizing branch of cytochrome oxidases but can be restored by engineering. Herein we describe the crystal structures of the periplasmic fragment from the wild-type subunit II (CyoA) of Escherichia coli quinol oxidase at 2.5-A resolution and of the mutant with the engineered dinuclear copper center (purple CyoA) at 2.3-A resolution. CyoA is folded as an 11-stranded mostly antiparallel beta-sandwich followed by three alpha-helices. The dinuclear copper center is located at the loops between strands beta 5-beta 6 and beta 9-beta 10. The two coppers are at a 2.5-A distance and symmetrically coordinated to the main ligands that are two bridging cysteines and two terminal histidines. The residues that are distinct in cytochrome c and quinol oxidases are around the dinuclear copper center. Structural comparison suggests a common ancestry for subunit II of cytochrome oxidase and blue copper-binding proteins.

  19. EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor.

    PubMed

    Das, Kuheli; Patra, Chiranjit; Sen, Chandana; Datta, Amitabha; Massera, Chiara; Garribba, Eugenio; El Fallah, Mohamed Salah; Beyene, Belete B; Hung, Chen-Hsiung; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Escudero, Daniel; Frontera, Antonio

    2016-12-30

    A new Cu(II) dinuclear complex, Cu2L2 (1) was afforded employing the potentially pentatentate Schiff base precursor H2L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H2L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H37Ra (ATCC 25177) and M. tuberculosis H37Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL(-1). A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.

  20. Dinuclear Zinc (II) Complexes of Macrocyclic Polyamine Ligands Containing an Imidazolium Bridge: Synthesis, Characterization, and Their Interaction with Plasmid DNA

    PubMed Central

    Huang, Jun; Huang, Qing-Dong; Zhang, Ji; Zhou, Li-Hong; Li, Qiang-Lin; Li, Kun; Jiang, Ning; Lin, Hong-Hui; Wu, Jiang; Yu, Xiao-Qi

    2007-01-01

    Two novel macrocyclic polyamine ligands and their dinuclear zinc (II) complexes were synthesized and characterized. Their interaction with plasmid DNA was studied by gel electrophoresis and fluorescence quenching experiment. The result showed that these complexes could bind DNA efficiently under physiological conditions.

  1. Luminescence dynamics and {sup 13}C NMR characteristics of dinuclear complexes exhibiting coupled lanthanide(III) cation pairs

    SciTech Connect

    Matthews, K.D.; Bailey-Folkes, S.A.; Kahwa, I.A.

    1992-08-20

    Luminescence and cross-polarization magic angle spinning (CP-MAS) {sup 13}C NMR properties of lanthanide dinuclear macrocyclic complexes of a compartmental Schiff base chelate (1) derived from the condensation of 2,6-diformyl-p-cresol and 3,6-dioxa-1,8-octanediamine are reported. The Schiff base chromophore in 1 is a strong light absorber and an efficient sensitizer for intense Tb{sup 3+}({sup 5}D{sub 4}) and Eu{sup 3+}({sup 5}D{sub 0})(T < 110 K ) emission which does not exhibit self-quenching effects. Emission from Tb{sup 3+} is sensitized by the ligand singlet state; in striking contrast, Eu{sup 3+} emission is sensitized by the triplet state and reveals an unusual nonradiative quenching process at T > 110 K with a thermal barrier of {approx} 2300 cm{sup {minus}1}. Weak emission is observed from Dy{sup 3+}({sup 4}F{sub 9/2}), Sm{sup 3+}({sup 4}G{sub 5/2}), and Pr{sup 3+}({sup 1}D{sub 2}) diluted in Gd{sup 3+} (i.e., from Gd{sup 3+}-Ln{sup 3+} heteropairs, Ln = Pr, Sm, Dy). Intramolecular metal-metal (Ln-Ln = 4 {Angstrom}) interactions account for the greatly quenched emission from Sm{sup 3+}-Sm{sup 3+} and Dy{sup 3+}-Dy{sup 3+} homopairs compared to Gd{sup 3+}-Ln heteropairs (Ln = Sm, Dy). Gd{sup 3+}-Ln{sup 3+} emission lifetimes at 77 K are 1610 (Tb{sup 3+}), 890 (Eu{sup 3+}), 14 (Dy{sup 3+}) and {approx} 13 {mu}s (Sm{sup 3+}). Nonradiative relaxation processes at 77 K in dilute Ln{sup 3+}:Gd{sub 2}1(NO{sub 3}){sub 4}{center_dot}H{sub 2}O, being temperature independent for Sm{sup 3+} and Eu{sup 3+} but temperature dependent for Tb{sup 3+}, follow the energy gap law with {alpha} {approx} - 10{sup {minus}3} cm and B {approx} 2 x 10{sup 8} s{sup {minus}1}. CP-MAS data show paramagnetic broadening of {sup 13}C resonances which increases with the magnetic moment of Ln{sup 3+}. Surprisingly, no significant shifts in resonance positions corresponding to the changing nature of paramagnetic Ln{sup 3+} ions are observed. 43 refs., 8 figs., 2 tabs.

  2. New dinuclear cobalt(II) and zinc(II) complexes of a carboxylate-rich dinucleating ligand: synthesis, structure, spectroscopic characterization, and their interactions with sugars.

    PubMed

    Bera, Manindranath; Curtiss, Ashley B S; Musie, Ghezai T; Powell, Douglas R

    2012-11-19

    Sugar-metal ion interactions in aqueous medium are involved in many biochemical processes such as the transport and storage of metals, the function and regulation of sugar-metabolizing metalloenzymes, the mechanism of action of metal-containing pharmaceuticals, and toxic metal metabolism. To understand such interactions we synthesized and fully characterized two new dinuclear cobalt(II) and zinc(II) complexes as carbohydrate binding models for xylose/glucose isomerases (XGI). Synthesis of the dicobalt complex, Na3[Co2(ccdp)(μ-HCO2)]BF4·9H2O·2CH3OH (1), was performed in methanol with stoichiometric amounts of Co(BF4)2·6H2O and the dinucleating ligand, H5ccdp (H5ccdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[carboxymethyl]-1,3-diaminopropan-2-ol), in the presence of NaOH at ambient temperature in an argon glovebox. Similarly, the dizinc complex, [NMe4]2[Zn2(ccdp)(μ-OAc)]·CH3OH (2), was synthesized from Zn(OAc)2·2H2O and H5ccdp in the presence of NMe4OH at ambient temperature in methanol. Binding of the complexes with carbohydrates was investigated under different reaction conditions. In aqueous alkaline media, complexes 1 and 2 showed chelating ability towards the biologically important sugars, d-glucose and d-xylose, and a polyalcohol enzyme inhibitor (xylitol). In solution, each complex forms a 1:1 complex-substrate bound product with specific binding constant values. Synthesis, characterization details, and substrate binding using spectroscopic techniques and single-crystal X-ray diffraction are reported.

  3. Dissymmetrical U-shaped π-stacked supramolecular assemblies by using a dinuclear Cu(I) clip with organophosphorus ligands and monotopic fully π-conjugated ligands.

    PubMed

    El Sayed Moussa, Mehdi; Guillois, Kevin; Shen, Wenting; Réau, Régis; Crassous, Jeanne; Lescop, Christophe

    2014-11-03

    Reactions between the U-shaped binuclear Cu(I) complex A that bears short metal-metal distances and the cyano-capped monotopic π-conjugated ligands 1-5 that carry gradually bulkier polyaromatic terminal fragments lead to the formation of π-stacked supramolecular assemblies 6-10, respectively, in yields of 50-80 %. These derivatives have been characterized by multinuclear NMR spectroscopic analysis and X-ray diffraction studies. Their solid-state structures show the selective formation of U-shaped supramolecular assemblies in which two monotopic π-conjugated systems present large (6, 7, and 9) or medium (8 and 10) intramolecular π overlap, thus revealing π-π interactions. These assemblies self-organize into head-to-tail π-stacked dimers that in turn self-assemble to afford infinite columnar π stacks. The nature, extent, and complexity of the intermolecular contacts within the head-to-tail π-stacked dimer depend on the nature of the terminal polyaromatic fragment carried by the cyano-capped monotopic ligand, but it does not alter the result of the self-assembling process. These results demonstrate that the dinuclear molecular clip A that bears short metal-metal distances allows selective supramolecular assembly processes driven by the formation of intra- and intermolecular short π-π interactions in the resulting self-assembled structures; thus, demonstrating that their shape is not only dictated by the symmetry of the building blocks. This approach opens perspectives toward the formation of extended π-stacked columns based on dissymmetrical and functional π-conjugated systems.

  4. Heterobimetallic dinuclear lanthanide alkoxide complexes as acid-base difunctional catalysts for transesterification.

    PubMed

    Zeng, Ruijie; Sheng, Hongting; Zhang, Yongcang; Feng, Yan; Chen, Zhi; Wang, Junfeng; Chen, Man; Zhu, Manzhou; Guo, Qingxiang

    2014-10-03

    A practical lanthanide(III)-catalyzed transesterification of carboxylic esters, weakly reactive carbonates, and much less-reactive ethyl silicate with primary and secondary alcohols was developed. Heterobimetallic dinuclear lanthanide alkoxide complexes [Ln2Na8{(OCH2CH2NMe2)}12(OH)2] (Ln = Nd (I), Sm (II), and Yb (III)) were used as highly active catalysts for this reaction. The mild reaction conditions enabled the transesterification of various substrates to proceed in good to high yield. Efficient activation of transesterification may be endowed by the above complexes as cooperative acid-base difunctional catalysts, which is proposed to be responsible for the higher reactivity in comparison with simple acid/base catalysts.

  5. Two new oximate-bridged square-planar dinuclear nickel(II) complexes.

    PubMed

    Bera, Manindranath; Noll, Bruce C

    2007-12-01

    The synthesis and characterization of two new dinuclear nickel(II) complexes, namely bis{mu-3-[2-(dimethylamino)ethylimino]butan-2-one oximato}dinickel(II) bis(perchlorate) acetonitrile solvate, [Ni2(C8H16N3O)2](ClO4)2 x CH3CN, (I), and bis{mu-3-[2-(dimethylamino)ethylimino]-3-phenylpropan-2-one oximato}dinickel(II) bis(perchlorate), [Ni2(C13H18N3O)2](ClO4)2, (II), are reported. Single-crystal X-ray analyses of the complexes reveal that the nickel(II) ions are in square-planar N3O environments and form six-membered (NiNO)2 metallacycles. The cation in (II) possesses crystallographically imposed inversion symmetry.

  6. Magnetic exchange couplings from noncollinear perturbation theory: dinuclear CuII complexes.

    PubMed

    Phillips, Jordan J; Peralta, Juan E

    2014-08-07

    To benchmark the performance of a new method based on noncollinear coupled-perturbed density functional theory [J. Chem. Phys. 138, 174115 (2013)], we calculate the magnetic exchange couplings in a series of triply bridged ferromagnetic dinuclear Cu(II) complexes that have been recently synthesized [Phys. Chem. Chem. Phys. 15, 1966 (2013)]. We find that for any basis-set the couplings from our noncollinear coupled-perturbed methodology are practically identical to those of spin-projected energy-differences when a hybrid density functional approximation is employed. This demonstrates that our methodology properly recovers a Heisenberg description for these systems, and is robust in its predictive power of magnetic couplings. Furthermore, this indicates that the failure of density functional theory to capture the subtle variation of the exchange couplings in these complexes is not simply an artifact of broken-symmetry methods, but rather a fundamental weakness of current approximate density functionals for the description of magnetic couplings.

  7. Dinuclear iridium(III) complexes consisting of back-to-back tpy-(ph)n-tpy bridging ligands (n = 0, 1, or 2) and terminal cyclometallating tridentate N-C-N ligands.

    PubMed

    Auffrant, Audrey; Barbieri, Andrea; Barigelletti, Francesco; Collin, Jean-Paul; Flamigni, Lucia; Sabatini, Cristiana; Sauvage, Jean-Pierre

    2006-12-25

    Three dinuclear iridium(III) complexes consisting of a conjugated bis-tpy type bridging ligand and cyclometallating capping tridentate ligands of the 1,3-di-2-pyridylbenzene family have been prepared (tpy, 2,2',6',2' '-terpyridine). The two tpy units of the bridge are connected via their back-positions (4') either directly or with a p-phenylene or p-biphenylene spacer. The synthesis relies on the reaction between the dinuclear [Ir(dpb)Cl2]2 complex (dpb-H =1,3-dipyridyl-4,6-dimethylbenzene) and the corresponding bis-tpy ligand. Electrochemical measurements afford metal-centered oxidation and ligand-centered reduction potentials; from the oxidation steps, no evidence is obtained for a strong coupling between the two iridium(III) subunits of the dinuclear species. For all complexes, ground-state absorption data in the 380 nm to visible region show a trend which is consistent with the presence of charge-transfer (CT) transitions involving different degrees of electronic delocalization at the bridging ligands. (dpb)Ir(tpy-tpy)Ir(dpb)4+ exhibits an appreciable luminescence at room temperature (phi = 3.0 x 10(-3); tau = 3.3 ns), whereas no emission from the other binuclear complexes is detected. All binuclear complexes luminesce at 77 K, and a metal-to-ligand CT nature for (dpb)Ir(tpy-tpy)Ir(dpb)4+ is suggested, whereas a ligand-centered (LC) emission is proposed for (dpb)Ir(tpy-(ph)2-tpy)Ir(dpb)4+ on the basis of the comparison with the phosphorescence properties of the free bridging ligand, tpy-(ph)2-tpy. Transient absorbance experiments at room temperature afford the absorption spectra and lifetimes of the non-emissive excited states. For (dpb)Ir(tpy-ph-tpy)Ir(dpb)4+ and (dpb)Ir(tpy-(ph)2-tpy)Ir(dpb)4+, the spectra exhibit a broad profile peaking around 780 nm, quite intense in the case of (dpb)Ir(tpy-(ph)2-tpy)Ir(dpb)4+, and lifetimes of 160 and 440 ps, respectively.

  8. Catalytic photooxidation of alcohols by an unsymmetrical tetra(pyridyl)pyrazine-bridged dinuclear Ru complex.

    PubMed

    Chen, Weizhong; Rein, Francisca N; Scott, Brian L; Rocha, Reginaldo C

    2011-05-09

    The dinuclear complexes [(tpy)Ru(tppz)Ru(bpy)(L)](n+) (where L is Cl(-) or H(2)O, tpy and bpy are the terminal ligands 2,2':6',2''-terpyridine and 2,2'-bipyridine, and tppz is the bridging backbone 2,3,5,6-tetrakis(2-pyridyl)pyrazine) were prepared and structurally and electronically characterized. The mononuclear complexes [(tpy)Ru(tppz)](2+) and [(tppz)Ru(bpy)(L)](m+) were also prepared and studied for comparison. The proton-coupled, multi-electron photooxidation reactivity of the aquo dinuclear species was shown through the photocatalytic dehydrogenation of a series of primary and secondary alcohols. Under simulated solar irradiation and in the presence of a sacrificial electron acceptor, the photoactivated chromophore-catalyst complex (in aqueous solutions at room temperature and ambient pressure conditions) can perform the visible-light-driven conversion of aliphatic and benzylic alcohols into the corresponding carbonyl products (i.e., aldehydes or ketones) with 100% product selectivity and several tens of turnover cycles, as probed by NMR spectroscopy and gas chromatography. Moreover, for aliphatic substrates, the activity of the photocatalyst was found to be highly selective toward secondary alcohols, with no significant product formed from primary alcohols. Comparison of the activity of this tppz-bridged complex with that of the analogue containing a back-to-back terpyridine bridge (tpy-tpy, i.e., 6',6''-bis(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine) demonstrated that the latter is a superior photocatalyst toward the oxidation of alcohols. The much stronger electronic coupling with significant delocalization across the strongly electron-accepting tppz bridge facilitates charge trapping between the chromophore and catalyst centers and therefore is presumably responsible for the decreased catalytic performance.

  9. Decomposition of dinuclear manganese complexes for the preparation of nanostructured oxide materials.

    PubMed

    Hill, Jonathan P; Palza, Humberto; Alam, Sher; Ariga, Katsuhiko; Schumacher, Amy Lea; D'Souza, Francis; Anson, Christopher E; Powell, Annie K

    2008-09-15

    The crystal structures of several dinuclear complexes of manganese are reported, and the decomposition and analysis of the nanostructured products derived from them are presented. 1,4,7,10-Tetraazacyclododecane (cyclen) forms dinuclear complexes 1-4 containing doubly oxo-bridged or oxo-acetato bridging ligands depending on the manganese salt used for the reaction. Doubly oxo-bridged 1 crystallizes in the orthorhombic space group Pnma, a = 22.3850(14) A, b = 9.1934(5) A, c = 13.2424(10) A, V = 2725.2(3) A(3). 2, containing [Mn(SCN)5](3-) conteranions, crystallizes in monoclinic space group I2/a with a = 18.2699(10) A, b = 11.2384(6) A, c = 18.6432(9) A, alpha = 90.00 degrees, beta = 114.510(6) degrees, gamma = 90.00 degrees, V = 3483.0(3) A(3). Oxo-acetato-bridged 3 crystallizes in orthorhombic space group Pca21, a = 13.9322(11) A, b = 16.2332(13) A, c = 14.6794(8) A, V = 3320.0(4) A(3). Compound 4 consists of a templated quasi-one-dimensional manganese oxalate crystallized in the triclinic space group P1, a = 9.5442(11) A, b = 10.3758(10) A, c = 21.851(2) A, alpha = 83.720(12) degrees, beta = 80.106(13) degrees, gamma = 85.457(13) degrees, V = 2114.9(4) A(3). Compounds 1, 3, and 4 decompose to nanostructured oxide materials, which may be isolated in bulk as lamellar-structured particles or microspheres or deposited on substrates.

  10. Cellular and biomolecular responses of human ovarian cancer cells to cytostatic dinuclear platinum(II) complexes.

    PubMed

    Lin, Miaoxin; Wang, Xiaoyong; Zhu, Jianhui; Fan, Damin; Zhang, Yangmiao; Zhang, Junfeng; Guo, Zijian

    2011-03-01

    Polynuclear platinum(II) complexes represent a class of potential anticancer agents that have shown promising pharmacological properties in preclinical studies. The nature of cellular responses induced by these complexes, however, is poorly understood. In this research, the cellular responses of human ovarian cancer COC1 cells to dinuclear platinum(II) complexes {[cis-Pt(NH₃)₂Cl]₂L¹}(NO₃)₂ (1) and {[cis-Pt(NH₃)₂Cl]₂L²}(NO₃)₂ (2) (L¹ = α,α'-diamino-p-xylene, L² = 4,4'-methylenedianiline) has been studied using cisplatin as a reference. The effect of platinum complexes on the proliferation, death mode, mitochondrial membrane potential, and cell cycle progression has been examined by MTT assay and flow cytometry. The activation of cell cycle checkpoint kinases (CHK1/2), extracellular signal-regulated kinases (ERK1/2), and p38 mitogen-activated protein kinase (p38 MAPK) of the cells by the complexes has also been analyzed using phospho-specific flow cytometry. Complex 1 is more cytotoxic than complex 2 and cisplatin at most concentrations; complex 2 and cisplatin are comparably cytotoxic. These complexes kill the cells through an apoptotic or apoptosis-like pathway characterized by exposure of phosphatidylserine and dissipation of mitochondrial membrane potential. Complex 1 shows the strongest inductive effect on the morphological changes of the cells, followed by cisplatin and complex 2. Complexes 1 and 2 arrest the cell cycle in G2 or M phase, while cisplatin arrests the cell cycle in S phase. The influence of these complexes on CHK1/2, ERK1/2, and p38 MAPK varies with the dose of the drugs or reaction time. Activation of phospho-ERK1/2 and phospho-p38 MAPK by these complexes is closely related to the cytostatic activity. The results demonstrate that dinuclear platinum(II) complexes can induce some cellular responses different from those caused by cisplatin.

  11. Synthesis and structural characterization of dinuclear Cd2+, Hg2+ and Fe2+ complexes with neutral bi and tetradentate flexible pyrazole-based ligands

    NASA Astrophysics Data System (ADS)

    Beheshti, Azizolla; Lalegani, Arash; Behvandi, Fatemeh; Safaeiyan, Forough; Sarkarzadeh, Afsoon; Bruno, Giuseppe; Amiri Rudbari, Hadi

    2015-02-01

    Four new complexes of [Hg2Cl4(bpp)]n (1), [Hg2Cl4(tdmpp)] (2), [Cd2I4(tdmpp)] (3) and [Fe2Cl4(tdmpp)] (4) were prepared by using the neutral N-donor ligands 1,3-bis(3,5-dimethyl-1-pyrazolyl)propane (bpp) and 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane (tdmpp) with different flexibility and appropriate metal salts of Cd(II), Hg(II) and Fe(II) ions. These compounds were characterized by the infrared spectroscopy, elemental analysis and X-ray crystallography. Flexible ligands and non-covalent Csbnd H⋯Cl hydrogen bonds play a major role in the crystal packing of compounds 1, 2 and 4. In the two-dimensional non-covalent structure of 1, there are two distinctly different coordination modes for the mercury atoms. One mercury atom has pseudo-trigonal bipyramidal geometry and the other adopts a distorted tetrahedral environment. In the dinuclear structures of 2 and 4 the neutral molecules are linked together by the Csbnd H⋯Cl hydrogen bonds, forming an infinite one-dimensional zigzag chain structure. Compounds 2-4 are isostructural with each other.

  12. Theoretical Proposal for the Whole Phosphate Diester Hydrolysis Mechanism Promoted by a Catalytic Promiscuous Dinuclear Copper(II) Complex.

    PubMed

    Esteves, Lucas F; Rey, Nicolás A; Dos Santos, Hélio F; Costa, Luiz Antônio S

    2016-03-21

    The catalytic mechanism that involves the cleavage of the phosphate diester model BDNPP (bis(2,4-dinitrophenyl) phosphate) catalyzed through a dinuclear copper complex is investigated in the current study. The metal complex was originally designed to catalyze catechol oxidation, and it showed an interesting catalytic promiscuity case in biomimetic systems. The current study investigates two different reaction mechanisms through quantum mechanics calculations in the gas phase, and it also includes the solvent effect through PCM (polarizable continuum model) single-point calculations using water as solvent. Two mechanisms are presented in order to fully describe the phosphate diester hydrolysis. Mechanism 1 is of the S(N)2 type, which involves the direct attack of the μ-OH bridge between the two copper(II) ions toward the phosphorus center, whereas mechanism 2 is the process in which hydrolysis takes place through proton transfer between the oxygen atom in the bridging hydroxo ligand and the other oxygen atom in the phosphate model. Actually, the present theoretical study shows two possible reaction paths in mechanism 1. Its first reaction path (p1) involves a proton transfer that occurs immediately after the hydrolytic cleavage, so that the proton transfer is the rate-determining step, which is followed by the entry of two water molecules. Its second reaction path (p2) consists of the entry of two water molecules right after the hydrolytic cleavage, but with no proton transfer; thus, hydrolytic cleavage is the rate-limiting step. The most likely catalytic path occurs in mechanism 1, following the second reaction path (p2), since it involves the lowest free energy activation barrier (ΔG(⧧) = 23.7 kcal mol(-1), in aqueous solution). A kinetic analysis showed that the experimental k(obs) value of 1.7 × 10(-5) s(-1) agrees with the calculated value k1 = 2.6 × 10(-5) s(-1); the concerted mechanism is kinetically favorable. The KIE (kinetic isotope effect) analysis

  13. Visible Light-Induced Electron Transfer from Di-mu-oxo Bridged Dinuclear Mn Complexes to Cr Centers in Silica Nanopores

    SciTech Connect

    Frei, Heinz; Weare, Walter W.; Pushkar, Yulia; Yachandra, Vittal K.; Frei, Heinz

    2008-06-03

    The compound (bpy)2MnIII(mu-O)2MnIV(bpy)2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single CrVI charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of MnIII(mu-O)2MnIV demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of CrVI centers. The FT-Raman spectrum upon visible light excitation of the CrVI-OII --> CrV-OI ligand-to-metal charge-transfer reveals electron transfer from MnIII(mu-O)2MnIV (Mn-O stretch at 700 cm-1) to CrVI, resulting in the formation of CrV and MnIV(mu-O)2MnIV (Mn-O stretch at 645 cm-1). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (DELTA Eo = -0.6 V) remain after several minutes, which points to spatial separation of CrV and MnIV(mu-O)2MnIV as a consequence of hole (OI) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well defined transition metal molecular units, with the ultimate goal of performing endothermic, multi-electron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.

  14. [The primary healthcare centres].

    PubMed

    Brambilla, Antonio; Maciocco, Gavino

    2014-04-01

    The central attributes of primary care are: first contact (accessibility), longitudinality (person- focused preventive and curative care overtime), patient-oriented comprehensiveness and coordination (including navigation towards secondary and tertiary care). Besides taking care of the needs of the individuals, primary health care teams are also looking at the community, especially when addressing social determinants of health. The rationale for the benefits for primary care for health has been found in: 1) greater access to needed services; 2) better quality of care; 3) a greater focus on prevention; 4) early management of health problems; 5) organizing and delivering high quality care for chronic non-communicable diseases. This paper describes the role of primary healthcare centres in strengthening community primary services and in reducing health inequalities. Furthemore, the experiences of Regional Health Services from Tuscany and Emilia-Romagna are discussed, with a brief overview of the literature.

  15. Should "Teacher Centred Teaching" Replace "Student Centred Learning"?

    ERIC Educational Resources Information Center

    Bailey, Patrick D.

    2008-01-01

    Mission statements of most HEIs across the UK support "student centred learning". In this paper, it is suggested that "teacher centred teaching" should also have a major role to play, improving the quality of the learning experience in higher education. Students are extremely diverse in their skills, weaknesses, and learning…

  16. Effects of Novel Dinuclear Cisplatinum(II) Complexes on the Electrical Properties of Human Molt-4 Leukemia Cells.

    PubMed

    Dobrzyńska, Izabela; Skrzydlewska, Elżbieta; Figaszewski, Zbigniew A

    2015-04-01

    The aim of this study was to determine the influence of cisplatin and novel dinuclear platinum(II) complexes on the membrane electrical properties and lipid peroxidation levels of the Molt-4 human leukemia cell line. Changes in cell function may affect the basal electrical surface properties of cell membranes. These changes can be detected using electrokinetic measurements. Surface charge densities of Molt-4 cells were measured as a function of pH. A four-component equilibrium model was used to describe the interaction between the ions in solution and on cell membrane surfaces. Agreement was found between the experimental and theoretical charge variation curves of the leukemia cells at pH 2.5-9. Lipid peroxidation was estimated by measuring levels of 8-iso-prostaglandine F2α [isoprostanes]. Acid and base functional group concentrations and average association constants with hydroxyl ions were smaller in cisplatin- or dinuclear platinum(II) complex-treated leukemia cell membranes compared to those in untreated cancer cells, and the average association constants with hydrogen ions were higher. Levels of lipid peroxidation products in cisplatin- or dinuclear platinum(II) complex-treated leukemia cell were higher than those found in untreated cancer cells.

  17. Structural, photoluminescence, and theoretical DFT studies of gold(I) and silver(I) metallacycle dinuclear complexes of 1-methylbenzimidazolediphenyl phosphine (MBDP) ligand

    NASA Astrophysics Data System (ADS)

    Jenkins, Darkus E.; Assefa, Zerihun

    2017-04-01

    The synthesis and structural characterization of the bridging ligand, 1-methyl benzimidazole diphenylphosphine (MBDP) and its coordination with Au(I) and Ag(I) metal ions is reported. Two ligands coordinate to the metal ions in head to tail fashion forming a metallacycle coordination consisting of strong M-M bonding interaction with Ausbnd Au = 2.808 and Agsbnd Ag = 3.017 Å. Linear coordination is observed for the gold, while the silver shows distorted tetrahedral arrangement. X-ray crystal data of [(MBDP)2Au2](CH3CN)(BF4)2 (2) crystallizes in the monoclinic system with the space group of P21/n with cell constants of a = 8.9993 (8) Å, b = 19.6166 (18) Å, c = 13.4484 (12) Å, β = 100.966 (2)°, R = 0.026, and Rw = 0.064. The structure of [(MBDP)2(CH3CN)4Ag2](BF4)2, (3) crystallizes in the P (-)1 space group and the unit cell is a = 10.5423 (10) Å, b = 10.7638 (10) Å, c = 12.3530 (12) Å; α = 88.592 (3)°, β = 73.097 (3)°, γ = 84.422 (3)°, V = 1334.8 (2) Å3 with Z = 1, R = 0.034 and Rw = 0.093. The coordinating ligand as well as both dinuclear compounds reported here are luminescent in the near UV region. As supported by the DFT theoretical work, the emission is suggested to be primarily ligand based π- π* transition.

  18. CMCC Data Distribution Centre

    NASA Astrophysics Data System (ADS)

    Aloisio, Giovanni; Fiore, Sandro; Negro, A.

    2010-05-01

    The CMCC Data Distribution Centre (DDC) is the primary entry point (web gateway) to the CMCC. It is a Data Grid Portal providing a ubiquitous and pervasive way to ease data publishing, climate metadata search, datasets discovery, metadata annotation, data access, data aggregation, sub-setting, etc. The grid portal security model includes the use of HTTPS protocol for secure communication with the client (based on X509v3 certificates that must be loaded into the browser) and secure cookies to establish and maintain user sessions. The CMCC DDC is now in a pre-production phase and it is currently used only by internal users (CMCC researchers and climate scientists). The most important component already available in the CMCC DDC is the Search Engine which allows users to perform, through web interfaces, distributed search and discovery activities by introducing one or more of the following search criteria: horizontal extent (which can be specified by interacting with a geographic map), vertical extent, temporal extent, keywords, topics, creation date, etc. By means of this page the user submits the first step of the query process on the metadata DB, then, she can choose one or more datasets retrieving and displaying the complete XML metadata description (from the browser). This way, the second step of the query process is carried out by accessing to a specific XML document of the metadata DB. Finally, through the web interface, the user can access to and download (partially or totally) the data stored on the storage device accessing to OPeNDAP servers and to other available grid storage interfaces. Requests concerning datasets stored in deep storage will be served asynchronously.

  19. RTEMS CENTRE - Support and Maintenance CENTRE to RTEMS Operating System

    NASA Astrophysics Data System (ADS)

    Silva, H.; Constantino, A.; Mota, M.; Freitas, D.; Zulianello, M.

    2007-08-01

    Real Time Operating System for Multiprocessor Systems (RTEMS) CENTRE is a project under the ESA-Portugal Task Force aiming to develop a support and maintenance centre to RTEMS operating system. The project can be summarized in two main streams, first one related to design, development, maintenance and integration of tools to augment and sustain RTEMS operating system and second stream linked to the creation of technical competences with a support site to RTEMS operating system in Europe. RTEMS CENTRE intends to minimize the cost of the incorporation/integration of airborne and space applications in this Real Time Operating System. The centre started officially in the 15th of November 2006 and is currently in the study definition and system engineering phase.

  20. Hydride reactivity of Ni(II)-X-Ni(II) entities: mixed-valent hydrido complexes and reversible metal reduction.

    PubMed

    Gehring, Henrike; Metzinger, Ramona; Herwig, Christian; Intemann, Julia; Harder, Sjoerd; Limberg, Christian

    2013-01-28

    After the lithiation of PYR-H(2) (PYR(2-) =[{NC(Me)C(H)C(Me)NC(6)H(3)(iPr)(2)}(2)(C(5)H(3)N)](2-)), which is the precursor of an expanded β-diketiminato ligand system with two binding pockets, its reaction with [NiBr(2) (dme)] led to a dinuclear nickel(II)-bromide complex, [(PYR)Ni(μ-Br)NiBr] (1). The bridging bromide ligand could be selectively exchanged for a thiolate ligand to yield [(PYR)Ni(μ-SEt)NiBr] (3). In an attempt to introduce hydride ligands, both compounds were treated with KHBEt(3). This treatment afforded [(PYR)Ni(μ-H)Ni] (2), which is a mixed valent Ni(I)-μ-H-Ni(II) complex, and [(PYR-H)Ni(μ-SEt)Ni] (4), in which two tricoordinated Ni(I) moieties are strongly antiferromagnetically coupled. Compound 4 is the product of an initial salt metathesis, followed by an intramolecular redox process that separates the original hydride ligand into two electrons, which reduce the metal centres, and a proton, which is trapped by one of the binding pockets, thereby converting it into an olefin ligand on one of the Ni(I) centres. The addition of a mild acid to complex 4 leads to the elimination of H(2) and the formation of a Ni(II)Ni(II) compound, [(PYR)Ni(μ-SEt)NiOTf] (5), so that the original Ni(II) (μ-SEt)Ni(II) X core of compound 3 is restored. All of these compounds were fully characterized, including by X-ray diffraction, and their molecular structures, as well as their formation processes, are discussed.

  1. Transition metal complexes of the novel hexadentate ligand 1,4-bis(di(N-methylimidazol-2-yl)methyl)phthalazine.

    PubMed

    Roggan, Stefan; Limberg, Christian; Knispel, Christina; Tilley, T Don

    2011-04-28

    The novel polydentate ligand 1,4-bis(di(N-methylimidazol-2-yl)methyl)phthalazine, bimptz, has been synthesized and its coordination chemistry was investigated. Bimptz is neutral and contains a central phthalazine unit, to which two di-(N-methylimidazol-2-yl)methyl groups are attached in the 1,4-positions. This ligand therefore provides up to 6 donor sites for coordination to metal ions. A series of metal complexes of bimptz was prepared and their molecular structures were determined by X-ray diffraction. Upon reaction of bimptz with two equivalents of MnCl(2)·4H(2)O, CoCl(2)·6H(2)O and [Ru(dmso)(4)Cl(2)], the dinuclear complexes [Mn(2)(bimptz)(µ-Cl)(2)Cl(2)] (1), [Co(2)(bimptz)(CH(3)OH)(2)(µ-Cl)(2)](PF(6))(2) (3) and [Ru(2)(bimptz)(dmso)(2)(µ-Cl)(2)](PF(6))(2) (4), respectively, were isolated. The latter were found to have similar solid state structures with octahedrally coordinated metal centers bridged by the phthalazine unit and two chloro ligands. The cobalt and ruthenium complexes 3 and 4 were isolated as PF(6)(-) salts and contain neutral methanol and dmso ligands, respectively, at the terminal coordination sites of the metal centres. The mononuclear ruthenium complex [Ru(Hbimptz)(2)](PF(6))(4) (6) was obtained from the reaction of two equivalents bimptz with [Ru(dmso)(4)Cl(2)]. In complex 6, three donor sites per ligand molecule are used for coordination of the Ru(ii) center. In each bimptz ligand, one of the remaining, dangling N-methylimidazole rings is protonated and forms a hydrogen bond with the unprotonated N-methylimidazole ring of the other bimptz ligand.

  2. Minister unveils new nanotech centres

    NASA Astrophysics Data System (ADS)

    Dumé, Belle

    2009-06-01

    Three new nanotechnology research centres are to be set up in France as part of a €70m government plan to help French companies in the sector. Researchers at the new centres, which will be located in Grenoble, Saclay (near Paris) and Toulouse, will be encouraged to collaborate with industry to develop new nanotech-based products. Dubbed NANO-INNOV, the new plan includes €46m for two new buildings at Saclay, with the rest being used to buy new equipment at the three centres and to fund grant proposals from staff to the French National Research Agency (ANR).

  3. Identification of dinuclear aromatics in the gas oil fraction of Kuwait petroleum

    SciTech Connect

    Ijam, M.J.; Qatami, S.Y.A.; Arif, S.F.

    1988-08-01

    For several decades removal of aromatics from crude oil fractions (e.g. kerosene and lubricating oils) has been practiced in oil refining to produce fuels and lubricants of lower aromatic content and hence of improved quality. These aromatics are suitable raw materials for the manufacture of aromatic solvents, aromatic process oils, high octane gasoline, and as basic materials for making detergents, perfumes and dyes. Detailed study of molecular structure and substituent effects on the retention characteristics of aromatic hydrocarbons have been reported on alumina, silica and various chemically bonded silicas containing -C/sub 18/, -NH/sub 2/, -R(NH)/sub 2//sub 2/, -CN, RCN, RON and phenyl-mercuric acetate for the compound class (ring-numbered) high performance liquid chromatography (2, 3, 8, 12, 24, 28). Previous work in this laboratory has demonstrated that individual normal and branched aliphatic hydrocarbons from kerosene and light gas oil were isolated and identified. This paper describes the extension of this work to cover the separation and identification of aromatic ring classes (mono-, di-, and tri-aromatics) in the gas oil fraction of Kuwait petroleum. Characterization and identification of the major components in the dinuclear aromatics is our primary objective in this study.

  4. Electrochemical behavior and dioxygen reactivity of tripodal dinuclear copper complexes linked by unsaturated rigid spacers.

    PubMed

    Gomila, Antoine; Le Poul, Nicolas; Kerbaol, Jean-Michel; Cosquer, Nathalie; Triki, Smaïl; Douziech, Bénédicte; Conan, Françoise; Le Mest, Yves

    2013-02-14

    New dinucleating ligands based on two tripodal tris(2-pyridylmethyl)amine (TMPA) units linked by a series of delocalized π-electrons spacers have been synthesized. Their di-Cu(II) complexes have been prepared and structurally characterized. As compared to the corresponding monotopic complexes, these dinuclear Cu(II) complexes reveal spectroscopic and voltammetric features ascribable to weakly perturbed electronic interactions. In the case of the anthracenyl spacer, observation both in the solid and in solution suggests that the existence of intramolecular π-π stacking interactions influences the geometry of the complex and hence its electronic properties. The bis-Cu(I) complexes were prepared electrochemically. In the specific case of the complex bearing a mono-alkyne spacer, addition of dioxygen in acetonitrile leads to the slow formation of a trans-μ-1,2 peroxo Cu(2) complex which shows good stability at 268 K (t(1/2) = 240 s). Analysis of the kinetics of the peroxo formation by UV-vis spectroscopy suggests that the increased activation barrier for intramolecular binding of dioxygen is due to the rigidity of the spacer.

  5. Synthesis and structure of dinuclear complexes of terbium(III) with 4-acetalbispyrazolone

    SciTech Connect

    Luqin Yang; Rudong Yang

    1994-12-01

    Two novel dinuclear complexes of terbium(III) with 1,5-bis(1`-phenyl-3`-methyl-5`-pyrazolone-4`)-1,5- pentanedione (H{sub 2}L), Tb{sub 2}L{sub 3}{center_dot}6H{sub 2}, Tb{sub 2}L{sub 3}{center_dot}5DMF, have been synthesized. The crystal structure of Tb{sub 2}L{sub 3}{center_dot}5DMF was determined by X-ray diffraction methods. Crystals are triclinic, space group P{rvec 1} with a = 16.957(5), b = 17.877(7), c = 18.269(2){Angstrom}, a = 110.35(2), {beta} = 101.29(2), {gamma} = 111.02(2){degrees}, V = 4511(6){Angstrom}{sup 3}, Mr = 2010.76 Z = 2, Dx = 1.48 g cm{sup -3}, {mu} = 16.45 cm{sub -1} F(000) = 2,052, R = 0.058 with 6574 reflections used in refinement. In the complex, L acts as a bridging ligand and bonds two terbium atoms with its two {beta}-diketone groups. Each terbium ion bonds to two DMF solvent molecules. The coordination number of the two terbium ions is eight. The eight oxygen atoms around the terbium make a distorted square antiprismatic coordination polyhedron.

  6. Synthesis and cell localization of self-assembled dinuclear lanthanide bioprobes.

    PubMed

    Chauvin, Anne-Sophie; Thomas, Frédéric; Song, Bo; Vandevyver, Caroline D B; Bünzli, Jean-Claude G

    2013-07-28

    Lanthanide bioprobes and bioconjugates are ideal luminescent stains in view of their low propensity to photobleaching, sharp emission lines and long excited state lifetimes permitting time-resolved detection for enhanced sensitivity. In this paper, we expand our previous work which demonstrated that self-assembled dinuclear triple-stranded helicates [Ln2(L(C2X))3] behave as excellent cell and tissue labels in immunocytochemical and immunohistochemical assays. The synthetic strategy of the hexadentate ditopic ligands incorporating dipicolinic acid, benzimidazole units and polyoxyethylene pendants is revisited in order to provide a more straightforward route and to give access to further functionalization of the polyoxyethylene arms by incorporating a terminal function X. Formation of the helicates [Ln2(L(C2X))3] (X=COOH, CH2OH, COEt, NH2, phthalimide) is ascertained by several experimental techniques and their stability tested against diethylenetriaminepentaacetate. Their photophysical properties (quantum yield, lifetime, radiative lifetime and sensitization efficiency) are presented and compared with those of the parent helicates [Ln2(L(C2))3]. Finally, the cellular uptake of five Eu(III) helicates is monitored by time-resolved luminescence microscopy and their localization in HeLa cells established by co-staining experiments.

  7. Slow magnetic relaxations in a ladder-type Dy(iii) complex and its dinuclear analogue.

    PubMed

    Boča, R; Stolárová, M; Falvello, L R; Tomás, M; Titiš, J; Černák, J

    2017-04-06

    The complex {[Dy2(PDOA)3(H2O)6]·2H2O}n (1) (H2PDOA = 1,2-phenylenedioxydiacetic acid) was prepared from aqueous solution. Its crystal structure, built up of {-Dy-O-C-O-}n chains interlinked by PDOA ligands yielding a ladder-like arrangement, was determined at 173 K. 1 exhibits slow magnetic relaxation under a small magnetic field BDC = 0.2 T with two (LF and HF) relaxation channels. The LF relaxation time at BDC = 0.2 T and T = 1.85 K is as slow as τ(LF) = 46 ms whereas the HF channel is τ(HF) = 1.4 ms. The mole fraction of the LF species is xLF = 0.76 at 1.85 K and it escapes progressively on heating. In the dinuclear analogue [Dy2(PDOA)3(H2O)6]·3.5H2O (2) one PDOA ligand forms a bis(chelate) bridge between the two Dy(iii) atoms yielding a local structure analogous to that in 1; however its AC susceptibility data show slightly different quantitative characteristics of the single-molecule magnetic behaviour.

  8. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    SciTech Connect

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-03

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-(3-(pyridin-2-yl)-pyrazolato) and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the C{sub benzoyl}N bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the (3-(pyridin-2-yl)-pyrazolato)(3-(pyridin-2-yl)-1H-pyrazole)Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.

  9. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    NASA Astrophysics Data System (ADS)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-01

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-{3-(pyridin-2-yl)-pyrazolato} and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the CbenzoylN bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the {3-(pyridin-2-yl)-pyrazolato}{3-(pyridin-2-yl)-1H-pyrazole}Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ɛ = 116 dm3 mol-1 cm-1) supports the presence of Cu(II) centres.

  10. Nanochemistry of metals

    NASA Astrophysics Data System (ADS)

    Sergeev, Gleb B.

    2001-10-01

    The results of studies on the nanochemistry of metals published in recent years are generalised. Primary attention is centred on the methods for the synthesis of nanoparticles and their chemical reactions. The means of stabilisation of nanoparticles which involve individual metals and incorporate atoms of several metals are considered as well as their physicochemical properties. Self-assembling processes of nanoparticles are described. The prospects of using metal nanoparticles in semiconductor devices, catalysis, biology and medicine are discussed. The bibliography includes 165 references.

  11. Two-electron redox chemistry at the dinuclear core of a TePt platform: chlorine photoreductive elimination and isolation of a Te(V)Pt(I) complex.

    PubMed

    Lin, Tzu-Pin; Gabbaï, François P

    2012-07-25

    As part of our interest in novel redox-active main group/transition metal platforms for energy applications, we have synthesized the chloride salt of [Te(III)Pt(I)Cl(o-dppp)(2)](+) ([1](+), o-dppp = o-(Ph(2)P)C(6)H(4)) by reaction of the new bis(phosphino) telluroether (o-(Ph(2)P)C(6)H(4))(2)Te with (Et(2)S)(2)PtCl(2). Complex [1](+) is chemically robust and undergoes a clean two-electron oxidation reaction in the presence of PhICl(2) to afford ClTe(III)Pt(III)Cl(3)(o-dppp)(2) (2), a complex combining a hypervalent four-coordinate tellurium atom and an octahedral platinum center. While the Te-Pt bond length is only slightly affected by the oxidation state of the TePt platform, DFT and NBO calculations show that this central linkage undergoes an umpolung from Te→Pt in [1](+) to Te←Pt in 2. This umpolung signals an increase in the electron releasing ability of the tellurium center upon switching from an eight-electron configuration in [1](+) to a hypervalent configuration in 2. Remarkably, the two-electron redox chemistry displayed by this new dinuclear platform is reversible as shown by the photoreductive elimination of a Cl(2) equivalent when 2 is irradiated at 350 nm in the presence of a radical trap such as 2,3-dimethyl-1,3-butadiene. This photoreductive elimination, which affords [1][Cl] with a maximum quantum yield of 4.4%, shows that main group/late transition metal complexes can mimic the behavior of their transition metal-only analogues and, in particular, undergo halogen photoelimination from the oxidized state. A last notable outcome of this study is the isolation and characterization of F(MeO)(2)Te(V)Pt(I)Cl(o-dppp)(2) (4), the first metalated hexavalent tellurium compound, which is formed by reaction of 2 with KF in the presence of MeOH.

  12. Synthesis and crystal structure of a dinuclear, monomeric Mn(II) p-semiquinonato complex.

    PubMed

    Nakamori, Harutaka; Matsumoto, Takahiro; Yatabe, Takeshi; Yoon, Ki-Seok; Nakai, Hidetaka; Ogo, Seiji

    2014-11-07

    Herein, we report the first crystal structure of a monomeric p-semiquinonato d-block complex and its reactivity toward dioxygen, closely associated with a biological system of an oxygen evolving centre of photosystem II.

  13. Spontaneous self-assembly of a giant spherical metal-oxide Keplerate: addition of one building block induces "immediate" formation of the complementary one from a constitutional dynamic library.

    PubMed

    Schäffer, Christian; Todea, Ana Maria; Gouzerh, Pierre; Müller, Achim

    2012-01-11

    The addition of dinuclear {Mo(2)} units to a dynamic library containing molybdates results in the spontaneous self-assembly of a giant spherical metal-oxide species of the type {(Mo)Mo(5)}(12){Mo(2)}(30) while the required pentagonal {(Mo)Mo(5)} building blocks are "immediately" formed.

  14. DNA interactions of new cytotoxic tetrafunctional dinuclear platinum complex trans,trans-[{PtCl2(NH3)}2(piperazine)].

    PubMed

    Brabec, Viktor; Christofis, Petros; Slámová, Martina; Kostrhunová, Hana; Nováková, Olga; Najajreh, Yousef; Gibson, Dan; Kaspárková, Jana

    2007-06-15

    A new tetrafunctional dinuclear platinum complex trans,trans-[{PtCl2(NH3)}2(piperazine)] with sterically rigid linking group was designed, synthesized and characterized. In this novel molecule, the DNA-binding features of two classes of the platinum compounds with proven antitumor activity are combined, namely trans oriented bifunctional mononuclear platinum complexes with a heterocyclic ligand and polynuclear platinum complexes. DNA-binding mode of this new complex was analyzed by various methods of molecular biology and biophysics. The complex coordinates DNA in a unique way and interstrand and intrastrand cross-links are the predominant lesions formed in DNA in cell-free media and in absence of proteins. An intriguing aspect of trans,trans-[{PtCl2(NH3)}2(piperazine)] is that, using a semi-rigid linker, interstrand cross-linking is diminished relative to other dinuclear platinum complexes with flexible linking groups and lesions that span several base pairs, such as tri- and tetrafunctional adducts, become unlikely. In addition, in contrast to the inability of trans,trans-[{PtCl2(NH3)}2(piperazine)] to cross-link two DNA duplexes, the results of the present work convincingly demonstrate that this dinuclear platinum complex forms specific DNA lesions which can efficiently cross-link proteins to DNA. The results substantiate the view that trans,trans-[{PtCl2(NH3)}2(piperazine)] or its analogues could be used as a tool for studies of DNA properties and their interactions or as a potential antitumor agent. The latter view is also corroborated by the observation that trans,trans-[{PtCl2(NH3)}2(piperazine)] is a more effective cytotoxic agent than cisplatin against human tumor ovarian cell lines.

  15. Dinuclear pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture.

    PubMed

    Ferrer, Montserrat; Gómez-Bautista, Daniel; Gutiérrez, Albert; Miranda, José R; Orduña-Marco, Guillermo; Oro, Luis A; Pérez-Torrente, Jesús J; Rossell, Oriol; García-Orduña, Pilar; Lahoz, Fernando J

    2014-02-03

    A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)](OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane]. The homometallic hexanuclear metallomacrocycles [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 [(1b)2], [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 (M' = Pd [(1c)2], Pt [(1d)2]), and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 (M' = Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature (1)H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 Å × 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.

  16. Quantum transport behavior of Ni-based dinuclear complexes in presence of zigzag graphene nanoribbon as electrode

    NASA Astrophysics Data System (ADS)

    Sarkar, Sunandan; Pramanik, Anup; Sarkar, Pranab

    2016-10-01

    Quantum transport properties of some Ni-based dinuclear complexes with different polydentate organic ligands have been studied by applying abinitio density functional theory along with nonequilibrium Green's function formulations. It is demonstrated that these materials are capable of showing multifunctional spin dependent properties by the influence of edge states of zigzag edged graphene nanoribbons. The current-voltage characteristics of these materials show spin dependent negative differential resistance behavior, spin filtering effect, and also voltage rectifying property. Proper tuning of these materials can alter these effects which may be utilized in various spintronic devices.

  17. Protonation equilibrium and hydrogen production by a dinuclear cobalt-hydride complex reduced by cobaltocene with trifluoroacetic acid.

    PubMed

    Mandal, Sukanta; Shikano, Shinya; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

    2013-10-16

    A dinuclear Co complex with bis(pyridyl)pyrazolato (bpp(-)) and terpyridine (trpy) ligands, [Co(III)2(trpy)2(μ-bpp)(OH)(OH2)](4+) (1(4+)), undergoes three-electron reduction by cobaltocene in acetonitrile to produce 1(+), which is in the protonation equilibrium with the Co(II)Co(III)-hydride complex, and the further protonation of the hydride by trifluoroacetic acid yields hydrogen quantitatively. The kinetic study together with the detection of the Co(II)Co(III)-hydride complex revealed the mechanism of the hydrogen production by the reaction of 1(+) with trifluoroacetic acid.

  18. The digital eczema centre utrecht.

    PubMed

    van Os-Medendorp, Harmieke; van Veelen, Carien; Hover, Maaike; Eland-de Kok, Petra; Bruijnzeel-Koomen, Carla; Sonnevelt, Gert-Jan; Mensing, Geert; Pasmans, Suzanne

    2010-01-01

    The University Medical Centre Utrecht (UMC Utrecht) has developed an eczema portal that combines e-consulting, monitoring and self-management training by a dermatology nurse online for patients and parents of young children with atopic dermatitis (AD). Patient satisfaction with the portal was high. It could be extended to become a Digital Eczema Centre for multidisciplinary collaboration between health-care providers from different locations and the patient. Before starting the construction of the Digital Eczema Centre, the feasibility was examined by carrying out a business case analysis. The purposes, strength and weaknesses showed that the Digital Eczema Centre offered opportunities to improve care for patients with AD. The financial analysis resulted in a medium/best case scenario with a positive result of euro50-240,000 over a period of five years. We expect that the Digital Eczema Centre will increase the accessibility and quality of care. The web-based patient record and the digital chain-of-care promote the involvement of patients, parents and multidisciplinary teams as well as the continuity and coordination of care.

  19. Mechanistic insight into the catechol oxidase activity by a biomimetic dinuclear copper complex.

    PubMed

    Granata, Alessandro; Monzani, Enrico; Casella, Luigi

    2004-10-01

    The biomimetic catalytic oxidation of 3,5-di- tert-butylcatechol by the dicopper(II) complex of the ligand alpha,alpha'-bis(bis[1-(1'-methyl-2'-benzimidazolyl)methyl]amino)- m-xylene in the presence of dioxygen has been investigated as a function of temperature and pH in a mixed aqueous/organic solvent. The catalytic cycle occurs in two steps, the first step being faster than the second step. In the first step, one molecule of catechol is oxidized by the dicopper(II) complex, and the copper(II) centers are reduced. From the pH dependence, it is deduced that the active species of the process is the monohydroxo form of the dinuclear complex. In the second step, the second molecule of catechol is oxidized by the dicopper(I)-dioxygen complex formed upon oxygenation of the reduced complex. In both cases, catechol oxidation is an inner-sphere electron transfer process involving binding of the catechol to the active species. The binary catechol-dicopper(II) complex formed in the first step could be characterized at very low temperature (-90 degrees C), where substrate oxidation is blocked. On the contrary, the ternary complex of dicopper(I)-O(2)-catechol relevant to the second step does not accumulate in solution and could not be characterized, even at low temperature. The investigation of the biphasic kinetics of the catalytic reaction over a range of temperatures allowed the thermodynamic (Delta H degrees and Delta S degrees ) and activation parameters (Delta H( not equal) and Delta S( not equal)) connected with the key steps of the catecholase process to be obtained.

  20. Hydroxy- and alkoxy-bridged dinuclear uranyl-Schiff base complexes: hydrolysis, transamination and extraction studies.

    PubMed

    Bharara, Mohan S; Heflin, Kathryn; Tonks, Stephen; Strawbridge, Kara L; Gorden, Anne E V

    2008-06-14

    The reaction of uranyl nitrate with 1,3-bis(salicylideneamino)-2-propanol (H(3)L1) and 1,3-bis(3,5-di-tert-butylsalicylideneamino)-2-propanol (H(3)L2) in the presence of triethylamine (Et(3)N) yielded hydroxy- and alkoxy-bridged dinuclear complexes; [(UO(2))(2)(L1)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)) and [(UO(2))(2)(L2)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)). The crystal structures of .(DMF)(2) and .(DMF)(2) exhibit an unsymmetrical central U(2)O(2) core involving bridging alkoxy- and hydroxy-oxygen atoms. The geometry around the uranium center in .(DMF)(2) and .(DMF)(2) is that of a distorted pentagonal bipyramid with the solvent molecule occupying the fifth coordination site. The flexible nature of the ligand backbone is more pronounced in .(DMF)(2) compared to .(DMF)(2), yielding two molecules per unit cell in different conformations. Under similar reaction conditions, using ethylenediamine as a base, the respective Salen-based uranyl compounds, [UO(2)(Salen)(MeOH)] () and [UO(2)(Bu(t)(2)-Salen)(MeOH)] () are obtained due to transamination of the ligand backbone. Complexes .(MeOH)(2) and .(MeOH)(2) when reacted with an excess of ethylenediamine failed to yield the respective Salen-based complexes, and , respectively. The new compounds have been characterized using solution (NMR and UV-Vis) and solid-state (IR, X-ray crystallography) techniques. Hydrolysis of .(MeOH)(2) and .(MeOH)(2) in the pH range 1-14 was studied using UV-Vis spectroscopy and compared with the hydrolysis of and [UO(2)(Salophen)(MeOH)] (). A two-phase extraction study suggests quantitative removal of uranyl ions from the aqueous phase at higher pH conditions.

  1. Visible Light-Induced Electron Transfer From Di-Mu-Oxo-Bridged Dinuclear Mn Complexes to Cr Centers in Silica Nanopores

    SciTech Connect

    Weare, W.W.; Pushkar, Y.; Yachandra, V.K.; Frei, H.

    2009-05-26

    The compound (bpy){sub 2}Mn{sup III}({mu}-O){sub 2}Mn{sup IV}(bpy){sub 2}, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single Cr{sup VI} charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-{mu}-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of Mn{sup III}({mu}-O){sub 2}Mn{sup IV} demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of Cr{sup VI} centers. The FT-Raman spectrum upon visible light excitation of the Cr{sup VI}-O{sup II} {yields} Cr{sup V}-O{sup I} ligand-to-metal charge transfer reveals electron transfer from Mn{sup III}({mu}-O){sub 2}Mn{sup IV} (Mn-O stretch at 700 cm{sup -1}) to Cr{sup VI}, resulting in the formation of Cr{sup V} and Mn{sup IV}({mu}-O){sub 2}Mn{sup IV} (Mn-O stretch at 645 cm{sup -1}). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments are corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products ({Delta}E{sub o} = -0.6 V) remain after several minutes, which points to spatial separation of Cr{sup V} and Mn{sup IV}({mu}-O){sub 2}Mn{sup IV} as a consequence of hole (O{sup I}) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well-defined transition metal molecular units, with the ultimate goal of performing endothermic, multielectron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.

  2. Spherical tokamaks with plasma centre-post

    NASA Astrophysics Data System (ADS)

    Ribeiro, Celso

    2013-10-01

    The metal centre-post (MCP) in tokamaks is a structure which carries the total toroidal field current and also houses the Ohmic heating solenoid in conventional or low aspect ratio (Spherical)(ST) tokamaks. The MCP and solenoid are critical components for producing the toroidal field and for the limited Ohmic flux in STs. Constraints for a ST reactor related to these limitations lead to a minimum plasma aspect ratio of 1.4 which reduces the benefit of operation at higher betas in a more compact ST reactor. Replacing the MCP is of great interest for reactor-based ST studies since the device is simplified, compactness increased, and maintenance reduced. An experiment to show the feasibility of using a plasma centre-post (PCP) is being currently under construction and involves a high level of complexity. A preliminary study of a very simple PCP, which is ECR(Electron Cyclotron Resonance)-assisted and which includes an innovative fuelling system based on pellet injection, has recently been reported. This is highly suitable for an ultra-low aspect ratio tokamak (ULART) device. Advances on this PCP ECR-assisted concept within a ULART and the associated fuelling system are presented here, and will include the field topology for the PCP ECR-assisted scheme, pellet ablation modeling, and a possible global equilibrium simulation. VIE-ITCR, IAEA-CRP contr.17592, National Instruments-Costa Rica.

  3. Person-centred reflective practice.

    PubMed

    Devenny, Bob; Duffy, Kathleen

    Person-centred health and person-centred care have gained prominence across the UK following the publication of reports on public inquiries exploring failings in care. Self-awareness and participation in reflective practice are recognised as vital to supporting the person-centred agenda. This article presents an education framework for reflective practice, developed and used in one NHS board in Scotland, and based on the tenets of the clinical pastoral education movement. Providing an insight into the usefulness of a spiritual component in the reflective process, the framework provides an opportunity for nurses and other healthcare professionals to examine the spiritual dimensions of patient encounters, their own values and beliefs, and the effect these may have on their practice.

  4. Design of a dinuclear nickel(II) bioinspired hydrolase to bind covalently to silica surfaces: synthesis, magnetism, and reactivity studies.

    PubMed

    Piovezan, Clovis; Silva, Jaqueline M R; Neves, Ademir; Bortoluzzi, Adailton J; Haase, Wolfgang; Tomkowicz, Zbigniew; Castellano, Eduardo E; Hough, Tessa C S; Rossi, Liane M

    2012-06-04

    Presented herein is the design of a dinuclear Ni(II) synthetic hydrolase [Ni(2)(HBPPAMFF)(μ-OAc)(2)(H(2)O)]BPh(4) (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4-methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni(II) complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized Ni(II)Ni(II) catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E = k(cat)/K(M)) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.

  5. A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH.

    PubMed

    Mola, Joaquim; Dinoi, Chiara; Sala, Xavier; Rodríguez, Montserrat; Romero, Isabel; Parella, Teodor; Fontrodona, Xavier; Llobet, Antoni

    2011-04-14

    The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[Ru(n)X(bpea)](2)(μ-bpp)}(m+) (for X = Cl, n = II, m = 1, trans-Ru(II)-Cl, 1(+); for X = OH, n = III, m = 3, trans-Ru(III)-OH, 2(3+)) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF(6)) with Ag(+) generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(II) to Ru(III) to generate the corresponding dinuclear complex trans-Ru(III)-OH, 2(PF(6))(3). The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(IV) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway.

  6. Theoretical study of effects of the entrance channel on the relative yield of complete fusion and quasifission in heavy-ion collisions within a dinuclear system approach

    NASA Astrophysics Data System (ADS)

    Soheyli, S.; Khanlari, M. Varasteh

    2016-09-01

    The relative yield of complete fusion and quasifission components for the 12C+204Pb , 19F+197Au , 30Si+186W , and 48Ca+168Er reactions which all lead to the compound nucleus 216Ra are analyzed to calculate the entrance channel effects by comparison of capture, complete fusion, and quasifission cross sections, emission barriers (Bfus*,Bq f ), as well as complete fusion probability estimated by statistical method within the framework of the dinuclear system model. The difference among complete fusion probabilities calculated by the dinuclear system model for different entrance channels can be explained by the hindrance to complete fusion due to the larger inner fusion barrier Bfus* for the transformation of the dinuclear system into a compound nucleus and the increase of the quasifission contribution due to the decreasing of the emission barrier Bq f of quasifission as a function of the angular momentum. Although these reactions with different entrance channels populate the same compound nucleus 216Ra at similar excitation energies, the model predicts the negligible quasifission probability for reactions having higher entrance channel mass asymmetry and the dominant decay channel is complete fission. For reactions induced by massive projectiles such as Si and Ca having lower entrance channel mass asymmetry, the quasifission component is dominant in the evolution of dinuclear system, and the fusion process is extremely hindered.

  7. Colourimetric and fluorescent detection of oxalate in water by a new macrocycle-based dinuclear nickel complex: a remarkable red shift of the fluorescence band.

    PubMed

    Rhaman, Md Mhahabubur; Fronczek, Frank R; Powell, Douglas R; Hossain, Md Alamgir

    2014-03-28

    A new macrocycle-based dinuclear nickel chemosensor selectively binds oxalate anions both in solution and the solid state, displaying a remarkable red shift of the fluorescence band with a visible colour change in water at physiological pH in the presence of an external dye.

  8. Deformation-induced structural transition in body-centred cubic molybdenum.

    PubMed

    Wang, S J; Wang, H; Du, K; Zhang, W; Sui, M L; Mao, S X

    2014-03-07

    Molybdenum is a refractory metal that is stable in a body-centred cubic structure at all temperatures before melting. Plastic deformation via structural transitions has never been reported for pure molybdenum, while transformation coupled with plasticity is well known for many alloys and ceramics. Here we demonstrate a structural transformation accompanied by shear deformation from an original <001>-oriented body-centred cubic structure to a <110>-oriented face-centred cubic lattice, captured at crack tips during the straining of molybdenum inside a transmission electron microscope at room temperature. The face-centred cubic domains then revert into <111>-oriented body-centred cubic domains, equivalent to a lattice rotation of 54.7°, and ~15.4% tensile strain is reached. The face-centred cubic structure appears to be a well-defined metastable state, as evidenced by scanning transmission electron microscopy and nanodiffraction, the Nishiyama-Wassermann and Kurdjumov-Sachs relationships between the face-centred cubic and body-centred cubic structures and molecular dynamics simulations. Our findings reveal a deformation mechanism for elemental metals under high-stress deformation conditions.

  9. Deformation-induced structural transition in body-centred cubic molybdenum

    PubMed Central

    Wang, S. J.; Wang, H.; Du, K.; Zhang, W.; Sui, M. L.; Mao, S. X.

    2014-01-01

    Molybdenum is a refractory metal that is stable in a body-centred cubic structure at all temperatures before melting. Plastic deformation via structural transitions has never been reported for pure molybdenum, while transformation coupled with plasticity is well known for many alloys and ceramics. Here we demonstrate a structural transformation accompanied by shear deformation from an original <001>-oriented body-centred cubic structure to a <110>-oriented face-centred cubic lattice, captured at crack tips during the straining of molybdenum inside a transmission electron microscope at room temperature. The face-centred cubic domains then revert into <111>-oriented body-centred cubic domains, equivalent to a lattice rotation of 54.7°, and ~15.4% tensile strain is reached. The face-centred cubic structure appears to be a well-defined metastable state, as evidenced by scanning transmission electron microscopy and nanodiffraction, the Nishiyama–Wassermann and Kurdjumov–Sachs relationships between the face-centred cubic and body-centred cubic structures and molecular dynamics simulations. Our findings reveal a deformation mechanism for elemental metals under high-stress deformation conditions. PMID:24603655

  10. Rapid Service/Prediction Centre

    DTIC Science & Technology

    2009-01-01

    respect to the 05 C04 system of the IERS Earth Orientation Centre (EOC) at the Paris Observatory by way of a robust linear estimator. Statistical...of each individual data point. The software computes the spline coefficients for every data point, which are then used to interpolate the Earth ...between daily rapid solutions at each daily solution epoch for 2008 and the Earth orientation parameters available in 05 C04 series produced in March 2009

  11. National Centre for Radio Astrophysics

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    India's National Centre for Radio Astrophysics (NCRA), located on the Pune University Campus, is part of the TATA INSTITUTE OF FUNDAMENTAL RESEARCH. At Khodad, 80 km from Pune, NCRA has set up the Giant Metrewave Radio Telescope (GMRT), the world's largest telescope operating at meter wavelengths. GMRT consists of 30 fully steerable dishes of 45 m diameter, spread over a 25 km area. Another meter...

  12. Synthesis and some first-row transition-metal complexes of the 1,2,4-triazole-based Bis(terdentate) ligands TsPMAT and PMAT.

    PubMed

    Klingele, Marco H; Moubaraki, Boujemaa; Murray, Keith S; Brooker, Sally

    2005-11-18

    The employment of a strategy based on nucleophilic substitution, rather than Schiff base condensation, for the preparation of 1,2,4-triazole-based ligands has been investigated and has led to the synthesis of two new ligands, 4-amino-3,5-bis{[N-(2-pyridylmethyl)-N-(4-toluenesulfonyl)amino]methyl}-4H-1,2,4-triazole (TsPMAT, 14) and 4-amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole (PMAT, 15). These are the first examples of bis(terdentate) ligands incorporating the 1,2,4-triazole unit. TsPMAT (14) forms a dinuclear 2:2 complex with Co(BF4)2.6 H2O even when reacted in a metal-to-ligand molar ratio of 2:1. Similarly, the reaction of PMAT (15) with Mn(ClO4)2.6H2O or M(BF4)2.6 H2O (M=Fe, Co, Ni, Zn) in a ligand-to-metal molar ratio of 1:1 has afforded a series of complexes with the general formula [M(II) (2)(PMAT)2]X4. The metal centres in these complexes of TsPMAT (14) and PMAT (15) are encapsulated by two ligand molecules and doubly bridged by the N2 units of the 1,2,4-triazole moieties, which gives rise to N6 coordination spheres that are strongly distorted from octahedral, as evidenced by the X-ray crystal structure analyses of [Co(II) (2)(TsPMAT)(2)](BF(4))(4)6 MeCN (246 MeCN) and [Fe(II) 2(PMAT)2](BF4)4DMF (27DMF). Studies of the magnetic properties of [Co(II) 2(TsPMAT)2](BF4)4.4 H2O (244 H2O), [Mn(II) 2(PMAT)2](ClO4)4 (26), and [Co(II) 2(PMAT)2](BF4)4 (28) have revealed weak antiferromagnetic coupling (J=-3.3, -0.16, and -2.4 cm(-1), respectively) between the two metal centres in these complexes.

  13. European Centre for Disease Prevention and Control.

    PubMed

    Evans, Roger

    2014-11-04

    The European Centre for Disease Prevention and Control was set up in 2005 to strengthen Europe's defences against infectious diseases. The centre is an independent agency of the European Union and is based in Stockholm, Sweden.

  14. Mono- and dinuclear cationic iridium(III) complexes bearing a 2,5-dipyridylpyrazine (2,5-dpp) ligand.

    PubMed

    Donato, Loïc; McCusker, Catherine E; Castellano, Felix N; Zysman-Colman, Eli

    2013-08-05

    The synthesis, X-ray structures, photophysical, and electrochemical characterization of mono- (1) and dinuclear (2) cationic iridium(III) complexes bearing a 2,5-dipyridylpyrazine (2,5-dpp) ancillary ligand are reported. Upon the complexation of a first equivalent of iridium, the photoluminescence shifts markedly into the deep red (λem = 710 nm, ΦPL = 0.9%) compared to other cationic iridium complexes such as [Ir(ppy)2(bpy)]PF6. With the coordination of a second equivalent of iridium, room temperature luminescence is completely quenched. Both 1 and 2 are luminescent at low temperatures but with distinct excited state decay kinetics; the emission of 2 is significantly red-shifted compared to 1. Emission both at 298 and 77 K results from a mixed charge-transfer state. Density functional theory (DFT) calculations and electrochemical behavior point to an electronic communication between the two iridium complexes.

  15. Dinuclear copper(I) and copper(I)/silver(I) complexes with condensed dithiolato ligands.

    PubMed

    Vicente, José; González-Herrero, Pablo; García-Sánchez, Yolanda; Bautista, Delia

    2008-11-17

    The Cu(III) complex Pr 4N[Cu{S 2C=( t-Bu-fy)} 2] ( 1) ( t-Bu-fy = 2,7-di- tert-butylfluoren-9-ylidene) reacts with [Cu(PR 3) 4]ClO 4 in 1:1 molar ratio in MeCN to give the dinuclear complexes [Cu 2{[SC=( t-Bu-fy)] 2S}(PR 3) n ] [ n = 2, R = Ph ( 2a); n = 3, R = To ( 3b); To = p-tolyl]. The analogue of 2a with R = To ( 2b) can be obtained from the reaction of 3b with 1/8 equiv of S 8. Compound 2b establishes a thioketene-exchange equilibrium in solution leading to the formation of [Cu 4{S 2C=( t-Bu-fy)} 2(PTo 3) 4] ( 4b) and [Cu 2{[SC=( t-Bu-fy)] 3S}(PTo 3) 2] ( 5b). Solid mixtures of 4b and 5b in varying proportions can be obtained when the precipitation of 2b is attempted using MeCN. The reactions of 1 with AgClO 4 and PPh 3, PTo 3 or PCy 3 in 1:1:4 molar ratio in MeCN afford the heterodinuclear complexes [AgCu{[SC=( t-Bu-fy)] 2S}(PR 3) 3] [R = Ph ( 6a), To ( 6b), Cy ( 6c)]. Complex 6c dissociates PCy 3 in solution to give the bis(phosphine) derivative [AgCu{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 7c), which undergoes the exchange of [M(PCy 3)] (+) units in CD 2Cl 2 solution to give small amounts of [Cu 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 2c) and [Ag 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 8c). Complexes 6a and b participate in a series of successive equilibria in solution, involving the dissociation of phosphine ligands and the exchange of [M(PCy 3)] (+) units to give 2a or 3b and the corresponding disilver derivatives [Ag 2{[SC=( t-Bu-fy)] 2S}(PR 3) 2] [R = Ph ( 8a), To ( 8b)], followed by thioketene-exchange reactions to give [AgCu{[SC=( t-Bu-fy)] 3S}(PR 3) 2] [R = Ph ( 9a), To ( 9b)]. Complexes 9a and b can be directly prepared from the reactions of 1 with AgClO 4 and PPh 3 or PTo 3 in 1:1:3 molar ratio in THF. The crystal structures of 3b, 6b, 6c, 7c, and 9a have been solved by single-crystal X-ray diffraction studies and, in the cases of 7c and 9a, reveal the formation of short Ag...Cu metallophilic contacts of 2.8157(4) and 2.9606(6) A, respectively.

  16. Mono and dinuclear phosphinegold(I) sulfanylcarboxylates: influence of nuclearity and substitution of PPh3 for PEt3 on cytotoxicity.

    PubMed

    Barreiro, Elena; Casas, José S; Couce, María D; Sánchez, Agustín; Sánchez-Gonzalez, Angeles; Sordo, José; Vázquez-López, Ezequiel M

    2014-09-01

    Gold complexes of the type [Au(PEt3)(Hxspa)] were prepared by reacting triethylphosphinegold(I) chloride in ethanol/water (8:1) with the 3-(aryl)-2-sulfanylpropenoic acids H2xspa [x=p=3-phenyl-; f=3-(2-furyl)-; t=3-(2-thienyl)-; py=3-(2-pyridyl); Clp=3-(2-Chlorophenyl)-; -o-mp=3-(2-methoxyphenyl)-; -p-mp=3-(4-methoxyphenyl)-; -o-hp=3-(2-hydroxyphenyl)-; -p-hp=3-(4-hydroxyphenyl)-; -diBr-o-hp=3-(3,5-dibromo-2-hidroxyphenyl-); spa=2-sulfanylpropenoato] or 2-cyclopentylidene-2-sulfanylacetic acid (H2cpa) and KOH in a 1:1:1 mole ratio. The compounds were characterized by IR spectroscopy and FAB mass spectrometry and by (1)H, (13)C and (31)P NMR spectroscopy. The in vitro antitumor activity of these and of the previously described dinuclear [(AuPEt3)2(xspa)] complexes against the HeLa-229, A2780 and A2780cis cell lines was determined and compared with those of the analogous PPh3 complexes. The results show that the substitution of the PPh3 ligand by PEt3 is particularly effective in increasing the cytotoxicity of the dinuclear [(AuPR3)2(xspa)] complexes, giving rise to compounds that are significantly more active than cisplatin against the aforementioned cell lines. In addition, and as a preliminary test for nephrotoxicity, the cytotoxicity of the most active compounds against the normal renal LCC-PK1 cell line was evaluated and compared with that of cisplatin.

  17. A series of lanthanoid selenidoantimonates(V): rare examples of lanthanoid selenidoantimonates based on dinuclear lanthanide complexes.

    PubMed

    Xiao, Hong-Ping; Zhou, Jian; Zhao, Rong-Qing; Zhang, Wei-bing; Huang, Yong

    2015-04-07

    A series of new lanthanoid selenidoantimonates(V) [Ln(en)(tepa)SbSe4] (Ln = La (Ia), Ce (Ib), Pr (Ic); en = ethylenediamine, tepa = tetraethylenepentamine) and [Ln2(tepa)2(μ-OH)2Cl2]-{[Ln(tepa)]2(μ-OH)2(SbSe4)2} (Ln = Y (IIa), Sm (IIb), Gd (IIc), Tb (IId), Dy (IIe), and Tm (IIf)) were solvothermally synthesized and structurally characterized. The structures of Ia-c consist of neutral molecules [Ln(en)(tepa)SbSe4], where the tetrahedral [SbSe4](3-) anion acts as a ligand to chelate the [Ln(en)(tepa)](3+) cation. The structures of IIa-f contain isolated dinuclear [Ln2(tepa)2(μ-OH)2Cl2](2+) cations built up from two [Ln(tepa)Cl](2+) ions linked by two -OH bridging groups and organic decorated {[Ln(tepa)]2(μ-OH)2(SbSe4)2}(2-) anions based on two [Ln(tepa)SbSe4] units bridged by two -OH groups. Although a few lanthanoid selenidoantimonates(V) under solvothermal conditions have been reported, their lanthanide complexes normally appear mononuclear. Hence, IIa-f are rare examples of lanthanoid selenidoantimonates based on dinuclear lanthanide complexes. A preliminary investigation of nine lanthanoid selenidoantimonates(V) shows that the well-known lanthanide contraction has a significant influence on the formation of lanthanoid selenidoantimonates(V) under solvothermal conditions. The absorption edges of all compounds have been investigated by UV-vis spectroscopy, and density functional theory calculations for Ia and IIc have also been performed.

  18. Cleavage of an RNA model catalyzed by dinuclear Zn(II) complexes containing rate-accelerating pendants. Comparison of the catalytic benefits of H-bonding and hydrophobic substituents.

    PubMed

    Mohamed, Mark F; Brown, R Stan

    2010-12-17

    The transesterification of a simple RNA model, 2-hydroxypropyl p-nitrophenyl phosphate (2, HpNPP) promoted by seven dinuclear Zn(II) catalysts (3,4,5,6,7,8,9:Zn(II)2:(-OCH3)) based on the bis[bis(2-substituted-pyridinyl-6-methyl)]amine ligand system was investigated in methanol under sspH-controlled conditions at 25.0 ± 0.1 °C. The two metal complexing ligands were joined together via the amino N connected to a m-xylyl linker (3, 4, 5, 6, 7) where the 2-pyridinyl substituent = H, CH3, (CH)4, NH2, and NH(C═O)CH3, respectively, and a propyl linker (8, 9) where the ring substituent = H and CH3. All of the dinuclear complexes except 8:Zn(II)2 exhibit saturation kinetics for the kobs versus [catalyst] plots from which one can determine catalyst:substrate binding constants (KM), the catalytic rate constants for their decomposition (kcat), and the second order catalytic rate constants (k2cat = kcat/KM). In the case of 8:Zn(II)2, the plots of kobs versus [catalyst] as a function of sspH are linear, and the catalytic rate constants (k2cat) are defined as the gradients of the plots. Analysis of all of the data at the sspH optimum for each reaction indicates that the presence of the amino and acetamido H-bonding groups and the CH3 group provides similar increases of the kcat terms of 25−50 times that exhibited by the parent complex 3:Zn(II)2. However, in terms of substrate catalyst binding (KM), there is no clear trend that H-bonding groups or the CH3 group provides stronger binding than the parent complex. In terms of the overall second order catalytic rate constant, the CH3, amino, and NH(C═O)CH3 groups provide 20, 10, and 68 times the k2cat observed for the parent complex. In the case of 9:Zn(II)2, the presence of the methyl groups provides a 1000-fold increase in activity (judged by k2cat) over the parent complex 8:Zn(II)2. The results are interpreted to indicate that H-bonding effects may be important for catalysis and less so for substrate binding, but the

  19. Dinuclear uranium alkoxides. Preparation and structures of KU/sub 2/(OCMe/sub 3/)/sub 9/, U/sub 2/(OCMe/sub 3/)/sub 9/, and U/sub 2/(OCHMe/sub 2/)/sub 10/, containing (U(IV),U(IV)), (U(IV),U(V)), and (U(V), U(V)), respectively

    SciTech Connect

    Cotton, F.A.; Marler, D.O.; Schwotzer, W.

    1984-12-05

    The structural results by x-ray crystallography are reported for three uranium alkoxides, two of which are new compounds. All three are dinuclear in the solid state, and they contain the following combinations of oxidation states; (U(IV), U(VI)), (U(V), U(IV)), and (U(V), U(V)). The crystal parameters and U...U bond distances are given for all three compounds. The terminal alkoxide groups in all three compounds display nearly linear U-O-C arrangements, with U-O-C bond angles between 160 and 176/sup 0/. This appears to be a general feature of uranium alkoxides and suggests a high degree of O..pi.. ..-->.. U contributions to the metal-oxygen bonds.

  20. Density functional study for the bridged dinuclear center based on a high-resolution X-ray crystal structure of ba3 cytochrome c oxidase from Thermus thermophilus.

    PubMed

    Du, Wen-Ge Han; Noodleman, Louis

    2013-12-16

    Strong electron density for a peroxide type dioxygen species bridging the Fea3 and CuB dinuclear center (DNC) was observed in the high-resolution (1.8 Å) X-ray crystal structures (PDB entries 3S8G and 3S8F) of ba3 cytochrome c oxidase (CcO) from Thermus thermophilus. The crystals represent the as-isolated X-ray photoreduced CcO structures. The bridging peroxide was proposed to arise from the recombination of two radiation-produced HO(•) radicals formed either very near to or even in the space between the two metals of the DNC. It is unclear whether this peroxide species is in the O2(2-), O2(•)(-), HO2(-), or the H2O2 form and what is the detailed electronic structure and binding geometry including the DNC. In order to answer what form of this dioxygen species was observed in the DNC of the 1.8 Å X-ray CcO crystal structure (3S8G), we have applied broken-symmetry density functional theory (BS-DFT) geometric and energetic calculations (using OLYP potential) on large DNC cluster models with different Fea3-CuB oxidation and spin states and with O2(2-), O2(•)(-), HO2(-), or H2O2 in the bridging position. By comparing the DFT optimized geometries with the X-ray crystal structure (3S8G), we propose that the bridging peroxide is HO2(-). The X-ray crystal structure is likely to represent the superposition of the Fea3(2+)-(HO2(-))-CuB(+) DNC's in different states (Fe(2+) in low spin (LS), intermediate spin (IS), or high spin (HS)) with the majority species having the proton of the HO2(-) residing on the oxygen atom (O1) which is closer to the Fea3(2+) site in the Fea3(2+)-(HO-O)(-)-CuB(+) conformation. Our calculations show that the side chain of Tyr237 is likely trapped in the deprotonated Tyr237(-) anion form in the 3S8G X-ray crystal structure.

  1. Mono- and dinuclear iron complexes of bis(1-methylimidazol-2-yl)ketone (bik): structure, magnetic properties, and catalytic oxidation studies.

    PubMed

    Bruijnincx, Pieter C A; Buurmans, Inge L C; Huang, Yuxing; Juhász, Gergely; Viciano-Chumillas, Marta; Quesada, Manuel; Reedijk, Jan; Lutz, Martin; Spek, Anthony L; Münck, Eckard; Bominaar, Emile L; Klein Gebbink, Robertus J M

    2011-10-03

    The newly synthesized dinuclear complex [Fe(III)(2)(μ-OH)(2)(bik)(4)](NO(3))(4) (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) Å) and Fe-O distances (1.941(2)/1.949(2) Å) compared to other unsupported Fe(III)(2)(μ-OH)(2) complexes. The bridging hydroxide groups of 1 are strongly hydrogen-bonded to a nitrate anion. The (57)Fe isomer shift (δ = 0.45 mm s(-1)) and quadrupole splitting (ΔE(Q) = 0.26 mm s(-1)) obtained from Mössbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable-temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm(-1) and H = JS(1)·S(2)) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 Å, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 Å) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [Fe(II)(bik)(3)](2+) species. Variable-temperature magnetic susceptibility measurements of [Fe(II)(bik)(3)](OTf)(2) (2) revealed spin-crossover behavior. Thermal hysteresis was observed with 2, due to a loss of cocrystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [Fe(II)(bik)(3)](OTf)(2) (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O(2), and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen

  2. Synthesis, magnetic behaviour, and X-ray structures of dinuclear copper complexes with multiple bridges. Efficient and selective catalysts for polymerization of 2,6-dimethylphenol.

    PubMed

    Murugavel, Ramaswamy; Pothiraja, Ramasamy; Gogoi, Nayanmoni; Clérac, Rodolphe; Lecren, Lollita; Butcher, Ray J; Nethaji, Munirathinam

    2007-06-21

    The use of a potentially tridentate mono-anionic bridging ligand, 1,3-bis(3,5-dimethylpyrazol-1-yl)-propan-2-ol (bdmpp-H), in assembling new dimeric copper complexes with interesting magnetic properties has been investigated. The reaction of copper hydroxide or copper acetate with phenyl phosphinic acid or diphenyl phosphinic acid in the presence of bdmpp-H produces the dinuclear complexes [Cu(bdmpp)(ppi)]2 (1) and [Cu(bdmpp)(dppi-H)]2(dppi)2 (2) (ppi-H = phenylphosphinic acid: dppi-H = diphenylphosphinic acid), respectively. The products have been characterized with the help of analytical, thermal, and spectroscopic (IR, UV-vis, and EPR) techniques. Single crystal X-ray diffraction studies of 1 and 2 reveal that the two bdmpp ligands hold together the dimeric copper unit in each complex through mu-O alkoxide and the pyrazolyl nitrogen ligating centers. Two phenyl phosphinate ligands additionally bridge the dicopper core in 1 to result in octahedral coordination geometry around each metal ion. The diphenyl phosphinic acid acts as a terminal ligand in 2, and thus completes a square pyramidal geometry around each copper ion. Both complexes show a very short Cu...Cu separation (3.001 and 3.065 angstroms for 1 and 2, respectively). The investigation of the magnetic properties reveals the efficiency of the double alkoxide bridge between the two paramagnetic copper ions to mediate strong antiferromagnetic interactions [J/k(B) = -620(5) K (-431(4) cm(-1)) and -685(5) K (-476(4) cm(-1)) for 1 and 2, respectively]. Compounds 1 and 2, along with a few other copper phosphate complexes, were tested as catalysts for the oxidative polymerization of 2,6-dimethylphenol; 1 and 2 were found to be efficient catalysts with an increased selectivity for the formation of the polyphenylene ether. However a related mononuclear octahedral copper complex [Cu(imz)4(dtbp)2] (dtbp-H = di-tert-butylphosphate) was found to be more efficient.

  3. Mono- and Dinuclear Iron Complexes of Bis(1-methylimidazol-2-yl)ketone (bik): Structure, Magnetic Properties and Catalytic Oxidation Studies

    PubMed Central

    Bruijnincx, Pieter C. A.; Buurmans, Inge L. C.; Huang, Yuxing; Juhász, Gergely; Viciano-Chumillas, Marta; Quesada, Manuel; Reedijk, Jan; Lutz, Martin; Spek, Anthony L.; Münck, Eckard; Bominaar, Emile L.; Klein Gebbink, Robertus J. M.

    2011-01-01

    The newly synthesized dinuclear complex [FeIII2(μ-OH)2(bik)4](NO3)4 (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) Å) and Fe–O distances (1.941(2)/1.949(2) Å) compared to other unsupported FeIII2(μ-OH)2 complexes. The bridging hydroxide groups of 1 are strongly hydrogen bonded to a nitrate anion. The 57Fe isomer shift (δ = 0.45 mm s−1) and quadrupole splitting (ΔEQ = 0.26 mm s−1) obtained from Mössbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm−1 and = JS1·S2) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 Å, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 Å) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [FeII(bik)3]2+ species. Variable temperature magnetic susceptibility measurements of [FeII(bik)3](OTf)2 (2) revealed spin crossover behavior. Thermal hysteresis was observed with 2, due to a loss of co-crystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [FeII(bik)3](OTf)2 (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O2, and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen peroxide yielding epoxides was observed under

  4. Interplay of metal ions and urease

    PubMed Central

    Carter, Eric L.; Flugga, Nicholas; Boer, Jodi L.; Mulrooney, Scott B.; Hausinger, Robert P.

    2009-01-01

    Summary Urease, the first enzyme to be crystallized, contains a dinuclear nickel metallocenter that catalyzes the decomposition of urea to produce ammonia, a reaction of great agricultural and medical importance. Several mechanisms of urease catalysis have been proposed on the basis of enzyme crystal structures, model complexes, and computational efforts, but the precise steps in catalysis and the requirement of nickel versus other metals remain unclear. Purified bacterial urease is partially activated via incubation with carbon dioxide plus nickel ions; however, in vitro activation also has been achieved with manganese and cobalt. In vivo activation of most ureases requires accessory proteins that function as nickel metallochaperones and GTP-dependent molecular chaperones or play other roles in the maturation process. In addition, some microorganisms control their levels of urease by metal ion-dependent regulatory mechanisms. PMID:20046957

  5. The DEMETER Science Mission Centre

    NASA Astrophysics Data System (ADS)

    Lagoutte, D.; Brochot, J. Y.; de Carvalho, D.; Elie, F.; Harivelo, F.; Hobara, Y.; Madrias, L.; Parrot, M.; Pinçon, J. L.; Berthelier, J. J.; Peschard, D.; Seran, E.; Gangloff, M.; Sauvaud, J. A.; Lebreton, J. P.; Stverak, S.; Travnicek, P.; Grygorczuk, J.; Slominski, J.; Wronowski, R.; Barbier, S.; Bernard, P.; Gaboriaud, A.; Wallut, J. M.

    2006-04-01

    The DEMETER Scientific Mission Centre (SMC) has been developed and is operated by the Laboratoire de Physique et Chimie de l'Environnement (LPCE). The SMC commands the instruments of the scientific payload, collects and distributes DEMETER data and associated products to the DEMETER international community. The SMC has been designed to maximize scientific return and to reduce development and exploitation costs for the DEMETER project. This paper describes the SMC's data processing system, data server and methods of payload operation, and presents associated hardware and software architectures.

  6. Cooperative reactivity of early-late heterodinuclear transition metal complexes with polar organic substrates

    PubMed

    Gade; Memmler; Kauper; Schneider; Fabre; Bezougli; Lutz; Galka; Scowen; McPartlin

    2000-02-18

    A comprehensive investigation into the cooperative reactivity of two chemically complementary metal-complex fragments in early-late heterodinuclear complexes has been carried out. Reaction of the partially fluorinated tripodal amidozirconium complexes [HC-(SiMe2NR)3Zr(mu-Cl)2Li(OEt2)2] (R = 2-FC6H4: 2a, 2,3,4-F3C6H4: 2b) with K[CpM(CO)2] (M=Fe, Ru) afforded the stable metal-metal bonded heterodinuclear complexes [HC[SiMe2NR]3-Zr-MCp(CO)2] (3-6). Reaction of the dinuclear complexes with methyl isonitrile as well as the heteroallenes CO2, CS2, RNCO and RNCS led to insertion into the polar metal-metal bond. Two of these complexes, [HC[SiMe2N(2-FC6-H4)]3Zr(S2C)Fe(CO)2Cp] (9a) and [HC-[SiMe2N(2-FC2H4)]3Zr-(SCNPh)Fe(CO)2-Cp] (12), have been structurally characterized by a single crystal X-ray structure analysis, proving the structural situation of the inserted substrate as a bridging ligand between the early and late transition metal centre. The reactivity towards organic carbonyl derivatives proved to be varied. Reaction of the heterobimetallic complexes with benzyl and ethylbenzoate led to the cleavage of the ester generating the respective alkoxozirconium complexes [HC[SiMe2N(2-FC6H4)]3ZrOR] (R = Ph-CH2: 13a, Et: 13b) along with [CpFe-[C(O)Ph](CO)2], whereas the analogous reaction with ethyl formate gave 13b along with [CpFeH(CO)2]; this latter complex results from the instability of the formyliron species initially formed. Aryl aldehydes were found to react with the Zr-M complexes according to a Cannizzaro disproportionation pattern yielding the aroyliron and ruthenium complexes along with the respective benzoxyzirconium species. The transfer of the aldehyde hydrogen atom in the course of the reaction was established in a deuteriation experiment. [HC[SiMe2-N(2-FC6H4)]3Zr-M(CO)2Cp] reacted with lactones to give the ring-opened species containing an alkoxozirconium and an acyliron or acylruthenium fragment; the latter binds to the early transition metal centre through

  7. Perceptual centres in speech - an acoustic analysis

    NASA Astrophysics Data System (ADS)

    Scott, Sophie Kerttu

    Perceptual centres, or P-centres, represent the perceptual moments of occurrence of acoustic signals - the 'beat' of a sound. P-centres underlie the perception and production of rhythm in perceptually regular speech sequences. P-centres have been modelled both in speech and non speech (music) domains. The three aims of this thesis were toatest out current P-centre models to determine which best accounted for the experimental data bto identify a candidate parameter to map P-centres onto (a local approach) as opposed to the previous global models which rely upon the whole signal to determine the P-centre the final aim was to develop a model of P-centre location which could be applied to speech and non speech signals. The first aim was investigated by a series of experiments in which a) speech from different speakers was investigated to determine whether different models could account for variation between speakers b) whether rendering the amplitude time plot of a speech signal affects the P-centre of the signal c) whether increasing the amplitude at the offset of a speech signal alters P-centres in the production and perception of speech. The second aim was carried out by a) manipulating the rise time of different speech signals to determine whether the P-centre was affected, and whether the type of speech sound ramped affected the P-centre shift b) manipulating the rise time and decay time of a synthetic vowel to determine whether the onset alteration was had more affect on P-centre than the offset manipulation c) and whether the duration of a vowel affected the P-centre, if other attributes (amplitude, spectral contents) were held constant. The third aim - modelling P-centres - was based on these results. The Frequency dependent Amplitude Increase Model of P-centre location (FAIM) was developed using a modelling protocol, the APU GammaTone Filterbank and the speech from different speakers. The P-centres of the stimuli corpus were highly predicted by attributes of

  8. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    SciTech Connect

    DeWitt, J.G.

    1992-12-01

    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 [Angstrom]. The Fe-Fe distance was determined to be 3.4 [Angstrom]. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  9. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    SciTech Connect

    DeWitt, Jane G.

    1992-12-01

    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 Å. The Fe-Fe distance was determined to be 3.4 Å. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  10. Synthesis, characterization, crystal structure, DNA- and HSA-binding studies of a dinuclear Schiff base Zn(II) complex derived from 2-hydroxynaphtaldehyde and 2-picolylamine

    NASA Astrophysics Data System (ADS)

    Kazemi, Zahra; Rudbari, Hadi Amiri; Mirkhani, Valiollah; Sahihi, Mehdi; Moghadam, Majid; Tangestaninejad, Sharam; Mohammadpoor-Baltork, Iraj

    2015-09-01

    A tridentate Schiff base ligand NNO donor (HL: 1-((E)-((pyridin-2-yl)methylimino)methyl)naphthalen-2-ol was synthesized from condensation of 2-hydroxynaphtaldehyde and 2-picolylamine. Zinc complex, Zn2L2(NO3)2, was prepared from reaction of Zn(NO3)2 and HL at ambient temperature. The ligand and complex were characterized by FT-IR, 1H NMR, 13C NMR and elemental analysis (CHN). Furthermore, the structure of dinuclear Zn(II) complex was determined by single crystal X-ray analysis. The complex, Zn2L2(NO3)2, is centrosymmetric dimer in which deprotonated phenolates bridge the two Zn(II) atoms and link the two halves of the dimer. In the structure, Zinc(II) ions have a highly distorted six-coordinate structure bonded to two oxygen atoms from a bidentate nitrate group, the pyridine nitrogen, an amine nitrogen and phenolate oxygens. The interaction of dinuclear Zn(II) complex with fish sperm DNA (FS-DNA) and HSA was investigated under physiological conditions using fluorescence quenching, UV-Vis spectroscopy, molecular dynamics simulation and molecular docking methods. The estimated binding constants for the DNA-complex and HSA-complex were (3.60 ± 0.18) × 104 M-1 and (1.35 ± 0.24) × 104 M-1, respectively. The distance between dinuclear Zn(II) complex and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Molecular docking studies revealed the binding of dinuclear Zn(II) complex to the major groove of FS-DNA and IIA site of protein by formation of hydrogen bond, π-cation and hydrophobic interactions.

  11. A dinuclear ruthenium(II) complex as turn-on luminescent probe for hypochlorous acid and its application for in vivo imaging

    PubMed Central

    Liu, Zonglun; Gao, Kuo; Wang, Beng; Yan, Hui; Xing, Panfei; Zhong, Chongmin; Xu, Yongqian; Li, Hongjuan; Chen, Jianxin; Wang, Wei; Sun, Shiguo

    2016-01-01

    A dinuclear ruthenium(II) complex Ruazo was designed and synthesized, in which oxidative cyclization of the azo and o-amino group was employed for the detection of hypochlorous acid (HClO) in aqueous solution. The non-emissive Ruazo formed highly luminescent triazole-ruthenium(II) complex in presence of HClO and successfully imaged HClO in living cell and living mouse. PMID:27356618

  12. A novel dinuclear iridium(III) complex as a G-quadruplex-selective probe for the luminescent switch-on detection of transcription factor HIF-1α

    NASA Astrophysics Data System (ADS)

    Lu, Lihua; Wang, Modi; Mao, Zhifeng; Kang, Tian-Shu; Chen, Xiu-Ping; Lu, Jin-Jian; Leung, Chung-Hang; Ma, Dik-Lung

    2016-03-01

    A novel dinuclear Ir(III) complex 5 was discovered to be specific to G-quadruplex DNA, and was utilized in a label-free G-quadruplex-based detection platform for transcription factor activity. The principle of this assay was demonstrated by using HIF-1α as a model protein. Moreover, this HIF-1α detection assay exhibited potential use for biological sample analysis.

  13. Dinuclear Ru/Ni, Ir/Ni, and Ir/Pt complexes with bridging phenanthroline-5,6-dithiolate: synthesis, structure, and electrochemical and photophysical behavior.

    PubMed

    Schallenberg, David; Neubauer, Antje; Erdmann, Elisa; Tänzler, Marco; Villinger, Alexander; Lochbrunner, Stefan; Seidel, Wolfram W

    2014-09-02

    We report the synthesis and full characterization of dinuclear complexes with the bridging ligand phenanthroline-5,6-dithiolate (phendt(2-)) featuring the [Ru(bpy)2](2+) or Ir(ppy)2](+) fragment at the diimine donor center and the [Ni(dppe)](2+) or [Pt(phen)](2+) complex moiety at the dithiolate group. The molecular structures of the mononuclear complexes [(C5H5)2Ti(S,S'-phendt)] and [(ppy)2Ir{N,N'-phendt-(C2H4CN)2}](PF6) as well as the dinuclear complex [(C5H5)(PPh3)Ru(phendt)Ni(dppe)](PF6) determined by X-ray diffraction (XRD) studies are compared. Photophysical studies with mononuclear [(bpy)2Ru{phendt-(C2H4CN)2}](2+) and [(ppy)2Ir{phendt-(C2H4CN)2}](+) as well as dinuclear [(bpy)2Ru(phendt)Ni(dppe)](2+) and [(ppy)2Ir(phendt)Ni(dppe)](+) uncovered an effective luminescence quenching in the dinuclear complexes. Lifetime measurements at room temperature, steady-state measurements at low temperature, electrochemical investigations, and DFT calculations provide evidence for a very efficient energy transfer from the Ru/Ir to the Ni complex moiety with a rate constant k > 5 × 10(9) s(-1). In comparison, the [Ru]phendt[Ni] complex displays a higher quenching efficiency with reduced excited state lifetime, whereas the [Ir]phendt[Ni] complex is characterized by an unaltered lifetime of the thermally equilibrated excited state.

  14. A novel dinuclear iridium(III) complex as a G-quadruplex-selective probe for the luminescent switch-on detection of transcription factor HIF-1α

    PubMed Central

    Lu, Lihua; Wang, Modi; Mao, Zhifeng; Kang, Tian-Shu; Chen, Xiu-Ping; Lu, Jin-Jian; Leung, Chung-Hang; Ma, Dik-Lung

    2016-01-01

    A novel dinuclear Ir(III) complex 5 was discovered to be specific to G-quadruplex DNA, and was utilized in a label-free G-quadruplex-based detection platform for transcription factor activity. The principle of this assay was demonstrated by using HIF-1α as a model protein. Moreover, this HIF-1α detection assay exhibited potential use for biological sample analysis. PMID:26932240

  15. Luminescent dinuclear copper(I) complexes bearing 1,4-bis(diphenylphosphino)butane and functionalized 3-(2'-pyridyl)pyrazole mixed ligands.

    PubMed

    Chen, Jing-Lin; Guo, Zong-Hao; Yu, Hua-Guang; He, Li-Hua; Liu, Sui-Jun; Wen, He-Rui; Wang, Jin-Yun

    2016-01-14

    A family of new dinuclear Cu(i) complexes with 1,4-bis(diphenylphosphino)butane (dppb) and functionalized 3-(2'-pyridyl)pyrazole mixed ligands has been synthesized and characterized. It is revealed that all these Cu(i) complexes include a [Cu2(dppb)2](2+) framework with the two Cu(i) atoms doubly bridged by a pair of dppb to generate a fourteen-membered Cu2P4C8 ring, and functionalized 3-(2'-pyridyl)pyrazole adopts a neutral chelating coordination mode without the N-H bond cleavage of the pyrazolyl ring. All these dinuclear Cu(i) complexes display a relatively weak low-energy absorption in CH2Cl2 solution, which is closely related to the variation of the Cu-N and Cu-P bonds caused by the substituent on the pyrazolyl ring. These dinuclear Cu(i) complexes are all emissive in solution and solid states at ambient temperature, which can be well modulated through structural modification of 3-(2'-pyridyl)pyrazole. It is shown that introduction of the trifluoromethyl group into the pyrazolyl ring is helpful for enhancing the luminescence properties of Cu(i) pyrazole phosphine complexes.

  16. Nuclear Science Centre, New Delhi

    SciTech Connect

    Mehta, G.; Potukuchi, P.; Roy, A.

    1995-08-01

    Argonne is collaborating with the Nuclear Science Centre (NSC), New Delhi, to develop a new type of superconducting accelerating structure for low-velocity heavy ions. A copper model has been evaluated and tests on the niobium prototype are currently in progress. Some technical details of this project are described in the Superconducting Linac Development section of this report. All funding for the prototype has come from the NSC, and they have also stationed two staff members at ATLAS for the past two years to gain experience and work on this project. Additional NSC personnel visited ATLAS for extended periods during 1994 for electronics and cryogenics experience and training. Two NSC staff members are scheduled to spend several months at ANL during 1995 to continue tests and developments of the prototype resonators and to initiate fabrication of the production models for their linac project.

  17. Metal-coordination-driven dynamic heteroleptic architectures.

    PubMed

    De, Soumen; Mahata, Kingsuk; Schmittel, Michael

    2010-05-01

    Dynamic heteroleptic coordination at metal centres is quite common in Nature and often related to a specific biological function, such as in zinc finger proteins and in hemoglobin for oxygen transport. To achieve the required high heteroleptic fidelity, representative biological systems avail themselves of "intramolecular" multidentate coordination using the protein backbone as a "superligand". In contrast, dynamic heteroleptic coordination at a single metal centre in solution requires to bind different freely exchanging ligands under thermodynamic control. In this tutorial review we present the emerging principles of how to assemble dissimilar ligands at dynamically exchanging metal centres, with a particular emphasis on using the precepts for the fabrication of heteroleptic supramolecular assemblies in solution.

  18. The International Centre for Theoretical Physics

    NASA Astrophysics Data System (ADS)

    Hussain, Faheem

    2008-07-01

    This talk traces in brief the genesis of the Abdus Salam International Centre for Theoretical Physics, Trieste, as one of Prof. Abdus Salam's major achievements. It outlines why Salam felt the necessity for establishing such a centre to help physicists in the developing world. It situates the founding of the Centre within Salam's broader vision of the causes of underdevelopment and of science as an engine for scientific, technological, economic and social development. The talk reviews the successes and failures of the ICTP and gives a brief overall view of the current status of the Centre.

  19. The Press Research Centre, 1956-1976.

    ERIC Educational Resources Information Center

    Press Research Centre, Krakow (Poland).

    In 1956, the Press Research Centre was established in Cracow, Poland by a group of journalists and publishers, for the purpose of instituting press research that would have practical applications. The aims of the Centre were to conduct studies on the history of the Polish press, the contemporary press, press readership, and editorial techniques.…

  20. The Irish Centre for Talented Youth

    ERIC Educational Resources Information Center

    Gilheany, Sheila

    2005-01-01

    Conducting potency tests on penicillin, discussing rocket technology with a NASA astronaut, analysing animal bone fragments from medieval times, these are just some of the activities which occupy the time of students at The Irish Centre for Talented Youth. The Centre identifies young students with exceptional academic ability and then provides…

  1. The European standards of Haemophilia Centres

    PubMed Central

    Giangrande, Paul; Calizzani, Gabriele; Menichini, Ivana; Candura, Fabio; Mannucci, Pier Mannuccio; Makris, Michael

    2014-01-01

    Introduction The European haemophilia community of professionals and patients has agreed on the principles of haemophilia care to address comprehensive optimal delivery of care which is nowadays scattered throughout Europe. Many of the health facilities call themselves Haemophilia Centres despite their variation in size, expertise and services provided. Only a small number of countries have Haemophilia Centre accreditation systems in place. Methods In the framework of the European Haemophilia Network project, following an inclusive process of stakeholder involvement, the European Guidelines for the certification of haemophilia centres have been developed in order to set quality standards for European Haemophilia Centres and criteria for their certification. Results The Guidelines define the standards and criteria for the designation of two levels of care delivery: European Haemophilia Treatment Centres, providing local routine care, and European Haemophilia Comprehensive Care Centres, providing specialised and multi-disciplinary care and functioning as tertiary referral centres. Additionally, they define standards about general requirements, patient care, provision of an advisory service and establishment of network of clinical and specialised services. Conclusions The implementation of the European Guidelines for the certification of Haemophilia Centres will contribute to the reduction of health inequalities through the standardisation of quality of care in European Union Member States and could represent a model to be taken into consideration for other rare disease groups. PMID:24922293

  2. Promotion in Call Centres: Opportunities and Determinants

    ERIC Educational Resources Information Center

    Gorjup, Maria Tatiana; Valverde, Mireia; Ryan, Gerard

    2008-01-01

    Purpose: The purpose of this paper is to examine the quality of jobs in call centres by focusing on the opportunities for promotion in this sector. More specifically, the research questions focus on discovering whether promotion is common practise in the call centre sector and on identifying the factors that affect this.…

  3. Metal binding studies and EPR spectroscopy of the manganese transport regulator MntR.

    PubMed

    Golynskiy, Misha V; Gunderson, William A; Hendrich, Michael P; Cohen, Seth M

    2006-12-26

    Manganese transport regulator (MntR) is a member of the diphtheria toxin repressor (DtxR) family of transcription factors that is responsible for manganese homeostasis in Bacillus subtilis. Prior biophysical studies have focused on the metal-mediated DNA binding of MntR [Lieser, S. A., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2003) Biochemistry 42, 12634-12642], as well as metal stabilization of the MntR structure [Golynskiy, M. V., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2005) Biochemistry 44, 3380-3389], but only limited data on the metal-binding affinities for MntR are available. Herein, the metal-binding affinities of MntR were determined by using electron paramagnetic resonance (EPR) spectroscopy, as well as competition experiments with the fluorimetric dyes Fura-2 and Mag-fura-2. MntR was not capable of competing with Fura-2 for the binding of transition metal ions. Therefore, the metal-binding affinities and stoichiometries of Mag-fura-2 for Mn2+, Co2+, Ni2+, Zn2+, and Cd2+ were determined and utilized in MntR/Mag-fura-2 competition experiments. The measured Kd values for MntR metal binding are comparable to those reported for DtxR metal binding [Kd from 10(-)7 to 10(-4) M; D'Aquino, J. A., et al. (2005) Proc. Natl. Acad. Sci. U.S.A. 102, 18408-18413], AntR [a homologue from Bacillus anthracis; Sen, K. I. et al. (2006) Biochemistry 45, 4295-4303], and generally follow the Irving-Williams series. Direct detection of the dinuclear Mn2+ site in MntR with EPR spectroscopy is presented, and the exchange interaction was determined, J = -0.2 cm-1. This value is lower in magnitude than most known dinuclear Mn2+ sites in proteins and synthetic complexes and is consistent with a dinuclear Mn2+ site with a longer Mn...Mn distance (4.4 A) observed in some of the available crystal structures. MntR is found to have a surprisingly low binding affinity (approximately 160 microM) for its cognate metal ion Mn2+. Moreover, the results of DNA binding studies in

  4. Metal Preferences and Metallation*

    PubMed Central

    Foster, Andrew W.; Osman, Deenah; Robinson, Nigel J.

    2014-01-01

    The metal binding preferences of most metalloproteins do not match their metal requirements. Thus, metallation of an estimated 30% of metalloenzymes is aided by metal delivery systems, with ∼25% acquiring preassembled metal cofactors. The remaining ∼70% are presumed to compete for metals from buffered metal pools. Metallation is further aided by maintaining the relative concentrations of these pools as an inverse function of the stabilities of the respective metal complexes. For example, magnesium enzymes always prefer to bind zinc, and these metals dominate the metalloenzymes without metal delivery systems. Therefore, the buffered concentration of zinc is held at least a million-fold below magnesium inside most cells. PMID:25160626

  5. Electrochemical and photochemical-driven hydrogen evolution catalyzed by a dinuclear CoII-CoII complex

    NASA Astrophysics Data System (ADS)

    Fu, Ling-Zhi; Zhou, Ling-Ling; Tang, Ling-Zhi; Zhang, Yun-Xiao; Zhan, Shu-Zhong

    2015-04-01

    The reaction of 2,6-diamino-3-[(2-carboxymethyl) phenylazo]-pyridine (L) and CoCl2·6H2O affords a dinuclear cobalt (II) complex [Co2L2Cl3]Cl 1, a molecular catalyst. Electrochemical studies indicate that 1 can electrocatalyze hydrogen evolution both from acetic acid and purely water media (pH 7.0), with a turnover frequency of 40.64 and 750.2 mol of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) to give H2 over a 48 h electrolysis period with 97% Faradaic yield and no observable decomposition of the catalyst. Photocatalytic experiments indicate that complex 1 in pH 4.0 aqueous solution under air, together with [Ru(bpy)3]Cl2 and ascorbic acid as a sacrificial electron donor, in the presence of blue light (λmax = 469 nm) also can produce hydrogen with a TON = 425 mol of H2 (mol of cat)-1.

  6. Aggregation-induced white-light emission from the triple-stranded dinuclear Sm(iii) complex.

    PubMed

    Leng, Jiaqi; Li, Hongfeng; Chen, Peng; Sun, Wenbin; Gao, Ting; Yan, Pengfei

    2014-08-28

    A novel bis-β-diketone ligand, 4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)(phenoxy)-1,1'-binaphthalene (BTPB), is designed for synthesis of a white light emissive lanthanide complex. The ligand bears two benzoyl β-diketonate sites linked by a 1,1'-binaphthoxy spacer. Reaction of the doubly negatively charged bis-bidentate ligand with lanthanide ions forms triple-stranded dinuclear complexes Sm2(BTPB)3(H2O)4 () and Gd2(BTPB)3(H2O)4 (), which have been fully characterized by various spectroscopic techniques. UV-Vis absorption and emission spectroscopic techniques are used to investigate photophysical properties of the ligand and its complexes in THF and CHCl3. In some cases aggregation of the ligand results in the appearance of a new luminescence band at about 510 nm in addition to the monomer fluorescence. In complex , partial energy transfer from BTPB results in Sm(iii)-based red light emission in addition to the BTPB-based blue/green emission. With the variation of the excited wavelength and concentration of the solution, complex shows a tunable white light emission with the balance of three primary colors. This is an unusual case of observation of white light emission from a single molecule Sm(iii) complex.

  7. Dinuclear fluoro-peroxovanadium(v) complexes with symmetric and asymmetric peroxo bridges: syntheses, structures and DFT studies.

    PubMed

    Chrappová, Jana; Schwendt, Peter; Sivák, Michal; Repiský, Michal; Malkin, Vladimir G; Marek, Jaromír

    2009-01-21

    Two new dinuclear fluoro peroxovanadium(v) complexes, Cs3[V2O2(O2)4F] x H2O (1) and Cs3[V2O2(O2)3F3] x 2HF x H2O (2), were prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and X-ray crystallography. While the anion in possesses an asymmetric structure with a micro-eta1:eta2 bridging peroxo group, the [V2O2(O2)3F3]3- ion in exhibits a symmetrical structure with a unique mu-fluoro and micro-eta2:eta2 peroxo double bridge. The X-ray structure data were compared with equilibrium and vibrationally-averaged (effective) DFT calculated geometries. The decomposition reactions of and in aqueous solution were studied by 51V NMR spectroscopy. The calculations of vibrationally averaged NMR chemical shifts (DFT-GIAO) were used to support the empirical assignment of NMR signals and afforded excellent agreement with experimental values for the studied peroxovanadium species. The ESI mass spectra of the prepared compounds are in accordance with the assignment of NMR spectra and with DFT study.

  8. Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

    PubMed Central

    Apps, Michael G.; Johnson, Ben W.; Sutcliffe, Oliver B.; Brown, Sarah D.; Wheate, Nial J.

    2014-01-01

    Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand. PMID:24893964

  9. Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

    SciTech Connect

    Berto, Timothy C.; Speelman, Amy L.; Zheng, Sheng; Lehnert, Nicolai

    2013-01-01

    High-spin non-heme iron–nitrosyls are of direct interest to both the chemical and biological communities as these species exhibit interesting chemical properties and act as direct models for enzymatic intermediates. The electronic ground state of the ferrous NO complexes, {Fe–NO}7, is best described as high-spin FeIII antiferromagnetically coupled to NO-, generating the spectroscopically observed S = 3/2 ground state. These species have been identified as catalytically relevant to a variety of NO-reducing enzymes such as bacterial nitric oxide reductase (NorBC) and flavo(rubredoxin) nitric oxide reductase (FNOR). Recently, the corresponding one-electron reduced {Fe–NO}8 (nitroxyl) complexes have also been implicated as biologically significant species. In this review the available spectroscopic data for {Fe–NO}7 and {Fe–NO}8 mono- and dinuclear non-heme iron–nitrosyls are summarized, and the implications of these results with respect to the electronic structures and reactivities of these species, in particular towards NO reduction, are discussed.

  10. Structural Studies on Dinuclear Ruthenium(II) Complexes That Bind Diastereoselectively to an Antiparallel Folded Human Telomere Sequence

    PubMed Central

    2013-01-01

    We report DNA binding studies of the dinuclear ruthenium ligand [{Ru(phen)2}2tpphz]4+ in enantiomerically pure forms. As expected from previous studies of related complexes, both isomers bind with similar affinity to B-DNA and have enhanced luminescence. However, when tested against the G-quadruplex from human telomeres (which we show to form an antiparallel basket structure with a diagonal loop across one end), the ΛΛ isomer binds approximately 40 times more tightly than the ΔΔ, with a stronger luminescence. NMR studies show that the complex binds at both ends of the quadruplex. Modeling studies, based on experimentally derived restraints obtained for the closely related [{Ru(bipy)2}2tpphz]4+, show that the ΛΛ isomer fits neatly under the diagonal loop, whereas the ΔΔ isomer is unable to bind here and binds at the lateral loop end. Molecular dynamics simulations show that the ΔΔ isomer is prevented from binding under the diagonal loop by the rigidity of the loop. We thus present a novel enantioselective binding substrate for antiparallel basket G-quadruplexes, with features that make it a useful tool for quadruplex studies. PMID:24088028

  11. The Canadian Astronomy Data Centre

    NASA Astrophysics Data System (ADS)

    Ball, Nicholas M.; Schade, D.; Astronomy Data Centre, Canadian

    2011-01-01

    The Canadian Astronomy Data Centre (CADC) is the world's largest astronomical data center, holding over 0.5 Petabytes of information, and serving nearly 3000 astronomers worldwide. Its current data collections include BLAST, CFHT, CGPS, FUSE, Gemini, HST, JCMT, MACHO, MOST, and numerous other archives and services. It provides extensive data archiving, curation, and processing expertise, via projects such as MegaPipe, and enables substantial day-to-day collaboration between resident astronomers and computer specialists. It is a stable, powerful, persistent, and properly supported environment for the storage and processing of large volumes of data, a condition that is now absolutely vital for their science potential to be exploited by the community. Through initiatives such as the Common Archive Observation Model (CAOM), the Canadian Virtual Observatory (CVO), and the Canadian Advanced Network for Astronomical Research (CANFAR), the CADC is at the global forefront of advancing astronomical research through improved data services. The CAOM aims to provide homogeneous data access, and hence viable interoperability between a potentially unlimited number of different data collections, at many wavelengths. It is active in the definition of numerous emerging standards within the International Virtual Observatory, and several datasets are already available. The CANFAR project is an initiative to make cloud computing for storage and data-intensive processing available to the community. It does this via a Virtual Machine environment that is equivalent to managing a local desktop. Several groups are already processing science data. CADC is also at the forefront of advanced astronomical data analysis, driven by the science requirements of astronomers both locally and further afield. The emergence of 'Astroinformatics' promises to provide not only utility items like object classifications, but to directly enable new science by accessing previously undiscovered or intractable

  12. Big Surveys, Big Data Centres

    NASA Astrophysics Data System (ADS)

    Schade, D.

    2016-06-01

    Well-designed astronomical surveys are powerful and have consistently been keystones of scientific progress. The Byurakan Surveys using a Schmidt telescope with an objective prism produced a list of about 3000 UV-excess Markarian galaxies but these objects have stimulated an enormous amount of further study and appear in over 16,000 publications. The CFHT Legacy Surveys used a wide-field imager to cover thousands of square degrees and those surveys are mentioned in over 1100 publications since 2002. Both ground and space-based astronomy have been increasing their investments in survey work. Survey instrumentation strives toward fair samples and large sky coverage and therefore strives to produce massive datasets. Thus we are faced with the "big data" problem in astronomy. Survey datasets require specialized approaches to data management. Big data places additional challenging requirements for data management. If the term "big data" is defined as data collections that are too large to move then there are profound implications for the infrastructure that supports big data science. The current model of data centres is obsolete. In the era of big data the central problem is how to create architectures that effectively manage the relationship between data collections, networks, processing capabilities, and software, given the science requirements of the projects that need to be executed. A stand alone data silo cannot support big data science. I'll describe the current efforts of the Canadian community to deal with this situation and our successes and failures. I'll talk about how we are planning in the next decade to try to create a workable and adaptable solution to support big data science.

  13. Oxidation of methane by a biological dicopper centre.

    PubMed

    Balasubramanian, Ramakrishnan; Smith, Stephen M; Rawat, Swati; Yatsunyk, Liliya A; Stemmler, Timothy L; Rosenzweig, Amy C

    2010-05-06

    Vast world reserves of methane gas are underutilized as a feedstock for the production of liquid fuels and chemicals owing to the lack of economical and sustainable strategies for the selective oxidation of methane to methanol. Current processes to activate the strong C-H bond (104 kcal mol(-1)) in methane require high temperatures, are costly and inefficient, and produce waste. In nature, methanotrophic bacteria perform this reaction under ambient conditions using metalloenzymes called methane monooxygenases (MMOs). MMOs thus provide the optimal model for an efficient, environmentally sound catalyst. There are two types of MMO. Soluble MMO (sMMO) is expressed by several strains of methanotroph under copper-limited conditions and oxidizes methane with a well-characterized catalytic di-iron centre. Particulate MMO (pMMO) is an integral membrane metalloenzyme produced by all methanotrophs and is composed of three subunits, pmoA, pmoB and pmoC, arranged in a trimeric alpha(3)beta(3)gamma(3) complex. Despite 20 years of research and the availability of two crystal structures, the metal composition and location of the pMMO metal active site are not known. Here we show that pMMO activity is dependent on copper, not iron, and that the copper active site is located in the soluble domains of the pmoB subunit rather than within the membrane. Recombinant soluble fragments of pmoB (spmoB) bind copper and have propylene and methane oxidation activities. Disruption of each copper centre in spmoB by mutagenesis indicates that the active site is a dicopper centre. These findings help resolve the pMMO controversy and provide a promising new approach to developing environmentally friendly C-H oxidation catalysts.

  14. Review of CERN Data Centre Infrastructure

    NASA Astrophysics Data System (ADS)

    Andrade, P.; Bell, T.; van Eldik, J.; McCance, G.; Panzer-Steindel, B.; Coelho dos Santos, M.; Traylen and, S.; Schwickerath, U.

    2012-12-01

    The CERN Data Centre is reviewing strategies for optimizing the use of the existing infrastructure and expanding to a new data centre by studying how other large sites are being operated. Over the past six months, CERN has been investigating modern and widely-used tools and procedures used for virtualisation, clouds and fabric management in order to reduce operational effort, increase agility and support unattended remote data centres. This paper gives the details on the project's motivations, current status and areas for future investigation.

  15. Planetary Radars Operating Centre PROC

    NASA Astrophysics Data System (ADS)

    Catallo, C.; Flamini, E.; Seu, R.; Alberti, G.

    2007-12-01

    Planetary exploration by means of radar systems, mainly using Ground Penetrating Radars (GPR) plays an important role in Italy. Numerous scientific international space programs are currently carried out jointly with ESA and NASA by Italian Space Agency, the scientific community and the industry. Three important experiments under Italian leadership ( designed and manufactured by the Italian industry), provided by ASI either as contribution to ESA programs either within a NASA/ASI joint venture framework, are now operating: MARSIS on-board Mars Express, SHARAD on-board Mars Reconnaissance Orbiter and CASSINI Radar on-board Cassini spacecraft. In order to support all the scientific communities, institutional customers and experiment teams operation three Italian dedicated operational centers have been realized, namely SHOC, (Sharad Operating Centre), MOC (Marsis Operating Center) and CASSINI PAD ( Processing Altimetry Data). Each center is dedicated to a single instrument management and control, data processing and distribution. Although they had been conceived to operate autonomously and independently one from each other, synergies and overlaps have been envisaged leading to the suggestion of a unified center, the Planetary Radar Processing Center (PROC). PROC is conceived in order to include the three operational centers, namely SHOC, MOC and CASSINI PAD, either from logistics point of view and from HW/SW capabilities point of view. The Planetary Radar Processing Center shall be conceived as the Italian support facility to the scientific community for on-going and future Italian planetary exploration programs. Therefore, scalability, easy use and management shall be the design drivers. The paper describes how PROC is designed and developed, to allow SHOC, MOC and CASSINI PAD to operate as before, and to offer improved functionalities to increase capabilities, mainly in terms of data exchange, comparison, interpretation and exploitation. Furthermore, in the frame of

  16. Bifunctional Zn(II)Ln(III) dinuclear complexes combining field induced SMM behavior and luminescence: enhanced NIR lanthanide emission by 9-anthracene carboxylate bridging ligands.

    PubMed

    Palacios, María A; Titos-Padilla, Silvia; Ruiz, José; Herrera, Juan Manuel; Pope, Simon J A; Brechin, Euan K; Colacio, Enrique

    2014-02-03

    There were new dinuclear Zn(II)-Ln(III) complexes of general formulas [Zn(μ-L)(μ-OAc)Ln(NO3)2] (Ln(III) = Tb (1), Dy (2), Er (3), and Yb (4)), [Zn(μ-L)(μ-NO3)Er(NO3)2] (5), [Zn(H2O)(μ-L)Nd(NO3)3]·2CH3OH (6), [Zn(μ-L)(μ-9-An)Ln(NO3)2]·2CH3CN (Ln(III) = Tb (7), Dy (8), Er (9), Yb(10)), [Zn(μ-L)(μ-9-An)Yb(9-An)(NO3)3]·3CH3CN (11), [Zn(μ-L)(μ-9-An)Nd(9-An)(NO3)3]·2CH3CN·3H2O (12), and [Zn(μ-L)(μ-9-An)Nd(CH3OH)2(NO3)]ClO4·2CH3OH (13) prepared from the reaction of the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L), with ZnX2·nH2O (X = NO3(-) or OAc(-)) salts, Ln(NO3)3·nH2O, and, in some instances, 9-anthracenecarboxylate anion (9-An). In all these complexes, the Zn(II) ions invariably occupy the internal N3O2 site whereas the Ln(III) ions show preference for the O4 external site, giving rise to a Zn(μ-diphenoxo)Ln bridging fragment. Depending on the Zn(II) salt and solvent used in the reaction, a third bridge can connect the Zn(II) and Ln(III) metal ions, giving rise to triple-bridged diphenoxoacetate in complexes 1-4, diphenoxonitrate in complex 5, and diphenoxo(9-anthracenecarboxylate) in complexes 8-13. Dy(III) and Er(III) complexes 2, 8 and 3, 5, respectively, exhibit field induced single molecule magnet (SMM) behavior, with Ueff values ranging from 11.7 (3) to 41(2) K. Additionally, the solid-state photophysical properties of these complexes are presented showing that ligand L(2-) is able to sensitize Tb(III)- and Dy(III)-based luminescence in the visible region through an energy transfer process (antenna effect). The efficiency of this process is much lower when NIR emitters such as Er(III), Nd(III), and Yb(III) are considered. When the luminophore 9-anthracene carboxylate is incorporated into these complexes, the NIR luminescence is enhanced which proves the efficiency of this bridging ligand to act as antenna group. Complexes 2, 3, 5, and 8 can be considered as dual materials

  17. A new regime for mechanical annealing and strong sample-size strengthening in body centred cubic molybdenum.

    PubMed

    Huang, Ling; Li, Qing-Jie; Shan, Zhi-Wei; Li, Ju; Sun, Jun; Ma, Evan

    2011-11-22

    Because of crystal symmetry, body centred cubic (BCC) metals have large differences in lattice friction between screw and edge dislocations, and manifest generally different mechanical behaviours from face centred cubic (FCC) metals. Although mechanical annealing (significant drop in stored dislocation density in response to applied stress) has been observed in FCC metals, it has not been observed in BCC metals so far. Here we show that significant mechanical annealing does occur in BCC Mo pillars, when their diameters decrease to hundreds of nanometers. In addition, there exists a critical diameter for focused ion beam milled pillars, below which the strengthening exponent increases dramatically, from ~0.3 to ~1. Thus, a new regime of size effects in BCC metals is discovered that converges to that of FCC metals, revealing deep connection in the dislocation dynamics of the two systems.

  18. Towards Human-Centred Design

    NASA Astrophysics Data System (ADS)

    Bannon, Liam J.

    The field of HCI has evolved and expanded dramatically since its origin in the early 1980’s. The HCI community embraces a large community of researchers and practitioners around the world, from a variety of disciplinary backgrounds in the human and social sciences, engineering and informatics, and more recently, the arts and design disciplines. This kaleidoscope of cultures and disciplines as seen at INTERACT Conferences provides a rich pool of resources for examining our field. Applications are increasingly exploring our full range of sensory modalities, and merging the digital and physical worlds. WiFi has opened up a huge design space for mobile applications. A focus on usability of products and services has been complemented by an emphasis on engagement, enjoyment and experience. With the advent of ubiquitous computing, and the emergence of “The Internet of Things”, new kinds of more open infrastructures make possible radically new kinds of applications. The sources of innovation have also broadened, to include human and social actors outside of the computing and design organizations. The question is to what extent is our mainstream thinking in the HCI field ready for the challenges of this Brave New World? Do the technological and social innovations that we see emerging require us to re-shape, or even, re-create, our field, or is it a case of a more gradual evolution and development of that which we already know? In this closing Keynote, I will provide a perspective on the evolution and development of the HCI field, looking backwards as well as forwards, in order to determine what are some of the changes of significance in the field. This “broad-brush” approach to what I term “ human-centred design” will be complemented by the examination of specific projects and applications, to help anchor some of the discussion. Areas such as user-centred design, participatory design, computer-supported cooperative work and learning, and interaction design, in

  19. Identity Theft: A Study in Contact Centres

    NASA Astrophysics Data System (ADS)

    Moir, Iain; Weir, George R. S.

    This paper explores the recent phenomenon of identity theft. In particular, it examines the contact centre environment as a mechanism for this to occur. Through a survey that was conducted amongst forty-five contact centre workers in the Glasgow area we determined that contact centres can and do provide a mechanism for identity theft. Specifically, we found a particularly high incidence of agents who had previously dealt with phone calls that they considered suspicious. Furthermore, there are agents within such environments who have previously been offered money in exchange for customers' details, or who know of fellow workers who received such offers. Lastly, we identify specific practices within contact centres that may contribute to the likelihood of identity theft.

  20. Dinuclear iron(II)-cyanocarbonyl complexes linked by two/three bridging ethylthiolates: relevance to the active site of [Fe] hydrogenases.

    PubMed

    Liaw, Wen-Feng; Tsai, Wen-Ting; Gau, Hung-Bin; Lee, Chien-Ming; Chou, Shin-Yuan; Chen, Wen-Yuan; Lee, Gene-Hsiang

    2003-04-21

    Dinuclear iron(II)-cyanocarbonyl complex [PPN](2)[Fe(CN)(2)(CO)(2)(mu-SEt)](2) (1) was prepared by the reaction of [PPN][FeBr(CN)(2)(CO)(3)] and [Na][SEt] in THF at ambient temperature. Reaction of complex 1 with [PPN][SEt] produced the triply thiolate-bridged dinuclear Fe(II) complex [PPN][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)] (2) with the torsion angle of two CN(-) groups (C(5)N(2) and C(3)N(1)) being 126.9 degrees. The extrusion of two sigma-donor CN(-) ligands from Fe(II)Fe(II) centers of complex 1 as a result of the reaction of complex 1 and [PPN][SEt] reflects the electron-rich character of the dinuclear iron(II) when ligated by the third bridging ethylthiolate. The Fe-S distances (2.338(2) and 2.320(3) A for complexes 1 and 2, respectively) do not change significantly, but the Fe(II)-Fe(II) distance contracts from 3.505 A in complex 1 to 3.073 A in complex 2. The considerably longer Fe(II)-Fe(II) distance of 3.073 A in complex 2, compared to the reported Fe-Fe distances of 2.6/2.62 A in DdHase and CpHase, was attributed to the presence of the third bridging ethylthiolate, instead of pi-accepting CO-bridged ligand as observed in [Fe] hydrogenases. Additionally, in a compound of unusual composition ([Na.(5)/(2)H(2)O][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)])(n)((1)/(2)O(Et)(2))(n) (3), the Na(+) cations and H(2)O molecules combining with dinuclear [(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)](-) anions create a polymeric framework wherein two CN(-) ligands are coordinated via CN(-)-Na(+)/CN(-)-(Na(+))(2) linkages, respectively.

  1. Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

    PubMed

    Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

    2017-01-17

    Trinuclear versus dinuclear heterodimetallic U(V)O2(+)Co(2+) complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

  2. Quasifission and fission rates and their lifetimes in asymmetric reactions forming 216Ra within a dinuclear system approach

    NASA Astrophysics Data System (ADS)

    Khanlari, M. Varasteh; Soheyli, S.

    2017-02-01

    Background: The study of evolution of asymmetric dinuclear systems (DNSs) formed in heavy ion collisions is a topic of intense research. The DNS evolution leads to a variety of reaction channels such as deep inelastic, complete fusion, quasifission, fast fission, fusion-fission, and evaporation of particles. The time evolution of the DNS in the quasifission process and the role of relevant parameters are still not fully understood. Purpose: The influence of the entrance channel mass asymmetry on the time evolution of an excited and rotating DNS, populated via four reactions with different entrance channel mass asymmetry parameters which all lead to the compound nucleus 216Ra, is explored. Method: The driving potential, emission barriers for the binary decay (namely the quasifission and intrinsic fusion barriers), rate of the quasifission channel, and the lifetime of an excited DNS, as well as the fission rate and fission lifetime of the compound nucleus 216Ra formed in the 12C+204Pb,19F+197Au,30Si+186W , and 48Ca+168Er reactions, are calculated by the dinuclear system approach. Results: Our results show that the intrinsic fusion barrier values are equal to zero for the 12C+204Pb and 19F+197Au reactions. Therefore, the quasifission signature is extremely hindered for these reactions, while the 30Si+186W and 48Ca+168Er calculated results contain quasifission contributions. Provided the quasifission rate is nonzero, the quasifission rate increases with increasing orbital angular momentum ℓ of the composite system for a given excitation energy ECN * of the compound nucleus. On the other hand, the quasifission lifetime decreases moderately with increasing ℓ . Furthermore, both quasifission and fission rates increase with increasing excitation energy ECN *, while the quasifission and fission lifetimes decrease with increasing ECN * for a given ℓ . Conclusions: Although these reactions with different entrance channels populate the same compound nucleus 216Ra at

  3. Fine-tuning terminal solvent ligands to rationally enhance the energy barrier in dinuclear dysprosium single-molecule magnets.

    PubMed

    Zhang, Kun; Yuan, Chen; Guo, Fu-Sheng; Zhang, Yi-Quan; Wang, Yao-Yu

    2016-12-20

    In search of simple approaches to rationally enhance the energy barriers in polynuclear dysprosium single-molecule magnets, a new system containing two structurally closely related dinuclear dysprosium complexes, namely [Dy2(L)2(DBM)2(DMF)2] (1) and [Dy2(L)2(DBM)2(DMA)2]·2DMA (2) (HDBM = dibenzoylmethane, H2L = 2-hydroxy-N'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide), is introduced and the structure-dependent magnetic properties are investigated. The two complexes display only slight variations in the coordination geometries of the Dy(iii) ion but display remarkably different magnetic behaviors. By replacing the DMF (dimethylformamide) ligand in complex 1 with DMA (dimethylacetamide) in 2 while retaining the same coordination atoms, we were able to create a 3-fold enhancement in the energy barrier, from 24 K for complex 1 to 77 K for complex 2. Complete-active-space self-consistent field (CASSCF) calculations revealed that the charge distribution surrounding the Dy(iii) centers in 1 and 2 is the key factor in determining the relaxation properties of the SMMs. The introduction of an electron-donating CH3 group in DMA to replace the hydrogen in DMF resulted in a larger average charge along the magnetic axes of complex 2 compared to complex 1, which resulted in a stronger easy-axis ligand field, thus increasing the energy difference between the ground and the first excited states of complex 2. This work presents a simple method to rationally enhance the energy barrier in polynuclear lanthanide SMMs through fine-tuning of the electrostatic potential of the atoms along the magnetic axis.

  4. Reduction of Toxoplasma gondii Development Due to Inhibition of Parasite Antioxidant Enzymes by a Dinuclear Iron(III) Compound.

    PubMed

    Portes, J A; Souza, T G; dos Santos, T A T; da Silva, L L R; Ribeiro, T P; Pereira, M D; Horn, A; Fernandes, C; DaMatta, R A; de Souza, W; Seabra, S H

    2015-12-01

    Toxoplasma gondii, the causative agent of toxoplasmosis, is an obligate intracellular protozoan that can infect a wide range of vertebrate cells. Here, we describe the cytotoxic effects of the dinuclear iron compound [Fe(HPCINOL)(SO4)]2-μ-oxo, in which HPCINOL is the ligand 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol, on T. gondii infecting LLC-MK2 host cells. This compound was not toxic to LLC-MK2 cells at concentrations of up to 200 μM but was very active against the parasite, with a 50% inhibitory concentration (IC50) of 3.6 μM after 48 h of treatment. Cyst formation was observed after treatment, as indicated by the appearance of a cyst wall, Dolichos biflorus lectin staining, and scanning and transmission electron microscopy characteristics. Ultrastructural changes were also seen in T. gondii, including membrane blebs and clefts in the cytoplasm, with inclusions similar to amylopectin granules, which are typically found in bradyzoites. An analysis of the cell death pathways in the parasite revealed that the compound caused a combination of apoptosis and autophagy. Fluorescence assays demonstrated that the redox environment in the LLC-MK2 cells becomes oxidant in the presence of the iron compound. Furthermore, a reduction in superoxide dismutase and catalase activities in the treated parasites and the presence of reactive oxygen species within the parasitophorous vacuoles were observed, indicating an impaired protozoan response against these radicals. These findings suggest that this compound disturbs the redox equilibrium of T. gondii, inducing cystogenesis and parasite death.

  5. Reduction of Toxoplasma gondii Development Due to Inhibition of Parasite Antioxidant Enzymes by a Dinuclear Iron(III) Compound

    PubMed Central

    Portes, J. A.; Souza, T. G.; dos Santos, T. A. T.; da Silva, L. L. R.; Ribeiro, T. P.; Pereira, M. D.; Horn, A.; Fernandes, C.; DaMatta, R. A.; de Souza, W.

    2015-01-01

    Toxoplasma gondii, the causative agent of toxoplasmosis, is an obligate intracellular protozoan that can infect a wide range of vertebrate cells. Here, we describe the cytotoxic effects of the dinuclear iron compound [Fe(HPCINOL)(SO4)]2-μ-oxo, in which HPCINOL is the ligand 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol, on T. gondii infecting LLC-MK2 host cells. This compound was not toxic to LLC-MK2 cells at concentrations of up to 200 μM but was very active against the parasite, with a 50% inhibitory concentration (IC50) of 3.6 μM after 48 h of treatment. Cyst formation was observed after treatment, as indicated by the appearance of a cyst wall, Dolichos biflorus lectin staining, and scanning and transmission electron microscopy characteristics. Ultrastructural changes were also seen in T. gondii, including membrane blebs and clefts in the cytoplasm, with inclusions similar to amylopectin granules, which are typically found in bradyzoites. An analysis of the cell death pathways in the parasite revealed that the compound caused a combination of apoptosis and autophagy. Fluorescence assays demonstrated that the redox environment in the LLC-MK2 cells becomes oxidant in the presence of the iron compound. Furthermore, a reduction in superoxide dismutase and catalase activities in the treated parasites and the presence of reactive oxygen species within the parasitophorous vacuoles were observed, indicating an impaired protozoan response against these radicals. These findings suggest that this compound disturbs the redox equilibrium of T. gondii, inducing cystogenesis and parasite death. PMID:26392498

  6. Characteristic effect of an anticancer dinuclear platinum(II) complex on the higher-order structure of DNA.

    PubMed

    Kida, Naoko; Katsuda, Yousuke; Yoshikawa, Yuko; Komeda, Seiji; Sato, Takaji; Saito, Yoshihiro; Chikuma, Masahiko; Suzuki, Mari; Imanaka, Tadayuki; Yoshikawa, Kenichi

    2010-06-01

    It is known that a 1,2,3-triazolato-bridged dinuclear platinum(II) complex, [{cis-Pt(NH(3))(2)}(2)(micro-OH)(micro-1,2,3-ta-N (1),N (2))](NO(3))(2) (AMTA), shows high in vitro cytotoxicity against several human tumor cell lines and circumvents cross-resistance to cisplatin. In the present study, we examined a dose- and time-dependent effect of AMTA on the higher-order structure of a large DNA, T4 phage DNA (166 kbp), by adapting single-molecule observation with fluorescence microscopy. It was found that AMTA induces the shrinking of DNA into a compact state with a much higher potency than cisplatin. From a quantitative analysis of the Brownian motion of individual DNA molecules in solution, it became clear that the density of a DNA segment in the compact state is about 2,000 times greater than that in the absence of AMTA. Circular dichroism spectra suggested that AMTA causes a transition from the B to the C form in the secondary structure of DNA, which is characterized by fast and slow processes. Electrophoretic measurements indicated that the binding of AMTA to supercoiled DNA induces unwinding of the double helix. Our results indicate that AMTA acts on DNA through both electrostatic interaction and coordination binding; the former causes a fast change in the secondary structure from the B to the C form, whereas the latter promotes shrinking in the higher-order structure as a relatively slow kinetic process. The shrinking effect of AMTA on DNA is attributable to the possible increase in the number of bridges along a DNA molecule. It is concluded that AMTA interacts with DNA in a manner markedly different from that of cisplatin.

  7. Ligand modulation of a dinuclear platinum compound leads to mechanistic differences in cell cycle progression and arrest.

    PubMed

    Menon, Vijay R; Peterson, Erica J; Valerie, Kristoffer; Farrell, Nicholas P; Povirk, Lawrence F

    2013-12-15

    Despite similar structures and DNA binding profiles, two recently synthesized dinuclear platinum compounds are shown to elicit highly divergent effects on cell cycle progression. In colorectal HCT116 cells, BBR3610 shows a classical G2/M arrest with initial accumulation in S phase, but the derivative compound BBR3610-DACH, formed by introduction of the 1,2-diaminocyclohexane (DACH) as carrier ligand, results in severe G1/S as well as G2/M phase arrest, with nearly complete S phase depletion. The origin of this unique effect was studied. Cellular interstrand crosslinking as assayed by comet analysis was similar for both compounds, confirming previous in vitro results obtained on plasmid DNA. Immunoblotting revealed a stabilization of p53 and concomitant transient increases in p21 and p27 proteins after treatment with BBR3610-DACH. Cell viability assays and cytometric analysis of p53 and p21 null cells indicated that BBR3610-DACH-induced cell cycle arrest was p21-dependent and partially p53-dependent. However, an increase in the levels of cyclin E was observed with steady state levels of CDK2 and Cdc25A, suggesting that the G1 block occurs downstream of CDK/cyclin complex formation. The G2/M block was corroborated with decreased levels of cyclin A and cyclin B1. Surprisingly, BBR3610-DACH-induced G1 block was independent of ATM and ATR. Finally, both compounds induced apoptosis, with BBR3610-DACH showing a robust PARP-1 cleavage that was not associated with caspase-3/7 cleavage. In summary, BBR3610-DACH is a DNA binding platinum agent with unique inhibitory effects on cell cycle progression that could be further developed as a chemotherapeutic agent complementary to cisplatin and oxaliplatin.

  8. Perspectives on recycling centres and future developments.

    PubMed

    Engkvist, I-L; Eklund, J; Krook, J; Björkman, M; Sundin, E

    2016-11-01

    The overall aim of this paper is to draw combined, all-embracing conclusions based on a long-term multidisciplinary research programme on recycling centres in Sweden, focussing on working conditions, environment and system performance. A second aim is to give recommendations for their development of new and existing recycling centres and to discuss implications for the future design and organisation. Several opportunities for improvement of recycling centres were identified, such as design, layout, ease with which users could sort their waste, the work environment, conflicting needs and goals within the industry, and industrialisation. Combining all results from the research, which consisted of different disciplinary aspects, made it possible to analyse and elucidate their interrelations. Waste sorting quality was recognized as the most prominent improvement field in the recycling centre system. The research identified the importance of involving stakeholders with different perspectives when planning a recycling centre in order to get functionality and high performance. Practical proposals of how to plan and build recycling centres are given in a detailed checklist.

  9. The Imperial College Thermophysical Properties Data Centre

    NASA Astrophysics Data System (ADS)

    Angus, S.; Cole, W. A.; Craven, R.; de Reuck, K. M.; Trengove, R. D.; Wakeham, W. A.

    1986-07-01

    The IUPAC Thermodynamic Tables Project Centre in London has at its disposal considerable expertise on the production and utilization of high-accuracy equations of state which represent the thermodynamic properties of substances. For some years they have been content to propagate this information by the traditional method of book production, but the increasing use of the computer in industry for process design has shown that an additional method was needed. The setting up of the IUPAC Transport Properties Project Centre, also at Imperial College, whose products would also be in demand by industry, afforded the occasion for a new look at the problem. The solution has been to set up the Imperial College Thermophysical Properties Data Centre, which embraces the two IUPAC Project Centres, and for it to establish a link with the existing Physical Properties Data Service of the Institution of Chemical Engineers, thus providing for the dissemination of the available information without involving the Centres in problems such as those of marketing and advertising. This paper outlines the activities of the Centres and discusses the problems in bringing their products to the attention of industry in suitable form.

  10. Dinuclear complexes formed with the triazacyclononane derivative ENOTA4-: high-pressure 17O NMR evidence of an associative water exchange on [MnII2(ENOTA)(H2O)2].

    PubMed

    Balogh, Edina; He, Zhenjie; Hsieh, Wenyuan; Liu, Shuang; Tóth, Eva

    2007-01-08

    Mn2+ has five unpaired d-electrons, a long electronic relaxation time, and labile water exchange, all of which make it an attractive candidate for contrast agent application in medical magnetic resonance imaging. In the quest for stable and nonlabile Mn2+ complexes, we explored a novel dimeric triazacyclononane-based ligand bearing carboxylate functional groups, H4ENOTA. The protonation constants of the ligand and the stability constants of the complexes formed with some endogenously important metals (Ca2+, Cu2+, Zn2+), as well as with Mn2+ and Ce3+, have been assessed by NMR methods, potentiometry, and UV-vis spectrophotometry. Overall, the thermodynamic stability of the complexes is lower as compared to that of the corresponding NOTA analogues (H3NOTA, 1,4,7-triaazacyclononane-1,4,7-triacetic acid). The crystal structure of Mn2(ENOTA)(H2O) x 5H2O contains two six-coordinated Mn2+, in addition to the three amine nitrogens and the two oxygens from the pendent monodentate carboxylate groups, and one water (Mn2) or one bridging carboxylate oxygen (Mn1) completes the coordination sphere of the metal ion. In an aqueous solution, this bridging carboxylate is replaced by a water molecule, as evidenced by the 17O chemical shifts and proton relaxivity data that point to monohydration for both metal ions in the dinuclear complex. A variable-temperature and -pressure 17O NMR study has been performed on [Mn2(ENOTA)(H2O)2] to assess the rate and, for the first time on a Mn2+ chelate, also the mechanism of the water exchange. The inner sphere water is slightly more labile in [Mn2(ENOTA)(H2O)2] (k298ex = 5.5 x 107 s-1) than in the aqua ion (2.1 x 107 s-1, Merbach, A. E.; et al. Inorg. Chem. 1980, 19, 3696). The water exchange proceeds via an almost limiting associative mechanism, as evidenced by the large negative activation volume (deltaV = -10.7 cm3 mol-1). The proton relaxivities measured on [Mn2(ENOTA)(H2O)2] show a low-field dispersion at approximately 0.1 MHz arising from

  11. Mössbauer investigation of the photoexcited spin states and crystal structure analysis of the spin-crossover dinuclear complex [{Fe(bt)(NCS)(2)}(2)bpym] (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine).

    PubMed

    Gaspar, Ana B; Ksenofontov, Vadim; Reiman, Sergey; Gütlich, Philipp; Thompson, Amber L; Goeta, Andrés E; Muñoz, M Carmen; Real, José A

    2006-12-13

    The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) environment. The average Fe--N bond length of 2.15(9) Angstrom indicates that compound 1 is in the high-spin state (HS-HS) at 293 K. Crystal structure determinations at 240, 175 and 30 K gave a cell comparable to that seen at 293 K, but reduced in volume. At 30 K, the average Fe--N distance is 1.958(4) Angstrom, showing that the structure is clearly low spin (LS-LS). At 175 K the average Fe--N bond length of 2.052(11) Angstrom suggests that there is an intermediate phase. Mössbauer investigations of the light-induced excited spin state trapping (LIESST) effect (lambda=514 nm, 25 mW cm(-2)) in 1 (4.2 K, H(ext)=50 kOe) show that the excited spin states correspond to the HS-HS and HS-LS pairs. The dynamics of the relaxation of the photoexcited states studied at 4.2 K and H(ext)=50 kOe demonstrate that HS-HS pairs revert with time to both HS-LS and LS-LS configurations. The HS-LS photoexcited pairs relax with time back to the ground LS-LS configuration. Complex [{Fe(0.15)Zn(0.85)(bt)(NCS)(2)}(2)bpym] (2) exhibits a continuous spin transition centred around 158 K in contrast to the two-step transition observed for 1. The different spin-crossover behaviour observed for 2 is due to the decrease of cooperativity (intermolecular interactions) imposed by the matrix of Zn(II) ions. This

  12. Metal-ion mutagenesis: conversion of a purple acid phosphatase from sweet potato to a neutral phosphatase with the formation of an unprecedented catalytically competent Mn(II)Mn(II) active site.

    PubMed

    Mitić, Natasa; Noble, Christopher J; Gahan, Lawrence R; Hanson, Graeme R; Schenk, Gerhard

    2009-06-17

    The currently accepted paradigm is that the purple acid phosphatases (PAPs) require a heterovalent, dinuclear metal-ion center for catalysis. It is believed that this is an essential feature for these enzymes in order for them to operate under acidic conditions. A PAP from sweet potato is unusual in that it appears to have a specific requirement for manganese, forming a unique Fe(III)-mu-(O)-Mn(II) center under catalytically optimal conditions (Schenk et al. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 273). Herein, we demonstrate, with detailed electron paramagnetic resonance (EPR) spectroscopic and kinetic studies, that in this enzyme the chromophoric Fe(III) can be replaced by Mn(II), forming a catalytically active, unprecedented antiferromagnetically coupled homodivalent Mn(II)-mu-(H)OH-mu-carboxylato-Mn(II) center in a PAP. However, although the enzyme is still active, it no longer functions as an acid phosphatase, having optimal activity at neutral pH. Thus, PAPs may have evolved from distantly related divalent dinuclear metallohydrolases that operate under pH neutral conditions by stabilization of a trivalent-divalent metal-ion core. The present Mn(II)-Mn(II) system models these distant relatives, and the results herein make a significant contribution to our understanding of the role of the chromophoric metal ion as an activator of the nucleophile. In addition, the detailed analysis of strain broadened EPR spectra from exchange-coupled dinuclear Mn(II)-Mn(II) centers described herein provides the basis for the full interpretation of the EPR spectra from other dinuclear Mn metalloenzymes.

  13. Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies.

    PubMed

    Banerjee, Ishita; Samanta, Pabitra Narayan; Das, Kalyan Kumar; Ababei, Rodica; Kalisz, Marguerite; Girard, Adrien; Mathonière, Corine; Nethaji, M; Clérac, Rodolphe; Ali, Mahammad

    2013-02-07

    Four dinuclear bis(μ-Cl) bridged copper(II) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L(X) ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH(2)) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu(t)-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

  14. Formation of dinuclear, macrocyclic, and chain structures from HgI(2) and a semirigid benzimidazole-based bridging ligand: an example of ring-opening supramolecular isomerism.

    PubMed

    Su, Cheng-Yong; Goforth, Andrea M; Smith, Mark D; zur Loye, Hans-Conrad

    2003-09-08

    The reactions of HgI(2) with the semirigid ditopic ligand 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bbimms) afforded three new complexes, [Hg(2)(mu-I)(2)I(2)(bbimms)] (1), [Hg(2)I(4)(bbimms)(2)] (2), and catena-poly[HgI(2)(bbimms)] (3). The ligand and all complexes have been structurally characterized by single-crystal X-ray diffraction. 1 is a triply bridged dinuclear complex comprised of two Hg(II) ions, one bridging ligand, two bridging I(-) anions, and two terminal I(-) anions. 2 is a dinuclear metallamacrocycle comprised of two Hg(II) ions, two bridging ligands, and four terminal I(-) anions, while 3 is a helical chain with the repeating unit of HgI(2)(bbimms). 2 and 3 can be classified as supramolecular isomers, and both are related to the triply bridged precursor 1 via the addition of one more ligand in a ring-opening process.

  15. Lanthanide dinuclear complexes constructed from mixed oxygen-donor ligands: the effect of substituent positions of the neutral ligand on the magnetic dynamics in Dy analogues.

    PubMed

    Zhu, Wen-Hua; Li, Shan; Gao, Chen; Xiong, Xia; Zhang, Yan; Liu, Li; Powell, Annie K; Gao, Song

    2016-03-21

    Two series of lanthanide dinuclear complexes with the general formulae, [Ln(n-PNO)(Bza)3(H2O)] {Bza = benzoic acid; n = 3, n-PNO = 3-picoline N-oxide, Dy(1) and Er(2); and n = 4, n-PNO = 4-picoline N-oxide, Nd(3), Eu(4), Gd(5), Tb(6), Dy(7), Er(8) and Y(9)} have been successfully synthesized by the hydrothermal method. Single-crystal X-ray diffraction experiments illustrate that the two series of compounds possess similar carboxylic ligand-bridged dinuclear structure and coordination geometry around the lanthanide ions despite the different methyl-substituent positions on the neutral ligand. Comparative studies of the Dy analogues in the static-field measurements reveal only a little difference with a small butterfly-shaped opening for complex 1 and a close hysteresis loop for 7 at 2.0 K. However, systematic investigations of the alternating-current (ac) measurements indicate that the different substituent positions of the picoline N-oxide ligand have a significant effect on the magnetic relaxation dynamics. A more substantial suppression of the quantum tunnelling of magnetization (QTM) effect and pronounced slow magnetic relaxation were observed in complex 7 as compared to 1 under both zero and a 1 kOe static field.

  16. Series of dinuclear and tetranuclear lanthanide clusters encapsulated by salen-type and β-diketionate ligands: single-molecule magnet and fluorescence properties.

    PubMed

    Sun, Wen-Bin; Han, Bing-Lu; Lin, Po-Heng; Li, Hong-Feng; Chen, Peng; Tian, Yong-Mei; Murugesu, Muralee; Yan, Peng-Fei

    2013-10-07

    Three dinuclear [Ln2H2OL(1)2(acac)2]·solvent (1, Ln = Gd, solvent = 2CH2Cl2; 2, Ln = Tb, no solvent; 3, Ln = Er, solvent = (C2H5)2O), and two tetranuclear lanthanide clusters [Ln4(μ3-OH)2L(2)2(acac)6]·2(solvent) (4, Ln = Tb, solvent = CH3OH; 5, Ln = Dy, solvent = CH3CN) were characterized in terms of structure, fluorescence and magnetism. The dinuclear lanthanide complexes were constructed by a rigid salen-type ligand H2L(1) = N,N'-bis(salicylidene)-o-phenylenediamine and β-diketonate (acac = acetylacetonate) ligands, while the tetranuclear clusters were formed from the flexible ligand H2L(2) = N,N'-bis(salicylidene)-1,2-ethanediamine. Crystal structure analysis indicates that the rigid ligand favors the double-decker sandwich structure (Ln2L(1)2), in which the two lanthanide ions have different coordination numbers and geometry, while the more flexible ligand (H2L(2)) leads to planar tetranuclear clusters. The relationship between their respective magnetic anisotropy and ligand-field geometries and their fluorescence properties was investigated. The Dy and Tb-containing clusters exhibit typical visible fluorescence properties, and single-molecule magnet behavior is seen in complex 5.

  17. CMS centres worldwide: A new collaborative infrastructure

    SciTech Connect

    Taylor, Lucas; Gottschalk, Erik; /Fermilab

    2010-01-01

    The CMS Experiment at the LHC is establishing a global network of inter-connected 'CMS Centres' for controls, operations and monitoring. These support: (1) CMS data quality monitoring, detector calibrations, and analysis; and (2) computing operations for the processing, storage and distribution of CMS data. We describe the infrastructure, computing, software, and communications systems required to create an effective and affordable CMS Centre. We present our highly successful operations experiences with the major CMS Centres at CERN, Fermilab, and DESY during the LHC first beam data-taking and cosmic ray commissioning work. The status of the various centres already operating or under construction in Asia, Europe, Russia, South America, and the USA is also described. We emphasise the collaborative communications aspects. For example, virtual co-location of experts in CMS Centres Worldwide is achieved using high-quality permanently-running 'telepresence' video links. Generic Web-based tools have been developed and deployed for monitoring, control, display management and outreach.

  18. Acid-rock drainage at Skytop, Centre County, Pennsylvania, 2004

    USGS Publications Warehouse

    Hammarstrom, Jane M.; Brady, Keith; Cravotta, Charles A.

    2005-01-01

    Recent construction for Interstate Highway 99 (I?99) exposed pyrite and associated Zn-Pb sulfide minerals beneath a >10-m thick gossan to oxidative weathering along a 40-60-m deep roadcut through a 270-m long section of the Ordovician Bald Eagle Formation at Skytop, near State College, Centre County, Pennsylvania. Nearby Zn-Pb deposits hosted in associated sandstone and limestone in Blair and Centre Counties were prospected in the past; however, these deposits generally were not viable as commercial mines. The pyritic sandstone from the roadcut was crushed and used locally as road base and fill for adjoining segments of I?99. Within months, acidic (pH1,000 mg/L), seep waters at the base of the cut contain >100 mg/L dissolved Zn and >1 mg/L As, Co, Cu, and Ni. Lead is relatively immobile (<10 ?g/L in seep waters). The salts sequester metals and acidity between rainfall events. Episodic salt dissolution then contributes pulses of contamination including acid to surface runoff and ground water. The Skytop experience highlights the need to understand dynamic interactions of mineralogy and hydrology in order to avoid potentially negative environmental impacts associated with excavation in sulfidic rocks.

  19. Optimizing Data Centre Energy and Environmental Costs

    NASA Astrophysics Data System (ADS)

    Aikema, David Hendrik

    Data centres use an estimated 2% of US electrical power which accounts for much of their total cost of ownership. This consumption continues to grow, further straining power grids attempting to integrate more renewable energy. This dissertation focuses on assessing and reducing data centre environmental and financial costs. Emissions of projects undertaken to lower the data centre environmental footprints can be assessed and the emission reduction projects compared using an ISO-14064-2-compliant greenhouse gas reduction protocol outlined herein. I was closely involved with the development of the protocol. Full lifecycle analysis and verifying that projects exceed business-as-usual expectations are addressed, and a test project is described. Consuming power when it is low cost or when renewable energy is available can be used to reduce the financial and environmental costs of computing. Adaptation based on the power price showed 10--50% potential savings in typical cases, and local renewable energy use could be increased by 10--80%. Allowing a fraction of high-priority tasks to proceed unimpeded still allows significant savings. Power grid operators use mechanisms called ancillary services to address variation and system failures, paying organizations to alter power consumption on request. By bidding to offer these services, data centres may be able to lower their energy costs while reducing their environmental impact. If providing contingency reserves which require only infrequent action, savings of up to 12% were seen in simulations. Greater power cost savings are possible for those ceding more control to the power grid operator. Coordinating multiple data centres adds overhead, and altering at which data centre requests are processed based on changes in the financial or environmental costs of power is likely to increase this overhead. Tests of virtual machine migrations showed that in some cases there was no visible increase in power use while in others power use

  20. Dual emission and excited-state mixed-valence in a quasi-symmetric dinuclear Ru-Ru complex.

    PubMed

    Kreitner, Christoph; Grabolle, Markus; Resch-Genger, Ute; Heinze, Katja

    2014-12-15

    The synthesis and characterization of the new dinuclear dipeptide [(EtOOC-tpy)Ru(tpy-NHCO-tpy)Ru(tpy-NHCOCH3)](4+) 3(4+) of the bis(terpyridine)ruthenium amino acid [(HOOC-tpy)Ru(tpy-NH2)](2+) 1(2+) are described, and the properties of the dipeptide are compared to those of the mononuclear complex [(EtOOC-tpy)Ru(tpy-NHCOCH3)](2+) 4(2+) carrying the same functional groups. 3(4+) is designed to serve a high electronic similarity of the two ruthenium sites despite the intrinsic asymmetry arising from the amide bridge. This is confirmed via UV-vis absorption and NMR spectroscopy as well as cyclic voltammetry. 4(2+) and 3(4+) are emissive at room temperature, as expected. Moreover, 3(4+) exhibits dual emission from two different triplet states with different energies and lifetimes at room temperature. This is ascribed to the presence of a unique thermal equilibrium between coexisting [Ru(II)(tpy-NHCO-tpy(·-))Ru(III)] and [Ru(III)(tpy-NHCO-tpy(·-))Ru(II)] states leading to an unprecedented excited-state Ru(II)Ru(III) mixed-valent system via the radical anion bridge tpy-NHCO-tpy(·-). The mixed-valent cation 3(5+), on the other hand, shows no measurable interaction of the Ru(II)Ru(III) centers via the neutral bridge tpy-NHCO-tpy (Robin-Day class I). Reduction of 3(4+) to the radical cation 3(3+) by decamethylcobaltocene is bridge-centered as evidenced by rapid-freeze electron paramagnetic resonance spectroscopy. Interestingly, all attempts to observe 3(3+) via NMR and UV-vis absorption spectroscopy only led to the detection of the diamagnetic complex 3-H(3+) in which the bridging amide is deprotonated. Hence 3-H(3+) (and 4-H(+)) appear to reduce protons to dihydrogen. The ease of single and double deprotonation of 4(2+) and 3(4+) to 4-H(+), 3-H(3+), and 3-2H(2+) was demonstrated using a strong base and was studied using NMR and UV-vis absorption spectroscopies. The equilibrating excited triplet states of 3(4+) are reductively quenched by N,N-dimethylaniline assisted by

  1. Targeted guanine oxidation by a dinuclear copper(II) complex at single stranded/double stranded DNA junctions.

    PubMed

    Li, Lei; Murthy, Narasimha N; Telser, Joshua; Zakharov, Lev N; Yap, Glenn P A; Rheingold, Arnold L; Karlin, Kenneth D; Rokita, Steven E

    2006-09-04

    A dinuclear copper(II) complex [Cu(II)2(PD'O-)(H2O)2](ClO4)3 (5) with terminal Cu(II)-H(2)O moieties and a Cu...Cu distance of 4.13 A (X-ray structure) has been synthesized and characterized by EPR spectroscopy (ferromagnetic coupling observed) and cyclic voltammetry. Dizinc(II) and mononuclear copper(II) analogues [Zn(II)2(PD'O-)(H2O)2]3+ (7) and [Cu(II)(mPD'OH)(H2O)]2+ (6), respectively, have also been synthesized and structurally characterized. Reacting 5/MPA/O(2) (MPA = 3-mercaptopropionic acid) with DNA leads to a highly specific oxidation of guanine (G) at a junction between single- and double-stranded DNA. Mass spectrometric analysis of the major products indicates a gain of +18 and +34 amu relative to initial DNA strands. The most efficient reaction requires G at the first and second unpaired positions of each strand extending from the junction. Less reaction is observed for analogous targets in which the G cluster is farther from the junction or contains less than four Gs. Consistent with our previous systems, the multinuclear copper center is required for selective reaction; mononuclear complex 6 is not effective. Hydrogen peroxide as a substitute for MPA/O2 also does not lead to activity. Structural analysis of a [Cu(II)2(PD'O-)(G)]3+ complex (8) and dizinc analogue [Zn(II)(2)(PD'O-)(G)](ClO4)3 (9) (G = guanosine) reveals coordination of the G O6 and N7 atoms with the two copper (or zinc) centers and suggests that copper-G coordination likely plays a role in recognition of the DNA target. The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed.

  2. Bureaucracy, professionalization and school centred innovation strategies

    NASA Astrophysics Data System (ADS)

    Morris, Paul

    1990-03-01

    This paper examines an attempt to promote a school centred innovation strategy within a highly centralized educational system. The School Based Curriculum Project Scheme, which was introduced into Hong Kong in 1988, is analysed in terms of a professional-bureaucratic dichotomy. It is argued that the operational details of the scheme are designed to satisfy a range of bureaucratic concerns and these are not conducive to promoting the professional work ethic which is required for school centred innovation. Finally the paper identifies the implications which arise for policies designed to promote curriculum innovation.

  3. Byurakan Astrophysical Observatory as Cultural Centre

    NASA Astrophysics Data System (ADS)

    Mickaelian, A. M.; Farmanyan, S. V.

    2016-12-01

    NAS RA V. Ambartsumian Byurakan Astrophysical Observatory is presented as a cultural centre for Armenia and the Armenian nation in general. Besides being scientific and educational centre, the Observatory is famous for its unique architectural ensemble, rich botanical garden and world of birds, as well as it is one of the most frequently visited sightseeing of Armenia. In recent years, the Observatory has also taken the initiative of the coordination of the Cultural Astronomy in Armenia and in this field, unites the astronomers, historians, archaeologists, ethnographers, culturologists, literary critics, linguists, art historians and other experts.

  4. Writing Centre Tutoring Sessions: Addressing Students' Concerns

    ERIC Educational Resources Information Center

    Winder, Roger; Kathpalia, Sujata S.; Koo, Swit Ling

    2016-01-01

    The guiding principle behind university writing centres is to focus on the process of writing rather than the finished product, prioritising higher order concerns related to organisation and argumentation of texts rather than lower order concerns of grammar and punctuation. Using survey-based data, this paper examines students' concerns regarding…

  5. Person-Centred (Deictic) Expressions and Autism

    ERIC Educational Resources Information Center

    Hobson, R. Peter; Garcia-Perez, Rosa M.; Lee, Anthony

    2010-01-01

    We employed semi-structured tests to determine whether children with autism produce and comprehend deictic (person-centred) expressions such as "this"/"tilde" "here"/"there" and "come"/"go", and whether they understand atypical non-verbal gestural deixis in the form of directed head-nods to indicate location. In Study 1, most participants…

  6. Centre National d'Etudes Spatiales

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    The Centre National d'Etudes Spatiales (CNES) draws up, proposes and conducts France's space policy. Its role is to develop the uses of space, to meet the civilian and military needs of public bodies and of the scientific community, and to foster the development and dissemination of new applications, designed to create wealth and jobs....

  7. Crystallographic Data Centre Services and Publications.

    ERIC Educational Resources Information Center

    Cambridge Univ. (England). Chemical Lab.

    The Cambridge Crystallographic Data Centre is concerned with the retrieval, evaluation, synthesis, and dissemination of structural data based on diffraction methods. The source of input is almost entirely primary journals. Bibliographic information and numeric data on crystal and molecular structures are on magnetic tapes. The bibliographic file…

  8. Examining Whiteness in a Children's Centre

    ERIC Educational Resources Information Center

    Clarke, Verity; Watson, Debbie

    2014-01-01

    This article utilises critical whiteness theory to explore the ethnic discourses observed in a children's centre in South London. Whilst critical whiteness has been used as a framework to understand race, racism and multiculturalism in a number of settings, including education, there are few studies that have sought to understand ethnicity in…

  9. Visiting a science centre: what's on offer?

    NASA Astrophysics Data System (ADS)

    Russell, Ian

    1990-09-01

    Science centres are a valuable resource, used more frequently by family groups and primary school parties than by secondary schools. The importance of affective learning, involving attitude changes, is stressed. Provided the right approach is used, accompanying adults can help children get the most out of a visit.

  10. Cactus: The Centres of a Triangle

    ERIC Educational Resources Information Center

    Hyde, Hartley

    2009-01-01

    This is the first of two articles which describe how to use "JavaSketchPad" to explore the centres of a triangle. This introductory exercise is suggested in the GSP "Workshop Guide". Students can use "JavaSketchPad Interactive Geometry" (JSP) at home at no cost. They are likely to impress their parents with their enthusiasm for geometry and all…

  11. Oo-Za-We-Kwun Centre Incorporated

    ERIC Educational Resources Information Center

    Findlay, P. R.; And Others

    1976-01-01

    The Centre is described as being designed to help native people participate more effectively in a modern Canadian environment. The residential family program includes a five-week Life Skills course followed by a two-year transfer of learning period during which counseling, paid employment, and community activities are available. (Author/MS)

  12. Industry Restructuring: Extracts from Centre Publications.

    ERIC Educational Resources Information Center

    Hall, William C., Ed.

    This document contains excerpts from material previously published by Australia's TAFE (Technical and Further Education) National Centre for Research and Development on the subjects of industry restructuring, the reasons for restructuring, revising curricula, and providing a service to business and industry. Its contents are "Industry…

  13. Self Assessment and Student-Centred Learning

    ERIC Educational Resources Information Center

    McDonald, Betty

    2012-01-01

    This paper seeks to show how self assessment facilitates student-centred learning (SCL) and fills a gap in the literature. Two groups of students were selected from a single class in a tertiary educational institution. The control group of 25 was selected randomly by the tossing of an unbiased coin (heads = control group). They were trained in the…

  14. In the Field: The Canadian Ecology Centre.

    ERIC Educational Resources Information Center

    Magee, Clare

    2000-01-01

    The Canadian Ecology Centre (Ontario) offers year-round residential and day programs in outdoor and environmental education for secondary students, field placement and internship opportunities for college students, and ecotourism programs, while providing employment and tax revenues to the local community. Dubbed consensus environmentalism, the…

  15. Centring the Subject in Order to Educate

    ERIC Educational Resources Information Center

    Webster, R. Scott

    2007-01-01

    It is important for educators to recognise that the various calls to decentre the subject--or self--should not be interpreted as necessarily requiring the removal of the subject altogether. Through the individualism of the Enlightenment the self was centred. This highly individualistic notion of the sovereign self has now been decentred especially…

  16. Myanmar: The Community Learning Centre Experience.

    ERIC Educational Resources Information Center

    Middelborg, Jorn; Duvieusart, Baudouin, Ed.

    A community learning centre (CLC) is a local educational institution outside the formal education system, usually set up and managed by local people. CLCs were first introduced in Myanmar in 1994, and by 2001 there were 71 CLCs in 11 townships. The townships are characterized by remoteness, landlessness, unemployment, dependency on one cash crop,…

  17. Early Childhood Centre Administrator Certification. Project Report.

    ERIC Educational Resources Information Center

    Ferguson, E. Elaine

    This document presents the process for obtaining certification for the position of early childhood centre administrator (ECCA) in Nova Scotia, Canada. Following an introduction describing the development of the process and its pilot testing, Chapter 1 of the document details the four-step process: (1) application, including training in the ECCA…

  18. Tuned by metals: the TET peptidase activity is controlled by 3 metal binding sites.

    PubMed

    Colombo, Matteo; Girard, Eric; Franzetti, Bruno

    2016-02-08

    TET aminopeptidases are dodecameric particles shared in the three life domains involved in various biological processes, from carbon source provider in archaea to eye-pressure regulation in humans. Each subunit contains a dinuclear metal site (M1 and M2) responsible for the enzyme catalytic activity. However, the role of each metal ion is still uncharacterized. Noteworthy, while mesophilic TETs are activated by Mn(2+), hyperthermophilic TETs prefers Co(2+). Here, by means of anomalous x-ray crystallography and enzyme kinetics measurements of the TET3 aminopeptidase from the hyperthermophilic organism Pyrococcus furiosus (PfTET3), we show that M2 hosts the catalytic activity of the enzyme, while M1 stabilizes the TET3 quaternary structure and controls the active site flexibility in a temperature dependent manner. A new third metal site (M3) was found in the substrate binding pocket, modulating the PfTET3 substrate preferences. These data show that TET activity is tuned by the molecular interplay among three metal sites.

  19. Dinuclear oxidative addition reactions using an isostructural series of Ni2, Co2, and Fe2 complexes.

    PubMed

    Behlen, Michael J; Zhou, You-Yun; Steiman, Talia J; Pal, Sudipta; Hartline, Douglas R; Zeller, Matthias; Uyeda, Christopher

    2016-12-20

    A family of low-valent Ni2, Co2, and Fe2 naphthyridine-diimine (NDI) complexes is presented. Ligand-based π* orbitals are sufficiently low-lying to fall within the metal 3d manifold, resulting in electronic structures that are highly delocalized across the conjugated [NDI]M2 system. This feature confers stability to metal-metal interactions during two-electron redox reactions, as demonstrated in a prototypical oxidative addition of allyl chloride.

  20. Synthesis, characterization, and structure-activity relationship of the antimicrobial activities of dinuclear N-heterocyclic carbene (NHC)-silver(I) complexes.

    PubMed

    Sakamoto, Ryosuke; Morozumi, Soichiro; Yanagawa, Yuki; Toyama, Mizuki; Takayama, Akihiko; Kasuga, Noriko Chikaraishi; Nomiya, Kenji

    2016-10-01

    The three dinuclear silver(I) complexes of N-heterocyclic carbene (NHC) ligands, [Ag2(L-1a)](PF6)2·2CH3CN (Ag-1a), [Ag2(L-2)2](PF6)2·H2O (Ag-2), and [Ag2(L-4)2](PF6)2·2CH3CN (Ag-4), were synthesized by reactions of Ag2O with the corresponding PF6(-) salt of the NHC precursors indicated as H4L-1(PF6)4, H2L-2(PF6)2, and H2L-4(PF6)2. H4L-1(PF6)4, which is the precursor of ligand L-1, was formed as mixed crystals of two geometric isomers, i.e., H4L-1a(PF6)4 (major) and H4L-1b(PF6)4 (minor), each of which was not isolated as single species. Ag2O reacted with the mixed isomers of H4L-1(PF6)4 to give a single, pure crystalline silver(I) complex Ag-1a with one isomer (L-1a) as the major product. The molecular structures of the precursors and their silver(I) complexes were determined by X-ray crystallography. A mononuclear NHC-silver(I) complex (Ag-3) was prepared by the reaction of Ag2O with the precursor HL-3Cl. The silver(I) complexes and NHC precursors prepared here were characterized by CHN elemental analysis, FTIR, Thermogravimetry/Differential thermal analysis, X-ray crystallography and solution ((1)H and (13)C) NMR spectroscopy. Organometallic silver(I) complexes Ag-1a, Ag-2, and Ag-4 were dinuclear C-Ag-C bonding complexes, whereas Ag-3 was a mononuclear C-Ag-Cl bonding complex. These complexes are highly soluble in organic solvents such as acetone, acetonitrile, and dimethyl sulfoxide, and light-stable in the solid-state and in solution over one year. The antimicrobial activities of four silver(I) complexes and their NHC precursors against selected bacteria, yeasts, and molds in water-suspension systems were evaluated via the minimum inhibitory concentration; the activities were strongly dependent on the molecular structures of the dinuclear silver(I) complexes, which suggests a structure-activity relationship.

  1. Dinuclear dysprosium SMMs bridged by a neutral bipyrimidine ligand: two crystal systems that depend on different lattice solvents lead to a distinct slow relaxation behaviour.

    PubMed

    Sun, Wen-Bin; Yan, Bing; Jia, Li-Hui; Wang, Bing-Wu; Yang, Qian; Cheng, Xin; Li, Hong-Feng; Chen, Peng; Wang, Zhe-Ming; Gao, Song

    2016-06-07

    Two dinuclear dysprosium complexes with the Dy(iii) ions bridged by the neutral bipyrimidine (BPYM) ligand were synthesized and magnetically characterized. They crystallized in a monoclinic and triclinic crystal system, respectively, with almost the same structural core, only differing in the lattice solvent molecules. Alternating current (ac) susceptibility measurements revealed that they exhibit significant slow relaxation of magnetization until 25 K in the absence of a dc field. The single and double relaxation processes were assigned to one and two types of Dy(iii) environments in the two dimmers, respectively, with barriers of 266 and 345 K under zero field conditions. The magnetic hysteresis loops of 1 and 2 were both observed up to 2.5 K.

  2. Chromatin folding and DNA replication inhibition mediated by a highly antitumor-active tetrazolato-bridged dinuclear platinum(II) complex

    PubMed Central

    Imai, Ryosuke; Komeda, Seiji; Shimura, Mari; Tamura, Sachiko; Matsuyama, Satoshi; Nishimura, Kohei; Rogge, Ryan; Matsunaga, Akihiro; Hiratani, Ichiro; Takata, Hideaki; Uemura, Masako; Iida, Yutaka; Yoshikawa, Yuko; Hansen, Jeffrey C.; Yamauchi, Kazuto; Kanemaki, Masato T.; Maeshima, Kazuhiro

    2016-01-01

    Chromatin DNA must be read out for various cellular functions, and copied for the next cell division. These processes are targets of many anticancer agents. Platinum-based drugs, such as cisplatin, have been used extensively in cancer chemotherapy. The drug–DNA interaction causes DNA crosslinks and subsequent cytotoxicity. Recently, it was reported that an azolato-bridged dinuclear platinum(II) complex, 5-H-Y, exhibits a different anticancer spectrum from cisplatin. Here, using an interdisciplinary approach, we reveal that the cytotoxic mechanism of 5-H-Y is distinct from that of cisplatin. 5-H-Y inhibits DNA replication and also RNA transcription, arresting cells in the S/G2 phase, and are effective against cisplatin-resistant cancer cells. Moreover, it causes much less DNA crosslinking than cisplatin, and induces chromatin folding. 5-H-Y will expand the clinical applications for the treatment of chemotherapy-insensitive cancers. PMID:27094881

  3. Synthesis, crystal structures and magnetic properties of dinuclear copper(II) compounds with NNO tridentate Schiff base ligands and bridging aliphatic diamine and aromatic diimine linkers.

    PubMed

    Rigamonti, Luca; Forni, Alessandra; Pievo, Roberta; Reedijk, Jan; Pasini, Alessandro

    2011-04-07

    The synthesis and the characterization of new dinuclear copper(II) compounds of general formula [(L(a-d))(2)Cu(2)(μ-N-N)](ClO(4))(2) (1-6) with either neutral aliphatic diamine (N-N = piperazine, pip) or aromatic diimine (N-N = 4,4'-bipyridine, 4,4'-bipy) linker are reported. The copper ligands L(-) (L(a-) = (E)-2-((2-aminoethylimino)methyl)phenolate, L(b-) = (E)-2-((2-aminopropylimino)methyl)-phenolate, L(c-) = (E)-2-((2-aminoethylimino)methyl)4-nitrophenolate, L(d-) = (E)-2-((2-aminoethylimino)methyl)4-methoxyphenolate) are NNO tridentate Schiff bases derived from the monocondensation of a substituted salicylaldehyde 5-G-salH (G = NO(2), H, OMe) with ethylenediamine, en, or 1,3-propylenediamine, tn. The crystal structures of compounds [(L(a))(2)Cu(2)(MeOH)(2)(μ-4,4'-bipy)](ClO(4))(2) (1·2MeOH), [(L(b))(2)Cu(2)(MeOH)(2)(μ-4,4'-bipy)](ClO(4))(2) (2·2MeOH), [(L(d))(2)Cu(2)(μ-4,4'-bipy)](ClO(4))(2) (4), [(L(a))(2)Cu(2)(μ-pip)](ClO(4))(2) (5) and [(L(b))(2)Cu(2)(μ-pip)](ClO(4))(2) (6) have been determined, revealing the preferred (e-e)-chair conformation of the bridging piperazine in compounds 5 and 6. The presence of hydrogen-bond-mediated intermolecular interactions, that involve the methanol molecules, yields dimers of dinuclear units for 1·2MeOH, and infinite zig-zag chains for 2·2MeOH. The temperature dependences of the magnetic susceptibilities χ(M)(T) for all compounds were measured, indicating the presence of antiferromagnetic Cu-Cu exchange. For the compounds 2-4 with 4,4'-bipy, the coupling constants J are around -1 cm(-1), while in compound 1 no interaction could be detected. The compounds 5 and 6 with piperazine display higher Cu-Cu magnetic interactions through the σ-bonding backbone of the bridging molecule, with J around -8 cm(-1), and the coupling is favoured by the (e-e)-chair conformation of the diamine ring. The non-aromatic, but shorter, linker piperazine gives rise to stronger Cu-Cu antiferromagnetic couplings than the aromatic, but

  4. Collaborating at a distance: operations centres, tools, and trends

    SciTech Connect

    Gottschalk, Erik E.; /Fermilab

    2009-05-01

    Successful operation of the LHC and its experiments is crucial to the future of the worldwide high-energy physics program. Remote operations and monitoring centres have been established for the CMS experiment in several locations around the world. The development of remote centres began with the LHC{at}FNAL ROC and has evolved into a unified approach with distributed centres that are collectively referred to as 'CMS Centres Worldwide'. An overview of the development of remote centres for CMS will be presented, along with a synopsis of collaborative tools that are used in these centres today and trends in the development of remote operations capabilities for high-energy physics.

  5. Multiple-path dissociation mechanism for mono- and dinuclear tris(hydroxamato)iron(III) complexes with dihydroxamic acid ligands in aqueous solution.

    PubMed

    Boukhalfa, H; Crumbliss, A L

    2000-09-18

    Linear synthetic dihydroxamic acids ([CH3N(OH)C=O)]2(CH2)n; H2Ln) with short (n = 2) and long (n = 8) hydrocarbon-connecting chains form mono- and dinuclear complexes with Fe(III) in aqueous solution. At conditions where the formation of Fe2(Ln)3 is favored, complexes with each of the two ligand systems undergo [H+]-induced ligand dissociation processes via multiple sequential and parallel paths, some of which are common and some of which are different for the two ligands. The pH jump induced ligand dissociation proceeds in two major stages (I and II) where each stage is shown to be comprised of multiple components (Ix, where x = 1-3 for L2 and L8, and IIy, where y = 1-3 for L2 and y = 1-4 for L8). A reaction scheme consistent with kinetic and independent ESI-MS data is proposed that includes the tris-chelated complexes (coordinated H2O omitted for clarity) (Fe2(Ln)3, Fe2(L2)2(L2H)2, Fe(LnH)3, Fe(L8)(L8H)), bis-chelated complexes (Fe2(Ln)2(2+), Fe(LnH)2+, Fe(L8)+), and monochelated complexes (Fe(LnH)2+). Analysis of kinetic data for ligand dissociation from Fe2(Ln)(LnH)3+ (n = 2, 4, 6, 8) allows us to estimate the dielectric constant at the reactive dinuclear Fe(III) site. The existence of multiple ligand dissociation paths for the dihydroxamic acid complexes of Fe(III) is a feature that distinguishes these systems from their bidentate monohydroxamic acid and hexadentate trihydroxamic acid counterparts and may be a reason for the biosynthesis of dihydroxamic acid siderophores, despite higher environmental molar concentrations necessary to completely chelate Fe(III).

  6. Synthesis and structure of dimeric anthracene-9-carboxylato bridged dinuclear erbium(III) complex, [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)].

    PubMed

    Kusrini, Eny; Adnan, Rohana; Saleh, Muhammad I; Yan, Lim-Kong; Fun, Hoong-Kun

    2009-05-01

    We study the influence of the bulky aromatic rings, e.g. anthracence-9-carboxylic acid (9-ACA) with a large conjugated pi-system on the structure and spectroscopic properties of [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex where 9-AC=anthracence-9-carboxylato and DMF=N,N'-dimethylformamide. The complex has been prepared from the erbium chloride and 9-ACA in the mixture of H(2)O:DMF solution (4:1, v/v) followed by pH adjustment to 6. The complex is crystallized in a monoclinic system with space group P2(1)/n. The two Er(III) ions are double bridged by the deprotonated carboxyl groups of two 9-AC anions (O1 and O1A), forming an eight-coordination number. The chelating bidentate (O,O), chelating-bridging tridentate (O,O,O') and monodentate of 9-AC anions are observed in the dinuclear [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex. The Er-Er distance is 4.015A in the dimeric unit. Intramolecular O-Hcdots, three dots, centeredO and C-Hcdots, three dots, centeredO hydrogen bonds as well as numerous of intermolecular C-Hcdots, three dots, centeredpi interactions between the anthracene rings by edge-to-face interactions linked the dinuclear dimeric units into two-dimensional supramolecular network in a propeller-arrangement. Electronic absorption spectra of the Er(III) complex and its salt were measured. The emission spectrum of the complex is composed of a broad band due to the emission of intraligand pi*-->pi transition from the 9-AC anions and a shoulder peak originating from the 4f-4f emission transition of the Er(III) ions. The complex has a high thermal stability which can be attributed to the effectively increase the rigidity of the 9-AC anions.

  7. Dinuclear and 1D iron(III) Schiff base complexes bridged by 4-salicylideneamino-1,2,4-triazolate: X-ray structures and magnetic properties.

    PubMed

    Herchel, Radovan; Pavelek, Lubomír; Trávníček, Zdeněk

    2011-11-28

    Four new iron(III) complexes were obtained by the reaction of 4-salicylideneamino-1,2,4-triazole (Hsaltrz) and selected dinuclear μ-oxo-bridged iron(III) Schiff base complexes [{FeL(4)}(2)(μ-O)], where L(4) represents a terminal tetradentate dianionic Schiff-base ligand. X-ray structural analysis revealed a novel bridging mode of κN,κO of the saltrz ligand to form dinuclear complexes [{Fe(salen)(μ-saltrz)}(2)]·CH(3)OH (1) (H(2)salen = N,N'-ethylenebis(salicylimine)) and [{Fe(salpn)(μ-saltrz)}(2)] (2) (H(2)salpn = N,N'-1,2-propylenbis(salicylimine)), whereas one-dimensional (1D) zig-zag chains were formed in the case of [{Fe(salch)(μ-saltrz)}·0.5CH(3)OH](n) (3) (H(2)salch = N,N'-cyclohexanebis(salicylimine)) and [Fe(salophen)(μ-saltrz)](n) (4) (H(2)salophen = N,N'-o-phenylenebis(salicylimine)). It was also shown that the rigidity of the terminal ligand L(4) can be considered as the key factor for the molecular dimensionality of the products. The thorough magnetic analysis based on SQUID experiments, including the isotropic exchange and the zero-field splitting of both temperature and field dependent data, was performed for dimeric (1 and 2) and also for polymeric compounds (3 and 4) and revealed weak antiferromagnetic exchange mediated by the saltrz anions with much larger D-parameter (|D|≫|J|).

  8. Antibacterial, DNA interaction and cytotoxic activities of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Arthi, P.; Haleel, A.; Srinivasan, P.; Prabhu, D.; Arulvasu, C.; Kalilur Rahiman, A.

    2014-08-01

    A series of dinuclear nickel(II) and copper(II) complexes (1-6) of hexaaza macrocycles of 2,6-diformyl-4-methylphenol with three different benzoyl pendant-arms, 2,2‧-benzoyliminodi(ethylamine) trihydrochloride (L), 2,2‧-4-nitrobenzoyliminodi(ethylamine) trihydrochloride (L‧) and 2,2‧-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride (L″) have been synthesized and characterized by spectral methods. The electrochemical studies of these complexes depict two irreversible one electron reduction processes around E1pc = -0.62 to -0.76 V and E2pc = -1.21 to -1.31, and nickel(II) complexes (1-3) exhibit two irreversible one electron oxidation processes around E1pa = 1.08 to 1.14 V and E2pa = 1.71 to 1.74 V. The room temperature magnetic moment values (μeff, 1.52-1.54 BM) indicate the presence of an antiferromagnetic interaction in the binuclear copper(II) complexes (4-6) which is also observed from the broad ESR spectra with a g value of 2.14-2.15. The synthesized complexes (1-6) were screened for their antibacterial activity. The results of DNA interaction studies indicate that the dinuclear complexes can bind to calf thymus DNA by intercalative mode and display efficient cleavage of plasmid DNA. Further, the cytotoxic activity of complexes 2, 5 and 6 on human liver adenocarcinoma (HepG2) cell line has been examined. Nuclear-chromatin cleavage has also been observed with PI staining and comet assays.

  9. Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

    SciTech Connect

    Zhang, Yingjie; Karatchevtseva, Inna; Bhadbhade, Mohan; Tran, Toan Trong; Aharonovich, Igor; Fanna, Daniel J.; Shepherd, Nicholas D.; Lu, Kim; Li, Feng; Lumpkin, Gregory R.

    2016-02-15

    With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H{sub 2}phb) or terephthalic acid (H{sub 2}tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO{sub 2}){sub 2}(Hphb){sub 2}(phb)(DMF)(H{sub 2}O){sub 3}]·4H{sub 2}O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a µ{sub 2}-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO{sub 2})(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with µ{sub 4}-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C–O–U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated. - Graphical abstract: With the coordination of dimethylformamide, two new uranyl complexes with either 4-hydroxybenzoate or terephthalate have been synthesized under solvothermal conditions and structurally characterized. - Highlights: • Solvent facilitates the synthesis of two new uranium(VI) complexes. • A dinuclear complex with both penta- and hexagonal bipyramidal uranium polyhedral. • A unique µ{sub 2}-bridging mode of 4-hydroxybenzoate via alcohol oxygen for 5 f ions. • A 3D framework with uranium polyhedra and µ{sub 4}-terephthalate ligands. • Vibration modes and photoluminescence properties are reported.

  10. Dinuclear ruthenium complexes display loop isomer selectivity to c-MYC DNA G-quadriplex and exhibit anti-tumour activity.

    PubMed

    Zheng, Chuping; Liu, Yanan; Liu, Ying; Qin, Xiuying; Zhou, Yanhui; Liu, Jie

    2016-03-01

    G-quadruplex DNA, especially the cellular-myelocytomatosis viral oncogene (c-MYC) is closely associated with cell-cycle regulation, proliferation of tumour cells. In this work, the interaction between the c-MYC and two dinuclear Ru(II) complexes [(bpy)2Ru(bpibp)Ru(bpy)2](ClO4)4 (compound 1) and [(phen)2Ru(bpibp)Ru(phen)2](ClO4)4 (compound 2) have been studied. The data from UV-Visible, PCR-stop and Fluorescence resonance energy transfer (FRET) showed that two complexes can stabilize the structure of G-quadruplex in the c-MYC promoter and targeting the G-quadruplex loop isomers. Interestingly, the complex 2 has a greater effect on the 1:2:1 and 2:1:1 loop isomers while the 1 prefers to the 1:2:1 isomers. The mechanism studies revealed that complexes can induce apoptosis in HepG2 cells by generating ROS metabolites, triggering mitochondrial membrane potential loss and down-regulation of P-Akt (Akt also known as protein kinase B), P-p44/42 MAP kinase protein (P-p44/42), and c-MYC. Taken together, these results suggested that the two dinuclear complexes may both be candidates as anti-tumour agents as they may reduce the c-MYC gene expression. {bpibp: 4, 4'-bis (1, 10-phenanthroline-[5, 6-d] imidazole-2-yl)-biphenyl, bpy: 2,2-bipyridine, phen: 1,10-phenanthroline}.

  11. Solid- and solution-state studies of the novel mu-dicyanamide-bridged dinuclear spin-crossover system {[(Fe(bztpen)]2[mu-N(CN)2]}(PF6)3 x n H2O.

    PubMed

    Ortega-Villar, Norma; Thompson, Amber L; Muñoz, M Carmen; Ugalde-Saldívar, Víctor M; Goeta, Andrés E; Moreno-Esparza, Rafael; Real, José A

    2005-09-19

    The mononuclear diamagnetic compound {Fe(bztpen)[N(CN)2]}(PF6)CH3OH (1) (bztpen = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) has been synthesized and its crystal structure studied. Complex 1 can be considered to be the formal precursor of two new dinuclear, dicyanamide-bridged iron(II) complexes with the generic formula {[(Fe(bztpen)]2[mu-N(CN)2]}(PF6)3 x n H2O (n = 1 (2) or 0 (3)), which have been characterized in the solid state and in solution. In all three complexes, the iron atoms have a distorted [FeN6] octahedral coordination defined by a bztpen ligand and a terminal (1) or a bridging dicyanamide ligand (2 and 3). In the solid state, 2 and 3 can be considered to be molecular isomers that differ by the relative position of the phenyl ring of the two {Fe(bztpen)[N(CN)2]}+ halves (cis and trans, respectively). Depending on the texture of the sample, 2 exhibits paramagnetic behavior or displays a very incomplete spin transition at atmospheric pressure. Complex 3 undergoes a gradual two-step spin transition with no observed hysteresis in the solid state. Both steps are approximately 100 K wide, centered at approximately 200 K and approximately 350 K, with a plateau of approximately 80 K separating the transitions. The crystal structure of 3 has been determined in steps of approximately 50 K between 400 K and 90 K, which provides a fascinating insight into the structural behavior of the complex and the nature of the spin transition. Order-disorder transitions occur in the dicyanamide bridge and the PF6(-) ions simultaneously, with the spin-crossover behavior suggesting that these transitions may trigger the two-step character. In solution, 2 and 3 display very similar continuous spin conversions. Electrochemical studies of 2 and 3 show that the voltammograms are typical of dimeric systems with electronic coupling of the metals through the dicyanamide ligand.

  12. User-Centred Design Using Gamestorming.

    PubMed

    Currie, Leanne

    2016-01-01

    User-centered design (UX) is becoming a standard in software engineering and has tremendous potential in healthcare. The purpose of this tutorial will be to demonstrate and provide participants with practice in user-centred design methods that involve 'Gamestorming', a form of brainstorming where 'the rules of life are temporarily suspended'. Participants will learn and apply gamestorming methods including persona development via empathy mapping and methods to translate artefacts derived from participatory design sessions into functional and design requirements.

  13. The Metal-Rich Universe

    NASA Astrophysics Data System (ADS)

    Israelian, Garik; Meynet, Georges

    2012-10-01

    Preface; Part I. Abundances in the Galaxy: Field Stars: 1. Metal-rich stars and stellar populations: A brief history and new results; 2. The metal-rich nature of stars with planets; 3. Solar chemical peculiarities; 4. Kinematics of metal-rich stars with and without planets; 5. Elemental abundance trends in the metal-rich thin and thick disks; 6. Metal-rich massive stars - how metal-rich are they?; 7. Hercules stream stars and the metal-rich thick disk; 8. Abundance survey of the galactic thick disk; Part II. Abundances in the Galaxy: Galactic Stars in Clusters, Bulges and Centre: 9. Galactic open clusters with super solar metallicities; 10. Old and very metal-rich open clusters in the BOCCE project; 11. Massive stars vs. nebular abundances in the Orion nebula; 12. Abundance surveys of metal-rich bulge stars; 13. Metal abundances in the galactic center; 14. Light elements in the galactic bulge; 15. Metallicity and ages of selected G-K giants; Part III. Observations - Abundances in Extragalactic Contexts: 16. Stellar abundances of early-type galaxies and galactic spheroids: Evidence for metal-rich stars; 17. Measuring chemical abundances in extragalactic metal-rich HII regions; 18. On the maximum oxygen abundance in metal-rich spiral galaxies; 19. Starbursts and their contribution to metal enrichment; 20. High metallicities at high redshifts; 21. Evolution of dust and elemental abundances in quasar DLAs and GRB afterglows as a function of cosmic time; 22. Dust, metals and diffuse interstellar bands in damped Lyman Alpha systems; 23. Tracing metallicities in the Universe with the James Webb Space Telescope; Part IV. Stellar Populations and Mass Functions: 24. The stellar initial mass function of metal-rich populations; 25. IMF effects on the metallicity and colour evolution of disk galaxies; 26. The metallicity of circumnuclear star forming regions; 27. The stellar population of bulges; 28. The metallicity distribution of the stars in elliptical galaxies; 29. Wolf

  14. Canadian Educational Development Centre Websites: More Ebb than Flow?

    ERIC Educational Resources Information Center

    Simmons, Nicola

    2010-01-01

    This paper examines information portrayed on Canadian educational development (ED) centre websites and, in particular, whether information that corresponds to questions compiled from a literature search of ED centre practices is readily available from centre websites. This study phase is part of a larger national study of Canadian educational…

  15. Centre of the Cell: Science Comes to Life

    PubMed Central

    Balkwill, Frances; Chambers, Katie

    2015-01-01

    Centre of the Cell is a unique biomedical science education centre, a widening participation and outreach project in London’s East End. This article describes Centre of the Cell’s first five years of operation, the evolution of the project in response to audience demand, and the impact of siting a major public engagement project within a research laboratory. PMID:26340279

  16. Centre-Based Child Care Quality in Urban Australia

    ERIC Educational Resources Information Center

    Ishimine, Karin; Wilson, Rachel

    2009-01-01

    This study investigates the quality of childcare centres in urban Australian communities designated according to different bands of Centre Location Demographics (CLD). Childcare centres were assessed using the Early Childhood Environment Rating Scale- Revised Edition (ECERS-R) and the Early Childhood Environment Rating Scale-Extension (ECERS-E).…

  17. Assessment of functional incontinence in disabled living centres.

    PubMed

    Chadwick, Viv

    Disabled Living is part of the network of disabled living centres throughout Britain. These centres enable anyone to try out equipment that may help them with everyday activities of living. The centres are staffed by occupational therapists, physiotherapists, nurses, information providers, administration staff and volunteers.

  18. An x-ray absorption near edge structure spectroscopy study of metal coordination in Co(II)-substituted Carcinus maenas hemocyanin.

    PubMed Central

    Della Longa, S; Bianconi, A; Palladino, L; Simonelli, B; Congiu Castellano, A; Borghi, E; Barteri, M; Beltramini, M; Rocco, G P; Salvato, B

    1993-01-01

    High-resolution x-ray absorption near edge structure spectroscopy was used to characterize the metal sites in three different cobalt-substituted derivatives of Carcinus maenas hemocyanin (Hc), including a mononuclear cobalt, a dinuclear cobalt and a copper-cobalt hybrid derivative. Co(II) model complexes with structures exemplifying octahedral, trigonal bipyramidal, pseudo-tetrahedral, and square planar geometries were also studied. The results provide structural information about the metal binding site(s) in the Co-Hcs that extend earlier results from EPR and optical spectroscopy (Bubacco et al. 1992. Biochemistry. 31: 9294-9303). Experimental spectra were compared to those calculated for atomic clusters of idealized geometry, generated using a multiple scattering approach. The energy of the dipole forbidden 1s-->3d transition and of the absorption edge in the spectra for all cobalt Hc derivatives confirmed the cobaltous oxidation state which rules out the presence of an oxygenated site. Comparisons between data and simulations showed that the mononuclear and dinuclear Co(II) derivatives, as well as the hybrid derivative, contain four-coordinate Co(II) in distorted tetrahedral sites. Although the spectra for Co(II) in dinuclear metal sites more closely resemble the simulated spectrum for a tetrahedral complex than do spectra for the mononuclear derivative, the Co(II) sites in all derivatives are very similar. The Cu K-edge high resolution x-ray absorption near edge structure spectrum of the hybrid Cu-Co-Hc resembles that of deoxy-Hc demonstrating the presence of three-coordinate Cu(I). PMID:8312502

  19. Synthesis, Characterization, and Photochemistry of a Dinuclear Cyanide-Bridged Iron(II)-Platinum(IV) Mixed-Valence Compound and Its Implications for the Corresponding Iron(II)-Platinum(IV)-Iron(II) Complex.

    PubMed

    Pfennig, Brian W.; Lockard, Jenny V.; Cohen, Jamie L.; Watson, David F.; Ho, Douglas M.; Bocarsly, Andrew B.

    1999-06-14

    The mixed-valence compound [(NH(3))(5)Pt(IV)(&mgr;-NC)Fe(II)(CN)(5)].6H(2)O was synthesized by the substitution reaction of [Pt(IV)(NH(3))(5)OSO(2)CF(3)](OSO(2)CF(3))(3) and [Fe(II)(CN)(6)](4)(-) in aqueous solution and was characterized by UV/vis, IR, and resonance Raman spectroscopies, cyclic voltammetry, and single-crystal X-ray diffractometry. The monoclinic crystal (space group P2(1)/m (No. 11)) consists of a dinuclear, cyanide-bridged Fe(II)-Pt(IV) moiety with unit cell dimensions of a = 9.3241(5) Å, b = 14.0466(7) Å, c = 9.6938(4) Å, beta = 111.467(2) degrees, and Z = 2. There are also an average of six waters of hydration per unit cell. The R-factors for this structure are R = 3.66% and R(w) = 7.90%. The electronic spectrum reveals a broad intervalent (IT) charge-transfer absorption at approximately 420 nm (epsilon = 540 M(-)(1) cm(-)(1)). Both the ground-state spectroscopy and the electrochemistry of this compound are very similar to those of the corresponding trinuclear adduct [(NC)(5)Fe(II)(&mgr;-CN)Pt(IV)(NH(3))(4)(&mgr;-NC)Fe(II)(CN)(5)](4)(-), which has been reported previously. Classical Marcus-Hush theory has been applied in the analysis of the IT band of the dinuclear compound in an effort to elucidate a fuller understanding of the photophysics of the trinuclear complex. The data suggest that this latter, centrosymmetric species can be treated theoretically as two back-to-back dinuclear donor-acceptor (D-A) compounds of the form D-A/A-D, where the Pt(IV) inversion center acts as the acceptor for both halves of the molecule. The photochemistry of the dinuclear complex was also investigated.

  20. The "Magic" of Tutorial Centres in Hong Kong: An Analysis of Media Marketing and Pedagogy in a Tutorial Centre

    ERIC Educational Resources Information Center

    Koh, Aaron

    2014-01-01

    Why do more than three-quarters of Hong Kong's senior secondary students flock to tutorial centres like moths to light? What is the "magic" that is driving the popularity of the tutorial centre enterprise? Indeed, looking at the ongoing boom of tutorial centres in Hong Kong (there are almost 1,000 of them), it is difficult not to ask…

  1. Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl(-), Br(-); M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Wojciechowska, Agnieszka; Stoian, Sebastian A; Ozarowski, Andrew

    2017-03-06

    A series of monochloride-bridged, dinuclear metallacycles of the general formula [M2(μ-Cl)(μ-L)2](ClO4)3 have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (Lm), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO4)2·6H2O, MCl2, and the ligand, Lm or Lm*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M2(μ-Cl)(μ-L)2](BF4)3, L = Lm, M = Cu(II), and L = Lm*, M = Co(II), Cu(II), were prepared from the reaction of [M2(μ-F)(μ-L)2](BF4)3 and (CH3)3SiCl. The bromide-bridged complex [Cu2(μ-Br)(μ-Lm*)2](ClO4)3 was prepared by the first method. Three acyclic complexes, [Co2(μ-Lm)μ-Cl4], [Co2(μ-Lm*)Cl4], and [Co2(μ-Lm*)Br4], were also prepared. The structures of all [M2(μ-X)(μ-L)2](3+) (X = Cl(-), Br(-)) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn2(μ-Cl)(μ-Lm*)2](ClO4)3 and especially [Cd2(μ-Cl)(μ-Lm*)2](ClO4)3 demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm(-1) for [Cu2(μ-Cl)(μ-Lm)2](ClO4)3·xCH3CN, 720 cm(-1) for [Cu2(μ-Cl)(μ-Lm*)2](ClO4)3, and 945 cm(-1) for [Cu2(μ-Br)(μ-Lm*)2](ClO4)3·2CH3CN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm(-1) for [Ni2(μ-Cl)(μ-Lm*)2](ClO4)3, 55 cm(-1) for [Co2(μ-Cl)(μ-Lm*)2](ClO4)3, and 34 cm(-1) for [Fe2(μ-Cl)(μ-Lm*)2](ClO4

  2. Human-centred approaches in slipperiness measurement

    PubMed Central

    Grönqvist, Raoul; Abeysekera, John; Gard, Gunvor; Hsiang, Simon M.; Leamon, Tom B.; Newman, Dava J.; Gielo-Perczak, Krystyna; Lockhart, Thurmon E.; Pai, Clive Y.-C.

    2010-01-01

    A number of human-centred methodologies—subjective, objective, and combined—are used for slipperiness measurement. They comprise a variety of approaches from biomechanically-oriented experiments to psychophysical tests and subjective evaluations. The objective of this paper is to review some of the research done in the field, including such topics as awareness and perception of slipperiness, postural and balance control, rating scales for balance, adaptation to slippery conditions, measurement of unexpected movements, kinematics of slipping, and protective movements during falling. The role of human factors in slips and falls will be discussed. Strengths and weaknesses of human-centred approaches in relation to mechanical slip test methodologies are considered. Current friction-based criteria and thresholds for walking without slipping are reviewed for a number of work tasks. These include activities such as walking on a level or an inclined surface, running, stopping and jumping, as well as stair ascent and descent, manual exertion (pushing and pulling, load carrying, lifting) and particular concerns of the elderly and mobility disabled persons. Some future directions for slipperiness measurement and research in the field of slips and falls are outlined. Human-centred approaches for slipperiness measurement do have many applications. First, they are utilized to develop research hypotheses and models to predict workplace risks caused by slipping. Second, they are important alternatives to apparatus-based friction measurements and are used to validate such methodologies. Third, they are used as practical tools for evaluating and monitoring slip resistance properties of foot wear, anti-skid devices and floor surfaces. PMID:11794763

  3. Hunting for hardware changes in data centres

    NASA Astrophysics Data System (ADS)

    Coelho dos Santos, M.; Steers, I.; Szebenyi, I.; Xafi, A.; Barring, O.; Bonfillou, E.

    2012-12-01

    With many servers and server parts the environment of warehouse sized data centres is increasingly complex. Server life-cycle management and hardware failures are responsible for frequent changes that need to be managed. To manage these changes better a project codenamed “hardware hound” focusing on hardware failure trending and hardware inventory has been started at CERN. By creating and using a hardware oriented data set - the inventory - with detailed information on servers and their parts as well as tracking changes to this inventory, the project aims at, for example, being able to discover trends in hardware failure rates.

  4. Identification on Membrane and Characterization of Phosphoproteins Using an Alkoxide-Bridged Dinuclear Metal Complex as a Phosphate-Binding Tag Molecule

    PubMed Central

    Nakanishi, Tsuyoshi; Ando, Eiji; Furuta, Masaru; Kinoshita, Eiji; Kinoshita-Kikuta, Emiko; Koike, Tohru; Tsunasawa, Susumu; Nishimura, Osamu

    2007-01-01

    We have developed a method for on-membrane direct identification of phosphoproteins, which are detected by a phosphate-binding tag (Phos-tag) that has an affinity to phosphate groups with a chelated Zn2+ ion. This rapid profiling approach for phosphoproteins combines chemical inkjet technology for microdispensing of reagents onto a tiny region of target proteins with mass spectrometry for on-membrane digested peptides. Using this method, we analyzed human epidermoid carcinoma cell lysates of A-431 cells stimulated with epidermal growth factor, and identified six proteins with intense signals upon affinity staining with the phosphate-binding tag. It was already known that these proteins are phosphorylated, and our new approach proved to be effective at rapid profiling of phosphoproteins. Furthermore, we tried to determine their phosphorylation sites by MS/MS analysis after in-gel digestion of the corresponding spots on the 2DE gel to the rapid on-membrane identifications. As one example of use of information gained from the rapid-profiling approach, we successfully characterized a phosphorylation site at Ser-113 on prostaglandin E synthase 3. PMID:18166671

  5. Synthesis of a novel dinucleating aminocarboxylate macrocycle and structures of its dinuclear complexes with di- and trivalent transition and lanthanide metal ions.

    PubMed

    Brunner, Jens; Pritzkow, Hans; Krämer, Roland

    2005-01-21

    The synthesis of the new ligand L1(H4L1= 3,8,16,21-tetrakis(carboxylmethyl)-3,8,16,21,27,28-hexaazatricyclo[21.3.1.1(10,14)]octacosa-1(27),10,12,14(28),23,25-hexaen-5,18-diine) is reported. The solid-state structures of the four homodinuclear chelate complexes, [Zn2(L1)(H2O)2] x 6H2O, [Fe2(L1)(mu-O)] x 4H2O, [La2(L1)(NO3)2(H2O)2] x 6H2O and Na[Eu2(L1)(mu-AcO)3] x 3H2O, were determined by single-crystal X-ray structural analysis.

  6. Metallated metal-organic frameworks

    DOEpatents

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  7. WISB: Warwick Integrative Synthetic Biology Centre

    PubMed Central

    McCarthy, John

    2016-01-01

    Synthetic biology promises to create high-impact solutions to challenges in the areas of biotechnology, human/animal health, the environment, energy, materials and food security. Equally, synthetic biologists create tools and strategies that have the potential to help us answer important fundamental questions in biology. Warwick Integrative Synthetic Biology (WISB) pursues both of these mutually complementary ‘build to apply’ and ‘build to understand’ approaches. This is reflected in our research structure, in which a core theme on predictive biosystems engineering develops underpinning understanding as well as next-generation experimental/theoretical tools, and these are then incorporated into three applied themes in which we engineer biosynthetic pathways, microbial communities and microbial effector systems in plants. WISB takes a comprehensive approach to training, education and outreach. For example, WISB is a partner in the EPSRC/BBSRC-funded U.K. Doctoral Training Centre in synthetic biology, we have developed a new undergraduate module in the subject, and we have established five WISB Research Career Development Fellowships to support young group leaders. Research in Ethical, Legal and Societal Aspects (ELSA) of synthetic biology is embedded in our centre activities. WISB has been highly proactive in building an international research and training network that includes partners in Barcelona, Boston, Copenhagen, Madrid, Marburg, São Paulo, Tartu and Valencia. PMID:27284024

  8. KNMI Data Centre: Easy access for all

    NASA Astrophysics Data System (ADS)

    van de Vegte, John; Som de Cerff, Wim; Plieger, Maarten; de Vreede, Ernst; Sluiter, Raymond; Willem Noteboom, Jan; van der Neut, Ian; Verhoef, Hans; van Versendaal, Robert; van Binnendijk, Martin; Kalle, Henk; Knopper, Arthur; Spit, Jasper; Mastop, Joeri; Klos, Olaf; Calis, Gijs; Ha, Siu-Siu; van Moosel, Wim; Klein Ikkink, Henk-Jan; Tosun, Tuncay

    2013-04-01

    KNMI is the Dutch institute for weather, climate research and seismology. It disseminates weather information to the public at large, the government, aviation and the shipping industry in the interest of safety, the economy and a sustainable environment. To gain insight into long-term developments KNMI conducts research on climate change. Making the knowledge, data and information on hand at KNMI accessible is one core activity. A huge part of the KNMI information is from numerical models, insitu sensor networks and remote sensing satellites. This digital collection is mostly internal only available and is a collection of non searchable , non standardized file formats, lacking documentation and has no references to scientific publications. With the KNMI Data Centre (KDC) project these issues are tackled. In the project a user driven development approach with SCRUM was chosen to get maximum user involvement in a relative short development timeframe. Building on open standards and proven open source technology (which includes in-house developed software like ADAGUC WMS and Portal) resulted in a first release in December 2012 This presentation will focus on the aspects of KDC relating to its technical challenges, the development strategy and the initial usage results of the data centre.

  9. Sofia University GNSS Analysis Centre (SUGAC)

    NASA Astrophysics Data System (ADS)

    Simeonov, Tzvetan; Sidorov, Dmitry; Teferle, Norman; Guerova, Guergana; Egova, Evgenia; Vassileva, Keranka; Milev, Ivo; Milev, Georgi

    2015-04-01

    The Sofia University GNSS Analysis Centre (SUGAC, suada.phys.uni-sofia.bg) is a new analysis centre established via collaboration between the Department of Meteorology and Geophysics of Sofia University, the IPOS - BuliPOS GNSS network in Bulgaria and the University of Luxembourg. In April 2014, the first processing campaign took place. One year GNSS data from 7 stations of the BuliPOS network are processed in collaboration with the University of Luxembourg. Tropospheric products (Zenith Total Delay and gradients) with 5 min temporal resolution are obtained using the NAPEOS software, developed by ESA. The tropospheric products from this campaign will be used for validation of the Weather Research and Forecasting (WRF) model as well as for case studies during intense precipitation events and fog. In this work the WRF model validation for Bulgaria will be presented. Future work will be the establishment of autonomous near real-time processing of the regional ground-based GNSS network in Southeast Europe in support of the EUMETNET E-GVAP and COST ES1206 "Advanced Global Navigation Satellite Systems for Severe Weather Events and Climate" projects.

  10. Syntheses, crystal structures, and properties of new metal--5-bromonicotinate coordination polymers

    NASA Astrophysics Data System (ADS)

    Li, Wenjie; Li, Guoting; Lv, Lulu; Zhao, Hong; Wu, Benlai

    2015-05-01

    Four metal-5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic)2(H2O)2]n (1), [Ni(Brnic)2]n (2), [Ni(Brnic)(bpy)(H2O)2]n·n(Brnic)·4.5nH2O (3), and [Co2(Brnic)3(bpy)2(OH)]n·nH2O (4) have been synthesized and structurally characterized (bpy=4,4‧-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2-4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni2(Brnic)4] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni2(Brnic)2] and trigons [Co2(Brnic)3(OH)], 63-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1-4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni2(Brnic)4] and trigon [Co2(Brnic)3(OH)] cores, respectively.

  11. Service Delivery to Parents with an Intellectual Disability: Family-Centred or Professionally Centred?

    ERIC Educational Resources Information Center

    Wade, Catherine M.; Mildon, Robyn L.; Matthews, Jan M.

    2007-01-01

    Background: Studies support the use of family-centred practices in service delivery to families where a parent has an intellectual disability. This paper examines the importance of such practices to parents. Materials and Methods: Interview responses from 32 parents with intellectual disability were coded by two independent raters as reflecting…

  12. The Curriculum Development Centre of Malaysia. Studies of Curriculum Development Centres in Asia 2.

    ERIC Educational Resources Information Center

    Oon-Chye, Yeoh; And Others

    The Curriculum Development Centre (CDC) of Malaysia became an operating agency in January 1973 and became a division of the Malaysia Ministry of Education in May 1974. Its establishment was the culmination of over a decade of curriculum development efforts by the Ministry of Education. The CDC was an outgrowth of both the First and Second Malaysia…

  13. Systematic Assessment of Game-Centred Approach Practices--The Game-Centred Approach Assessment Scaffold

    ERIC Educational Resources Information Center

    Forrest, Gregory

    2015-01-01

    Background: Game-centred approaches (GCA) have been promoted as a more meaningful way to teach games and sports due to their connections with constructivist learning principles. However, the implementation is dependant on the teacher implementing it rather than just the model. There has been little research into what it means to use a GCA well and…

  14. The obtaining relative position of lunar centre masses and centre of the figure in selenocentric catalogues

    NASA Astrophysics Data System (ADS)

    Nefedjev, Yu. A.; Valeev, S. G.; Rizvanov, N. G.; Mikeev, R. R.; Varaksina, N. Yu.

    2010-05-01

    The relative position of lunar center masses relative to center of the figure in Kazan and Kiev selenocentric catalogues was customized. The expansions by spherical harmonics N=5 degree and order of the lunar function h(λ, β) with using the package ASNI USTU were executed. Module of the expansion of the local area to surfaces to full sphere was used. The parameters of cosmic missions are given for comparison (SAI; Bills, Ferrari). The normalized coefficients from expansions for eight sources hypsometric information are obtained: - Clementine (N=40), - Kazan (N=5), - Kiev (N=5), - SAI (N=10; Chuikova (1975)), - Bills, Ferrari, - Каguуа (Selena, Japan mission), - ULCN (The Uuified Lunaz Control Network 2005). The displacements of the lunar centre figure relative to lunar centre of the masses were defined from equations (Chuikova (1975)). The results of the obtaining relative position of the lunar centre masses and centre of the figure in Kazan selenocentric catalogue give good agreement with modern cosmic mission data.

  15. Synthesis, one- and two-photon photophysical and excited-state properties, and sensing application of a new phosphorescent dinuclear cationic iridium(III) complex.

    PubMed

    Xu, Wen-Juan; Liu, Shu-Juan; Zhao, Xin; Zhao, Ning; Liu, Zhi-Qiang; Xu, Hang; Liang, Hua; Zhao, Qiang; Yu, Xiao-Qiang; Huang, Wei

    2013-01-07

    A new phosphorescent dinuclear cationic iridium(III) complex (Ir1) with a donor-acceptor-π-bridge-acceptor-donor (D-A-π-A-D)-conjugated oligomer (L1) as a N^N ligand and a triarylboron compound as a C^N ligand has been synthesized. The photophysical and excited-state properties of Ir1 and L1 were investigated by UV/Vis absorption spectroscopy, photoluminescence spectroscopy, and molecular-orbital calculations, and they were compared with those of the mononuclear iridium(III) complex [Ir(Bpq)(2)(bpy)](+)PF(6)(-) (Ir0). Compared with Ir0, complex Ir1 shows a more-intense optical-absorption capability, especially in the visible-light region. For example, complex Ir1 shows an intense absorption band that is centered at λ=448 nm with a molar extinction coefficient (ε) of about 10(4) , which is rarely observed for iridium(III) complexes. Complex Ir1 displays highly efficient orange-red phosphorescent emission with an emission wavelength of 606 nm and a quantum efficiency of 0.13 at room temperature. We also investigated the two-photon-absorption properties of complexes Ir0, Ir1, and L1. The free ligand (L1) has a relatively small two-photon absorption cross-section (δ(max) =195 GM), but, when complexed with iridium(III) to afford dinuclear complex Ir1, it exhibits a higher two-photon-absorption cross-section than ligand L1 in the near-infrared region and an intense two-photon-excited phosphorescent emission. The maximum two-photon-absorption cross-section of Ir1 is 481 GM, which is also significantly larger than that of Ir0. In addition, because the strong B-F interaction between the dimesitylboryl groups and F(-) ions interrupts the extended π-conjugation, complex Ir1 can be used as an excellent one- and two-photon-excited "ON-OFF" phosphorescent probe for F(-) ions.

  16. Versatile Reactivity and Theoretical Evaluation of Mono- and Dinuclear Oxidovanadium(V) Compounds of Aroylazines: Electrogeneration of Mixed-Valence Divanadium(IV,V) Complexes.

    PubMed

    Dash, Subhashree P; Roy, Satabdi; Mohanty, Monalisa; Carvalho, M Fernanda N N; Kuznetsov, Maxim L; Pessoa, João Costa; Kumar, Amit; Patil, Yogesh P; Crochet, Aurélien; Dinda, Rupam

    2016-09-06

    The substituted hydrazones H2L(1-4) (L(1-4) = dibasic tridentate ONO(2-) donor ligands) obtained by the condensation of 2-hydroxy-1-naphthaldehyde and 2-aminobenzoylhydrazine (H2hnal-abhz) (H2L(1)) , 2-hydroxy-1-naphthaldehyde and 2-hydroxybenzoylhydrazine (H2hnal-hbhz) (H2L(2)), 2-hydroxy-1-acetonaphthone and benzoylhydrazine (H2han-bhz) (H2L(3)), or 2-hydroxy-1-acetonaphthone and 2-aminobenzoylhydrazine (H2han-abhz) (H2L(4)) are prepared and characterized. Reaction of ammonium vanadate with the appropriate H2L(1-4) results in the formation of oxidoethoxidovanadium(V) [V(V)O(OEt)(L(1-4))] (1-4) complexes. All compounds are characterized in the solid state and in solution by spectroscopic techniques (IR, UV-vis, (1)H, (13)C, and (51)V NMR, and electrospray ionization mass spectrometry). Single-crystal X-ray diffraction analysis of 1, 3, and 4 confirms the coordination of the corresponding ligands in the dianionic (ONO(2-)) enolate tautomeric form. In solution, the structurally characterized [V(V)O(OEt)(L)] compounds transform into the monooxido-bridged divanadium(V,V) [(V(V)OL)2-μ-O] complexes, with the processes being studied by IR and (1)H, (13)C, and (51)V NMR. The density functional theory (DFT) calculated Gibbs free energy of reaction 2[V(V)O(OEt)(L(4))] + H2O ⇆ [(V(V)OL(4))2-μ-O] + 2EtOH is only 2-3 kcal mol(-1), indicating that the dinuclear complexes may form in a significant amount. The electrochemical behavior of the complexes is investigated by cyclic voltammetry, with the V(V)-V(IV) E1/2(red) values being in the range 0.27-0.44 V (vs SCE). Upon controlled potential electrolysis, the corresponding (L)(O)V(IV)-O-V(V)(O)(L) mixed-valence species are obtained upon partial reduction of the [(V(V)OL)2-μ-O] complexes formed in solution, and some spectroscopic characteristics of these dinuclear mixed-valence complexes are investigated using DFT calculations and by electron paramagnetic resonance (EPR), with the formation of V(IV)-O-V(V) species being

  17. Isostructural dinuclear phenoxo-/acetato-bridged manganese(II), cobalt(II), and zinc(II) complexes with labile sites: kinetics of transesterification of 2-hydroxypropyl-p-nitrophenylphosphate.

    PubMed

    Arora, Himanshu; Barman, Suman K; Lloret, Francesc; Mukherjee, Rabindranath

    2012-05-21

    Using the dinucleating phenol-based ligand 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol] (HL(2)), in its deprotonated form, the six new dinuclear complexes [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][PF(6)] (M = Mn (2a), Co (3a), Zn (4a)) and [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][BPh(4)] (M = Mn (2b), Co (3b), Zn (4b)) have been synthesized. Crystallographic analyses on 2b·2MeCN, 3b·2MeCN, and 4b·2MeCN reveal that these complexes have closely similar μ-phenoxo bis(μ-carboxylato) structures. The physicochemical properties (absorption and ESI-MS spectral data, 2a,b, 3a,b, and 4a,b; (1)H NMR, 4a,b) of the cations of 2a-4a are identical with those of 2b-4b. Each metal ion is terminally coordinated by a pyrazole nitrogen and a pyridyl nitrogen from a 3-(pyridin-2-yl)pyrazole unit and a solvent molecule (MeCN). Thus, each metal center assumes distorted-octahedral M(II)N(3)O(3) coordination. Temperature-dependent magnetic studies on Mn(II) and Co(II) dimers reveal the presence of intramolecular antiferromagnetic (J = -8.5 cm(-1)) for 2b and ferromagnetic exchange coupling (J = +2.51 cm(-1)) for 3b, on the basis of the Hamiltonian H = -JS(1)·S(2). The exchange mechanism is discussed on the basis of magneto-structural parameters (M···M distance). Spectroscopic properties of the complexes have also been investigated. The pH titration and kinetics of phosphatase (transesterification) activity on 2-hydroxypropyl-p-nirophenylphosphate (HPNP) were studied in MeOH/H(2)O (33%, v/v) with 2a-4a, due to solubility reasons. This comparative kinetic study revealed the effect of the metal ion on the rate of hydrolysis of HPNP, which has been compared with what we recently reported for [Ni(II)(2)(L(2))(μ-O(2)CMe)(2)(MeOH)(H(2)O)][ClO(4)] (1a). The efficacy in the order of conversion of substrate to product (p-nitrophenolate ion) follows the order 4a > 3a > 2a > 1a, under identical experimental conditions. Notably, this trend follows the decrease of pK(a) values of

  18. Children's Centre "3 in 1 - together"

    NASA Astrophysics Data System (ADS)

    Gancheva, Hristina

    2013-04-01

    "There are only two ways to life your live. One is as though nothing is a miracle. The other is as though everything is a miracle." Albert Einstein Children's Centre "3 in 1" is an extracurricular unit linked to the High School of Zlatartitsa, St. Cyril and St. Methodius, accomplished with the help of the municipality and many volunteers from the local community. With its activity it forms in children patriotic spirit, love for nature, active citizenship, and an impulse for a healthy life through communication with nature, saving the traditions and history, insurance of equality of the kids of the local five ethnicities and participation in activities in the sphere of science, art, sport and tourism. The educational work is mainly directed towards kids with difficulties with communication, hyperactivity, aggression, problems in their families, or those deprived of parental care. For a few years in the Children's Centre there have been clubs of interests: "Gardeners" - kids cultivate a garden. They plow, dig, plant, put in, irrigate and weed under the watch of Ms Stafka Nikolova, parents, and volunteers of the local community. The ecologically clean products - vegetables and fruits, kids use to cook delicious meals, sell, or give away. Weeds are also utilized; they are making herbarium out of them. "Cooks" - "What to have for lunch, when mom is out?". One can learn a lot of wonderful recipes from the club "Cooks". Products are own made, raised with love. In 2010, on the on the annual traditional holiday of the garden soup in Zlataritsa, the little cooks won third prize for making a delicious vegetable soup. On the same day, the 26 years old Nadezhda Savova, Cultural and Social Anthropology PhD in Princeton, founded the second community bakery in Bulgaria in Children's Centre "3 in1". Nadezhda Savova was declared traveler of 2012 by National Geographic. After the baking house in Gabrovo and Zlataritsa, Nadezhda also founded such projects in Sofia, Varna and Ruse

  19. Initial experience with an Underwater Manifold Centre

    SciTech Connect

    Osborne, J.M.

    1984-10-01

    In July 1983 comingled production from the first two completed wells of the Shell/Esso Underwater Manifold Centre (the UMC), reached the Cormorant Alpha platform. This moment was the culmination of design and development effort which had begun as early as the spring of 1975. But being both the largest subsea system to become operational in the North Sea, and the first designed to the production of several subsea wells, whilst injecting into others, how would the UMC continue to perform. This paper details the operational experience gained to date with the UMC, tracing its brief history since it was first powered up in September 1982 to the present. This is discussed in the main body of the paper under the headings: Commissioning Experience; Operating Experience; Reliability and Maintenance.

  20. PRICE: primitive centred schemes for hyperbolic systems

    NASA Astrophysics Data System (ADS)

    Toro, E. F.; Siviglia, A.

    2003-08-01

    We present first- and higher-order non-oscillatory primitive (PRI) centred (CE) numerical schemes for solving systems of hyperbolic partial differential equations written in primitive (or non-conservative) form. Non-conservative systems arise in a variety of fields of application and they are adopted in that form for numerical convenience, or more importantly, because they do not posses a known conservative form; in the latter case there is no option but to apply non-conservative methods. In addition we have chosen a centred, as distinct from upwind, philosophy. This is because the systems we are ultimately interested in (e.g. mud flows, multiphase flows) are exceedingly complicated and the eigenstructure is difficult, or very costly or simply impossible to obtain. We derive six new basic schemes and then we study two ways of extending the most successful of these to produce second-order non-oscillatory methods. We have used the MUSCL-Hancock and the ADER approaches. In the ADER approach we have used two ways of dealing with linear reconstructions so as to avoid spurious oscillations: the ADER TVD scheme and ADER with ENO reconstruction. Extensive numerical experiments suggest that all the schemes are very satisfactory, with the ADER/ENO scheme being perhaps the most promising, first for dealing with source terms and secondly, because higher-order extensions (greater than two) are possible. Work currently in progress includes the application of some of these ideas to solve the mud flow equations. The schemes presented are generic and can be applied to any hyperbolic system in non-conservative form and for which solutions include smooth parts, contact discontinuities and weak shocks. The advantage of the schemes presented over upwind-based methods is simplicity and efficiency, and will be fully realized for hyperbolic systems in which the provision of upwind information is very costly or is not available.

  1. Distant Operational Care Centre: Design Project Report

    NASA Technical Reports Server (NTRS)

    1996-01-01

    The goal of this project is to outline the design of the Distant Operational Care Centre (DOCC), a modular medical facility to maintain human health and performance in space, that is adaptable to a range of remote human habitats. The purpose of this project is to outline a design, not to go into a complete technical specification of a medical facility for space. This project involves a process to produce a concise set of requirements, addressing the fundamental problems and issues regarding all aspects of a space medical facility for the future. The ideas presented here are at a high level, based on existing, researched, and hypothetical technologies. Given the long development times for space exploration, the outlined concepts from this project embodies a collection of identified problems, and corresponding proposed solutions and ideas, ready to contribute to future space exploration efforts. In order to provide a solid extrapolation and speculation in the context of the future of space medicine, the extent of this project's vision is roughly within the next two decades. The Distant Operational Care Centre (DOCC) is a modular medical facility for space. That is, its function is to maintain human health and performance in space environments, through prevention, diagnosis, and treatment. Furthermore, the DOCC must be adaptable to meet the environmental requirements of different remote human habitats, and support a high quality of human performance. To meet a diverse range of remote human habitats, the DOCC concentrates on a core medical capability that can then be adapted. Adaptation would make use of the DOCC's functional modularity, providing the ability to replace, add, and modify core functions of the DOCC by updating hardware, operations, and procedures. Some of the challenges to be addressed by this project include what constitutes the core medical capability in terms of hardware, operations, and procedures, and how DOCC can be adapted to different remote

  2. Common Myna Roosts Are Not Recruitment Centres

    PubMed Central

    Sarangi, Manaswini; Arvind, Chiti; Lakshman, Abhilash; Vidya, T. N. C.

    2014-01-01

    We studied communal roosting in the Common Myna (Acridotheres tristis) in the light of the recruitment centre hypothesis and predation at the roost. The number and sizes of flocks departing from and arriving at focal roosts were recorded over a two year period. We also recorded the sizes and behaviour of foraging flocks. We found that flock sizes of birds departing from roosts at sunrise were larger than those at the feeding site, suggesting that there was no recruitment from the roosts. Flocks entering the roosts during sunset were larger on average than those leaving the following sunrise, suggesting no consolidation of flocks in the morning. Flocks entering the roosts at sunset were also larger on average than those that had left that sunrise, although there was no recruitment at the feeding site. There was no effect of group size on the proportion of time spent feeding. Contrary to expectation, single birds showed lower apparent vigilance than birds that foraged in pairs or groups, possibly due to scrounging tactics being used in the presence of feeding companions. Thus, the recruitment centre hypothesis did not hold in our study population of mynas. Predation at dawn and dusk were also not important to communal roosting: predators near the roosts did not result in larger flocks, and resulted in larger durations of arrival/departure contrary to expectation. Since flock sizes were smallest at the feeding site and larger in the evening than in the morning, but did not coincide with predator activity, information transfer unrelated to food (such as breeding opportunities) may possibly give rise to the evening aggregations. PMID:25122467

  3. The Centre of Mass of a Triangular Plate

    ERIC Educational Resources Information Center

    Slusarenko, Viktor; Rojas, Roberto; Fuster, Gonzalo

    2008-01-01

    We present a derivation for the coordinates of the centre of mass--or centre of gravity--of a homogeneous triangular plate by using scaling and symmetry. We scale the triangular plate by a factor of 2 and divide its area into four plates identical to the original. By symmetry, we assert that the centre of mass of two identical masses lies at the…

  4. Complex Modelling Scheme Of An Additive Manufacturing Centre

    NASA Astrophysics Data System (ADS)

    Popescu, Liliana Georgeta

    2015-09-01

    This paper presents a modelling scheme sustaining the development of an additive manufacturing research centre model and its processes. This modelling is performed using IDEF0, the resulting model process representing the basic processes required in developing such a centre in any university. While the activities presented in this study are those recommended in general, changes may occur in specific existing situations in a research centre.

  5. Determination of cysteine and glutathione based on the inhibition of the dinuclear Cu(II)-catalyzed luminol-H2O2 chemiluminescence reaction.

    PubMed

    Chaichi, Mohammad Javad; Ehsani, Mahjoobeh; Khajvand, Tahereh; Golchoubian, Hamid; Rezaee, Ehsan

    2014-03-25

    The catalyzed luminol chemiluminescent reaction has received a great amount of attention because of its high sensitivity and low background signal which make the reaction an attractive analytical chemistry tool. The present study, introduces the beneficial catalytic effects of dinuclear Cu(II) complex [Cu2L2(TAE)]X2, where TAE=tetraacetylethane; L=N,N(')-dibenzylethylenediamine and X=ClO4 on the luminol chemiluminescent reaction as a novel probe for the determination of glutathione (GSH) and L-cysteine (CySH) in human serum and urine. The [Cu2L2(TAE)]X2 has exhibited highly efficient catalytic activity of luminol CL as an artificial peroxidase model at pH as low as 7.5 in water in the presence of H2O2⋅GSH and CySH can induce a sharp decrease in CL intensity from the [Cu2L2(TAE)]X2-catalyzed luminol system. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentrations of GSH and CySH in the range of 1.0×10(-7)-1.0×10(-4) M, with detection limits (S/N=3) of 2.7×10(-8) and 6.8×10(-8) M and RSD<4.2% (n=7) for GSH and CySH, respectively.

  6. Determination of cysteine and glutathione based on the inhibition of the dinuclear Cu(II)-catalyzed luminol-H2O2 chemiluminescence reaction

    NASA Astrophysics Data System (ADS)

    Chaichi, Mohammad Javad; Ehsani, Mahjoobeh; Khajvand, Tahereh; Golchoubian, Hamid; Rezaee, Ehsan

    2014-03-01

    The catalyzed luminol chemiluminescent reaction has received a great amount of attention because of its high sensitivity and low background signal which make the reaction an attractive analytical chemistry tool. The present study, introduces the beneficial catalytic effects of dinuclear Cu(II) complex [Cu2L2(TAE)]X2, where TAE = tetraacetylethane; L = N,N'-dibenzylethylenediamine and X = ClO4 on the luminol chemiluminescent reaction as a novel probe for the determination of glutathione (GSH) and L-cysteine (CySH) in human serum and urine. The [Cu2L2(TAE)]X2 has exhibited highly efficient catalytic activity of luminol CL as an artificial peroxidase model at pH as low as 7.5 in water in the presence of H2O2ṡGSH and CySH can induce a sharp decrease in CL intensity from the [Cu2L2(TAE)]X2-catalyzed luminol system. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentrations of GSH and CySH in the range of 1.0 × 10-7-1.0 × 10-4 M, with detection limits (S/N = 3) of 2.7 × 10-8 and 6.8 × 10-8 M and RSD < 4.2% (n = 7) for GSH and CySH, respectively.

  7. Novel dinuclear dimethylamido-3,5-dimethylpyrazolato and tetranuclear dimethylamido-3,5-dimethylpyrazolato-polyoxo zirconium(IV) complexes. Synthesis and structural characterisation.

    PubMed

    Sanz, Martial; Mosquera, Marta E G; Cuenca, Tomás

    2009-04-14

    The dinuclear dimethylamido-tris(3,5-dimethylpyrazolato)-zirconium(IV) complex [Zr(3,5-Me2Pz)3(NMe2)]2 1 is prepared by treatment of [Zr(NMe2)4] with 3 equivalents of 3,5-dimethylpyrazole (3,5-Me2PzH) with elimination of dimethylamine. When [Zr(NMe2)4] reacted with 2 equivalents of 3,5-Me2PzH, the bis(dimethylamido)-bis(3,5-dimethylpyrazolato)zirconium(IV) compound [Zr(3,5-Me2Pz)2(NMe2)2]2 2 is obtained. Hydrolysis of [Zr(3,5-Me2Pz)3(NMe2)]2 in wet toluene affords the tetranuclear oxo compound [Zr4(eta2-3,5-Me2Pz)4(NMe2)2(mu3-O)2(mu2-3,5-Me2Pz)4(mu2-NMe2)2] . All synthesised compounds are characterised by NMR spectroscopic and analytical methods. Single crystal X-ray diffraction analysis has established the molecular structures of 1 and 4.

  8. Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Yingjie; Karatchevtseva, Inna; Bhadbhade, Mohan; Tran, Toan Trong; Aharonovich, Igor; Fanna, Daniel J.; Shepherd, Nicholas D.; Lu, Kim; Li, Feng; Lumpkin, Gregory R.

    2016-02-01

    With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H2phb) or terephthalic acid (H2tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO2)2(Hphb)2(phb)(DMF)(H2O)3]·4H2O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a μ2-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO2)(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with μ4-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C-O-U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated.

  9. Reaction centres: the structure and evolution of biological solar power.

    PubMed

    Heathcote, Peter; Fyfe, Paul K; Jones, Michael R

    2002-02-01

    Reaction centres are complexes of pigment and protein that convert the electromagnetic energy of sunlight into chemical potential energy. They are found in plants, algae and a variety of bacterial species, and vary greatly in their composition and complexity. New structural information has highlighted features that are common to the different types of reaction centre and has provided insights into some of the key differences between reaction centres from different sources. New ideas have also emerged on how contemporary reaction centres might have evolved and on the possible origin of the first chlorophyll-protein complexes to harness the power of sunlight.

  10. Metals Sector

    EPA Pesticide Factsheets

    Find environmental regulatory information about the metals sector (NAICS 331 & 332), including NESHAPs for metal coatings, effluent guidelines for metal products, combustion compliance assistance, and information about foundry sand recycling.

  11. The development and operation of Edinburgh Parallel Computing Centre`s summer scholarship programme

    SciTech Connect

    Wilson, G.V.; MacDonald, N.B.; Thornborrow, C.; Brough, C.M.

    1994-12-31

    Between 1987 and 1994, more than 100 students in a broad range of disciplines worked as summer scholars at Edinburgh Parallel Computing Centre. Many of these students have since taken their parallel computing skills into graduate work and industry, and over a quarter of EPCC`s technical staff are alumni of the Programme. This report describes the evolution and present operation of the Summer Scholarship Programme, and its costs and benefits.

  12. Metal aminoboranes

    DOEpatents

    Burrell, Anthony K.; Davis, Benjamin J.; Thorn, David L.; Gordon, John C.; Baker, R. Thomas; Semelsberger, Troy Allen; Tumas, William; Diyabalanage, Himashinie Vichalya Kaviraj; Shrestha, Roshan P.

    2010-05-11

    Metal aminoboranes of the formula M(NH.sub.2BH.sub.3).sub.n have been synthesized. Metal aminoboranes are hydrogen storage materials. Metal aminoboranes are also precursors for synthesizing other metal aminoboranes. Metal aminoboranes can be dehydrogenated to form hydrogen and a reaction product. The reaction product can react with hydrogen to form a hydrogen storage material. Metal aminoboranes can be included in a kit.

  13. ACTRIS Data Centre: An atmospheric data portal

    NASA Astrophysics Data System (ADS)

    Myhre, C. Lund; Fahre Vik, A.; Logna, R.; Torseth, K.; Linné, H.; O'Connor, E.

    2012-04-01

    ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) is a European Project aiming at integrating European ground-based stations equipped with advanced instrumentation for studying aerosols, clouds, and short-lived gas-phase species. The ACTRIS activities result in improved atmospheric measurements data made at more than 60 European sites, from numerous instruments and includes variables measured by ground based in situ and remote sensing technologies. Core variables are in situ aerosol optical, physical and chemical properties, short-lived trace gases (volatile organic carbon and nitrogen oxides), aerosol scattering and extinction profiles, and cloud properties. The ACTRIS data centre (ACTRIS DC) is giving free and open access to all data resulting from the activities of the infrastructure network, complemented with data from other relevant networks and data bases. The overall goal is to facilitate scientists and other user groups access to atmospheric observational data, and to provide mature products for analysis and interpretation of atmospheric composition change. The ACTRIS DC aims at substantially increasing the number of high-quality data by providing long-term observational data relevant to climate and air quality research produced with standardized or comparable procedures throughout the network. The backbone of the ACTRIS DC is the three core data bases: - EARLINET Data Base hosting aerosol lidar data from more than 30 European sites - EBAS hosting ground based atmospheric in situ data from more than 1000 sites globally - Cloudnet hosting remote sensing cloud data and products from 5 European sites Furthermore, a joint portal is developed combining information from various data sources to gain new information not presently available from standalone databases or networks. The data centre will provide tools and services to facilitate the use of measurements for broad user communities. Higher level and integrated products will be

  14. Dinuclear Ruthenium(II) Complexes as Two-Photon, Time-Resolved Emission Microscopy Probes for Cellular DNA**

    PubMed Central

    Baggaley, Elizabeth; Gill, Martin R; Green, Nicola H; Turton, David; Sazanovich, Igor V; Botchway, Stanley W; Smythe, Carl; Haycock, John W; Weinstein, Julia A; Thomas, Jim A

    2014-01-01

    The first transition-metal complex-based two-photon absorbing luminescence lifetime probes for cellular DNA are presented. This allows cell imaging of DNA free from endogenous fluorophores and potentially facilitates deep tissue imaging. In this initial study, ruthenium(II) luminophores are used as phosphorescent lifetime imaging microscopy (PLIM) probes for nuclear DNA in both live and fixed cells. The DNA-bound probes display characteristic emission lifetimes of more than 160 ns, while shorter-lived cytoplasmic emission is also observed. These timescales are orders of magnitude longer than conventional FLIM, leading to previously unattainable levels of sensitivity, and autofluorescence-free imaging. PMID:24458590

  15. Dynamics of Gas Near the Galactic Centre

    NASA Astrophysics Data System (ADS)

    Jenkins, A.; Binney, J.

    1994-10-01

    We simulate the flow of gas in the Binney et al. model of the bar at the centre of the Milky Way. We argue that the flow of a clumpy interstellar medium is most realistically simulated by a sticky-particle scheme, and investigate two such schemes. In both schemes orbits close to the cusped orbit rapidly become depopulated. This depopulation places a lower limit on the pattern speed since it implies that in the (1, v) plane the cusped orbit lies significantly inside the peak of the Hi terminal-velocity envelope at 1 20. We find that the size of the central molecular disc and the magnitudes of the observed forbidden velocities constrain the eccentricity of the Galactic bar to values similar to that arbitrarily assumed by Binney et al. We study the accretion by the nuclear disc of matter shed by dying bulge stars. We estimate that mass loss by the bulge can replenish the Hi in the nuclear disc within two bar rotation periods, in good agreement with the predictions of the simulations. When accretion of gas from the bulge is included, fine-scale irregular structure persists in the nuclear disc. This structure gives rise to features in longitude-velocity plots which depend significantly on viewing angle, and consequently give rise to asymmetries in longitude. These asymmetries are, however, much less pronounced than those in the observational plots. We conclude that the addition of hydrodynamics to the Binney et al. model does not resolve some important discrepancies between theory and observation. The model's basic idea does, however, have high a priori probability and has enjoyed some significant successes, while a number of potentially important physical processes - most notably the self-gravity of interstellar gas - are neglected in the present simulations. In view of the deficiencies of our simulations and interesting parallels we do observe between simulated and observational longitude-velocity plots, we believe it would be premature to reject the Binney et al

  16. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center

    DOE PAGES

    Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

    2015-10-16

    A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex [TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate [TptBu,MeCrIII(O2)] (S=3/2) into [TptBu,MeCrV(O)2] (S=1/2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(TptBu,MeCr)2(μ-O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

  17. A novel route towards water-soluble luminescent iridium(iii) complexes via a hydroxy-bridged dinuclear precursor.

    PubMed

    Scarpelli, Francesca; Ionescu, Andreea; Ricciardi, Loredana; Plastina, Pierluigi; Aiello, Iolinda; La Deda, Massimo; Crispini, Alessandra; Ghedini, Mauro; Godbert, Nicolas

    2016-11-01

    The synthesis and photophysical characterization of a new family of luminescent water-soluble ionic iridium(iii) complexes of the general formula [(ppy)2Ir(bpy)]X are reported. The Ir(iii) complexes incorporate a cyclometalated 2-phenylpyridine (ppy), the ancillary ligand 2,2'-bipyridyl (bpy) and different counterions (X(-) = EtO(-), OH(-), EtOCH2CO2(-), MeOCH2CO2(-)). These complexes were obtained starting from the cyclometalated Ir(iii) chloro-bridged dimer [(ppy)2Ir(μ-Cl)]2, for the first time synthesized through a new microwave assisted synthetic procedure, and subsequently converted into the corresponding hydroxy-bridged dimer [(ppy)2Ir(μ-OH)]2. The latter was eventually used as a sole reagent for the synthesis of all the reported complexes by simply varying the nature of the reaction solvent from water to alcohols and glycol ethers. This study demonstrates the versatility of the [(ppy)2Ir(μ-OH)]2 complex as a precursor to water soluble ionic Ir(iii) complexes. Indeed, [(ppy)2Ir(μ-OH)]2 has shown its peculiar chemical reactivity due to both a strong base character and an unexpected oxidative ability towards the alcoholic function of glycol ethers. All the synthesized complexes exhibit, in water solution, an orange emission centred at 606 nm. Moreover, all complexes display the ability to give rise to gel phases in water upon increasing their concentration, and the photophysical study evidenced the various interactions governing the gelification process. The water-solubility of these new luminescent Ir(iii) complexes makes them potentially useful in bio-related systems.

  18. Metal allergy in Singapore.

    PubMed

    Goon, Anthony T J; Goh, C L

    2005-03-01

    This is a clinical epidemiologic study to determine the frequency of metal allergy among patch-tested patients in the years 2001-2003. The results are compared with those of previous studies. All patients diagnosed as having allergic contact dermatitis in the National Skin Centre, Singapore, from January 2001 to December 2003 were studied retrospectively. The frequency of positive patch tests to the following metals were nickel 19.9%, chromate 5.6%, cobalt 8.2% and gold 8.3%. The frequency of nickel allergy has been steadily rising over the last 20 years. The most common sources of nickel allergy are costume jewelry, belt buckles, wrist watches and spectacle frames. After declining from 1984 to 1990, chromate and cobalt allergies have also been steadily increasing subsequently. The most common sources of chromate allergy were cement, leather and metal objects. Most positive patch tests to cobalt are regarded as co-sensitization due to primary nickel or chromate allergies. There has been a steep increase in positive patch tests to gold from 2001 to 2003, which is difficult to explain because the relevance and sources of such positive patch tests can rarely be determined with certainty. There has been an overall rise in the frequency of metal allergy in the last 20 years.

  19. The young centre of the Earth

    NASA Astrophysics Data System (ADS)

    Uggerhøj, U. I.; Mikkelsen, R. E.; Faye, J.

    2016-05-01

    We treat, as an illustrative example of gravitational time dilation in relativity, the observation that the centre of the Earth is younger than the surface by an appreciable amount. Richard Feynman first made this insightful point and presented an estimate of the size of the effect in a talk; a transcription was later published in which the time difference is quoted as ‘one or two days’. However, a back-of-the-envelope calculation shows that the result is in fact a few years. In this paper we present this estimate alongside a more elaborate analysis yielding a difference of two and a half years. The aim is to provide a fairly complete solution to the relativity of the ‘aging’ of an object due to differences in the gravitational potential. This solution—accessible at the undergraduate level—can be used for educational purposes, as an example in the classroom. Finally, we also briefly discuss why exchanging ‘years’ for ‘days’—which in retrospect is a quite simple, but significant, mistake—has been repeated seemingly uncritically, albeit in a few cases only. The pedagogical value of this discussion is to show students that any number or observation, no matter who brought it forward, must be critically examined.

  20. The Charles Perkins Centre's Twins Research Node.

    PubMed

    Ferreira, Lucas C; Craig, Jeffrey M; Hopper, John L; Carrick, Susan E

    2016-08-01

    Twins can help researchers disentangle the roles of genes from those of the environment on human traits, health, and diseases. To realize this potential, the Australian Twin Registry (ATR), University of Melbourne, and the Charles Perkins Centre (CPC), University of Sydney, established a collaboration to form the Twins Research Node, a highly interconnected research facility dedicated specifically to research involving twins. This collaboration aims to foster the adoption of twin designs as important tools for research in a range of health-related domains. The CPC hosted their Twins Research Node's launch seminar entitled 'Double the power of your research with twin studies', in which experienced twin researchers described how twin studies are supporting scientific discoveries and careers. The launch also featured twin pairs who have actively participated in research through the ATR. Researchers at the CPC were surveyed before the event to gauge their level of understanding and interest in utilizing twin research. This article describes the new Twins Research Node, discusses the survey's main results and reports on the launch seminar.

  1. Radio polarimetry of Galactic Centre pulsars

    NASA Astrophysics Data System (ADS)

    Schnitzeler, D. H. F. M.; Eatough, R. P.; Ferrière, K.; Kramer, M.; Lee, K. J.; Noutsos, A.; Shannon, R. M.

    2016-07-01

    To study the strength and structure of the magnetic field in the Galactic Centre (GC), we measured Faraday rotation of the radio emission of pulsars which are seen towards the GC. Three of these pulsars have the largest rotation measures (RMs) observed in any Galactic object with the exception of Sgr A⋆. Their large dispersion measures, RMs and the large RM variation between these pulsars and other known objects in the GC implies that the pulsars lie in the GC and are not merely seen in projection towards the GC. The large RMs of these pulsars indicate large line-of-sight magnetic field components between ˜ 16 and 33 μG; combined with recent model predictions for the strength of the magnetic field in the GC this implies that the large-scale magnetic field has a very small inclination angle with respect to the plane of the sky (˜12°). Foreground objects like the Radio Arc or possibly an ablated, ionized halo around the molecular cloud G0.11-0.11 could contribute to the large RMs of two of the pulsars. If these pulsars lie behind the Radio Arc or G0.11-0.11 then this proves that low-scattering corridors with lengths ≳100 pc must exist in the GC. This also suggests that future, sensitive observations will be able to detect additional pulsars in the GC. Finally, we show that the GC component in our most accurate electron density model oversimplifies structure in the GC.

  2. Environmental Studies at the Guiana Space Centre

    NASA Astrophysics Data System (ADS)

    Richard, Sandrine

    2013-09-01

    The Environmental Commitment of the French Space Agency at the Guiana Space Centre (CNES / CSG) specifies that the environmental protection is a major stake. Consequently, CNES participates in numerous space programs that contribute significantly to a better knowledge, management and protection of our environment at a global scale.The studies and researches that are done at CNES / CSG meet several objectives:* Assessment of safety and environmental effects and risk related to the effects overflowing due to a pollution caused by ground and flight activities* Improvement of the studies related to the knowledge of the environment (flora and fauna monitoring).* Risk assessment and management which may affect the safety of people , property, and protection of public health and environment * Verification of the compliance of the results of impact studies of launch vehicle in flight phase provided by the launch operator (Technical Regulation) with the French Safety Operational Acts.In this note, study and research programs are presented. They allow a better knowledge of the surrounding environment and of impacts caused by the industrial activities done in Guiana Space Center.

  3. Transitional and Transformational Spaces: Mentoring Young Academics through Writing Centres

    ERIC Educational Resources Information Center

    Archer, Arlene; Parker, Shabnam

    2016-01-01

    The effectiveness of writing centre interventions on student writing in higher education has been well-documented in academic literacies studies. This paper changes the focus of investigation from student to consultant and, consequently, explores the way in which an academic writing centre can function as a mentoring environment for young…

  4. Research Informed Science Enrichment Programs at the Gravity Discovery Centre

    ERIC Educational Resources Information Center

    Venville, Grady; Blair, David; Coward, David; Deshon, Fred; Gargano, Mark; Gondwe, Mzamose; Heary, Auriol; Longnecker, Nancy; Pitts, Marina; Zadnik, Marjan

    2012-01-01

    Excursions to museums and science centres generally are great fun for students and teachers. The potential educational benefits beyond enjoyment, however, are rarely realised or analysed for their efficacy. The purpose of this paper is to describe four educational enrichment programs delivered at the Gravity Discovery Centre (GDC), near Gingin,…

  5. Is "Object-Centred Neglect" a Homogeneous Entity?

    ERIC Educational Resources Information Center

    Gainotti, Guido; Ciaraffa, Francesca

    2013-01-01

    The nature of object-centred (allocentric) neglect and the possibility of dissociating it from egocentric (subject-centred) forms of neglect are controversial. Originally, allocentric neglect was described by and in patients who reproduced all the elements of a multi-object scene, but left unfinished the left side of one or more of them. More…

  6. Girls' Groups and Boys' Groups at a Municipal Technology Centre

    ERIC Educational Resources Information Center

    Salminen-Karlsson, Minna

    2007-01-01

    This article describes the Swedish initiative of municipal technology centres from a gender point of view. These centres provide after-school technology education for children aged 6-16. By means of an ethnographic study, the effects of the use of single-sex groups in increasing the interest of girls and boys in technical activities have been…

  7. Family-Centred Practice: Collaboration, Competency and Evidence

    ERIC Educational Resources Information Center

    Espe-Sherwindt, Marilyn

    2008-01-01

    In the 1990s, the developing field of early intervention with young children with disabilities and their families adopted family-centred practice as its philosophical foundation. Family-centred practice includes three key elements: (1) an emphasis on strengths, not deficits; (2) promoting family choice and control over desired resources; and (3)…

  8. Problems and Prospects of Education Resource Centres in Nigeria

    ERIC Educational Resources Information Center

    Ekanem, Johnson Efiong

    2015-01-01

    Nigeria has good policies on Education and one of such policies is the establishment of Education Resource Centres in every State of the Federation, including the Federal Capital Territory, Abuja. The need is clearly articulated in the National Policy on Education. Despite the lofty plan, most of the centres are not fulfilling the need for their…

  9. Science Centres: A Resource for School and Community

    ERIC Educational Resources Information Center

    Pilo, Miranda; Mantero, Alfonso; Marasco, Antonella

    2011-01-01

    We present a science centre established in Genoa on an agreement between Municipality of Genoa and Department of Physics of University of Genoa. The aim is to offer children, young people and community an opportunity to approach science in a playful way. The centre staffs guide the visitors through the exhibits, attracting their interests towards…

  10. Design Considerations for an Intensive Autism Treatment Centre

    ERIC Educational Resources Information Center

    Deochand, Neil; Conway, Alissa A.; Fuqua, R. Wayne

    2015-01-01

    Individuals with autistic spectrum disorder (ASD) who display severe and challenging behaviour sometimes require centre-based intensive applied behaviour analysis (ABA) therapy to meet their health, safety and educational needs. Unfortunately, despite the need for centre-based treatment, there is a paucity of empirical research on building and…

  11. Investigating Teachers' Views of Student-Centred Learning Approach

    ERIC Educational Resources Information Center

    Seng, Ernest Lim Kok

    2014-01-01

    Conventional learning is based on low levels of students' participation where students are rarely expected to ask questions or to challenge the theories of the academic. A paradigm shift in curriculum has resulted in implementing student-centred learning (SCL) approach, putting students as the centre of the learning process. This mode of…

  12. Low-Income Parents' Adult Interactions at Childcare Centres

    ERIC Educational Resources Information Center

    Reid, Jeanne L.; Martin, Anne; Brooks-Gunn, Jeanne

    2017-01-01

    Little is known about the extent and nature of low-income parents' interactions with other parents and staff at childcare centres, despite the potential for these interactions to provide emotional, informational, and instrumental support. This study interviewed 51 parents at three childcare centres in low-income neighbourhoods in New York City.…

  13. A Comprehensive Placement Test Tool for Language Centres

    ERIC Educational Resources Information Center

    Jaime Pastor, Asuncion; Perez Guillot, Cristina; Candel-Mora, Miguel A.

    2012-01-01

    One of the main problems relating to language courses offered at language centres is measuring the students' entry-level skills in a fast, efficient and reliable way. This problem is particularly acute in language centres with large numbers of students, especially at the beginning of the academic year, as a mechanism has to be implemented which…

  14. Leading an Effective Improvement and Development Programme for Children's Centres

    ERIC Educational Resources Information Center

    Weston, Gill; Tyler, Mary

    2015-01-01

    This article reviews the process and achievements of leadership of an improvement and development programme for children's centres in the context of public value and Ofsted inspection. It analyses how the capacity has been developed of children's centre managers to work more strategically and collectively. Distributed leadership theory is applied…

  15. Evaluation of the Training Centre Infrastructure Fund (TCIF). Final Report

    ERIC Educational Resources Information Center

    Human Resources and Skills Development Canada, 2009

    2009-01-01

    The Training Centre Infrastructure Fund (TCIF) was initially announced in Budget 2004 and represented an immediate measure of the broader Workplace Skills Strategy. TCIF was a three-year $25 million pilot project, designed to address the growing need for union-employer training centres to replace aging equipment and simulators that were not up to…

  16. Centre Computer Base for Visually Handicapped Children, Students and Adults.

    ERIC Educational Resources Information Center

    Spencer, S.; And Others

    1987-01-01

    The Centre Computer Base is a list of hardware which can effectively operate the software of the Research Centre for the Education of the Visually Handicapped. Essential hardware contained on the list is described, along with a variety of "add-on" devices such as joysticks, touch-screens, speech synthesizers, braille embossers, etc.…

  17. Examination and Evaluation of Websites of Science Centres in Turkey

    ERIC Educational Resources Information Center

    Bozdogan, Aykut Emre; Bozdogan, Kerem

    2016-01-01

    Science centres which have a considerable importance and functions in developed countries are intended to be popularized in Turkey. At this point considering the fact that the first contact between science centres and visitors is usually provided with websites, it is quite important that the content of these websites should be designed and…

  18. Reducing cooling energy consumption in data centres and critical facilities

    NASA Astrophysics Data System (ADS)

    Cross, Gareth

    Given the rise of our everyday reliance on computers in all walks of life, from checking the train times to paying our credit card bills online, the need for computational power is ever increasing. Other than the ever-increasing performance of home Personal Computers (PC's) this reliance has given rise to a new phenomenon in the last 10 years ago. The data centre. Data centres contain vast arrays of IT cabinets loaded with servers that perform millions of computational equations every second. It is these data centres that allow us to continue with our reliance on the internet and the PC. As more and more data centres become necessary due to the increase in computing processing power required for the everyday activities we all take for granted so the energy consumed by these data centres rises. Not only are more and more data centres being constructed daily, but operators are also looking at ways to squeeze more processing from their existing data centres. This in turn leads to greater heat outputs and therefore requires more cooling. Cooling data centres requires a sizeable energy input, indeed to many megawatts per data centre site. Given the large amounts of money dependant on the successful operation of data centres, in particular for data centres operated by financial institutions, the onus is predominantly on ensuring the data centres operate with no technical glitches rather than in an energy conscious fashion. This report aims to investigate the ways and means of reducing energy consumption within data centres without compromising the technology the data centres are designed to house. As well as discussing the individual merits of the technologies and their implementation technical calculations will be undertaken where necessary to determine the levels of energy saving, if any, from each proposal. To enable comparison between each proposal any design calculations within this report will be undertaken against a notional data facility. This data facility will

  19. Stromal networking: cellular connections in the germinal centre.

    PubMed

    Denton, Alice E; Linterman, Michelle A

    2017-03-17

    Secondary lymphoid organs are organized into distinct zones, governed by different types of mesenchymal stromal cells. These stromal cell subsets are critical for the generation of protective humoral immunity because they direct the migration of, and interaction between, multiple immune cell types to form the germinal centre. The germinal centre response generates long-lived antibody-secreting plasma cells and memory B cells which can provide long-term protection against re-infection. Stromal cell subsets mediate this response through control of immune cell trafficking, activation, localization and antigen access within the secondary lymphoid organ. Further, distinct populations of stromal cells underpin the delicate spatial organization of immune cells within the germinal centre. Because of this, the interactions between immune cells and stromal cells in secondary lymphoid organs are fundamental to the germinal centre response. Herein we review how this unique relationship leads to effective germinal centre responses.

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

    PubMed

    Manes, Taylor A; Rose, Michael J

    2016-06-06

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

  1. Synthesis of [Pt(SnBu(t)3)(IBu(t))(μ-H)]2, a Coordinatively Unsaturated Dinuclear Compound which Fragments upon Addition of Small Molecules to Form Mononuclear Pt-Sn Complexes.

    PubMed

    Koppaka, Anjaneyulu; Yempally, Veeranna; Zhu, Lei; Fortman, George C; Temprado, Manuel; Hoff, Carl D; Captain, Burjor

    2016-01-04

    The reaction of Pt(COD)2 with one equivalent of tri-tert-butylstannane, Bu(t)3SnH, at room temperature yields Pt(SnBu(t)3)(COD)(H)(3) in quantitative yield. In the presence of excess Bu(t)3SnH, the reaction goes further, yielding the dinuclear bridging stannylene complex [Pt(SnBu(t)3)(μ-SnBu(t)2)(H)2]2 (4). The dinuclear complex 4 reacts rapidly and reversibly with CO to furnish [Pt(SnBu(t)3)(μ-SnBu(t)2)(CO)(H)2]2 (5). Complex 3 reacts with N,N'-di-tert-butylimidazol-2-ylidene, IBu(t), at room temperature to give the dinuclear bridging hydride complex [Pt(SnBu(t)3)(IBu(t))(μ-H)]2 (6). Complex 6 reacts with CO, C2H4, and H2 to give the corresponding mononuclear Pt complexes Pt(SnBu(t)3)(IBu(t))(CO)(H)(7), Pt(SnBu(t)3)(IBu(t))(C2H4)(H)(8), and Pt(SnBu(t)3)(IBu(t))(H)3 (9), respectively. The reaction of IBu(t) with the complex Pt(SnBu(t)3)2(CO)2 (10) yielded an abnormal Pt-carbene complex Pt(SnBu(t)3)2(aIBu(t))(CO) (11). DFT computational studies of the dimeric complexes [Pt(SnR3)(NHC)(μ-H)]2, the potentially more reactive monomeric complexes Pt(SnR3)(NHC)(H) and the trihydride species Pt(SnBu(t)3)(IBu(t))(H)3 have been performed, for NHC = IMe and R = Me and for NHC = IBu(t) and R = Bu(t). The structures of complexes 3-8 and 11 have been determined by X-ray crystallography and are reported.

  2. Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

    PubMed

    Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

    2016-02-24

    Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

  3. Mixed chloride/phosphine complexes of the dirhenium core. 10. Redox reactions of an edge-sharing dirhenium(III) non-metal-metal-bonded complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4).

    PubMed

    Cotton, F A; Dikarev, E V; Petrukhina, M A

    2001-12-17

    Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of 1 with 1 and 2 equiv of KC(8) result in an unusual face-sharing complex having an Re(2)(5+) core, Re(2)(mu-Cl)(3)Cl(2)(PMe(3))(4) (2), and a triply bonded Re(II) compound, 1,2,7,8-Re(2)Cl(4)(PMe(3))(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re(2)(4+) core, [Bu(n)()(4)N][1,2,7-Re(2)Cl(5)(PMe(3))(3)] (4). Oxidation of 1 with NOBF(4) yields a Re(IV) mononuclear compound, trans-ReCl(4)(PMe(3))(2) (5). Two isomers of the monomeric Re(III) anion, [ReCl(4)(PMe(3))(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) A is relatively short. The metal-metal bond length in anion 4 of 2.2354(7) A is consistent with the usual values for the triply bonded Re(2)(4+) core compounds. In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.

  4. Three new europium(III) methanetriacetate metal-organic frameworks: the influence of synthesis on the product topology.

    PubMed

    Cañadillas-Delgado, Laura; Fabelo, Oscar; Pasán, Jorge; Déniz, Mariadel; Martínez-Benito, Carla; Díaz-Gallifa, Pau; Martín, Tomás; Ruiz-Pérez, Catalina

    2014-02-01

    Three new metal-organic framework structures containing Eu(III) and the little explored methanetriacetate (C7H7O6(3-), mta(3-)) ligand have been synthesized. Gel synthesis yields a two-dimensional framework with the formula [Eu(mta)(H2O)3]n·2nH2O, (I), while two polymorphs of the three-dimensional framework material [Eu(mta)(H2O)]n·nH2O, (II) and (III), are obtained through hydrothermal synthesis at either 423 or 443 K. Compounds (I) and (II) are isomorphous with previously reported Gd(III) compounds, but compound (III) constitutes a new phase. Compound (I) can be described in terms of dinuclear [Eu2(H2O)4](6+) units bonded through mta(3-) ligands to form a two-dimensional framework with topology corresponding to a (6,3)-connected binodal (4(3))(4(6)6(6)8(3))-kgd net, where the dinuclear [Eu2(H2O)4](6+) units are considered as a single node. Compounds (II) and (III) have distinct three-dimensional topologies, namely a (4(12)6(3))(4(9)6(6))-nia net for (II) and a (4(10)6(5))(4(11)6(4))-K2O2; 36641 net for (III). The crystal density of (III) is greater than that of (II), consistent with the increase of temperature, and thereby autogeneous pressure, in the hydrothermal synthesis.

  5. Rediscovering the Teacher within Indian Child-Centred Pedagogy: Implications for the Global Child-Centred Approach

    ERIC Educational Resources Information Center

    Smail, Amy

    2014-01-01

    The Child-Centred Approach (CCA) is increasingly promoted within India and internationally as a response to the challenge of delivering quality education. From identifying and examining Indian indigenous and global concepts of CCA within traditional and contemporary child-centred pedagogic discourse, this paper reveals the complexities of…

  6. Direct comparison of 3-centre and 4-centre HBr elimination pathways in methyl-substituted vinyl bromides.

    PubMed

    Pandit, Shubhrangshu; Hornung, Balázs; Orr-Ewing, Andrew J

    2016-10-12

    Elimination of HBr from UV-photoexcited vinyl bromides can occur through both 3-centre and 4-centre transition states (TSs). The competition between these pathways is examined using velocity map imaging of HBr (v = 0-2, J) photofragments. The three vinyl bromides chosen for study have methyl substituents that block either the 3-centre or the 4-centre TS, or leave both pathways open. The kinetic energy distributions extracted from velocity map images of HBr from 193 nm photolysis of the three vinyl bromide compounds are approximately described by a statistical model of energy disposal among the degrees of freedom of the photoproducts, and are attributed to dissociation on the lowest electronic state of the molecule after internal conversion. Dissociation via the 4-centre TS gives greater average kinetic energy release than for the 3-centre TS pathway. The resonance enhanced multi-photon ionization (REMPI) schemes used to detect HBr restrict measurements to J ≤ 7 for v = 2 and J ≤ 15 for v = 0. Within this spectroscopic range, the HBr rotational temperature is colder for the 4-centre than for the 3-centre elimination pathway. Calculations of the intrinsic reaction coordinates and RRKM calculations of HBr elimination rate coefficients provide mechanistic insights into the competition between the pathways.

  7. The "magic" of tutorial centres in Hong Kong: An analysis of media marketing and pedagogy in a tutorial centre

    NASA Astrophysics Data System (ADS)

    Koh, Aaron

    2014-12-01

    Why do more than three-quarters of Hong Kong's senior secondary students flock to tutorial centres like moths to light? What is the "magic" that is driving the popularity of the tutorial centre enterprise? Indeed, looking at the ongoing boom of tutorial centres in Hong Kong (there are almost 1,000 of them), it is difficult not to ask these questions. This paper examines the phenomenon of tutorial centres in Hong Kong and seeks to understand what draws students to these centres. Combining theories of marketing semiotics and emotion studies, the author investigates the pivotal role of media marketing in generating the "magic" of tutorial centres, whose advertising strategy includes, for example, a display of billboard posters featuring stylishly-dressed "celebrity teachers". The author reviews some of the literature available on the subject of tutorial centres. In a case study approach, he then maps out the pedagogy he observed in an English tutorial class, seeking heuristic insights into the kind of teaching students in the study were looking for. He argues that part of the "magical" attraction of what are essentially "cram schools" is their formulaic pedagogy of teaching and reinforcing exam skills. Finally, the paper considers the social implications of the tutorial centre industry in terms of media marketing of education and unequal access to tutorial services.

  8. Student-Centred and Teacher-Centred Learning Environment in Pre-Vocational Secondary Education: Psychological Needs, and Motivation

    ERIC Educational Resources Information Center

    Smit, Karin; de Brabander, Cornelis J.; Martens, Rob L.

    2014-01-01

    In this study the perception of psychological needs and motivation in a student-centred and a teacher-centred learning environment are compared, using Self Determination Theory as a framework. The self-report Intrinsic Motivation Inventory was completed by 230 students (mean age 16.1 years) in pre-vocational secondary education. School records on…

  9. A rare tetranuclear thorium(IV) μ4 -oxo cluster and dinuclear thorium(IV) complex assembled by carbon-oxygen bond activation of 1,2-dimethoxyethane (DME).

    PubMed

    Travia, Nicholas E; Scott, Brian L; Kiplinger, Jaqueline L

    2014-12-15

    The synthesis and X-ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ4 -oxo cluster complex Th4 (μ4 -O)(μ-Cl)2 I6 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]6 and the dinuclear complex Th2 I5 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]3 (DME) (DME=dimethoxyethane) are formed by CO bond activation of 1,2-dimethoxyethane (DME) mediated by thorium iodide complexes.

  10. Rapid three-step cleavage of RNA and DNA model systems promoted by a dinuclear Cu(II) complex in methanol. energetic origins of the catalytic efficacy.

    PubMed

    Lu, Zhong-Lin; Liu, C Tony; Neverov, Alexei A; Brown, R Stan

    2007-09-19

    A dinuclear Cu(II) complex of 1,3-bis-N(1)-(1,5,9-triazacyclododecyl)propane with an associated methoxide (2-Cu(II)(2):(-OCH(3))) was prepared, and its kinetics of reaction with an RNA model (2-hydroxypropyl-p-nitrophenyl phosphate (1, HPNPP)) and two DNA models (methyl p-nitrophenyl phosphate (3) and iso-butyl p-chlorophenyl phosphate (4)) were studied in methanol solution at (s)(s)pH 7.2 +/- 0.2. X-ray diffraction structures of 2-Cu(II)(2):(-OH)(H(2)O)(CF(3)SO(3)-)(3):0.5CH(3)CH(2)OCH(2)CH(3) and 2-Cu(II)(2):(-OH)((C(6)H(5)CH(2)O)(2)PO(2)-)(CF(3)SO(3)-)2 show the mode of coordination of the bridging -OH and H(2)O between the two Cu(II) ions in the first complex and bridging -OH and phosphate groups in the second. The kinetic studies with 1 and 3 reveal some common preliminary steps prior to the chemical one of the catalyzed formation of p-nitrophenol. With 3, and also with the far less reactive substrate (4), two relatively fast events are cleanly observed via stopped-flow kinetics. The first of these is interpreted as a binding step which is linearly dependent on [catalyst] while the second is a unimolecular step independent of [catalyst] proposed to be a rearrangement that forms a doubly Cu(II)-coordinated phosphate. The catalysis of the cleavage of 1 and 3 is very strong, the first-order rate constants for formation of p-nitrophenol from the complex being approximately 0.7 s(-1) and 2.4 x 10(-3) s(-1), respectively. With substrate 3, 2-Cu(II)(2):(-OCH(3)) exhibits Michaelis-Mentin kinetics with a k(cat)/K(M) value of 30 M(-1) s(-1) which is 3.8 x 10(7)-fold greater than the methoxide promoted reaction of 3 (7.9 x 10(-7) M(-1) s(-1)). A free energy calculation indicates that the binding of 2-Cu(II)(2):(-OCH(3)) to the transition states for 1 and 3 cleavage stabilizes them by -21 and -24 kcal/mol, respectively, relative to that of the methoxide promoted reactions. The results are compared with a literature example where the cleavage of 1 in water is promoted by

  11. Immunoglobulin negative follicle centre cell lymphoma.

    PubMed Central

    Gregg, E. O.; Al-Saffar, N.; Jones, D. B.; Wright, D. H.; Stevenson, F. K.; Smith, J. L.

    1984-01-01

    Immunoglobulin (Ig) could not be detected on the surface or in the cytoplasm of neoplastic cells from five cases of follicle centre cell lymphoma with centroblastic/centrocytic follicular histology when examined by immunohistology of frozen or wax embedded sections. Examination by fluorescein labelled antibodies of cells in suspensions prepared from the biopsies revealed a monotypic surface Ig positive population in one case and a surface or cytoplasmic Ig kappa:lambda light chain imbalance in a further two cases consistent with neoplastic B cell involvement: in all cases the proportion of cells failing to express Ig or T cell markers ranged from 24 to 75%. The monoclonal antibodies B1 (Pan B cell), FMC4 (HLA class II) and J5 (cALL antigen) stained the majority of cells in suspension with residual cells staining with UCHT1 or OKT11 (T cell monoclonal antibodies). In frozen sections, neoplastic follicular cells did not stain with UCHT1. However, in the one case tested these cells stained with the antibodies B1 and FMC4. In paraffin sections J chain could be demonstrated in the cytoplasm of three out of five cases. Cells from four cases were cultured in vitro for Ig production: two failed to produce Ig and monotypic light chains were the sole Ig product of the remaining two cases. The failure to express Ig by the majority of the neoplastic cells from the cases described in this report is at variance with the follicular histology of these neoplasms. Mechanisms responsible for this failure are discussed with reference to current models of B cell differentiation. Images Figure 1 PMID:6437429

  12. Safe motherhood partners -- the International Children's Centre.

    PubMed

    1994-01-01

    The International Children's Centre (ICC) works worldwide to improve child health in the least developed countries. In its training and research projects the agency contributes to the Safe Motherhood Initiative to improve the health of mothers and infants. ICC is based in Paris, it was established in 1949, and the agency has cooperated with governments, nongovernmental organizations and international bodies like the World Health Organization (WHO) in child care. ICC's activities reflect concern for the health of women before and during pregnancy and the rest of their lives. The center's work comprises training, research, local projects, and information and documentation. Following the 1987 Nairobi conference on safe motherhood, ICC organized a seminar in Paris on maternal mortality in Sub-Saharan francophone Africa, which led to participation in the Safe Motherhood Initiative with a variety of training and research programs. ICC training is integrated, community-based, and multidisciplinary. Anthropology, psychology, economics and management have played a role in ICC training courses. The center runs an international course on maternal and child health from January to April each year and also organizes distance training courses on problem solving in health care. ICC training programs have taken place in Laos, Senegal, and Vietnam to strengthen the work of maternal and child health training centers there. A 4-week course on economic evaluation of health programs is held in Paris each July. In 1989 and 1990, ICC organized in collaboration with WHO safe motherhood workshops on research methodology in Benin and in Burkina Faso with participants from 6 francophone African countries. One research project in Benin is on risk factors for maternal and perinatal mortality and morbidity, and the other in Cameroon on improving surveillance of pregnancy, delivery, and the postnatal period. ICC focuses on long-term planning and action for the benefit of mothers and children.

  13. New roles for poison control centres in the developing countries.

    PubMed

    Laborde, Amalia

    2004-05-20

    The primary mission of poison control centres has always been an improvement in the poisoned patients' care and poison prevention. The need to reach this mission implies that many functions and roles must be accomplished. Many centres, even in developing countries, are multifunctional and provide a broad toxicological information service. However, the main challenges of poison centres in developing countries are still treatment information, formal training, laboratory services accessibility and availability of antidotes. At the same time poison centres from developing countries need to accomplish their public health mission through strengthening and expansion of some well-defined roles like toxico-surveillance and environmental health monitoring according to the prevailing and future toxicological problems. Poison control centres from developing countries continue to face old challenges but cannot ignore the new ones that appear in the globalised world. Poison centres have a vital role for environmental exposure surveillance systems for sentinel event detection. Poison centres offer real-time and continuous data needed for preparation and response during such events and also offer a means to report health concerns. Centres from South America were involved in some of the most important environmental health problems of the region e.g., lead contamination (children), children 'occupational' poisoning, and flour contamination with fusarium toxins. Furthermore, poison centres can be the markers of risk factors or identifiers of vulnerable population e.g., changes in drugs prescription patterns, unusual patterns of addiction, unexpected product uses, children abuse scenarios or undetected sources of environmental contamination. In an era of evidence-based medicine and research, toxico-vigilance based on the millions of cases registered by poison centres everyday acquires more and more importance. A new approach of the toxico-vigilance and preventive roles of poison

  14. In vitro DNA binding profile of enantiomeric dinuclear Cu(II)/Ni(II) complexes derived from l-/d-histidine-terepthaldehyde reduced Schiff base as potential chemotherapeutic agents.

    PubMed

    Yousuf, Imtiyaz; Arjmand, Farukh

    2016-11-01

    New chiral reduced Schiff base ligands, L1 and L2 derived from l-/d-histidine and terepthaldehyde, and their Cu(II) and Ni(II) dinuclear complexes 1 &2 (a and b) were synthesized and thoroughly characterized by various spectroscopic techniques. Comparative binding profile of both l-/d-enantiomeric Cu(II) and Ni(II) complexes with ct-DNA was studied by employing optical and spectroscopic techniques to evaluate their enantiopreferential selectivity towards molecular target DNA and thereby explore their relative chemotherapeutic potential. Quantitative assessment of DNA binding propensity was ascertained by calculating Kb, K and Ksv values of 1 &2 (a and b) which demonstrated higher binding affinity of l-enantiomeric Cu(II) complex, 1a and followed the order as 1a>1b>2a>2b. Scanning electron microscopy (SEM) was used to analyze the morphological changes of the DNA condensate in presence of complexes 1 (a and b). The SEM micrographs condensates revealed morphological transitions and formation of different structural features implicating the condensation process between the complexes and biomolecule occurred to form compact massive structures. The gel electrophoretic assay of complex 1a was carried out with pBR322 plasmid DNA which revealed an efficient cleaving ability of the complex via oxidative pathway with the involvement of singlet oxygen ((1)O2) and the superoxide anion (O2(•-)) radicals as the ROS responsible the cleavage reactions. Molecular docking studies of 1 (a and b) with DNA revealed selective recognition of G-C residues of the narrow minor groove of the DNA duplex and complex 1a demonstrated binding affinity towards DNA ascertained from its higher binding energy values. Furthermore, the cytotoxic assessment of 1a was examined on a panel of cancer cell lines of different histological origin employing SRB assay which revealed remarkably good cytotoxic activity towards HL60, HeLa and MCF7 cancer cell lines.

  15. Spectral and structural characterization of amidate-bridged platinum-thallium complexes with strong metal-metal bonds.

    PubMed

    Chen, Wanzhi; Liu, Fenghui; Matsumoto, Kazuko; Autschbach, Jochen; Le Guennic, Boris; Ziegler, Tom; Maliarik, Mikhail; Glaser, Julius

    2006-05-29

    The reactions of [Pt(NH3)2(NHCOtBu)2] and TlX3 (X = NO3-, Cl-, CF3CO2-) yielded dinuclear [{Pt(ONO2)(NH3)2(NHCOtBu)}Tl(ONO2)2(MeOH)] (2) and trinuclear complexes [{PtX(RNH2)2(NHCOtBu)2}2Tl]+ [X = NO3- (3), Cl- (5), CF3CO2- (6)], which were spectroscopically and structurally characterized. Strong Pt-Tl interaction in the complexes in solutions was indicated by both 195Pt and 205Tl NMR spectra, which exhibit very large one-bond spin-spin coupling constants between the heteronuclei (1J(PtTl)), 146.8 and 88.84 kHz for 2 and 3, respectively. Both the X-ray photoelectron spectra and the 195Pt chemical shifts reveal that the complexes have Pt centers whose oxidation states are close to that of Pt(III). Characterization of these complexes by X-ray diffraction analysis confirms that the Pt and Tl atoms are held together by very short Pt-Tl bonds and are supported by the bridging amidate ligands. The Pt-Tl bonds are shorter than 2.6 Angstrom, indicating a strong metal-metal attraction between these two metals. Compound 2 was found to activate the C-H bond of acetone to yield a platinum(IV) acetonate complex. This reactivity corresponds to the property of Pt(III) complexes. Density functional theory calculations were able to reproduce the large magnitude of the metal-metal spin-spin coupling constants. The couplings are sensitive to the computational model because of a delicate balance of metal 6s contributions in the frontier orbitals. The computational analysis reveals the role of the axial ligands in the magnitude of the coupling constants.

  16. Type I photosynthetic reaction centres: structure and function.

    PubMed Central

    Heathcote, Peter; Jones, Michael R; Fyfe, Paul K

    2003-01-01

    We review recent advances in the study of the photosystem I reaction centre, following the determination of a spectacular 2.5 A resolution crystal structure for this complex of Synechococcus elongatus. Photosystem I is proving different to type II reaction centres in structure and organization, and the mechanism of transmembrane electron transfer, and is providing insights into the control of function in reaction centres that operate at very low redox potentials. The photosystem I complex of oxygenic organisms has a counterpart in non-oxygenic bacteria, the strictly anaerobic phototrophic green sulphur bacteria and heliobacteria. The most distinctive feature of these type I reaction centres is that they contain two copies of a large core polypeptide (i.e. a homodimer), rather than a heterodimeric arrangement of two related, but different, polypeptides as in the photosystem I complex. To compare the structural organization of the two forms of type I reaction centre, we have modelled the structure of the central region of the reaction centre from green sulphur bacteria, using sequence alignments and the structural coordinates of the S. elongatus Photosystem I complex. The outcome of these modelling studies is described, concentrating on regions of the type I reaction centre where important structure-function relationships have been demonstrated or inferred. PMID:12594931

  17. Native NIR-emitting single colour centres in CVD diamond

    NASA Astrophysics Data System (ADS)

    Gatto Monticone, D.; Traina, P.; Moreva, E.; Forneris, J.; Olivero, P.; Degiovanni, I. P.; Taccetti, F.; Giuntini, L.; Brida, G.; Amato, G.; Genovese, M.

    2014-05-01

    Single-photon sources are a fundamental element for developing quantum technologies, and sources based on colour centres in diamonds are among the most promising candidates. The well-known nitrogen vacancy centres are characterized by several limitations, and thus few other defects have recently been considered. In the present work, we characterize, in detail, native efficient single colour centres emitting in the near infra-red (λ = 740-780 nm) in both standard IIa single-crystal and electronic-grade polycrystalline commercial chemical vapour deposited (CVD) diamond samples. In the former case, a high-temperature (T > 1000 °C) annealing process in vacuum is necessary to induce the formation/activation of luminescent centres with good emission properties, while in the latter case the annealing process has marginally beneficial effects on the number and performance of native centres in commercially available samples. Although displaying significant variability in several photo-physical properties (emission wavelength, emission rate instabilities, saturation behaviours), these centres generally display appealing photophysical properties for applications as single photon sources: short lifetimes (0.7-3 ns), high emission rates (˜50-500 × 103 photons s-1) and strongly (>95%) polarized light. The native centres are tentatively attributed to impurities incorporated in the diamond crystal during the CVD growth of high-quality type-IIa samples, and offer promising perspectives in diamond-based photonics.

  18. Self-aggregated dinuclear lanthanide(III) complexes as potential bimodal probes for magnetic resonance and optical imaging.

    PubMed

    Regueiro-Figueroa, Martín; Nonat, Aline; Rolla, Gabriele A; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Charbonnière, Loïc J; Botta, Mauro; Platas-Iglesias, Carlos

    2013-08-26

    Homodinuclear lanthanide complexes (Ln = La, Eu, Gd, Tb, Yb and Lu) derived from a bis-macrocyclic ligand featuring two 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetic acid chelating sites linked by a 2,6-bis(pyrazol-1-yl)pyridine spacer (H2L(3)) were prepared and characterized. Luminescence lifetime measurements recorded on solutions of the Eu(III) and Tb(III) complexes indicate the presence of one inner-sphere water molecule coordinated to each metal ion in these complexes. The overall luminescence quantum yields were determined (ϕ H2O = 0.01 for [Eu2(L(3))] and 0.50 for [Tb2(L(3))] in 0.01 M TRIS/HCl, pH 7.4; TRIS = tris(hydroxymethyl)aminomethane), pointing to an effective sensitization of the metal ion by the bispyrazolylpyridyl unit of the ligand, especially with Tb. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd2(L(3))] are characteristic of slowly tumbling systems, showing a low-field plateau and a broad maximum around 30 MHz. This suggests the occurrence of aggregation of the complexes giving rise to slowly rotating species. A similar behavior is observed for the analogous Gd(III) complex containing a 4,4'-dimethyl-2,2'-bipyridyl spacer ([Gd2(L(1))]). The relaxivity of [Gd2(L(3))] recorded at 0.5 T and 298 K (pH 6.9) amounts to 13.7 mM(-1)  s(-1). The formation of aggregates has been confirmed by dynamic light scattering (DLS) experiments, which provided mean particle sizes of 114 and 38 nm for [Gd2(L(1))] and [Gd2(L(3))], respectively. TEM images of [Gd2(L(3))] indicate the formation of nearly spherical nanosized aggregates with a mean diameter of about 41 nm, together with some nonspherical particles with larger size.

  19. Unusual dinuclear and mononuclear cyclometalated iridium complexes of 2,5-diaryl-1,3,4-oxadiazole derivatives.

    PubMed

    Zheng, Yonghao; Batsanov, Andrei S; Bryce, Martin R

    2011-04-18

    A family of new 2,5-diphenyl-1,3,4-oxadiazole (OXD) derivatives 8-11 bearing ortho-alkyl substituents on one of the phenyl rings is reported. The reactions of these OXDs with IrCl(3) under standard cyclometalating conditions did not give the usual μ-dichloro bridged diiridium OXD complexes. Instead, the novel diiridium complexes 12-14 and the monoiridium complex 15 were isolated and characterized by X-ray crystallography. It is proposed that the unusual structures arise because of the ortho-alkyl substituents leading to a substantial twisting of part of the OXD system which, for steric reasons, changes the normal course of the metal-ligand coordination reactions. Subsequent reactions of 13 and 15 gave the mononuclear complexes 16-18 with acac and picolinate anciliary ligands. The crystal structures of 16 and 18 are reported. Photoluminescence is observed in the green (16) and blue-green regions (17 and 18) at room temperature. Complexes 16-18 are phosphorescent at low temperature, with triplet lifetimes of 4.2-5.7 μs at 77 K.

  20. The conformation effect of the diamine bridge on the stability of dinuclear platinum(II) complexes and their hydrolysis.

    PubMed

    Esteves, Lucas F; Dos Santos, Hélio F; Costa, Luiz Antônio S

    2015-09-01

    In this paper, the hydrolysis process of a bisplatinum complex containing the flexible chain 1,6-hexanediamine between the two metal centers was investigated through the use of density functional theory (DFT) with the analysis of the role of the spacing group arrangement on the values of free energy activation barrier. All structures were fully optimized in aqueous solution using implicit model for solvent at DFT level. The energy profiles for the hydrolysis reaction were determined by using the supermolecule approach. Five transition states were proposed differing by the conformation of the bridge group, and the activation free energy calculated as a weighted average within the selected forms. The Gibbs population for reactant was used as a statistical weight leading to the predicted value of 23.1kcalmol(-1), in good accordance with experiment, 23.8kcalmol(-1). Our results suggests that for 1,6-hexanediamine bridge ligand, the extend forms with average torsional angle over the carbon chain larger than 130° have the greatest contribution to the hydrolysis kinetics. The results presented here point out that the hydrolysis mechanism might follow different paths for each conformation and each of these contributes to the observed energy barrier.

  1. A density functional theory study of the magnetic exchange coupling in dinuclear manganese(II) inverse crown structures.

    PubMed

    Vélez, Ederley; Alberola, Antonio; Polo, Víctor

    2009-12-17

    The magnetic exchange coupling constants between two Mn(II) centers for a set of five inverse crown structures have been investigated by means of a methodology based on broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic "guests" such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands and alkali metals (Na, Li). Magnetic exchange couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via an oxygen atom or hydride and very small antiferromagnetic couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide an understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.

  2. Defect centres and thermoluminescence in SrS : Bi phosphor

    NASA Astrophysics Data System (ADS)

    Singh, V.; Tiwari, M.; Rao, T. K. G.

    2004-11-01

    Thermoluminescence (TL) and electron spin resonance studies have been carried out on SrS:Bi phosphor. The TL glow curve is broad and indicates a dominant peak at 120 degrees C with two additional peaks, not clearly resolved, appearing as shoulders at around 180 and 250 degrees C. Two defect centres are observed at room temperature. One of them is characterized by an isotropic g-value 2.0034 and is assigned to an F+ centre. Step annealing measurements indicate a possible association between the F+ centre and the three TL peaks.

  3. Staff concerns in heroin-assisted treatment centres.

    PubMed

    Demaret, I; Lemaître, A; Ansseau, M

    2012-08-01

    Heroin-assisted treatment (HAT) is a solution for improving the condition of treatment-resistant heroin addicts. Since 1994, six randomized controlled trials have concluded that HAT is more efficacious than oral methadone for severe heroin addicts. We visited seven HAT treatment centres in four countries in order to observe diacetylmorphine (DAM) administration and to study the main concerns of the staff. Nurses were concerned by the risk taken if a previously intoxicated patient received his dose of DAM. Another concern was the smuggling of DAM doses. The HAT centres face a dilemma: treating patients while at the same time allowing their risky street habits in the centre.

  4. L'asthme allergique au centre tunisien

    PubMed Central

    Joobeur, Samah; Mhamed, Saousen Cheikh; Saad, Ahmed Ben; Mribah, Hathami; Dekhil, Asma; Rouatbi, Naceur; El Kamel, Ali

    2015-01-01

    L'asthme allergique pose un réel problème de santé publique vu sa prévalence et son coût de prise en charge élevés. Etudier le profil clinique, fonctionnel respiratoire, allergologique, thérapeutique et évolutif de l'asthme allergique dans une région du centre tunisien. Etude rétrospective portant sur 1132 dossiers de patients porteurs d'asthme allergique suivis dans le service de pneumologie et d'allergologie à l'hôpital de Monastir (Tunisie). L’âge moyen est de 27 ± 12,5 ans. 61,1% des patients sont âgés entre 16 et 39 ans. Une prédominance féminine est notée (56,7%). L'identification de l'allergène en cause s'est basée essentiellement sur les tests cutanés allergologiques (99,4%). Les principaux pneumallergènes identifiés sont les acariens (91,2%), suivis par les pollens (22,8%) et les phanères des animaux (12%). La classification selon la sévérité a conclu à un asthme intermittent à persistant léger chez 87.1% de nos patients. Le traitement s'est basé essentiellement sur la corticothérapie inhalée (67,6%). L'asthme dans notre étude a été jugé contrôlé dans 68,3% des cas, partiellement contrôlé dans 24,8% et non contrôlé dans 6,9% des cas. L'asthme allergique est une affection répandue qui touche essentiellement le sujet jeune en pleine activité. Une prise en charge adéquate permet de contrôler la maladie et de réduire ses répercussions sur le patient et la collectivité. PMID:26097637

  5. An enhanced Planetary Radar Operating Centre (PROC)

    NASA Astrophysics Data System (ADS)

    Catallo, C.

    2010-12-01

    Planetary exploration by means of radar systems, mainly using GPRs is an important role of Italy and numerous scientific international space programs are carried out jointly with ESA and NASA by Italian Space Agency, the scientific community and the industry. Three experiments under Italian leadership ( designed and manufactured by the Italian industry) provided by ASI within a NASA/ESA/ASI joint venture framework are successfully operating: MARSIS on-board MEX, SHARAD on-board MRO and CASSINI Radar on-board Cassini spacecraft: the missions have been further extended . Three dedicated operational centers, namely SHOC, (Sharad Operating Centre), MOC (Marsis Operating Center) and CASSINI PAD are operating from the missions beginning to support all the scientific communities, institutional customers and experiment teams operation Each center is dedicated to a single instrument management and control, data processing and distribution and even if they had been conceived to operate autonomously and independently one from each other, synergies and overlaps have been envisaged leading to the suggestion of a unified center, the Planetary Radar Processing Center (PROC). In order to harmonize operations either from logistics point of view and from HW/SW capabilities point of view PROC is designed and developed for offering improved functionalities to increase capabilities, mainly in terms of data exchange, comparison, interpretation and exploitation. PROC is, therefore, conceived as the Italian support facility to the scientific community for on-going and future Italian planetary exploration programs, such as Europa-Jupiter System Mission (EJSM) The paper describes how the new PROC is designed and developed, to allow SHOC, MOC and CASSINI PAD to operate as before, and to offer improved functionalities to increase capabilities, mainly in terms of data exchange, comparison, interpretation and exploitation aiding scientists to increase their knowledge in the field of surface

  6. PROC: a new Planetary Radars Operating Centre

    NASA Astrophysics Data System (ADS)

    Catallo, C.; Alberti, G.; Flamini, E.; Olivieri, A.; Orosei, R.

    2009-12-01

    Planetary exploration by means of radar systems, mainly using Ground Penetrating Radars (GPR) is an important role of Italy and numerous scientific international space programs are carried out jointly with ESA and NASA by Italian Space Agency, the scientific community and the industry. Actually three important experiments under Italian leadership ( designed and manufactured by the Italian industry) provided by ASI within a NASA/ESA/ASI joint venture framework are operating in the frame of an extended missions : MARSIS on-board Mars Express, SHARAD on-board Mars Reconnaissance Orbiter and CASSINI Radar on-board Cassini spacecraft. Three dedicated operational centers, namely SHOC, (Sharad Operating Centre), MOC (Marsis Operating Center) and CASSINI PAD are operating from the starting of the missions in order In order to support all the scientific communities, institutional customers and experiment teams operation Each center is dedicated to a single instrument management and control, data processing and distribution and even if they had been conceived to operate autonomously and independently one from each other, synergies and overlaps have been envisaged leading to the suggestion of a unified center, the Planetary Radar Processing Center (PROC). In order to harmonize operations either from logistics point of view and from HW/SW capabilities point of view PROC is designed and developed for offering improved functionalities to increase capabilities, mainly in terms of data exchange, comparison, interpretation and exploitation. PROC is, therefore, conceived as the Italian support facility to the scientific community for on-going and future Italian planetary exploration programs, such as Europa-Jupiter System Mission (EJSM) The paper describes how PROC is designed and developed, to allow SHOC, MOC and CASSINI PAD to operate as before, and to offer improved functionalities to increase capabilities, mainly in terms of data exchange, comparison, interpretation and

  7. Metal inks

    DOEpatents

    Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

    2014-02-04

    Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

  8. A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes.

    PubMed

    Reiher, Markus; Kirchner, Barbara; Hutter, Jürg; Sellmann, Dieter; Hess, Bernd Artur

    2004-09-20

    A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi* orbital upon electronic excitation from the singlet ground state S0 to the first excited singlet state S1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S1 state and approaches its minimum structure in the S1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These protonated thiolate functionalities bring protons close to the dinitrogen moiety. Because protonation does not change the pi*-antibonding character of the LUMO, the universal and well-directed character of the photochemical activation process makes it possible to protonate the dinitrogen complex before it is irradiated. The pi*-antibonding LUMO plays the central role in the activation process, since the diazenoid structure was obtained by excitation from various occupied orbitals as well as by a direct two-electron reduction (without photochemical activation) of the complex; that is, the important bending of N2 towards a diazenoid conformation can be achieved by populating the pi*-antibonding LUMO.

  9. Addiction Research Centres and the Nurturing of Creativity. Substance abuse research in a modern health care centre: the case of the Centre for Addiction and Mental Health.

    PubMed

    Rehm, Jürgen; Giesbrecht, Norman; Gliksman, Louis; Graham, Kathryn; Le, Anh D; Mann, Robert E; Room, Robin; Rush, Brian; Tyndale, Rachel F; Wells, Samantha

    2011-04-01

    The Centre for Addiction and Mental Health is one of the premier centres for research related to substance use and addiction. This research began more than 50 years ago with the Addiction Research Foundation (ARF), an organization that contributed significantly to knowledge about the aetiology, treatment and prevention of substance use, addiction and related harm. After the merger of the ARF with three other institutions in 1998, research on substance use continued, with an additional focus on comorbid substance use and other mental health disorders. In the present paper, we describe the structure of funding and organization and selected current foci of research. We argue for the continuation of this successful model of integrating basic, epidemiological, clinical, health service and prevention research under the roof of a health centre.

  10. Regional Centres for Space Science and Technology Education and ICG Information Centres affiliated to the United Nations

    NASA Astrophysics Data System (ADS)

    Gadimova, S.; Haubold, H. J.

    2009-06-01

    Based on resolutions of the United Nations General Assembly, Regional Centres for Space Science and Technology Education were established in India, Morocco, Nigeria, Brazil and Mexico. Simultaneously, education curricula were developed for the core disciplines of remote sensing, satellite communications, satellite meteorology, and space and atmospheric science. This paper provides a brief summary on the status of the operation of the regional centres with a view to use them as information centres of the International Committee on Global Navigation Satellite Systems (ICG), and draws attention to their educational activities.

  11. Dinuclear Cu(II) complexes of compartmental Schiff base ligands formed from unsymmetrical tripodal amines of varying arm lengths: Crystal structure of [Cu2L1](ClO4)2 and theoretical studies

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Sayin, Koray

    2016-05-01

    Three new dinuclear copper complexes were synthesized via condensation reaction of three new unsymmetrical N-capped tripodal amines and 2,6-diformyl-4-methylphenol, in the presence of copper(II) perchlorate. The solid-state structure of the dinuclear complex, [Cu2L1](ClO4)2, has been determined by X-ray crystallography, showing that the CuII centers have distorted square-pyramidal geometry with N3O2 coordination. The copper (II) ions are bridged by phenolic and hydroxyalkyl groups when in both cases, deprotonation of the hydrogen atoms of the OH groups occurs. The distance between the copper atoms is 3.062 Å. This compound consists of the dication [Cu2L1]2+ and two ClO4- anions in which one of ClO4- groups has a week interaction with one of the Cu atoms. All complexes were characterized by a variety of physico-chemical techniques such as elemental analyses, IR, mass spectra, conductivity measurements and electronic spectral studies. Computational investigation of mentioned binuclear Cu(II) complexes was done by using M062X method with LANL2DZ basis set in vacuo.

  12. In vitro and in vivo activity of a new unsymmetrical dinuclear copper complex containing a derivative ligand of 1,4,7-triazacyclononane: catalytic promiscuity of [Cu2(L)Cl3].

    PubMed

    de Almeida, Vicente R; Xavier, Fernando R; Osório, Renata E H M B; Bessa, Luiza M; Schilling, Eduardo L; Costa, Thiago G; Bortolotto, Tiago; Cavalett, Angélica; Castro, Frederico A V; Vilhena, Felipe; Alves, Odivaldo C; Terenzi, Hernán; Eleutherio, Elis C A; Pereira, Marcos D; Haase, Wolfgang; Tomkowicz, Zbigniew; Szpoganicz, Bruno; Bortoluzzi, Adailton J; Neves, Ademir

    2013-05-21

    Here we present the synthesis of the dinuclear complex [Cu(II)2(L)Cl3] (1), where L is the deprotonated form of the 3-[(4,7-diisopropyl-1,4,7-triazacyclononan-1-yl)methyl]-2-hydroxy-5-methylbenzaldehyde ligand. The complex was characterized by single crystal X-ray diffraction, potentiometric titration, mass spectrometry, electrochemical and magnetic measurements, EPR, UV-Vis and IR. Complex 1 is able to increase the hydrolysis rate of the diester bis-(2,4-dinitrophenyl)phosphate (2,4-BDNPP) by a factor of 2700, and also to promote the plasmidial DNA cleavage at pH 6 and to inhibit the formazan chromophore formation in redox processes at pH 7. Using Saccharomyces cerevisiae (BY4741) as a eukaryotic cellular model, we observed that 1 presents reduced cytotoxicity. In addition, treatment of wild-type and mutant cells lacking Cu/Zn-superoxide dismutase (Sod1) and cytoplasmic catalase (Ctt1) with 1 promotes increased survival after H2O2 or menadione (O2˙(-) generator) stress, indicating that 1 might act as a Sod1 and Ctt1 mimetic. Considered together, these results support considerations regarding the dynamic behaviour of an unsymmetrical dinuclear copper(II) complex in solid state and in aqueous pH-dependent solution.

  13. New insights into the comprehension of the magnetic properties of dinuclear Mn(III) compounds with the general formula [{MnL(NN)}2(μ-O)(μ-n-RC6H4COO)2]X2.

    PubMed

    Escriche-Tur, Luis; Font-Bardia, Mercè; Albela, Belén; Corbella, Montserrat

    2016-07-19

    Five new dinuclear Mn(iii) compounds with benzoato derivative bridges [{Mn(bpy)L}2(μ-O)(μ-n-RC6H4COO)2]X2 (n-R = 3-MeO, 4-MeO and 4-tBu, X = NO3(-) and ClO4(-)) were synthesised and characterised. According to X-ray diffraction, the X anions tend to be coordinated to the Mn ions and may occupy the place of the monodentate ligand L. Two structural isomers that only differ in one of their monodentate ligands have been obtained with the 3-MeOC6H4COO(-) bridges. For all compounds, the Mn(iii) ions display elongated octahedra with a pronounced rhombic distortion. To quantify these distortions separately, the elongation and rhombicity parameters Δ and ρ have been defined. The magnetic study shows a good relationship between the distortion of the coordination polyhedra and the zero field splitting parameters (DMn and EMn). From the magnetic data of a powder sample, it is possible to determine the sign and magnitude of DMn for ferromagnetic systems or weak antiferromagnetic systems with DMn < 0. For this kind of dinuclear compound, the R group at the meta position, the rhombic distortion of the octahedra, and large torsion angles between the Jahn-Teller axes lead to ferromagnetic interactions.

  14. Light-induced ESR centres in single crystal rutile

    NASA Astrophysics Data System (ADS)

    Hodgskiss, S. W.; Thorp, J. S.

    1983-04-01

    Electron spin resonance studies have been made on Verneuil-grown rutile single crystals, which were doped with a variety of transition gorup ions. Measurements were made at 9 GHz, both before and after UV irradiation, at temperatures in the range from 4.2 to 300 K. UV irradiation had two effects: (a) to affect the relative intensities of esr lines due to species already present, (b) to generate new esr spectra. Both effects are interpreted as representing a redistribution of charge amongst trapping centres. Seven UV generated centres have been identified and characterised in terms of their spin Hamiltonian parameters. Isochronal annealing techniques have been used to determine the ionisation temperatures of the traps. Observation of interactions and charge transfers between centres during isochronal annealing was used to determine the polarity and type of each centre.

  15. Nano-engineered pinning centres in YBCO superconducting films

    NASA Astrophysics Data System (ADS)

    Crisan, A.; Dang, V. S.; Mikheenko, P.

    2017-02-01

    For practical applications of superconducting materials in applied magnetic fields, artificial pinning centres in addition to natural ones are required to oppose the Lorentz force. These pinning centres are actually various types of defects in the superconductor matrix. The pinning centres can be categorised on their dimension (volume, surface or point) and on their character (normal cores or Δκ cores). Different samples have been produced by Pulsed Laser Deposition, with various thicknesses, temperatures and nanostructured additions to the superconducting matrix. They have been characterized by SQUID Magnetic Properties Measurement System and Physical Properties Measurement System, as well as by Transmission Electron Microscopy (TEM). Correlations between pinning architecture, TEM images, and critical currents at various fields and field orientations will be shown for a large number of YBa2Cu3Ox films with various types and architectures of artificial pinning centres.

  16. City Learning Centres for the 21st Century.

    ERIC Educational Resources Information Center

    PEB Exchange, 2000

    2000-01-01

    Examines England's City Learning Centres (CLC) component of the Excellence in Cities initiative aimed at driving up standards in inner city schools. CLC objectives, business involvement in the CLC initiative, funding, and technical guidelines in CLC development are discussed. (GR)

  17. METAL PHTHALOCYANINES

    DOEpatents

    Frigerio, N.A.

    1962-03-27

    A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

  18. Student centred teaching methods in a Chinese setting.

    PubMed

    Clarke, Janice

    2010-01-01

    This paper offers a discussion about using Western, student centred teaching methods with Chinese student nurses. There is increasing interest from Chinese nurse educators in student centred learning and an increase in partnerships between Chinese and Western universities. This paper suggests that the assumption that Western teaching methods are superior is now questioned and transferring Western style teaching to China requires a high degree of cultural sensitivity.

  19. Silicone metalization

    SciTech Connect

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  20. Silicone metalization

    SciTech Connect

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2006-12-05

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  1. Negotiation-centred versus client-centred: which approach should be used?

    PubMed

    Falardeau, Marlène; Durand, Marie José

    2002-06-01

    For nearly 20 years, Canadian occupational therapists have attached great importance to the client-centred approach within their practice. Professionals have agreed to define this approach through a philosophy built around the concepts of respect, power and partnership. But no reported work has really clarified what is meant by these three fundamental concepts. This article attempts to define the concepts of respect and power in the therapist-client relationship through a review of occupational therapy and related health and social sciences literature. It raises the question: "In the professional-client relationship, should the power reside with the client or is a more balanced approach needed?" This paper also proposes using the term negotiation instead of partnership, since negotiation seems to offer more applications for occupational therapy practice. The objective of the authors who advocate for greater negotiation between client and therapist is to stimulate analysis.

  2. A relational conceptual framework for multidisciplinary health research centre infrastructure

    PubMed Central

    2010-01-01

    Although multidisciplinary and team-based approaches are increasingly acknowledged as necessary to address some of the most pressing contemporary health challenges, many researchers struggle with a lack of infrastructure to facilitate and formalise the requisite collaborations. Specialised research centres have emerged as an important organisational solution, yet centre productivity and sustainability are frequently dictated by the availability and security of infrastructure funds. Despite being widely cited as a core component of research capacity building, infrastructure as a discrete concept has been rather analytically neglected, often treated as an implicit feature of research environments with little specification or relegated to a narrow category of physical or administrative inputs. The terms research infrastructure, capacity, and culture, among others, are deployed in overlapping and inconsistent ways, further obfuscating the crucial functions of infrastructure specifically and its relationships with associated concepts. The case is made for an expanded conceptualisation of research infrastructure, one that moves beyond conventional 'hardware' notions. Drawing on a case analysis of NEXUS, a multidisciplinary health research centre based at the University of British Columbia, Canada, a conceptual framework is proposed that integrates the tangible and intangible structures that interactively underlie research centre functioning. A relational approach holds potential to allow for more comprehensive accounting of the returns on infrastructure investment. For those developing new research centres or seeking to reinvigorate existing ones, this framework may be a useful guide for both centre design and evaluation. PMID:20925953

  3. [Interdisciplinary centres in hospitals? A review of the literature].

    PubMed

    Erbsen, Astrid; Rüdiger-Stürchler, Marjam; Heberer, Michael

    2010-01-01

    The treatment of complex disease patterns demands knowledge, and hence the collaboration of many medical disciplines. Interdisciplinary approaches to treatment are thus superior to multidisciplinary ones in terms of quality and costs. To make use of those benefits, interdisciplinary centres have emerged at many hospitals. Our review of the literature has sought to answer two questions: 1) Is there any evidence for the relationship 'creation of a centre = creation of interdisciplinarity'? 2) How can interdisciplinarity be fostered in centres? Medical and economic publications were identified via key terms in PubMed, Web of Knowledge and WISO. Using their references, further publications were researched. Contributions that complied with predefined criteria were included. For 75 of the 78 publications interdisciplinarity is the means to achieve a centre's objectives in quality and cost. Almost all the positive results achieved in centres, e.g., an increase in number of cases, are attributed to the seemingly established interdisciplinarity, without any evidence to substantiate this interrelation (question 1). The recommendations for creating the requested lively interdisciplinarity are insufficient, since technical arrangements dominate and the importance of social and therewith behavioural aspects is often forgotten--the findings of the respective literature remain unappreciated (question 2). Moreover, pertinent research as well as qualitative longitudinal research designs activating the knowledge of physicians, social scientists and economists should be used to investigate the interdisciplinarity sought for in centres.

  4. Health visitors: finding their place in children's centres.

    PubMed

    Potter, Barbara

    2010-11-01

    Children's centres aim to improve outcomes for children through the development of integrated services. Health visitors are expected to lead the delivery of child health promotion programmes in geographical areas that include children's centres. During 2007, a group of eight health visitors linked to Phase 2 children's centres in Bristol formed a learning set facilitated by a public health specialist to explore how their role as both caseworkers and public health practitioners could become part of an integrated children's centre team. They developed two linked models intended to help health visitors develop both aspects of their role in practice. First, a proposed management structure for a children's centre which included health visitors at both the strategic and practice delivery levels of the organisation. Second, a conceptualisation of how the proposed management structure would support and develop an integrated team. The paper then discusses an early attempt by one children's centre in Bristol to implement the two models through the development of an integrated outreach team.

  5. Comparison of centre of gravity and centre of pressure patterns in the golf swing.

    PubMed

    Smith, Aimée C; Roberts, Jonathan R; Kong, Pui Wah; Forrester, Stephanie E

    2017-03-01

    Analysing the centre of pressure (COP) and centre of gravity (COG) could reveal stabilising strategies used by golfers throughout the golf swing. This study identified and compared golfers' COP and COG patterns throughout the golf swing in medial-lateral (ML) and anterior-posterior (AP) directions using principal component analysis (PCA) and examined their relationship to clubhead velocity. Three-dimensional marker trajectories were collected using Vicon motion analysis and force plate data from two Kistler force plates for 22 low-handicap golfers during drives. Golfers' COG and COP were expressed as a percentage distance between their feet. PCA was performed on COG and COP in ML and AP directions. Relationships between principal component (PC) scores were examined using Pearson correlation and regression analysis used to examine the relationship with clubhead velocity. ML COP movements varied in magnitude (PC1), rate of change and timing (PC2 and PC3). The COP and COG PC1 scores were strongly correlated in both directions (ML: r = 0.90, P < .05; AP: r = 0.81, P < .05). Clubhead velocity, explained by three PCs (74%), related to timing and rate of change in COPML near downswing (PC2 and PC3) and timing of COGML late backswing (PC2). The relationship between COPML and COGML PC1 scores identified extremes of COP and COG patterns in golfers and could indicate a golfer's dynamic balance. Golfers with earlier movement of COP to the front foot (PC2) and rate of change (PC3) patterns in ML COP, prior to the downswing, may be more likely to generate higher clubhead velocity.

  6. A Crystallizable dinuclear tuck-in-tuck-over tuck-over dialkyl Tren uranium complex and double dearylation of BPh(4)(-) to give the BPh(2)-functionalized metallocycle [U{N(CH(2)CH(2)NSiMe(3))(2)(CH(2)CH(2)NSiMe(2)CHBPh(2))}(THF)].

    PubMed

    Gardner, Benedict M; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2009-08-05

    The unprecedented formation of a dinuclear tuck-in-tuck-over tuck-over dialkyl Tren-uranium(IV) complex and the first example of double dearylation of BPh(4)(-) in a molecular context to give a BPh(2)-functionalized uranium metallocycle are reported.

  7. Comparison of planned menus and centre characteristics with foods and beverages served in New York City child-care centres

    PubMed Central

    Breck, Andrew; Dixon, L Beth; Khan, Laura Kettel

    2016-01-01

    Objective The present study evaluated the extent to which child-care centre menus prepared in advance correspond with food and beverage items served to children. The authors identified centre and staff characteristics that were associated with matches between menus and what was served. Design Menus were collected from ninety-five centres in New York City (NYC). Direct observation of foods and beverages served to children were conducted during 524 meal and snack times at these centres between April and June 2010, as part of a larger study designed to determine compliance of child-care centres with city health department regulations for nutrition. Setting Child-care centres were located in low-income neighbourhoods in NYC. Results Overall, 87% of the foods and beverages listed on the menus or allowed as substitutions were served. Menu items matched with foods and beverages served for all major food groups by > 60%. Sweets and water had lower match percentages (40 and 32%, respectively), but water was served 68% of the time when it was not listed on the menu. The staff person making the food and purchasing decisions predicted the match between the planned or substituted items on the menus and the foods and beverages served. Conclusions In the present study, child-care centre menus included most foods and beverages served to children. Menus planned in advance have potential to be used to inform parents about which child-care centre to send their child or what foods and beverages their enrolled children will be offered throughout the day. PMID:27280341

  8. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes

    NASA Astrophysics Data System (ADS)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  9. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  10. Interaction of a dinuclear fluorescent Cd(II) complex of calix[4]arene conjugate with phosphates and its applicability in cell imaging.

    PubMed

    Sreenivasu Mummidivarapu, V V; Hinge, Vijaya Kumar; Rao, Chebrolu Pulla

    2015-01-21

    A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new

  11. Dinuclear manganese complexes containing chiral 1,4,7-triazacyclononane-derived ligands and their catalytic potential for the oxidation of olefins, alkanes, and alcohols.

    PubMed

    Romakh, Vladimir B; Therrien, Bruno; Süss-Fink, Georg; Shul'pin, Georgiy B

    2007-02-19

    Five new 1,4,7-triazacyclononane-derived compounds, sodium 3-(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)propionate (Na[LMe2R']) as well as the enantiopure derivatives (S)-1-(2-methylbutyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R''), SS-trans-2,5,8-trimethyl-2,5,8-triazabicyclo[7.4.01,9]tridecane (SS-LBMe3), (S)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R), and (R)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (R-LMe2R), have been synthesized. Reaction of manganese dichloride with the chiral macrocycles S-LMe2R and R-LMe2R in aqueous ethanol gives, upon oxidation with hydrogen peroxide, the brown dinuclear Mn(III)-Mn(IV) complexes which are enantiomers, [Mn2(S-LMe2R)2(mu-O)2]3+ (S,S-1) and [Mn2(R-LMe2R)2(mu-O)2]3+ (R,R-1). The single-crystal X-ray structure analyses of [S,S-1][PF6]3.0.5(CH3)2CO and [R,R-1][PF6]3.0.5(CH3)2CO show both enantiomers to contain Mn(III) and Mn(IV) centers, each of which being coordinated to three nitrogen atoms of a triazacyclononane ligand and each of which being bridged by two oxo and by two chiral hydroxypropyl pendent arms of the macrocycle. The enantiomeric complexes S,S-1 and R,R-1 were found to catalyze the oxidation of olefins, alkanes, and alcohols with hydrogen peroxide. In the epoxidation of indene the enantiomeric excess values attain 13%. The bond selectivities of the oxidation of linear and branched alkanes suggest the crucial step in this process to be the attack of a sterically hindered high-valent manganese-oxo species on the C-H bond.

  12. Specific Conformational Change in Giant DNA Caused by Anticancer Tetrazolato-Bridged Dinuclear Platinum(II) Complexes: Middle-Length Alkyl Substituents Exhibit Minimum Effect.

    PubMed

    Komeda, Seiji; Yoneyama, Hiroki; Uemura, Masako; Muramatsu, Akira; Okamoto, Naoto; Konishi, Hiroaki; Takahashi, Hiroyuki; Takagi, Akimitsu; Fukuda, Wakao; Imanaka, Tadayuki; Kanbe, Toshio; Harusawa, Shinya; Yoshikawa, Yuko; Yoshikawa, Kenichi

    2017-01-17

    Derivatives of the highly antitumor-active compound [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N2,N3)](2+) (5-H-Y), which is a tetrazolato-bridged dinuclear platinum(II) complex, were prepared by substituting a linear alkyl chain moiety at C5 of the tetrazolate ring. The general formula for the derivatives is [{cis-Pt(NH3)2}2(μ-OH)(μ-5-R-tetrazolato-N2,N3)](2+), where R is (CH2)nCH3 and n = 0 to 8 (complexes 1-9). The cytotoxicity of complexes 1-4 in NCI-H460 human non-small-cell lung cancer cells decreased with increasing alkyl chain length, and those of complexes 5-9 increased with increasing alkyl chain length. That is, the in vitro cytotoxicity of complexes 1-9 was found to have a U-shaped association with alkyl chain length. This U-shaped association is attributable to the degree of intracellular accumulation. Although circular dichroism spectroscopic measurement indicated that complexes 1-9 induced comparable conformational changes in the secondary structure of DNA, the tetrazolato-bridged complexes induced different degrees of DNA compaction as revealed by a single DNA measurement with fluorescence microsopy, which also had a U-shaped association with alkyl chain length that matched the association observed for cytotoxicity. Complexes 7-9, which had alkyl chains long enough to confer surfactant-like properties to the complex, induced DNA compaction 20 or 1000 times more efficiently than 5-H-Y or spermidine. A single DNA measurement with transmission electron microscopy revealed that complex 8 formed large spherical self-assembled structures that induced DNA compaction with extremely high efficiency. This result suggests that these structures may play a role in the DNA compaction that was induced by the complexes with the longer alkyl chains. The derivatization with a linear alkyl chain produced a series of complexes with unique cellular accumulation and DNA conformational change profiles and a potentially useful means of developing next-generation platinum

  13. Enzyme-like acceleration for the hydrolysis of a DNA model promoted by a dinuclear Zn(II) catalyst in dilute aqueous ethanol.

    PubMed

    Liu, C Tony; Neverov, Alexei A; Brown, R Stan

    2008-10-22

    The rates and products of cleavage of methyl (2-chloro-4-nitrophenyl) phosphate (2) promoted by a dinuclear Zn(II) complex (3) of 1,3-bis-N,N'(1,5,9-triazacyclododecyl)propane along with 1 equiv of ethoxide were investigated in ethanol solution containing small amounts of water (8 mM or=1.6 x 10(17) times relative to the background hydroxide reaction, suggesting that complex 3 promotes the hydrolysis at least 1000 times more effectively than ethanolysis.

  14. Copper coordination polymers based on single-chain or sheet structures involving dinuclear and tetranuclear copper(II) units: synthesis, structures, and magnetostructural correlations.

    PubMed

    Tandon, Santokh Singh; Bunge, Scott D; Motry, Douglas; Costa, José Sánchez; Aromí, Guillem; Reedijk, Jan; Thompson, Laurence K

    2009-06-01

    Reactions between the potentially pentadentate (N(2)O(3)), trianionic double Schiff-base ligand 2,6-bis[[(2-hydroxyethyl)imino]methyl]-4-methylphenol (H(3)L) and Cu(CH(3)CO(2))(2) or Cu(ClO(4))(2), in the presence of NaN(3), give novel coordination polymers with chain {[Cu(2)(H(2)L)(N(3))(3)](2).H(2)O}(n) (1) or sheet [Cu(2)(H(2)L)(N(3))(3)](n) (2) and [Cu(2)(HL)(N(3))](n)[ClO(4)](n) (3) structures, respectively. These clusters are comprised of repeating dinuclear units (1) or their dimers (2 and 3). In these compounds, H(3)L acts as a tridentate (N(2)O) monoanionic (1), tetradentate (ON(2)O) monoanionic (2), or pentadentate (O(3)N(2)) dianionic (3) ligand. Compound [Cu(2)(HL)(N(3))(2)(H(2)O)].0.5CH(3)OH (4) formed from the reaction of Cu(CH(3)CO(2))(2) with H(3)L under reflux, which did not afford crystals suitable for X-ray studies. X-ray structure determinations have revealed that the basic building block in 1-3 comprises two copper centers bridged through one mu-phenolate O atom from H(2)L(-) or HL(2-) and one mu-azido(N1,N1) ion. Compounds 1-3 unveil three different ways in which this Cu(2) basic unit may be organized in the crystalline phase at the supramolecular level through a variety of bridging interactions involving additional azide ligands or alkoxide groups from the side arms of the ligand H(3)L. Bulk magnetization measurements have served to demonstrate that the magnetic interactions are completely dominated by the strong antiferromagnetic coupling occurring within the Cu(2) building block, with coupling constants ranging from 330 to 560 cm(-1) (in the H = -JS(1)S(2) convention). These results together have been incorporated with data from the few related copper dimers reported exhibiting the same bridging pattern into a study aimed at extracting possible magnetostructural correlations within this Cu(2) unit. An earlier predicted correlation between J and the angle formed by the phenoxide bridge and the Cu(2) core has been identified for the first

  15. Synthesis of antitumor azolato-bridged dinuclear platinum(ii) complexes with in vivo antitumor efficacy and unique in vitro cytotoxicity profiles.

    PubMed

    Komeda, Seiji; Takayama, Hiroshi; Suzuki, Toshihiro; Odani, Akira; Yamori, Takao; Chikuma, Masahiko

    2013-05-01

    We synthesised four tetrazolato-bridged dinuclear Pt(ii) complexes, [{cis-Pt(NH3)2}2(μ-OH)(μ-5-R-tetrazolato-N2,N3)](n+), where R is CH3 (1), C6H5 (2), CH2COOC2H5 (3), or CH2COO(-) (4) and n = 2 (1-3) or 1 (4). Their structures were characterised by (1)H, (13)C, and (195)Pt NMR spectroscopy, mass spectrometry, and elemental analysis, and the crystal structure of 1 was determined by X-ray crystallography. The cytotoxicities of the complexes to human non-small-cell lung cancer (NSCLC) cell lines sensitive and resistant to cisplatin were assayed. Complex 1 was more cytotoxic than cisplatin in both PC-9 and PC-14 NSCLC cell lines, and cross-resistance to 1 in the cisplatin-resistant cells was largely circumvented. Complex 3 was moderately cytotoxic, whereas 2 and 4 were only marginally cytotoxic. We also determined the growth inhibitory activities of 1 and 3, as well as prototype azolato-bridged complexes [{cis-Pt(NH3)2}2(μ-OH)(μ-pyrazolato)](2+) (AMPZ), [{cis-Pt(NH3)2}2(μ-OH)(μ-1,2,3-triazolato-N1,N2)](2+) (AMTA), [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N1,N2)](2+) (5-H-X), and [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N2,N3)](2+) (5-H-Y), against a panel of 39 human cancer cell lines (JFCR39). The average 50% growth inhibition concentrations of the complexes against the JFCR39 cell lines ranged from 0.933 to 23.4 μM. The cytotoxicity fingerprints of the complexes based on the JFCR39 cytotoxicity data were similar to one another but completely different from the fingerprints of clinical platinum-based anticancer drugs. Complex 3 exhibited marked antitumor efficiency when tested in vivo on xenografts of PANC-1 pancreatic cancer in nude mice. The high potency of 3 confirmed that the tetrazolato-bridged structure exhibits high in vivo antitumor efficacy.

  16. Sure Start Children's Centres: time to make them better known.

    PubMed

    Thompson, Christine

    2010-01-01

    Health services have traditionally been available to local communities through general practices, health visitors and midwives. Since the introduction of the Sure Start Local programme in 1997 and Sure Start Children's Centres in 2004, an increasing number of children's centres are working with their local NHS to provide health services for the under fives, and improve the accessibility of these services to local families. Sure Start Children's Centres were set up in England as part of the Department for Children, Schools and Families' Children's Plan to improve outcomes for children and their families and contribute to the strategic objectives of Every Child Matters. Children's centres offer a range of integrated services from child health and maternity services to parenting and childcare provisions. They also deliver key health promotion activities and programmes that contribute to the public health priorities of Primary Care Trusts, e.g. breast-feeding, smoking in pregnancy, physical activity and healthy eating. There are now 3,500 children's centres offering easily accessible services to more than 2.4 million children and families across England. Health professionals are asked work proactively together to raise awareness of these among local communities so that more families can benefit from the services they offer.

  17. Synthesis, characterization and antibacterial activity of a tridentate Schiff base derived from cephalothin and sulfadiazine, and its transition metal complexes.

    PubMed

    Anacona, J R; Noriega, Natiana; Camus, Juan

    2015-02-25

    Metal(II) coordination compounds of a cephalothin Schiff base (H2L) derived from the condensation of cephalothin antibiotic with sulfadiazine were synthesized. The Schiff base ligand, mononuclear [ML(H2O)3] (M(II)=Mn,Co,Ni,Zn) complexes and magnetically diluted dinuclear copper(II) complex [CuL(H2O)3]2 were characterized by several techniques, including elemental and thermal analysis, molar conductance and magnetic susceptibility measurements, electronic, FT-IR, EPR and (1)H NMR spectral studies. The cephalothin Schiff base ligand H2L behaves as a dianionic tridentate NOO chelating agent. The biological applications of complexes have been studied on two bacteria strains (Escherichia coli and Staphylococcus aureus) by agar diffusion disc method.

  18. Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase

    NASA Astrophysics Data System (ADS)

    Brazzolotto, Deborah; Gennari, Marcello; Queyriaux, Nicolas; Simmons, Trevor R.; Pécaut, Jacques; Demeshko, Serhiy; Meyer, Franc; Orio, Maylis; Artero, Vincent; Duboc, Carole

    2016-11-01

    Hydrogen production through water splitting is one of the most promising solutions for the storage of renewable energy. [NiFe] hydrogenases are organometallic enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum. These enzymes provide inspiration for the design of new molecular catalysts that do not require precious metals. However, all heterodinuclear NiFe models reported so far do not reproduce the Ni-centred reactivity found at the active site of [NiFe] hydrogenases. Here, we report a structural and functional NiFe mimic that displays reactivity at the Ni site. This is shown by the detection of two catalytic intermediates that reproduce structural and electronic features of the Ni-L and Ni-R states of the enzyme during catalytic turnover. Under electrocatalytic conditions, this mimic displays high rates for H2 evolution (second-order rate constant of 2.5 × 104 M-1 s-1 turnover frequency of 250 s-1 at 10 mM H+ concentration) from mildly acidic solutions.

  19. Explaining the Sentinel-3 Marine Centre and related services

    NASA Astrophysics Data System (ADS)

    Bonekamp, Hans; Wilson, Hilary; Munro, Rosemary; Montagner, Francois; Provost, Dany

    2014-05-01

    This presentation provides an overview of the Sentinel-3 Marine Centre and related services and topics. In phase E of the Sentinel-3 program, EUMETSAT will be the Sentinel-3 satellite and Sentinel-3 Marine Centre operator. Verification and validation activities for the Marine Centre have recently started at EUMETSAT. The cal/val plans and mission performance set-up have been defined, together with ESA, to ensure that the core mission performance and operational products will be state of the art, and that new product definitions can be taken on board for operational services. To support the discussions in this session and ensure familiarity with the planned operational data streams, we will provide an overview of the set-up of product monitoring and services originating from the EUMETSAT premises. Major recent developments regarding EUMETSAT involvement in other areas of the sentinel program will also be presented.

  20. Height of centre of body mass during osteoarthritic gait.

    PubMed

    Khodadadeh, S; Whittle, M W; Bremble, G R

    1986-05-01

    Early attempts to locate the position of the centre of mass of the body during walking involved the use of cinematography, followed by kinetic analysis of the forces and couples acting about three axes at the ground and centre of mass. These methods, requiring data on the individual body segments, are too lengthy and complex for routine clinical use. A method is described which estimates both the trajectory and the mean height of the centre of mass, using only dynamic data from a single walk across one pair of force plates. Relating a possible trajectory height to the measured force vectors gives a profile for the horizontal velocity. The correct height is determined by seeking the smooth profile corresponding to the known horizontal velocity obtained by integration. Results are presented for 42 osteoarthritic patients undergoing total hip replacement operations.

  1. Stimulated emission from nitrogen-vacancy centres in diamond

    NASA Astrophysics Data System (ADS)

    Jeske, Jan; Lau, Desmond W. M.; Vidal, Xavier; McGuinness, Liam P.; Reineck, Philipp; Johnson, Brett C.; Doherty, Marcus W.; McCallum, Jeffrey C.; Onoda, Shinobu; Jelezko, Fedor; Ohshima, Takeshi; Volz, Thomas; Cole, Jared H.; Gibson, Brant C.; Greentree, Andrew D.

    2017-01-01

    Stimulated emission is the process fundamental to laser operation, thereby producing coherent photon output. Despite negatively charged nitrogen-vacancy (NV-) centres being discussed as a potential laser medium since the 1980s, there have been no definitive observations of stimulated emission from ensembles of NV- to date. Here we show both theoretical and experimental evidence for stimulated emission from NV- using light in the phonon sidebands around 700 nm. Furthermore, we show the transition from stimulated emission to photoionization as the stimulating laser wavelength is reduced from 700 to 620 nm. While lasing at the zero-phonon line is suppressed by ionization, our results open the possibility of diamond lasers based on NV- centres, tuneable over the phonon sideband. This broadens the applications of NV- magnetometers from single centre nanoscale sensors to a new generation of ultra-precise ensemble laser sensors, which exploit the contrast and signal amplification of a lasing system.

  2. Stimulated emission from nitrogen-vacancy centres in diamond

    PubMed Central

    Jeske, Jan; Lau, Desmond W. M.; Vidal, Xavier; McGuinness, Liam P.; Reineck, Philipp; Johnson, Brett C.; Doherty, Marcus W.; McCallum, Jeffrey C.; Onoda, Shinobu; Jelezko, Fedor; Ohshima, Takeshi; Volz, Thomas; Cole, Jared H.; Gibson, Brant C.; Greentree, Andrew D.

    2017-01-01

    Stimulated emission is the process fundamental to laser operation, thereby producing coherent photon output. Despite negatively charged nitrogen-vacancy (NV−) centres being discussed as a potential laser medium since the 1980s, there have been no definitive observations of stimulated emission from ensembles of NV− to date. Here we show both theoretical and experimental evidence for stimulated emission from NV− using light in the phonon sidebands around 700 nm. Furthermore, we show the transition from stimulated emission to photoionization as the stimulating laser wavelength is reduced from 700 to 620 nm. While lasing at the zero-phonon line is suppressed by ionization, our results open the possibility of diamond lasers based on NV− centres, tuneable over the phonon sideband. This broadens the applications of NV− magnetometers from single centre nanoscale sensors to a new generation of ultra-precise ensemble laser sensors, which exploit the contrast and signal amplification of a lasing system. PMID:28128228

  3. Centre of Excellence For Simulation Education and Innovation (CESEI).

    PubMed

    Qayumi, A Karim

    2010-01-01

    Simulation is becoming an integral part of medical education. The American College of Surgeons (ACS) was the first organization to recognize the value of simulation-based learning, and to award accreditation for educational institutions that aim to provide simulation as part of the experiential learning opportunity. Centre of Excellence for Simulation Education and Innovation (CESEI) is a multidisciplinary and interprofessional educational facility that is based at the University of British Columbia (UBC) and Vancouver Costal Health Authority (VCH). Centre of Excellence for Simulation Education and Innovation's goal is to provide excellence in education, research, and healthcare delivery by providing a technologically advanced environment and learning opportunity using simulation for various groups of learners including undergraduate, postgraduate, nursing, and allied health professionals. This article is an attempt to describe the infrastructure, services, and uniqueness of the Centre of Excellence for Simulation Education and Innovation.

  4. Structures of two superoxide dismutases from Bacillus anthracis reveal a novel active centre

    SciTech Connect

    Boucher, Ian W.; Kalliomaa, Anne K.; Levdikov, Vladimir M.; Blagova, Elena V.; Fogg, Mark J.; Brannigan, James A. Wilson, Keith S.; Wilkinson, Anthony J.

    2005-07-01

    The crystal structures of two manganese superoxide dismutases from B. anthracis were solved by X-ray crystallography using molecular replacement. The BA4499 and BA5696 genes of Bacillus anthracis encode proteins homologous to manganese superoxide dismutase, suggesting that this organism has an expanded repertoire of antioxidant proteins. Differences in metal specificity and quaternary structure between the dismutases of prokaryotes and higher eukaryotes may be exploited in the development of therapeutic antibacterial compounds. Here, the crystal structure of two Mn superoxide dismutases from B. anthracis solved to high resolution are reported. Comparison of their structures reveals that a highly conserved residue near the active centre is substituted in one of the proteins and that this is a characteristic feature of superoxide dismutases from the B. cereus/B. anthracis/B. thuringiensis group of organisms.

  5. Energy efficiency in U.K. shopping centres

    NASA Astrophysics Data System (ADS)

    Mangiarotti, Michela

    Energy efficiency in shopping centres means providing comfortable internal environment and services to the occupants with minimum energy use in a cost-effective and environmentally sensitive manner. This research considers the interaction of three factors affecting the energy efficiency of shopping centres: i) performance of the building fabric and services ii) management of the building in terms of operation, control, maintenance and replacement of the building fabric and services, and company's energy policy iii) occupants' expectation for comfort and awareness of energy efficiency. The aim of the investigation is to determine the role of the above factors in the energy consumption and carbon emissions of shopping centres and the scope for reducing this energy usage by changing one or all the three factors. The study also attempts to prioritize the changes in the above factors that are more cost-effective at reducing that energy consumption and identify the benefits and main economic and legal drivers for energy efficiency in shopping centres. To achieve these targets, three case studies have been analysed. Using energy data from bills, the performance of the selected case studies has been assessed to establish trends and current energy consumption and carbon emissions of shopping centres and their related causes. A regression analysis has attempted to break down the energy consumption of the landlords' area by end-use to identify the main sources of energy usage and consequently introduce cost-effective measures for saving energy. A monitoring and occupants' survey in both landlords' and tenants' areas have been carried out at the same time to compare the objective data of the environmental conditions with the subjective impressions of shoppers and shopkeepers. In particular, the monitoring aimed at assessing the internal environment to identify possible causes of discomfort and opportunities for introducing energy saving measures. The survey looked at

  6. Using a media centre to facilitate team-based learning.

    PubMed

    Ortega, Rafael A; Stanley, Glynne; Snavely, Adam

    2006-06-01

    Team-based learning is a relatively new educational approach in which learning occurs in three phases. Team-based learning is so named because in the third and final phase, students are organized into teams to participate in a classroom team-based learning session. In the Department of Anesthesiology at Boston University Medical Center, a multi-purpose Media Centre is used to facilitate the team-based learning approach. This Media Centre facilitates the creation and study of team-based learning educational materials distributed through a course website.

  7. Day-Care Centres: Risks and Prevention of Infection

    PubMed Central

    Herman, Dorli

    1988-01-01

    Children attending day-care centres are at increased risk of acquiring various infectious diseases, some with short- and long-term costs to individuals and society. Parents may approach their family physician for advice about placement of their child in day care. It is useful to have an understanding of the attributes of good day-care facilities and of the infections commonly acquired in this setting. In co-operation with day-care personnel and public health authorities, family physicians can help to implement strategies effective in reducing the incidence of infectious diseases in day-care centres. PMID:21253184

  8. Metal Detectors.

    ERIC Educational Resources Information Center

    Harrington-Lueker, Donna

    1992-01-01

    Schools that count on metal detectors to stem the flow of weapons into the schools create a false sense of security. Recommendations include investing in personnel rather than hardware, cultivating the confidence of law-abiding students, and enforcing discipline. Metal detectors can be quite effective at afterschool events. (MLF)

  9. Linking chemical electron-proton transfer to proton pumping in cytochrome c oxidase: broken-symmetry DFT exploration of intermediates along the catalytic reaction pathway of the iron-copper dinuclear complex.

    PubMed

    Noodleman, Louis; Han Du, Wen-Ge; Fee, James A; Götz, Andreas W; Walker, Ross C

    2014-07-07

    After a summary of the problem of coupling electron and proton transfer to proton pumping in cytochrome c oxidase, we present the results of our earlier and recent density functional theory calculations for the dinuclear Fe-a3-CuB reaction center in this enzyme. A specific catalytic reaction wheel diagram is constructed from the calculations, based on the structures and relative energies of the intermediate states of the reaction cycle. A larger family of tautomers/protonation states is generated compared to our earlier work, and a new lowest-energy pathway is proposed. The entire reaction cycle is calculated for the new smaller model (about 185-190 atoms), and two selected arcs of the wheel are chosen for calculations using a larger model (about 205 atoms). We compare the structural and redox energetics and protonation calculations with available experimental data. The reaction cycle map that we have built is positioned for further improvement and testing against experiment.

  10. Mixed ligand μ-phenoxo-bridged dinuclear copper(II) complexes with diimine co-ligands: efficient chemical nuclease and protease activities and cytotoxicity.

    PubMed

    Loganathan, Rangasamy; Ramakrishnan, Sethu; Suresh, Eringathodi; Palaniandavar, Mallayan; Riyasdeen, Anvarbatcha; Akbarsha, Mohamad Abdulkadhar

    2014-04-28

    The water soluble mixed ligand copper(II) complexes of the type [Cu(sal)(diimine)(ClO4)]21-5, where sal is salicylaldehyde and diimine is 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp, 3), 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-tmp, 4) or dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 5), and [Cu(sal)(phen)(NO3)]2 (2a) have been successfully isolated and characterized by elemental analysis and other spectral techniques. The DNA binding and cleavage properties of 1-5 have been explored by using various physical and biochemical methods. The coordination geometry around copper(II) in the X-ray structures of 1, 2, 2a and 4 is described as an elongated octahedron. The UV-Vis and EPR spectral and ESI-MS studies reveal that in solution the dinuclear complexes dissociate into essentially mononuclear [Cu(sal)(diimine)]+ species with square-based geometry. The absorption spectral titrations and competitive DNA binding studies reveal that the intrinsic DNA binding affinity of the complexes depends upon the diimine co-ligand and is of the order of dpq (5) > 3,4,7,8-tmp (4) > 5,6-dmp (3) > phen (2) > bpy (1). The complexes 2 and 5 are involved in a partial intercalative interaction with DNA base pairs, while 3 and 4 are involved in a hydrophobic interaction with DNA and 1 is involved in an electrostatic interaction with DNA, which is supported by viscosity studies. Interestingly, only 3 and 4 are selective in exhibiting a positive induced CD band (ICD) upon binding to DNA suggesting that they induce a B to A conformational change in DNA. All the complexes exhibit an oxidative DNA cleavage ability, which varies as 5 > 4 > 3 > 2 > 1. While 4 and 5 are unique in displaying prominent double-strand DNA cleavage even in the absence of an activator, 2 and 3 display only single-strand DNA cleavage. Interestingly, all the complexes exhibit oxidative double-strand DNA cleavage in the presence of ascorbic acid, with 4 and 5 showing

  11. Studies of Transition Metal Complexes Using Dynamic NMR Techniques.

    NASA Astrophysics Data System (ADS)

    Coston, Timothy Peter John

    Available from UMI in association with The British Library. This Thesis is primarily concerned with the quantitative study of fluxional processes in, predominantly platinum(IV) complexes, with the ligands 1,1,2,2-tetrakis(methylthio)ethane (MeS)_2CHCH(SMe)_2 , and 1,1,2,2-tetrakis(methylthio)ethene (MeS) _2C=C(SMe)_2. Quantitative information relating to the energetics of these processes has been obtained by a combination of one- and two-dimensional NMR techniques. Chapter One provides an introduction to the background of fluxional processes in transition metal complexes together with data concerning the energetics of the processes that have already been studied by NMR techniques. Chapter Two provides a thorough grounding in NMR techniques, in particular those concerned with the quantitative measurement of rates involved in chemical exchange processes. A description of the use of 2D EXSY NMR spectroscopy in obtaining rate data is given. The properties of the magnetic isotope of platinum are given in Chapter Three. A general survey is also given of some additional compounds that have already been studied by platinum-195 spectroscopy. Chapter Four is concerned with the quantitative study of low temperature (<293 K) fluxionality (sulphur inversion) in the complexes (PtXMe_3 (MeS)_2CHCH(SMe) _2) (X = Cl, Br, I). These complexes were studied by dynamic nuclear magnetic resonance and the information regarding the rates of sulphur inversion was obtained by complete band-shape analysis. Chapter Five is concerned with high temperature (>333 K) fluxionality, of the previous complexes, as studied by a combination of one- and two -dimensional NMR techniques. Aside from obtaining thermodynamic parameters for all the processes, a new novel mechanism is proposed. Chapter Six is primarily concerned with the NMR investigation of the new dinuclear complexes ((PtXMe _3)_2(MeS) _2CHCH(SMe)_2) (X = Cl, Br, I). The solution properties have been established and thermo-dynamic parameters

  12. Sequence variation at the oxygen-evolving centre of photosystem II: a new class of 'rogue' cyanobacterial D1 proteins.

    PubMed

    Murray, James W

    2012-02-01

    Photosystem II is the oxygen-evolving enzyme of photosynthesis. It is a membrane-bound protein-pigment complex. The oxygen is produced at the oxygen-evolving centre (OEC), a Mn(4)CaO(5) metallocluster, which is largely ligated by amino acids of the D1 protein. The OEC-ligating residues are invariant between most cyanobacteria and higher plants. In this study, a new class of cyanobacterial D1 proteins has been identified in which the OEC metal-ligating residues are very different to the consensus. This new class of 'rogue' D1 proteins is associated with diazotrophic cyanobacteria. Their function, activity and origins are discussed.

  13. Volumetric modulated arc therapy in prostate cancer patients with metallic hip prostheses in a UK centre

    PubMed Central

    Ng, Wee Loon; Brunt, John; Temple, Simon; Saipillai, Mohammed; Haridass, Anoop; Wong, Helen; Malik, Zafar; Eswar, Chinnamani

    2015-01-01

    Aim This study aimed to investigate whether IMRT using VMAT is a viable and safe solution in dose escalated RT in these patients. Background An increasing number of prostate cancer patients are elderly and have hip prostheses. These implants pose challenges in radiotherapy treatment planning. Although intensity modulated radiotherapy (IMRT) is commonly used, there is a lack of clinical studies documenting its efficacy and toxicities in this subgroup of patients. Materials and methods The data from 23 patients with hip prostheses and non-metastatic prostate cancer treated with VMAT (volumetric modulated arc therapy) between 2009 and 2011, were retrospectively analyzed. Baseline characteristics, treatment details and outcome data were collected on all patients. The median follow up was 40.9 months. MRI-CT image fusion was performed and the treatment plans were created using RapidArc™ (RA) techniques utilizing 1 or 2 arcs and 10 MV photon beams. Results 96% of patients were treated with a dose of 72 Gy/32 fractions over 44 days. 21/23 plans met the PTV targets. The mean homogeneity index was 1.07. 20/23 plans met all OAR constraints (rectum, bladder). Two plans deviated from rectal constraints, four from bladder constraints; all were classed as minor deviations. One patient experienced late grade 3 genitourinary toxicity. Three other patients experienced late grade 2 or lower gastrointestinal toxicity. One patient had biochemical failure and one had a non-prostate cancer related death. Conclusions VMAT provides an elegant solution to deliver dose escalated RT in patients with unilateral and bilateral hip replacements with minimal acute and late toxicities. PMID:26109914

  14. Linear distortion of octahedral metal centres by multiple hydrogen bonds in modular ML(4) systems.

    PubMed

    Turner, David R; Hursthouse, M B; Light, M E; Steed, Jonathan W

    2004-06-21

    A series of compounds of the type [M(1)(4)(H(2)O)(2)]SO(4)[middle dot]2H(2)O containing a simple urea-based pyridyl ligand have been synthesised and characterised by X-ray crystallography. The enclathrated water exists within discrete linearly stacked cavities and causes significant distortions in the M-OH(2) bonds due to the presence of a strongly hydrogen bonded water square.

  15. Sulphide mineralization and wall-rock alteration in ophiolites and modern oceanic spreading centres

    USGS Publications Warehouse

    Koski, R.A.

    1983-01-01

    Massive and stockwork Fe-Cu-Zn (Cyprus type) sulphide deposits in the upper parts of ophiolite complexes represent hydrothermal mineralization at ancient accretionary plate boundaries. These deposits are probable metallogenic analogues of the polymetallic sulphide deposits recently discovered along modern oceanic spreading centres. Genetic models for these deposits suggest that mineralization results from large-scale circulation of sea-water through basaltic basement along the tectonically active axis of spreading, a zone of high heat flow. The high geothermal gradient above 1 to 2 km deep magma chambers emplaced below the ridge axis drives the convective circulation cell. Cold oxidizing sea-water penetrating the crust on the ridge flanks becomes heated and evolves into a highly reduced somewhat acidic hydrothermal solvent during interaction with basaltic wall-rock. Depending on the temperature and water/rock ratio, this fluid is capable of leaching and transporting iron, manganese, and base metals; dissolved sea-water sulphate is reduced to sulphide. At the ridge axis, the buoyant hydrothermal fluid rises through permeable wall-rocks, and fluid flow may be focussed along deep-seated fractures related to extensional tectonic processes. Metal sulphides are precipitated along channelways as the ascending fluid undergoes adiabatic expansion and then further cooling during mixing with ambient sub-sea-floor water. Vigorous fluid flow results in venting of reduced fluid at the sea-floor/sea-water interface and deposition of massive sulphide. A comparison of sulphide mineralization and wall-rock alteration in ancient and modern spreading centre environments supports this genetic concept. Massive sulphide deposits in ophiolites generally occur in clusters of closely spaced (< 1-5 km) deposits. Individual deposits are a composite of syngenetic massive sulphide and underlying epigenetic stockwork-vein mineralization. The massive sulphide occurs as concordant tabular

  16. Student Experience of a Scenario-Centred Curriculum

    ERIC Educational Resources Information Center

    Bell, Sarah; Galilea, Patricia; Tolouei, Reza

    2010-01-01

    In 2006 UCL implemented new scenario-centred degree programmes in Civil and Environmental Engineering. The new curriculum can be characterised as a hybrid of problem-based, project-based and traditional approaches to learning. Four times a year students work in teams for one week on a scenario which aims to integrate learning from lecture and…

  17. Education at the Centre? Australia's National Union Education Program

    ERIC Educational Resources Information Center

    Brown, Tony; Yasukawa, Keiko

    2009-01-01

    Australian trade unions are at a pivotal moment. In 2007-2008, a review of the training and education programs of the Education and Campaign Centre (ECC), the education arm of the Australian Council of Trade Unions (ACTU), was conducted through a series of interviews with leaders of twenty-five unions. The review found that Australian unions do…

  18. Openness--A Way Forward: Development Education Research Centre

    ERIC Educational Resources Information Center

    Hare-Heremia, Mahora

    2014-01-01

    Education is a vital aspect in the lives of humankind. It contributes and shapes our future as citizens of the world. To understand it is to discover the many hidden talents the world has in store for all. The Development Education Research Centre (DERC) holds many resources that aid in the development of education at a global level. With the…

  19. Analytical model of peptide mass cluster centres with applications

    PubMed Central

    Wolski, Witold E; Farrow, Malcolm; Emde, Anne-Katrin; Lehrach, Hans; Lalowski, Maciej; Reinert, Knut

    2006-01-01

    Background The elemental composition of peptides results in formation of distinct, equidistantly spaced clusters across the mass range. The property of peptide mass clustering is used to calibrate peptide mass lists, to identify and remove non-peptide peaks and for data reduction. Results We developed an analytical model of the peptide mass cluster centres. Inputs to the model included, the amino acid frequencies in the sequence database, the average length of the proteins in the database, the cleavage specificity of the proteolytic enzyme used and the cleavage probability. We examined the accuracy of our model by comparing it with the model based on an in silico sequence database digest. To identify the crucial parameters we analysed how the cluster centre location depends on the inputs. The distance to the nearest cluster was used to calibrate mass spectrometric peptide peak-lists and to identify non-peptide peaks. Conclusion The model introduced here enables us to predict the location of the peptide mass cluster centres. It explains how the location of the cluster centres depends on the input parameters. Fast and efficient calibration and filtering of non-peptide peaks is achieved by a distance measure suggested by Wool and Smilansky. PMID:16995952

  20. A Learner-Centred Mock Conference Model for Undergraduate Teaching

    ERIC Educational Resources Information Center

    Kumar, Kari

    2011-01-01

    This essay describes a mock conference model of instruction suitable for use in undergraduate teaching, and which adheres to principles of learner-centred instruction and universal design for learning. A staged process of learner preparation for the conference is outlined, and student and instructor roles during preconference, conference, and…

  1. Lively Bureaucracy? The ESRC's Doctoral Training Centres and UK Universities

    ERIC Educational Resources Information Center

    Lunt, Ingrid; McAlpine, Lynn; Mills, David

    2014-01-01

    This paper explores the changing relationships between the UK government, its research councils and universities, focusing on the governing, funding and organisation of doctoral training. We use the Doctoral Training Centres (DTCs) funded by the Economic and Social Research Council (ESRC) as a prism through which to study the shifting nature of…

  2. Language Experiences of Preverbal Children in Australian Childcare Centres

    ERIC Educational Resources Information Center

    Nyland, Berenice

    2009-01-01

    This paper explores the language experiences of preverbal infants in Australian childcare centres with the aim of examining cultural regulation within the childcare context. Language is defined as a social and communicative act that is related to the development of voluntary action (Vygotsky 1962; Lock 1980; Leontiev 1994). The study uses…

  3. Automation of (64)Cu production at Turku PET Centre.

    PubMed

    Elomaa, Viki-Veikko; Jurttila, Jori; Rajander, Johan; Solin, Olof

    2014-07-01

    At Turku PET Centre automation for handling solid targets for the production of (64)Cu has been built. The system consists of a module for moving the target from the irradiation position into a lead transport shield and a robotic-arm assisted setup for moving the target within radiochemistry laboratory. The main motivation for designing automation arises from radiation hygiene.

  4. Training Leisure Centre Instructors: Client Motivational Profiles Examined

    ERIC Educational Resources Information Center

    Kniveton, Bromley H.

    2005-01-01

    Purpose: To investigate the motivations of clients attending leisure centres/clubs. It is noted that training programmes for instructors tend to neglect this, particularly in relation to the gender and age of clients. Design/methodology/approach: In this study 460 recreational athletes including equal numbers of males and females in the two age…

  5. Grid Operation at Tokyo Tier-2 Centre for ATLAS

    NASA Astrophysics Data System (ADS)

    Matsunaga, Hiroyuki; Isobe, Tadaaki; Mashimo, Tetsuro; Sakamoto, Hiroshi; Ueda, Ikuo

    International Centre for Elementary Particle Physics, the University of Tokyo, has been involved in the Worldwide LHC Computing Grid since 2003. After extensive R&D experience of the PC computing farm, disk and tape storage systems, network technology and the integration of these components, it is now operating a regional centre for the ATLAS data analysis. The regional centre includes an ATLAS Tier-2 site which is running the gLite middleware developed by the Enabling Grids for E-sciencE (EGEE) project. One of the biggest challenges at the regional centre is efficient data transfer between the Tier-2 site in Tokyo and other sites, in particular the associated Tier-1 site in France, because the large round trip time due to the long distance makes it difficult to transfer data at a high rate. We have been studying to achieve a good performance of the data transfer, and some results of network tests and ATLAS data transfer are described. Hardware and software components and the operational experience are also reported in this article.

  6. Constructing Learning Spaces? Videoconferencing at Local Learning Centres in Sweden

    ERIC Educational Resources Information Center

    Logdlund, Ulrik

    2010-01-01

    This article explores videoconferencing in the context of local learning centres in Sweden. The practice is described as a "learning space" in which adult learners construct socio-spatial relations. The study goes beyond a sociological apprehension of actors and opposes the idea of the material as neutral, passive and conformed by…

  7. Al-Manakh. Language Centre Journal, Volume 4, Number 1.

    ERIC Educational Resources Information Center

    Al Manakh, Journal of The Language Centre, 1980

    1980-01-01

    This issue of a journal devoted primarily to teaching English as a second language to engineering students contains the following articles: (1) "The Contribution of Educational Technology to ELT [English Language Teaching]" by Mike Laflin; (2) "Looking Again at Student-Centred Study Skills" by Andrew E. Seymour; (3)…

  8. Space-Centred English Language Learning: The Cyprus Case

    ERIC Educational Resources Information Center

    Kurt, Mustafa; Kurt, Sevinc

    2013-01-01

    This paper discusses a study conducted in the Ledra/Lokmaci Milieu in Cyprus, the area in the centre of the divided walled city of Nicosia where Greek and Turkish Cypriots have to use English to communicate with one another. The aim of the study was to locate the effects of a learning space on language learners, teachers and syllabus designers.…

  9. Learner Centred Design for a Hybrid Interaction Application

    ERIC Educational Resources Information Center

    Wood, Simon; Romero, Pablo

    2010-01-01

    Learner centred design methods highlight the importance of involving the stakeholders of the learning process (learners, teachers, educational researchers) at all stages of the design of educational applications and of refining the design through an iterative prototyping process. These methods have been used successfully when designing systems…

  10. Revitalization of Indigenous Culture in Child Care Centre

    ERIC Educational Resources Information Center

    Kulhankova, Jana

    2011-01-01

    In this study, I address contemporary ways of looking after children and care giving roles women play in today's Aboriginal community in Brisbane, Australia. Data were collected through participant observation and interviews during field work in a family care centre managed by Indigenous women with the staff and their clients. My main contribution…

  11. Democratising Turkey through Student-Centred Pedagogy: Opportunities and Pitfalls

    ERIC Educational Resources Information Center

    Altinyelken, Hülya Kosar

    2015-01-01

    Global reform talk on pedagogy has been converging around student-centred pedagogy (SCP) in recent decades. One of the significant appeals of this pedagogical model is its democratisation potentials. This article seeks to empirically study SCP's role in democratising learning and promoting social democratisation by taking the case of Turkey, a…

  12. Introduction of ICT and Multimedia into Cambodia's Teacher Training Centres

    ERIC Educational Resources Information Center

    Dionys, David

    2012-01-01

    This article describes the integration of ICT in the teacher training centres of Cambodia. It focuses on the collaboration between the Teacher Training Department of the Ministry of Education, Youth and Sports (MoEYS) of Cambodia and VVOB (Flemish Association for Development Cooperation and Technical Assistance), which is aimed at improving ICT…

  13. Frambu Health Centre: Promoting Family Focused Care for Disabled Children.

    ERIC Educational Resources Information Center

    Storhaug, Kari; Vandvik, Inger Helene

    1983-01-01

    The article describes services of the Frambu Health Centre in Norway, which has evolved during the past 30 years from a summer camp for children with poliomyelitis to a modern information and treatment center for families with disabled members, and offers fortnightly courses for patients with rare congenital and/or hereditary disorders. (Author/MC)

  14. Scottish Schools Science Equipment Research Centre Bulletin No. 55.

    ERIC Educational Resources Information Center

    1972

    Instructions for the construction of the following apparatus for the secondary school science laboratory are included in this issue of the Scottish Schools Science Equipment Research Centre Bulletin: a cheap water purifier using an expendable deionizer can; a simple amplifier suitable for detecting or displaying D. C. currents of 1 microamp or…

  15. An African-Centred Approach to Land Education

    ERIC Educational Resources Information Center

    Engel-Di Mauro, Salvatore; Carroll, Karanja Keita

    2014-01-01

    Approaches to environmental education which are engaging with place and critical pedagogy have not yet broadly engaged with the African world and insights from Africana Studies and Geography. An African-centred approach facilitates people's reconnection to places and ecosystems in ways that do not reduce places to objects of conquest and…

  16. Person-centred care: Principle of Nursing Practice D.

    PubMed

    Manley, Kim; Hills, Val; Marriot, Sheila

    This is the fifth article in a nine-part series describing the Principles of Nursing Practice developed by the Royal College of Nursing (RCN) in collaboration with patient and service organisations, the Department of Health, the Nursing and Midwifery Council, nurses and other healthcare professionals. This article discusses Principle D, the provision of person-centred care.

  17. Radiation from an off-centred rotating dipole in vacuum

    NASA Astrophysics Data System (ADS)

    Pétri, J.

    2016-12-01

    When a neutron star forms, after the collapse of its progenitor, a strong magnetic field survives in its interior. This magnetic topology is usually assumed to be well approximated by a dipole located right at the centre of the star. However, there is no particular reason why this dipole should be attached to this very special point. A slight shift from the stellar centre could have strong implications for the surrounding electromagnetic field configuration leading to clear observational signatures. We study the effect of the most general off-centred dipole anchored in the neutron star interior. Exact analytical solutions are given in vacuum outside the star to any order of accuracy in the small parameter ɛ = d/R, where d is the displacement of the dipole from the stellar centre and R the neutron star radius. As a simple diagnostic of this decentred dipole, the spin-down luminosity and the torque exerted on its crust are computed to the lowest leading order in ɛ. Results are compared to earlier works and a discussion on repercussions on pulsar braking index and multiwavelength light curves is proposed.

  18. Design of Curriculum Development Centres. Educational Building Report 15.

    ERIC Educational Resources Information Center

    Hamel, Jean-Pierre

    Periodic adaptations of the curriculum to new needs with continuous analysis of results and feedback are some of the functions performed in many Asian countries by an institution called a Curriculum Development Centre (CDC). The first part of the study analyzes the function of a CDC, examines in general terms what sort of facilities are needed,…

  19. National Centre for Vocational Education Research 2009 Strategic Plan

    ERIC Educational Resources Information Center

    National Centre for Vocational Education Research (NCVER), 2009

    2009-01-01

    National Centre for Vocational Education Research (NCVER) was established in 1981 as a not-for-profit company owned by the Commonwealth and state and territory ministers with responsibility for vocational education and training (VET). It is a professional, independent body at arm's length from government. The company initially conducted research…

  20. Physical Activity Promotion in Call Centres: Employers' Perspectives

    ERIC Educational Resources Information Center

    Renton, Sheila J.; Lightfoot, Nancy E.; Maar, Marion A.

    2011-01-01

    This study followed a predominantly qualitative approach to explore the perspectives of employers in Sudbury, Ontario, Canada, call centres (CCs) regarding physical activity (PA) promotion in workplaces, by identifying current practices and employers' motivation to promote PA, as well as perceived facilitators and barriers. In-depth interviews…

  1. Evaluation of telemedicine centres in Madhya Pradesh, Central India.

    PubMed

    Bali, Surya; Gupta, Arti; Khan, Asif; Pakhare, Abhijit

    2016-04-01

    In a developing country such as India, there is substantial inequality in health care distribution. Telemedicine facilities were established in Madhya Pradesh in 2007-2008. The purpose of this study was to evaluate the infrastructure, equipment, manpower, and functional status of Indian Space and Research Organisation (ISRO) telemedicine nodes in Madhya Pradesh. All district hospitals and medical colleges with nodes were visited by a team of three members. The study was conducted from December 2013-January 2014. The team recorded the structural facility situation and physical conditions on a predesigned pro forma. The team also conducted interviews with the nodal officers, data entry operator and other relevant people at these centres. Of the six specialist nodes, four were functional and two were non-functional. Of 10 patient nodes, two nodes were functional, four were semi-functional and four were non-functional. Most of the centres were not working due to a problem with their satellite modem. The overall condition of ISRO run telemedicine centres in Madhya Pradesh was found to be poor. Most of these centres failed to provide telemedicine consultations. We recommend replacing this system with another cost effective system available in the state wide area network (SWAN). We suggest the concept of the virtual out-patient department.

  2. Cyberage Narratives: Creative Computing in After-School Centres

    ERIC Educational Resources Information Center

    Klerfelt, Anna

    2006-01-01

    In this article two computer-produced multimedia stories created by children in their after-school centre are analysed, building on the assumption that children draw that which is important for them. The aim is to make visible the significance of narrative structure, reaccentuation, intertextuality, multivoicedness and various levels of…

  3. Centres for People with Intellectual Disabilities: Attendees' Perceptions of Benefit

    ERIC Educational Resources Information Center

    Gajewska, Urszula; Trigg, Richard

    2016-01-01

    Background: Day and community learning centres aim to provide intellectually disabled (ID) people with social support, life skills and greater control over their lives. However, there is little research exploring the benefits of attendance from the perspective of attendees and whether these goals are met. Materials and methods: Unstructured…

  4. The Makana Regional Centre of Expertise: Experiments in Social Learning

    ERIC Educational Resources Information Center

    Lotz-Sisitka, Heila; O'Donoghue, Rob; Wilmot, Di

    2010-01-01

    This article deliberates the possibilities for Regional Centres of Expertise (RCEs) to become "experiments" in social learning. The purpose of the article is to advance the broader research agenda of RCEs through reflection on the empirical research agenda of one RCE, Makana RCE in South Africa. As such it opens questions on how we might…

  5. Fungal genetic resource centres and the genomic challenge.

    PubMed

    Ryan, Matthew J; Smith, David

    2004-12-01

    Fungal research and education has for many years been supported by public service genetic resource centres, whose roles have been to maintain, preserve and supply living cultures to the research community. In the genomic era, genetic resource centres are perhaps more important than ever before. The cultures held, many of which are described and validated by expert biosystematists, are valuable resources for the future. There is a need to supply genomic and proteomic research programmes with fully characterised organisms, as usage of organisms from unreliable sources can prove disastrous, not least in economical terms. However, mycologists often require more than just the organisms, for example, their associated information is vital for bioinformatic applications and some researchers may only require genomic DNA from the organism rather than the organism per se. Genetic resource centres are continually adapting to meet the needs of their users and the wider mycological research community, this associated with OECD international initiatives should ensure they exist to support research for many years to come. This review considers the impact of such initiatives, the current roles of fungal genetic resource centres, the mechanisms used to preserve organisms in a stable manner and the range of resources that are offered for genomic research.

  6. Evaluation of the Centres of Excellence in Higher Education

    ERIC Educational Resources Information Center

    Kettunen, Juha Matti

    2011-01-01

    This study presents an evaluation of the centres of excellence in higher education in Finland. This approach is an example of enhancement-led evaluation aiming to improve the long-term development of education. The study presents the Degree Programme in Civil Engineering of the Turku University of Applied Sciences, which was awarded the…

  7. Yggdrasyll, a Concept for a Virtual Data Centre

    NASA Astrophysics Data System (ADS)

    de Wolf, H.; Beerthuizen, P.; Plevier, C.

    2009-05-01

    YGGDRASILL is the name for a Virtual Data Centre, an infrastructural solution to make a large variety of data available in a simple and uniform way to a user community, while only requiring minimal effort from the data providers. In many cases, science projects want and need to make their results available to the community, thus acting as data provider to related projects. However, most of these projects are focussed on the domain-specific scientific activities and cannot afford to spend significant technical and administrative effort on setting up a facility that provides search and download functions. It is not sufficient to make it possible to download the data, it must also be possible for users to find the appropriate data. The concept of a virtual data centre delivers a solution to this problem, by offering a central web portal that offers users advanced functions to locate and download data products. The YGGDRASILL virtual data centre improves this concept by minimizing the effort to act as a data provider in the virtual data centre. In addition to facilitating the delivery of data products that have been prepared in advance, YGGDRASILL provides also the means to create customized data products by processing on-demand. The development of YGGDRASILL was driven by the needs from the Dutch national project on climate Change, "Climate changes Spatial Planning" (http://www.klimaatvoorruimte.nl).

  8. [The main missions of the National Palliative Care Resource Centre].

    PubMed

    Doré-Pautonnier, Delphine; Baussant-Crenn, Camille; Frattini, Marie-Odile; Mino, Jean-Christophe; Rennesson, Marina

    2011-09-01

    The French National Palliative Care Resource Centre (CNDR) provides people impacted by the end of life, death and bereavement with a range of constantly evolving services. Spreading the palliative approach in order to enable everyone to benefit from it and appropriate it constitutes the main mission of the CNDR.

  9. Toward a Student-Centred Process of Teaching Arithmetic

    ERIC Educational Resources Information Center

    Eriksson, Gota

    2011-01-01

    This article describes a way toward a student-centred process of teaching arithmetic, where the content is harmonized with the students' conceptual levels. At school start, one classroom teacher is guided in recurrent teaching development meetings in order to develop teaching based on the students' prerequisites and to successively learn the…

  10. Let's Talk! ESL Students' Needs and Writing Centre Philosophy

    ERIC Educational Resources Information Center

    Moussu, Lucie

    2013-01-01

    When university/college faculty members believe that ESL students' writing skills are not equivalent to those of native speakers, they frequently send these ESL students to their institution's writing centres (WCs). However, this often results in frustration for WC staff, the students, and faculty members. This article first describes ESL…

  11. A User-Centred Design and Evaluation of IR Interfaces

    ERIC Educational Resources Information Center

    Ahmed, S. M. Zabed; McKnight, Cliff; Oppenheim, Charles

    2006-01-01

    This paper presents a user-centred design and evaluation methodology for ensuring the usability of IR interfaces. The methodology is based on sequentially performing: a competitive analysis, user task analysis, heuristic evaluation, formative evaluation and a summative comparative evaluation. These techniques are described, and their application…

  12. Fractures of the mandibular coronoid process: a two centres study.

    PubMed

    Boffano, Paolo; Kommers, Sofie C; Roccia, Fabio; Gallesio, Cesare; Forouzanfar, Tymour

    2014-10-01

    The aim of this study was to assess the characteristics of patients with coronoid fractures treated in two European centres over 10 years and to briefly review the literature. This study is based on 2 systematic computer-assisted databases that have continuously recorded patients hospitalized with maxillofacial fractures and surgically treated in two European centres between 2001 and 2010. During the 10 years, 1818 patients and 523 patients with maxillofacial fractures were admitted to the two centres respectively: 21 patients (16 males, 5 females) were admitted with 21 coronoid fractures and 28 associated maxillofacial fractures. A mean age of 42.1 years was observed. The fractures were mainly the result of motor vehicle accidents, followed by assaults and falls. The most frequently observed associated maxillofacial fracture was a zygomatic fracture (13 fractures). In both centres, mandibular coronoid fractures are treated unless a severe dislocation of the fractured coronoid is observed or a functional mandibular impairment is encountered. Conservative treatment can be used, together with the open reduction and internal fixation of associated fractures. The crucial point is to prevent ankylosis, which may be prevented by correct and early postoperative physiotherapy and mandibular function.

  13. Centre for Applied Language Studies, University of Limerick, Ireland

    ERIC Educational Resources Information Center

    Chambers, Angela; Atkinson, David; Farr, Fiona

    2015-01-01

    The Centre for Applied Language Studies (CALS), founded in 1997, brings together researchers and postgraduate students from several disciplines in language studies, and is structured in three research clusters: New learning environments; Discourse, society and identity; and Plurilingualism and language policy. There is a certain amount of…

  14. Lipids in photosynthetic reaction centres: structural roles and functional holes.

    PubMed

    Jones, Michael R

    2007-01-01

    Photosynthetic proteins power the biosphere. Reaction centres, light harvesting antenna proteins and cytochrome b(6)f (or bc(1)) complexes are expressed at high levels, have been subjected to an intensive spectroscopic, biochemical and mutagenic analysis, and several have been characterised to an informatively high resolution by X-ray crystallography. In addition to revealing the structural basis for the transduction of light energy, X-ray crystallography has brought molecular insights into the relationships between these multicomponent membrane proteins and their lipid environment. Lipids resolved in the X-ray crystal structures of photosynthetic proteins bind light harvesting cofactors, fill intra-protein cavities through which quinones can diffuse, form an important part of the monomer-monomer interface in multimeric structures and may facilitate structural flexibility in complexes that undergo partial disassembly and repair. It has been proposed that individual lipids influence the biophysical properties of reaction centre cofactors, and so affect the rate of electron transfer through the complex. Lipids have also been shown to be important for successful crystallisation of photosynthetic proteins. Comparison of the three types of reaction centre that have been structurally characterised reveals interesting similarities in the position of bound lipids that may point towards a generic requirement to reinforce the structure of the core electron transfer domain. The crystallographic data are also providing new opportunities to find molecular explanations for observed effects of different types of lipid on the structure, mechanism and organisation of reaction centres and other photosynthetic proteins.

  15. VCD spectroscopy as an excellent probe of chiral metal complexes containing a carbon monoxide vibrational chromophore.

    PubMed

    Fusè, Marco; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Zerla, Daniele; Rimoldi, Isabella; Contini, Alessandro; Cesarotti, Edoardo

    2015-06-07

    Vibrational circular dichroism, VCD, gives evidence that the carbon monoxide chromophore in a heteroleptic cyclopentadienyl Ru(ii)-carbonyl complex is very sensitive to the chirality of the metal centre and becomes an excellent probe to define the configuration of chiral metal complexes.

  16. History of metal contamination in Lake Illawarra, NSW, Australia.

    PubMed

    Schneider, Larissa; Maher, William; Potts, Jaimie; Batley, Graeme; Taylor, Anne; Krikowa, Frank; Chariton, Anthony; Zawadzki, Atun; Heijnis, Henk; Gruber, Bernd

    2015-01-01

    Lake Illawarra has a long history of sediment contamination, particularly by metals, as a result of past and current industrial operations and land uses within the catchment. In this study, we examined the history of metal contamination in sediments using metal analysis and (210)Pb and (137)Cs dating. The distributions of copper, zinc, arsenic, selenium, cadmium and lead concentrations within sediment cores were in agreement with historical events in the lake, and indicated that metal contamination had been occurring since the start of industrial activities in Port Kembla in the late 1800 s. Most metal contamination, however, has occurred since the 1960s. Sedimentation rates were found to be 0.2 cm year(-1) in Griffins Bay and 0.3 cm year(-1) in the centre of the lake. Inputs from creeks bringing metals from Port Kembla in the northeast of the lake and a copper slag emplacement from a former copper refinery on the Windang Peninsula were the main sources of metal inputs to Lake Illawarra. The metals of highest concern were zinc and copper, which exceeded the Australian and New Zealand sediment quality guideline values at some sites. Results showed that while historical contamination persists, current management practices have resulted in reduced metal concentrations in surface sediments in the depositional zones in the centre of the lake.

  17. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  18. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiu-Mei; Li, Peng; Gao, Wei; Liu, Feng; Liu, Jie-Ping

    2016-12-01

    Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H2O)4]·3H2O (Ln=Gd (1) and Tb (2) and Dy (3), H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1-3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO)2 double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectively sense Pb2+ and Fe3+ ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb2+ and Fe3+ ions is exceedingly rare example.

  19. Identifying Centres of Plant Biodiversity in South Australia

    PubMed Central

    Guerin, Greg R.; Biffin, Ed; Baruch, Zdravko; Lowe, Andrew J.

    2016-01-01

    We aimed to identify regional centres of plant biodiversity in South Australia, a sub-continental land area of 983,482 km2, by mapping a suite of metrics. Broad-brush conservation issues associated with the centres were mapped, specifically climate sensitivity, exposure to habitat fragmentation, introduced species and altered fire regimes. We compiled 727,417 plant species records from plot-based field surveys and herbarium records and mapped the following: species richness (all species; South Australian endemics; conservation-dependent species; introduced species); georeferenced weighted endemism, phylogenetic diversity, georeferenced phylogenetic endemism; and measures of beta diversity at local and state-wide scales. Associated conservation issues mapped were: climate sensitivity measured via ordination and non-linear modelling; habitat fragmentation represented by the proportion of remnant vegetation within a moving window; fire prone landscapes assessed using fire history records; invasive species assessed through diversity metrics, species distribution and literature. Compared to plots, herbarium data had higher spatial and taxonomic coverage but records were more biased towards major transport corridors. Beta diversity was influenced by sampling intensity and scale of comparison. We identified six centres of high plant biodiversity for South Australia: Western Kangaroo Island; Southern Mount Lofty Ranges; Anangu Pitjantjatjara Yankunytjatjara lands; Southern Flinders Ranges; Southern Eyre Peninsula; Lower South East. Species composition in the arid-mediterranean ecotone was the most climate sensitive. Fragmentation mapping highlighted the dichotomy between extensive land-use and high remnancy in the north and intensive land-use and low remnancy in the south. Invasive species were most species rich in agricultural areas close to population centres. Fire mapping revealed large variation in frequency across the state. Biodiversity scores were not always

  20. The IOC Centres of Excellence bring prevention to sports medicine.

    PubMed

    Engebretsen, Lars; Bahr, Roald; Cook, Jill L; Derman, Wayne; Emery, Carolyn A; Finch, Caroline F; Meeuwisse, Willem H; Schwellnus, Martin; Steffen, Kathrin

    2014-09-01

    The protection of an athlete's health and preventing injuries and illnesses in sport are top priorities for the IOC and its Medical Commission. The IOC therefore partners with selected research centres around the world and supports research in the field of sports medicine. This has enabled the IOC to develop an international network of expert scientists and clinicians in sports injury and disease prevention research. The IOC wants to promote injury and disease prevention and the improvement of physical health of the athlete by: (1) establishing long-term research programmes on injury and disease prevention (including studies on basic epidemiology, risk factors, injury mechanisms and intervention), (2) fostering collaborative relationships with individuals, institutions and organisations to improve athletes' health, (3) implementing and collaborating with applied, ongoing and novel research and development within the framework and long-term strategy of the IOC and (4) setting up knowledge translation mechanisms to share scientific research results with the field throughout the Olympic Movement and sports community and converting these results into concrete actions to protect the health of the athletes. In 2009, the IOC also identified four research centres that had an established track record in research, educational and clinical activities to achieve these ambitions: (1) the Australian Centre for Research into Injury in Sport and its Prevention (ACRISP), Australia; (2) the Sport Injury Prevention Research Centre (SIPRC), Canada; (3) the Clinical Sport and Exercise Medicine Research (CSEM), South Africa and (4) the Oslo Sports Trauma Research Center (OSTRC), Norway. This paper highlights the work carried out by these four IOC Centres of Excellence over the past 6 years and their contribution to the world of sports medicine.