Sample records for metal ligand anchored

  1. Cellulose based macromolecular chelator having pyrocatechol as an anchored ligand: synthesis and applications as metal extractant prior to their determination by flame atomic absorption spectrometry.

    PubMed

    Gurnani, Vibha; Singh, Ajai K; Venkataramani, B

    2003-12-23

    Pyrocatechol is immobilized on cellulose via NHCH(2)CH(2)NHSO(2)C(6)H(4)NN linker and the resulting macromolecular chelator characterized by IR, TGA, CPMAS (13)C NMR and elemental analyses. It has been used for enrichment of Cu(II), Zn(II), Fe(III), Ni(II), Co(II), Cd(II) and Pb(II) prior to their determination by flame atomic absorption spectrometry (FAAS). The pH ranges for quantitative sorption (98.0-99.4%) are 4.0-7.0, 5.0-6.0, 3.0-4.0, 5.0-7.0, 5.0-8.0, 7.0-8.0 and 4.0-5.0, respectively. The desorption was found quantitative with 0.5 mol dm(-3) HCl/HNO(3) (for Pb). The sorption capacity of the matrix for the seven metal ions has been found in the range 85.3-186.2 mumol g(-1). The optimum flow rate of metal ion solution for quantitative sorption of metal onto pyrocatechol functionalized cellulose as determined by column method, is 2-6 cm(3) min(-1), whereas for desorption it is 2-4 cm(3) min(-1). The tolerance limits for NaCl, NaBr, NaI, NaNO(3), Na(2)SO(4), Na(3)PO(4,) humic acid, EDTA, ascorbic acid, citric acid, sodium tartrate, Ca(II) and Mg(II) in the sorption of all the seven metal ions are reported. Ascorbic acid is tolerable up to 0.8 mmol dm(-3) with Cu and Pb where as sodium tartrate does not interfere up to 0.6 mmol dm(-3) with Pb. There is no interference of NaBr, NaCl and NaNO(3) up to a concentration of 0.5 mol dm(-3), in the sorption of Cu(II), Cd(II) and Fe(III) on to the chelating cellulose matrix The preconcentration factors are between 75 and 300 and t(1/2) values metal ions. Simultaneous sorption of Cu, Zn, Ni and Co is possible at pH 5.0 if their total concentration does not exceed lowest sorption capacity. The present matrix coupled with FAAS has been used to enrich and determine the seven metal ions in river and tap water samples (relative standard deviation (R.S.D.) 1.05-7.20%) and synthetic certified water sample SLRS-4 (NRC, Canada) with R.S.D. approximately 2.03%. The cobalt present in pharmaceutical vitamin tablets was also preconcentrated on the modified cellulose and determined by FAAS (R.S.D. approximately 1.87%). PMID:18969255

  2. Distearoyl anchor-painted erythrocytes with prolonged ligand retention and circulation properties in vivo

    PubMed Central

    Shi, Guixin; Mukthavaram, Rajesh; Kesari, Santosh

    2014-01-01

    Red blood cells (RBCs) attract significant interest as carriers of biomolecules, drugs and nanoparticles. In this regard, versatile technologies to attach molecules and ligands to the RBC surface are of great importance. Reported here is a fast and efficient surface painting strategy to attach ligands to the surface of RBCs, and the factors that control the stability and circulation properties of the modified RBCs in vivo. Distearoyl phosphatidylethanolamine anchor-conjugated immunoglobulin (IgG) efficiently incorporates in the RBC membrane following 15–30 min incubation. The optimized RBCs show prolonged circulation in vivo (70% of the injected dose after 48h) and efficient retention of IgG in the membrane with terminal half-life of 73 hours. The IgG construct is gradually lost from the RBCs mainly due to the transfer to plasma components, liver endothelial cells and Kupffer cells. The ligand retention efficiency is partially dictated by ligand type, anchor type, and ligand concentration in the membrane, while RBC half-life is determined by initial concentration of the ligand in the membrane and presence of PEG linker between the ligand and the anchor. This work provides important guidance for non-covalent surface painting of RBCs as well as other types of blood borne cells for in vivo therapeutic and targeting applications. PMID:23798381

  3. Preparation and characterization of Ag nanoparticle-embedded blank and ligand-anchored silica gels.

    PubMed

    Im, Hee-Jung; Lee, Byung Cheol; Yeon, Jei-Won

    2013-11-01

    Ag nanoparticles, used for halogen (especially iodine) adsorption and an evaluation of halogen behavior, were embedded in synthesized inorganic-organic hybrid gels. In particular, an irradiation method using an electron beam plays a part in introducing Ag nanoparticles to the organofunctionalized silica gels from AgNO3 solutions in a simple way at atmospheric pressure and room temperature. For preparation of the Ag nanoparticle-embedded inorganic-organic hybrid gels, ligands of ethylenediamine (NH2CH2CH2NH-, TMSen) and mercapto (HS-) functionalized three-dimensional porous SiO2 sol-gels were first synthesized through hydrolysis and condensation reactions, and Ag nanoparticles were then embedded into the ethylenediamine- and mercapto-anchored silica gels each, through electron-beam irradiation. The addition of ligands yielded larger average pore sizes than the absence of any ligand. Moreover, the ethylenediamine ligand led to looser structures and better access of the Ag nanoparticles to the ethylenediamine-anchored gel. As a result, more Ag nanoparticles were introduced into the ethylenediamine-anchored gel. The preparation and characterization of Ag nanoparticle-embedded blank and ligand-anchored silica gels are discussed in detail. PMID:24245307

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

    SciTech Connect

    Gladysz, J.A.

    1993-08-10

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

  5. Binding constants of membrane-anchored receptors and ligands depend strongly on the nanoscale roughness of membranes

    PubMed Central

    Hu, Jinglei; Lipowsky, Reinhard; Weikl, Thomas R.

    2013-01-01

    Cell adhesion and the adhesion of vesicles to the membranes of cells or organelles are pivotal for immune responses, tissue formation, and cell signaling. The adhesion processes depend sensitively on the binding constant of the membrane-anchored receptor and ligand proteins that mediate adhesion, but this constant is difficult to measure in experiments. We have investigated the binding of membrane-anchored receptor and ligand proteins with molecular dynamics simulations. We find that the binding constant of the anchored proteins strongly decreases with the membrane roughness caused by thermally excited membrane shape fluctuations on nanoscales. We present a theory that explains the roughness dependence of the binding constant for the anchored proteins from membrane confinement and that relates this constant to the binding constant of soluble proteins without membrane anchors. Because the binding constant of soluble proteins is readily accessible in experiments, our results provide a useful route to compute the binding constant of membrane-anchored receptor and ligand proteins. PMID:24006364

  6. Ligand Intermediates in Metal-Catalyzed Reactions

    SciTech Connect

    Gladysz, John A.

    1999-07-31

    The longest-running goal of this project has been the synthesis, isolation, and physical chemical characterization of homogeneous transition metal complexes containing ligand types believed to be intermediates in the metal-catalyzed conversion of CO/H{sub 2}, CO{sub 2}, CH{sub 4}, and similar raw materials to organic fuels, feedstocks, etc. In the current project period, complexes that contain unusual new types of C{sub x}(carbide) and C{sub x}O{sub y} (carbon oxide) ligands have been emphasized. A new program in homogeneous fluorous phase catalysis has been launched as described in the final report.

  7. Sorption of Heavy Metal Ions on New Metal-Ligand Complexes Chemically Derived from Lycopodium clavatum

    Microsoft Academic Search

    Erol Pehlivan; Mustafa Ersoz; Salih Yildiz; Harry J. Duncan

    1994-01-01

    Sorption of heavy metal ions from aqueous solution has been investigated as a function of pH using a novel exchanger system whereby Lycopodium clavatum is functionalized with carboxylate and glyoxime metal-ligand complexes. The new ligand exchangers were prepared using a reaction of diaminosporopollenin with various metal-ligand complexes of glyoxime and monocarboxylic acid. The sorptive behavior of these metal-ligand exchangers and

  8. Crystalline capsules: metal-organic frameworks locked by size-matching ligand bolts.

    PubMed

    Wang, Hao; Xu, Jian; Zhang, Da-Shuai; Chen, Qiang; Wen, Rong-Mei; Chang, Ze; Bu, Xian-He

    2015-05-11

    Metal-organic frameworks (MOFs) are shown to be good examples of a new class of crystalline porous materials for guest encapsulation. Since the encapsulation/release of guest molecules in MOF hosts is a reversible process in nature, how to prevent the leaching of guests from the open pores with minimal and nondestructive modifications of the structure is a critical issue. To address this issue, we herein propose a novel strategy of encapsulating guests by introducing size-matching organic ligands as bolts to lock the pores of the MOFs through deliberately anchoring onto the open metal sites in the pores. Our proposed strategy provides a mechanical way to prevent the leaching of guests and thereby has less dependence on the specific chemical environment of the hosts, thus making it applicable for a wide variety of existing MOFs once the size-matching ligands are employed. PMID:25800154

  9. Very strong metal ligand aromatic cation-? interactions in transition metal complexes: intermolecular interaction in tetraphenylborate salts

    Microsoft Academic Search

    Miloš K. Mil?i?; Zoran D. Tomi?; Snežana D. Zari?

    2004-01-01

    Strong intermolecular interactions between ligands in cationic metal complexes and aromatic rings of tetraphenylborate anion, so-called metal ligand aromatic cation-? (MLAC?) interactions, were found by screening Cambridge Structural Database. Distances between phenyl ring and ligand are shorter in these structures than in previously reported MLAC? interactions by 0.2 Å.

  10. Metal complexes of some thiocarbohydrazone ligands: synthesis and structure

    Microsoft Academic Search

    Azza A. A. Abu-Hussen; Adel A. A. Emara

    2004-01-01

    The synthesis, structure, physico-chemical investigation and biological studies of some metal complexes of thiocarbohydrazone ligands are described. The ligands were obtained by condensation of N,N?-thiocarbohydrazide with carbonyl compounds such as 2-hydroxyacetophenone or 5-chlorosalicylaldehyde. A variety of binuclear or mononuclear complexes were obtained with the ligands in mono-, bi- and\\/or tri-deprotonated forms. The bonding sites are the azomethine nitrogen atom, phenolic

  11. Sorption of heavy metal ions on new metal-ligand complexes chemically derived from Lycopodium clavatum

    SciTech Connect

    Pehlivan, E.; Ersoz, M.; Yildiz, S. [Univ. of Selcuk, Konya (Turkey); Duncan, H.J. [Univ. of Glasgow, Scotland (United Kingdom)

    1994-08-01

    Sorption of heavy metal ions from aqueous solution has been investigated as a function of pH using a novel exchanger system whereby Lycopodium clavatum is functionalized with carboxylate and glyoxime metal-ligand complexes. The new ligand exchangers were prepared using a reaction of diaminosporopollenin with various metal-ligand complexes of glyoxime and monocarboxylic acid. The sorptive behavior of these metal-ligand exchangers and the possibilities to remove and to recover selectively heavy metal cations using these systems are discussed on the basis of their chemical natures and their complexing properties.

  12. Using measurements of anchoring energies of liquid crystals on surfaces to quantify proteins captured by immobilized ligands.

    PubMed

    Govindaraju, Thimmaiah; Bertics, Paul J; Raines, Ronald T; Abbott, Nicholas L

    2007-09-12

    We describe a simple optical method that employs measurement of the interaction energy of a liquid crystal (LC) with a surface (the so-called anchoring energy) to report proteins captured on surfaces through specific interactions with immobilized binding groups. To define the sensitivity and dynamic range of the response of the LC, we covalently immobilized a tyrosine-containing, 13-residue peptide sequence (Y1173) from the epidermal growth factor receptor/kinase (EGFR) at which autophosphorylation takes place and to which the adapter protein Shc binds. We determined that, on peptide-decorated (Y1173 or pY1173, where pY1173 is the corresponding phosphopeptide) surfaces incubated against anti-phosphotyrosine antibody, the anchoring energy of the LC decreased systematically from 4.4 to 1.4 microJ/m2 (with SEM=0.3 microJ/m2 for n=5) as the antibody concentration increased from 10 pM to 100 nM. Over the same range of antibody concentrations in solution and densities of immobilized peptides, independent ellipsometric measurements were not sufficiently sensitive to report the captured antibody (ellipsometric thicknesses were <0.1 nm). These results, when combined with control experiments reported in this article, provide the first demonstration of the use of anchoring energy measurements of LCs to report proteins captured by immobilized ligands on surfaces. The sensitivity and dynamic range of the methodology suggest that it may offer the basis of a simple yet broadly useful principle for reporting the interactions between proteins and other biomolecules that underlie complex and poorly understood chemical and biological events. PMID:17705384

  13. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand.

    PubMed

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N(2) to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H(2) remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N(2) splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with ?-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H(2) at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting. PMID:21697873

  14. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    NASA Astrophysics Data System (ADS)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with ?-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  15. Selection for a Single Self-Assembled Macrocycle from a Hybrid Metal-Ligand Hydrogen-Bonded (MLHB) Ligand Subunit.

    PubMed

    Sommer, Samantha K; Henle, Ernst A; Zakharov, Lev N; Pluth, Michael D

    2015-07-20

    To expand the interface between self-assembled metal-ligand and hydrogen-bonded architectures, here we report the preparation, self-assembly, and metal-ligand binding of a pyridyl quinolone ligand (5-PYQ). The 5-PYQ ligand self-associates through quinolone hydrogen bonding, and it binds to metal centers through the pyridine ligand component. As a first step toward investigating more-complex hybrid metal-ligand hydrogen-bonded (MLHB) architectures, we report investigations of 5-PYQ with mono- and bis-platinated anthracene precursors. These results demonstrate that the 5-PYQ ligand maintains hydrogen bonding interactions while binding to square-planar platinum centers, but that generation of coordination compounds with closed topology erodes the hydrogen bonding fidelity to favor ambidentate coordination modes of the 5-PYQ ligand. PMID:26146881

  16. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Microsoft Academic Search

    Bjorn Askevold; Jorge Torres Nieto; Samat Tussupbayev; Martin Diefenbach; Eberhardt Herdtweck; Max C. Holthausen; Sven Schneider

    2011-01-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation\\/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We

  17. Synthesis of new copper nanoparticle-decorated anchored type ligands: applications as non-enzymatic electrochemical sensors for hydrogen peroxide.

    PubMed

    Ensafi, Ali A; Zandi-Atashbar, N; Ghiaci, M; Taghizadeh, M; Rezaei, B

    2015-02-01

    In this work, copper nanoparticles (CuNPs) decorated on two new anchored type ligands were utilized to prepare two electrochemical sensors. These ligands are made from bonding amine chains to silica support including SiO2-pro-NH2 (compound I) and SiO2-pro-NH-cyanuric-NH2 (compound II). The morphology of synthesized CuNPs was characterized by transmission electron microscopy (TEM). The nano-particles were in the range of 13-37 nm with the average size of 23 nm. These materials were used to modify carbon paste electrode. Different electrochemical techniques, including cyclic voltammetry, electrochemical impedance spectroscopy and hydrodynamic chronoamperometry, were used to study the sensor behavior. These electrochemical sensors were used as a model for non-enzymatic detection of hydrogen peroxide (H2O2). To evaluate the abilities of the modified electrodes for H2O2 detection, the electrochemical signals were compared in the absence and presence of H2O2. From them, two modified electrodes showed significant responses vs. H2O2 addition. The amperograms illustrated that the sensors were selective for H2O2 sensing with linear ranges of 5.14-1250 ?mol L(-1) and 1.14-1120 ?mol L(-1) with detection limits of 0.85 and 0.27 ?mol L(-1) H2O2, sensitivities of 3545 and 11,293 ?A mmol(-1)L and with response times less than 5s for I/CPE and II/CPE, respectively. As further verification of the selected sensor, H2O2 contained in milk sample was analyzed and the obtained results were comparable with the ones from classical control titration method. PMID:25492200

  18. The role of metals and ligands in organic hydroformylation.

    PubMed

    Gonsalvi, Luca; Guerriero, Antonella; Monflier, Eric; Hapiot, Frédéric; Peruzzini, Maurizio

    2013-01-01

    In this chapter the effect of transition metals and of ancillary stabilizing ligands on the activity, regioselectivity, and chemoselectivity in hydroformylation reactions applied to organic synthesis will be reviewed, highlighting recent cases of particular interest, including examples of both homogeneous and heterogeneous catalytic reactions. PMID:23571859

  19. Transition metal complexes of bidentate Schiff base ligands

    Microsoft Academic Search

    Mehmet Tümer; Cumali Çelik; Hüseyin Köksal; Selahattin Serin

    1999-01-01

    New Schiff base ligands derived from vanillin (HL1), 4-dimethylaminobenzaldehyde (HL2) and 3,5-di-t-butyl-4-hydroxybenzaldehyde (HL3) with N-(pyridyl)-3-methoxy-4-hydroxy-5-aminobenzylamine (2) and their copper(II), cobalt(II), nickel(II), oxovanadium(IV) and zinc(II) transition metal complexes have been synthesized and characterized by elemental analyses, electronic and i.r. spectra, molar conductance data and by 1H and 13C n.m.r. spectra. The results indicate that the ligands coordinate through azomethine nitrogen and

  20. A Modified Metallic Coil Embolization Technique for Pulmonary Arteriovenous Malformations Using Coil Anchors and Occlusion Balloon Catheters

    SciTech Connect

    Mori, Kensaku [Institute of Clinical Medicine, University of Tsukuba, Department of Diagnostic and Interventional Radiology (Japan)], E-mail: moriken@md.tsukuba.ac.jp; Shiigai, Masanari [Tsukuba Medical Center Hospital, Department of Radiology (Japan); Saida, Tsukasa; Anno, Izumi [Institute of Clinical Medicine, University of Tsukuba, Department of Diagnostic and Interventional Radiology (Japan); Wada, Mitsuyoshi [Seinan Medical Center Hospital, Department of Radiology (Japan); Minami, Manabu [Institute of Clinical Medicine, University of Tsukuba, Department of Diagnostic and Interventional Radiology (Japan)

    2008-05-15

    Purpose. To evaluate the feasibility and efficacy of a modified metallic coil embolization technique for pulmonary arteriovenous malformations (PAVMs) using coil anchors and occlusion balloon catheters. Methods. Five consecutive female patients with 6 PAVMs were included in the present study. One of the 6 PAVMs was of the complex type with four feeding arteries. An occlusion balloon catheter was inserted into the feeding artery as close to the venous sac as possible. The coil anchor, which was a simple W-shaped bent stainless steel wire with two markers at each end, was deployed prior to embolization to prevent the systemic migration of embolic materials. Then, metallic coils were deployed around the coil anchors under inflow stoppage using the inflated occlusion balloon catheter. In the complex-type PAVM, the main feeder was occluded by this technique and the other three small feeders were embolized with metallic coils only. Results. In all 5 cases, occlusion balloon catheters could be inserted into the feeding arteries just proximal to the venous sacs, coil anchors were easily deployed, and complete occlusion was achieved without any migration of metallic coils or paradoxical embolism during the procedure. Conclusions. The modified metallic coil embolization technique with coil anchors and occlusion balloon catheters was feasible and considered to be useful in preventing procedure-related complications.

  1. Synthesis and NMR characterization of ligand-capped metal and metal-oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Sharma, Ramesh

    Ligand-capped metal and metal-oxide nanoparticles (NPs) have some interesting and useful physical properties that are not present in their respective bulk materials. These properties are of research interest in many applications such as catalysis, drug delivery, biological imaging, and plasmonics. In such applications, it is critical to understand the surface structure of NPs and the roles played by the surface bound ligands. To characterize surface environment, ligand dynamics, and exchange kinetics, ligand-capped metal and metal-oxide NPs are synthesized and studied by multinuclear NMR. Phosphines and phosphonic acids are used to passivate metal (gold and silver) and metal-oxide (tin dioxide) NPs in different sizes (1-5 nm) by following published procedures or original synthesis methods. In both solution and solid state NMR, the 31P chemical shift of surface-bound ligands are distinctly different from those observed for free ligands. Additionally, NMR line widths in surface-bound ligands are highly broadened compared to those of free ligands. The lines are broadened due to both homogeneous and inhomogeneous broadening mechanisms, determined through hole burning NMR and spin-spin relaxation measurements. In small particles (< 2 nm), the main source of line broadening is inhomogeneous and originates due to structural heterogeneity and underlying chemical shift distributions. In large particles (> 2 nm), both inhomogeneous and homogeneous line broadening mechanisms are present. When the particles' sizes increase from small to large, the homogeneous broadening mechanism becomes dominant due to strong nuclear-electron interaction and reintroduction of residual dipolar coupling as shown by a combination of 1H, 13C and 31P NMR. Results from a series of ligand exchange experiments in silver and gold NPs further indicate the presence of Au(I) and Ag(I) on the particle surfaces.

  2. Electrophilic Metal Alkyl Chemistry in New Ligand Environments

    SciTech Connect

    Jordan, Richard F. [University of Chicago] University of Chicago

    2013-06-30

    The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH2=CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (?-diimine)PdMe{sup +} species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (?-diimine)PdMe{sup +} catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (?-diimine)PdMe{sup +} species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

  3. Synthesis and NMR characterization of ligand-capped metal and metal-oxide nanoparticles

    Microsoft Academic Search

    Ramesh Sharma

    2009-01-01

    Ligand-capped metal and metal-oxide nanoparticles (NPs) have some interesting and useful physical properties that are not present in their respective bulk materials. These properties are of research interest in many applications such as catalysis, drug delivery, biological imaging, and plasmonics. In such applications, it is critical to understand the surface structure of NPs and the roles played by the surface

  4. Reactivity of halide and pseudohalide ligands in transition-metal complexes

    SciTech Connect

    Kukushkin, Yu.N.; Kukushkin, V.Yu.

    1985-10-01

    The experimental material on the reactions of coordinated halide ligands, as well as cyanide, azido, thiocyanato, and cyanato ligands, in transition-metal complexes has been generalized in this review.

  5. 8-Hydroxyquinoline anchored to silica gel via new moderate size linker: synthesis and applications as a metal ion collector for their flame atomic absorption spectrometric determination.

    PubMed

    Goswami, Anupama; Singh, Ajai K; Venkataramani, B

    2003-08-29

    The silica gel modified with (3-aminopropyl-triethoxysilane) was reacted with 5-formyl-8-hydroxyquinoline (FHOQ(x)) to anchor 8-quinolinol ligand on the silica gel. It was characterised with cross polarisation magic angle spinning (CPMAS) NMR and diffuse reflectance infrared Fourier transformation (DRIFT) spectroscopy and used for the preconcentration of Cu(II), Pb(II), Ni(II), Fe(III), Cd(II), Zn(II) and Co(II) prior to their determination by flame atomic absorption spectrometry. The surface area of the modified silica gel has been found to be 227 m(2) g(-1) and the two pKa values as 3.8 and 8.0. The optimum pH ranges for quantitative sorption are 4.0-7.0, 4.5-7.0, 3.0-6.0, 5.0-8.0, 5.0-8.0, 5.0-8.0 and 4.0-7.0 for Cu, Pb, Fe, Zn, Co, Ni and Cd, respectively. All the metals can be desorbed with 2.5 mol l(-1) HCl or HNO(3). The sorption capacity for these metal ions is in range of 92-448.0 micromol g(-1) and follows the order Cdmetal ions are reported. The preconcentration factors are 150, 250, 200, 300, 250, 300 and 200 for Cd, Co, Zn, Cu, Pb, Fe and Ni, respectively and t(1/2) values <1 min except for Ni. The 95% extraction by batch method takes < or =25 min. The simultaneous enrichment and determination of all the metals are possible if the total load of the metal ions is less than sorption capacity. In river water samples all these metal ions were enriched with the present ligand anchored silica gel and determined with flame atomic absorption spectrometer (R.S.D.< or =6.4%). Cobalt contents of pharmaceutical samples (vitamin tablet) were preconcentrated with the present chelating silica gel and estimated by flame AAS, with R.S.D. approximately 1.4%. The results are in the good agreement with the certified value, 1.99 microg g(-1) of the tablets. Iron and copper in certified reference materials (synthetic) SLRS-4 and SLEW-3 have been enriched with the modified silica gel and estimated with R.S.D.<5%. PMID:18969140

  6. Band alignment in molecular devices: Influence of anchoring group and metal work function

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Guo; Prodan, Emil; Car, Roberto; Selloni, Annabella

    2008-06-01

    Density functional theory calculations are carried out to investigate the electronic properties of molecular junctions formed by amine- and thiol-terminated alkane monolayers sandwiched between two metal (Au, Ag) electrodes. Based on extensive analysis of molecular monolayers of varying densities, we establish a relationship between the alignment of the molecular energy levels and the interface dipoles, which shows that the band alignment (BA) in the limit of long, isolated chains is independent of the link group and can be computed from a reference system of noninteracting molecule+metal molecule metal electrodes. The main difference between the amine and thiol linkers is the effective dipole moment at the contact. This is very large, about 4.5 D, for amine linkers, leading to a strong dependence of the BA on the monolayer density and a slow convergence to the isolated molecule limit. Instead, this convergence is relatively fast for S anchors due to the very small, ˜0.2D , effective dipoles at the contacts.

  7. Enhancement of interface anchoring and densification of Y2O3 coating by metal substrate manipulation in aerosol deposition process

    NASA Astrophysics Data System (ADS)

    Kim, Jinwoo; Lee, Je In; Park, Dong Soo; Park, Eun Soo

    2015-01-01

    The interface anchoring and densification of Y2O3 coatings prepared by aerosol deposition (AD) process were systematically investigated for various types of metal substrates. At initial anchoring stage in AD process, the kinetic energy of impacted particles is converted to the heat energy, which instantly elevates the interface temperature between coating layer and substrate. Thus, the Sn substrate with low melting temperature (˜505 K) results in strong impact anchoring by local interface melting during AD process. On the other hand, the continuous collision and fracture of impacted particles lead to solid consolidation and densification of deposited coating layers. Thus, the SUS substrate with high hardness (˜173 Hv) leads to a highly densified coating layer. Indeed, the bulk metallic glass (BMG) substrates, which have unique low processable temperature (<800 K) called supercooled liquid region and ultra-high hardness (>500 Hv), give rise to both excellent interface anchoring and densification of thick Y2O3 layers with a nano-crystalline structure by AD process. These advantages of the BMG substrates can be used more widely by forming metallic glass buffer layer on various substrates applied to AD process.

  8. Coinage metal complexes supported by the tri- and tetraphosphine ligands.

    PubMed

    Dau, Minh Thuy; Shakirova, Julia R; Karttunen, Antti J; Grachova, Elena V; Tunik, Sergey P; Melnikov, Alexey S; Pakkanen, Tapani A; Koshevoy, Igor O

    2014-05-01

    A series of tri- and tetranuclear phosphine complexes of d(10) metal ions supported by the polydentate ligands, bis(diphenylphosphinomethyl)phenylphosphine (PPP) and tris(diphenylphosphinomethyl)phosphine (PPPP), were synthesized. All the compounds under study, [AuM2(PPP)2](3+) (M = Au (1), Cu (2), Ag (3)), [M4(PPPP)2](4+) (M = Ag (4), Au (5)), [AuAg3(PPPP)2](4+) (6), and [Au2Cu2(PPPP)2(NCMe)4](4+) (7), were characterized crystallographically. The trinuclear clusters 1-3 contain a linear metal core, while in the isostructural tetranuclear complexes 4-6 the metal framework has a plane star-shaped arrangement. Cluster 7 adopts a structural motif that involves a digold unit bridged by two arms of the PPPP phosphines and decorated two spatially separated Cu(I) ions chelated by the remaining P donors. The NMR spectroscopic investigation in DMSO solution revealed the heterometallic clusters 2, 3, and 6 are stereochemically nonrigid and undergo reversible metal ions redistribution between several species, accompanied by their solvation-desolvation. The complexes 1-3 and 5-7 exhibit room temperature luminescence in the solid state (?em = 6-64%) in the spectral region from 450 to 563 nm. The phosphorescence observed originates from the triplet excited states, determined by the metal cluster-centered d?* ? p? transitions. PMID:24750114

  9. Biological activity studies on metal complexes of novel tridentate Schiff base ligand. Spectroscopic and thermal characterization

    Microsoft Academic Search

    Gehad G. Mohamed; M. M. Omar; Amr A. Ibrahim

    2009-01-01

    Metal complexes of novel Schiff base (HL) ligand, prepared via condensation of 4-aminoantipyrine and 2-aminophenol, are prepared. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, ESR spectra and thermal analyses (TG, DTG and DTA). From

  10. The emerging role of calcium-modulating cyclophilin ligand in posttranslational insertion of tail-anchored proteins into the endoplasmic reticulum membrane.

    PubMed

    Yamamoto, Yasunori; Sakisaka, Toshiaki

    2015-06-01

    Tail-anchored (TA) proteins, a class of membrane proteins having an N-terminal cytoplasmic region anchored to the membrane by a single C-terminal transmembrane domain, are posttranslationally inserted into the endoplasmic reticulum (ER) membrane. In yeasts, the posttranslational membrane insertion is mediated by the Guided Entry of TA Proteins (GET) complex. Get3, a cytosolic ATPase, targets newly synthesized TA proteins to the ER membrane, where Get2 and Get3 constitute the Get3 receptor driving the membrane insertion. While mammalian cells employ TRC40 and WRB, mammalian homologs of Get3 and Get1, respectively, they lack the gene homologous to Get2. We recently identified calcium-modulating cyclophilin ligand (CAML) as a TRC40 receptor, indicating that CAML was equivalent to Get2 in the context of the membrane insertion. On the other hand, CAML has been well characterized as a signaling molecule that regulates various biological processes, raising the question of how the two distinct actions of CAML, the membrane insertion and the signal transduction, are assembled. In this review, we summarize recent progress of the molecular mechanism of the membrane insertion of TA proteins and discuss the possibility that CAML could sense the various signals at the ER membrane, thereby controlling TA protein biogenesis. PMID:25869254

  11. The role of metal ion-ligand interactions during divalent metal ion adsorption.

    PubMed

    Eldridge, Daniel S; Crawford, Russell J; Harding, Ian H

    2015-09-15

    A suite of seven different divalent metal ions (Ca(II), Cd(II), Cu(II), Mg(II), Ni(II), Pb(II), Zn(II)) was adsorbed from solution onto two Fe2O3 samples, quartz SiO2 and three different amphoteric polystyrene latices (containing amine and carboxyl functional groups). For the metal oxides, a high correlation was observed between the pH at which 50% of the metal was removed from solution (pH50) and the first hydrolysis constant for the metal ion (pK1). For the polystyrene latices, a much higher correlation was observed between the pH50 and pKc (equilibrium constant describing metal-carboxyl affinity) as opposed to pK1. These observations provide evidence of a strong relationship that exists between a metal's affinity for a particular ligand in solution and for that metal ion's affinity for the same ligand present as part of an adsorbing surface. The isoelectric point of the amphoteric latex surface can be increased by decreasing the carboxyl content of the latex surface. For all 7 metal ions, this resulted in a substantial decrease, for any given pH, in adsorption. We suggest that this may be partly due to the decreased carboxyl content, but is dominantly attributable to the presence of less favorable electrostatic conditions. This, in turn, demonstrates that electrostatics play a controlling role in metal ion adsorption onto amphoteric latex surfaces and, in addition to the nature of the metal ion, also controls the pH at which adsorption takes place. PMID:26001134

  12. Evaluation of metal-mediated DNA binding of benzoxazole ligands by electrospray ionization mass spectrometry.

    PubMed

    Mazzitelli, Carolyn L; Rodriguez, Mireya; Kerwin, Sean M; Brodbelt, Jennifer S

    2008-02-01

    The binding of a series of benzoxazole analogs with different amide- and ester-linked side chains to duplex DNA in the absence and presence of divalent metal cations is examined. All ligands were found to form complexes with Ni2+, Cu2+, and Zn2+, with 2:1 ligand/metal cation binding stoichiometries dominating for ligands containing shorter side chains (2, 6, 7, and 8), while 1:1 complexes were the most abundant for ligands with long side chains (9, 10, and 11). Ligand binding with duplex DNA in the absence of metal cations was assessed, and the long side-chain ligands were found to form low abundance complexes with 1:1 ligand/DNA binding stoichiometries. The ligands with the shorter side chains only formed DNA complexes in the presence of metal cations, most notably for 7 and 8 binding to DNA in the presence of Cu2+. The binding of long side-chain ligands was enhanced by Cu2+ and to a lesser degree by Ni2+ and Zn2+. The cytotoxicities of all of the ligands against the A549 lung cancer and MCF7 breast cancer cell lines were also examined. The ligands exhibiting the most dramatic metal-enhanced DNA binding also demonstrated the greatest cytotoxic activity. Both 7 and 8 were found to be the most cytotoxic against the A549 lung cancer cell line and 8 demonstrated moderate cytotoxicity against MCF7 breast cancer cells. Metal ions also enhanced the DNA binding of the ligands with the long side chains, especially for 9, which also exhibited the highest level of cytotoxicity of the long side-chain compounds. PMID:17583529

  13. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    SciTech Connect

    Bartsch, Richard A.

    2012-06-04

    The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

  14. Synergetic gating of metal-latching ligands and metal-chelating proteins for mesoporous silica nanovehicles to enhance delivery efficiency.

    PubMed

    Wu, Shanshan; Deng, Qingqing; Huang, Xuan; Du, Xuezhong

    2014-09-10

    Stimuli-responsive drug delivery systems are highly desirable for improved therapeutic efficacy and minimized adverse effects of drugs. Mesoporous silica nanoparticles (MSNs) functionalized with pentadentate ligands, N-(3-trimethoxysilylpropyl)ethylenediamine triacetate (TSP-DATA), in the presence of metal ions with and without myoglobin (Mb)-containing surface-accessible histidine residues, were constructed for pH-triggered controlled release. The DATA ligands immobilized on the MSN pore outlets could encapsulate cargo within the pores by metal latching across pore openings, and release efficiency increased with the increase of surface density of the DATA ligands. The release efficiencies for the metal-chelating protein nanogates, through multiple-site binding of Mb with the metal-chelating ligands, were higher than those for the metal-latching ligand nanogates but were almost independent of surface density of the ligands investigated. Both the metal-latching ligands and the metal-chelating proteins played a synergetic role in gating MSNs for high-loading drug delivery and stimuli-responsive controlled release. The constructed Mb-Cu(2+)-gated MSN delivery system has promising applications in targeted drug therapy of tumors. PMID:25137673

  15. New Coordination Polymers Based on Transition Metal Squarates and Pyrazine Ligands

    Microsoft Academic Search

    Christian Näther; Jan Greve

    2003-01-01

    Three new coordination polymers have been prepared by hydrothermal reaction of squaric acid, pyrazine and the metal halides FeCl2· 4H 2O, CoBr2 and NiBr2. In their crystal structures the metal atoms are coordinated by four water molecules and two pyrazine ligands within slightly distorted octahedra. The pyrazine ligands connect the metal atoms via µ-N,N'-coordination to linear chains which are connected

  16. Surface engineered and ligand anchored nanobioconjugate: an effective therapeutic approach for oral insulin delivery in experimental diabetic rats.

    PubMed

    Sharma, Rajeev; Gupta, Umesh; Garg, Neeraj K; Tyagi, Rajeev K; Jain, N K

    2015-03-01

    The present study was designed to enhance intestinal absorption of insulin by nanobioconjugate formulated with PEGylation and Concanavalin A based targeted synergistic approach. The attempts were aimed at maximizing bioavailability and therapeutic efficacy of insulin by incorporating it in Concanavalin A anchored PEGylated nanoconstructs. The Con A anchored PEGylated PLGA diblock copolymer was synthesized by modified surface functionalization method, and was then characterized by FTIR and 1H NMR spectrum analysis. The nanoparticles from synthesized polymers were prepared and characterized for mean size and distribution by laser diffraction spectroscopy. The physicochemically characterized (by SEM and TEM) formulations were evaluated for optimum particle size, polydispersity index, zeta potential and entrapment efficiency 196.3±4.5 nm, 0.15±0.04, -25.6±1.68 and 44.6±3.5% respectively. The insulin encapsulation efficiency and in vitro release were assessed by bicinchoninic protein assay (BCA). The in vitro results corroborated in vivo studies carried out in experimentally created diabetic albino rats. The nano-encapsulated insulin was discovered to meet the requirements by achieving better stability, improved absorption and enhanced oral bioavailability elucidated by in vivo and in vitro bioassays. PMID:25679489

  17. Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand.

    PubMed

    Davenport, T C; Tilley, T D

    2015-07-01

    A series of dinuclear and tetranuclear first-row transition metal complexes were synthesized with the dinucleating ligand 2,7-bis(di(2-pyridyl)fluoromethyl)-1,8-naphthyridine (DPFN). The coordination pocket and rigidity of the DPFN ligand enforces pseudo-octahedral geometries about the metal centers that contain chloro, hydroxo, and aqua bridging ligands forming a "diamond" shaped configuration with metal-metal distances varying from 2.7826(5) to 3.2410(11) Å. Each metal center in the dinuclear complexes has an additional open coordination site that accommodates terminal ligands in a syn geometry of particular interest in catalyst design. The complexes are characterized by electronic spectroscopy, electrochemistry and potentiometric titration methods. PMID:25420206

  18. Universal spectrochemical series of six-coordinate octahedral metal complexes for modifying the ligand field splitting.

    PubMed

    Ishii, Tomohiko; Tsuboi, Shino; Sakane, Genta; Yamashita, Masahiro; Breedlove, Brian K

    2009-01-28

    We studied a novel universal spectrochemical series of six-coordinated octahedral 3d transition metal complexes, which can be used for any combination of central metal atom and ligand molecules. A two dimensional spectrochemical series could be used to estimate the ligand field splitting energy of not only known compounds but also the unknown compounds. Therefore, it should be possible to control the physical properties, such as the electronic and magnetic properties and the optical phenomena of octahedral transition metal complexes by modifying the ligand field splitting. PMID:19378561

  19. Metallophore mapping in complex matrices by metal isotope coded profiling of organic ligands.

    PubMed

    Deicke, Michael; Mohr, Jan Frieder; Bellenger, Jean-Philippe; Wichard, Thomas

    2014-12-01

    Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals. PMID:25298978

  20. Open layers based on metal-oxide chains linked by cyclohexanedicarboxylate ligands

    E-print Network

    Wang, Xiqu

    Open layers based on metal-oxide chains linked by cyclohexanedicarboxylate ligands Inn Hoe Kim a Accepted 8 October 2009 Available online 29 October 2009 Keywords: Metal-oxide organic compounds Indium hydroxide Cyclohexanedicarboxylic acid Synthesis Crystal structure a b s t r a c t Three layered metal-oxide

  1. Determination of Strong Metal Ligands (S(II-))in Natural Waters

    NASA Astrophysics Data System (ADS)

    Kramer, J.; Smith, D. S.; Bell, R. A.; Ernste, M.

    2003-12-01

    Reduced sulfide (S(II-)) ligands have been measured in oxic freshwaters at 1-100s nM. "Group B" metals, such as Ag(I), Hg(II), Cu(I) and Pb(II) bind strongly to S(II-) ligands. Their role in aqueous metal speciation and suppression of metal toxicity make S(II-) ligands an important analytical challenge. S(II-) is probably stabilized in oxic environments as metal-sulfide (M-S) clusters within natural organic matter (NOM). S(II-) species are measured by Cr(II) reduction of M-S, acid reaction, purge and trap to capture H2S and measurement as the methylene diamine complex (CRS). But CRS may also detect other sulfur species. Silver is an excellent probe metal for determination of strong ligand sites(SLS)in NOM. A competitive ligand method, using Ag(I), is demonstrated. The bound Ag-ligand and the "free" silver ion concentration are measured during the titration. The total strong ligand (Lt) is determined by a Grans' approach. These values are used to determine the (Lt) and the conditional binding constant, K'. Measured Lt concentrations match CRS concentrations, and conditional stability constants for a 1:1 M-L stoichiometry range from log K'= 11+ to 13, consistent with known Ag-S(II-) values. Furthermore SLS and Lt correlate with water-effect ratios (WERs) for silver

  2. Low molecular weight metal ligands: Indicators of metal-induced stress

    SciTech Connect

    Mason, A.Z.; Jenkins, K.D. (California State Univ., Long Beach (USA))

    1988-09-01

    The authors have used EDTA-based metal chelate buffer system to control the speciation of Cd in seawater in order to examine the relationships between free Cd ion activity (Cd{sup +2}) and Cd bioavailability, accumulation and toxicity in the errant polychaete, Neanthes arenceodentata. At external concentrations of (Cd{sup +2}) below 10{sup {minus}10} M, the accumulated dose of Cd in the organism at steady state condition is proportional to the concentrations of metal in the media. An order of magnitude increase in total body load of Cd is observed for each order of magnitude increase in (Cd{sup +2}) in the seawater. At (Cd{sup +2}) greater than 10{sup {minus}9} M, however, the accumulation of Cd by the organisms exceeded proportionality relative to the (Cd{sup +2}) in the seawater. Subcellular fractionation studies show that this increase in accumulation in total body load is due to the combined effects of increased metal accumulation in two cytosolic ligand pools. At 10{sup {minus}9} M (Cd{sup +2}), there is elevated levels of Cd in the metallothionein pool (MT) which appears to reflect induction of the protein. At Cd{sup +2} higher than 10{sup {minus}8} M, there is no further accumulation of Cd on MT, but there is a dramatic increase of Cd in the low molecular weight ligand pool.

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

    PubMed

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

    2015-05-01

    Highly selective, narcissistic self-sorting can be achieved in the formation of self-assembled cages of rare earth metals with multianionic salicylhydrazone ligands. The assembly process is highly sensitive to the length of the ligand and the coordination geometry. Most surprisingly, high-fidelity sorting is possible between ligands of identical coordination angle and geometry, differing only in a single functional group on the ligand core, which is not involved in the coordination. Supramolecular effects allow discrimination between pendant functions as similar as carbonyl or methylene groups in a complex assembly process. PMID:25784462

  4. Nucleophilicites of the metal carbonyl anions: Effects of ligands, solvent, and countercation

    SciTech Connect

    Lai, Chungkung; Feighery, W.G.; Zhen, Yueqian; Atwood, J.D. (State Univ. of New York, Buffalo (USA))

    1989-10-04

    The effects of ligand environment, solvent, and countercation on the nucleophilicity of metal carbonyl anions have been measured. The reactions of the metal carbonyl anion with MeI were measured by infrared stopped-flow spectrometry. The nucleophilicity was found to be relatively unaffected by changes in solvent. Also, a rather small effect of the countercation was observed with a slower rate for the more interacting cation. The rate of reaction of the ligands with MeI was found to directly parallel the donor capability of the ligand. The oxidation potentials of the anions were also measured and are reported. 11 refs., 1 fig., 3 tabs.

  5. Design and Formation of a Large, Tetrahedral, Metal-ligand Cluster Using 1,1'-Binaphthyl Ligands

    SciTech Connect

    Biros, Shannon M.; Yeh, Robert M.; Raymond, Kenneth N.

    2008-03-13

    Many chemists have been fascinated with the development of discrete supramolecular structures that encapsulate guest molecules. These structures can be assembled through covalent or hydrogen bonds, electrostatic or metal-ligand interactions. These host structures have provided valuable insight into the forces involved in small molecule recognition. Our work has focused on the design and study of metal-ligand clusters of varying sizes. The naphthalene [M{sub 4}L{sub 6}]{sup 12-} cluster 1, shown in Figure 1, has demonstrated diastereoselective guest binding and chiral induction properties as well as the ability to catalyze reactions carried out inside the cavity in an enzyme-like manner. However, the size of the cavity (ca. 300-500 {angstrom}{sup 3}) has often limited the scope of substrates for these transformations.

  6. Tetrachelate porphyrin chromophores for metal oxide semiconductor sensitization: effect of the spacer length and anchoring group position.

    PubMed

    Rochford, Jonathan; Chu, Dorothy; Hagfeldt, Anders; Galoppini, Elena

    2007-04-18

    Four Zn(II)-tetra(carboxyphenyl)porphyrins in solution and bound to metal oxide (TiO2, ZnO, and ZrO2) nanoparticle films were studied to determine the effect of the spacer length and anchoring group position (para or meta) on their binding geometry and photoelectrochemical and photophysical properties. The properties of three types of anchoring groups (COOH and COONHEt3) for four Zn(II)-porphyrins (Zn(II)-5,10,15,20-tetra(4-carboxyphenyl)porphyrin (p-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-carboxyphenyl)porphyrin (m-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-(4-carboxyphenyl)phenyl)porphyrin (m-ZnTCP2P), and Zn(II)-5,10,15,20-tetra(3-ethynyl(4-carboxyphenyl)phenyl)porphyrin (m-ZnTC(PEP)P)) were compared. In m-ZnTCPP, m-ZnTCP2P, and m-ZnTC(PEP)P the four anchoring groups are in the meta position on the meso-phenyl rings of the porphyrin macrocycle, thus favoring a planar binding mode to the metal oxide surfaces. The three meta-substituted porphyrin salts have rigid spacer units of increasing length (phenyl (P), biphenyl (P2), and diphenylethynyl (PEP)) between the porphyrin ring and the carboxy anchoring groups, thus raising the macrocycle from the metal oxide surface. All porphyrins studied here, when bound to TiO2 and ZnO, exhibited quenching of the fluorescence emission, consistent with electron injection into the conduction band of the semiconductor. Steady-state UV-vis and fluorescence studies of p-ZnTCPP on insulating ZrO2 showed evidence of aggregation and exciton coupling. This was not observed in any of the meta-substituted porphyrins. The photoelectrochemical properties (IPCE, Voc, and Isc) of the porphyrins bound to TiO2 films in solar cells have been measured and rationalized with respect to the sensitizer binding geometry and distance from the surface. PMID:17385856

  7. 8Hydroxyquinoline anchored to silica gel via new moderate size linker: synthesis and applications as a metal ion collector for their flame atomic absorption spectrometric determination

    Microsoft Academic Search

    Anupama Goswami; Ajai K. Singh; B. Venkataramani

    2003-01-01

    The silica gel modified with (3-aminopropyl-triethoxysilane) was reacted with 5-formyl-8-hydroxyquinoline (FHOQx) to anchor 8-quinolinol ligand on the silica gel. It was characterised with cross polarisation magic angle spinning (CPMAS) NMR and diffuse reflectance infrared Fourier transformation (DRIFT) spectroscopy and used for the preconcentration of Cu(II), Pb(II), Ni(II), Fe(III), Cd(II), Zn(II) and Co(II) prior to their determination by flame atomic absorption

  8. PREDICTING SEDIMENT METAL TOXICITY USING A SEDIMENT BIOTIC LIGAND MODEL: METHODOLOGY AND INITIAL APPLICATION

    EPA Science Inventory

    An extension of the simultaneously extracted metals/acid-volatile sulfide (SEM/AVS) procedure is presented that predicts the acute and chronic sediment metals effects concentrations. A biotic ligand model (BLM) and a pore water?sediment partitioning model are used to predict the ...

  9. Self-healing multiphase polymers via dynamic metal-ligand interactions.

    PubMed

    Mozhdehi, Davoud; Ayala, Sergio; Cromwell, Olivia R; Guan, Zhibin

    2014-11-19

    A new self-healing multiphase polymer is developed in which a pervasive network of dynamic metal-ligand (zinc-imidazole) interactions are programmed in the soft matrix of a hard/soft two-phase brush copolymer system. The mechanical and dynamic properties of the materials can be tuned by varying a number of molecular parameters (e.g., backbone/brush degree of polymerization and brush density) as well as the ligand/metal ratio. Following mechanical damage, these thermoplastic elastomers show excellent self-healing ability under ambient conditions without any intervention. PMID:25348857

  10. Supercritical carbon dioxide-soluble ligands for extracting actinide metal ions from porous solids (EMSP Project Number 64965)

    SciTech Connect

    Dietz, M. L.; Barrans, Jr., R. E.; Herlinger, A. W.; Brennecke, J. F.

    2000-04-24

    The objective of this project is to develop novel, substituted diphosphonic acid ligands that can be used for supercritical carbon dioxide extraction (SCDE) of actinide ions from solid wastes. Specifically, selected diphosphonic acids, which are known to form extremely stable complexes with actinides in aqueous and organic solution, are to be rendered carbon dioxide-soluble by the introduction of appropriate alkyl- or silicon-containing substituents. The metal complexation chemistry of these new ligands in SC-CO{sub 2} will then be investigated and techniques for their use in actinide extraction from porous solids developed. This report summarizes the work performed during the first 1.3 years of a 3-year program. Because the planned studies of metal complexation and the development of techniques for actinide removal from solids are dependent on the availability of suitable ligands, efforts to date have focused primarily on the synthesis of selected alkyl- or silicon-containing diphosphonic acids. The authors' principal targets have been derivatives in which the silicon-containing groups either serve as the ester function or are attached to the anchor carbon of the diphosphonic acid. Because methylenediphosphonic acid (MDPA) is commercially available and because its esterification with simple alcohols to yield symmetrical diesters is well-established, their initial studies have focused on this ligand and its reactions with silyl alcohols. Success has been achieved in the reaction of MDPA and its ethylene, propylene, and butylene analogs with 3-(trimethylsilyl)-1-propanol. Using a procedure similar to that previously employed for the synthesis of C-8 dialkylmethylenediphosphonic acids, this series of alkylenediphosphonic acids has been esterified in good yield (ca. 60%) to the symmetrically-substituted diesters. Vapor phase osmometric and cryoscopic studies of these compounds in toluene and 1-decanol, respectively, indicate that their aggregation properties closely parallel those of the dialkyl-substituted alkylenediphosphonic acids, specifically, the P,P{prime}-bis(2-ethylhexyl)alkylenediphosphonic acids, H{sub 2}DEH[ADP]. Infrared spectroscopy and molecular mechanics methods have been employed to obtain information about the structures of the dimers of P,P{prime}-di-[3-(trimethylsilyl)-1-propylene]methylenediphosphonic acid, H{sub 2}TMSP[MDP], and its propylene analog. Infrared spectroscopy has also been employed to provide qualitative information on the binding of various metal ions by H{sub 2}TMSP[MDP]. The metal complexation properties of this ligand have been found to be similar to those of di-(2-ethylhexyl)methylenediphosphonic acid, examined previously. Studies of the extraction of various cations (e.g., Fe(III), Th(IV), Am(III)) by H{sub 2}TMSP[MDP] and its ethylene analog in conventional organic diluents (e.g., o-xylene) indicate that the extraction behavior of the silyl-derivatized diphosphonic acids closely mimics that of conventional alkylenediphosphonic acids. Thus, derivatization has no adverse impact on the complexation or extraction properties of the diphosphonic acids.

  11. Metal Complexes of Macrocyclic Schiff-Base Ligand: Preparation, Characterisation, and Biological Activity

    PubMed Central

    Ahmed, Riyadh M.; Yousif, Enaam I.; Hasan, Hasan A.; Al-Jeboori, Mohamad J.

    2013-01-01

    A new macrocyclic multidentate Schiff-base ligand Na4L consisting of two submacrocyclic units (10,21-bis-iminomethyl-3,6,14,17-tricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21,-decaene-23,24-disodium) and its tetranuclear metal complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) are reported. Na4L was prepared via a template approach, which is based on the condensation reaction of sodium 2,4,6-triformyl phenolate with ethylenediamine in mole ratios of 2?:?3. The tetranuclear macrocyclic-based complexes were prepared from the reaction of the corresponding metal chloride with the ligand. The mode of bonding and overall geometry of the compounds were determined through physicochemical and spectroscopic methods. These studies revealed tetrahedral geometries about Mn, Co, and Zn atoms. However, square planar geometries have been suggested for NiII and CuII complexes. Biological activity of the ligand and its metal complexes against Gram positive bacterial strain Staphylococcus aureus and Gram negative bacteria Escherichia coli revealed that the metal complexes become more potentially resistive to the microbial activities as compared to the free ligand. However, these metal complexes do not exhibit any effects on the activity of Pseudomonas aeruginosa bacteria. There is therefore no inhibition zone. PMID:23935414

  12. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds; Synthesis, characterization and biological evolution

    NASA Astrophysics Data System (ADS)

    Kumar Naik, K. H.; Selvaraj, S.; Naik, Nagaraja

    2014-10-01

    Present work reviews that, the synthesis of (E)-N";-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M2+L]X2, where M2+ = Mn, Co, Ni, Cu, Sr and Cd, L = (7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X = Cl-. Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective ?-glucosidase inhibitory activity than free Schiff base ligand.

  13. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds: synthesis, characterization and biological evolution.

    PubMed

    Kumar Naik, K H; Selvaraj, S; Naik, Nagaraja

    2014-10-15

    Present work reviews that, the synthesis of (E)-N'-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M(2+)L]X2, where M(2+)=Mn, Co, Ni, Cu, Sr and Cd, L=(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X=Cl(-). Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective ?-glucosidase inhibitory activity than free Schiff base ligand. PMID:24858195

  14. A flexible zwitterion ligand based lanthanide metal-organic framework for luminescence sensing of metal ions and small molecules.

    PubMed

    Wen, Rong-Mei; Han, Song-De; Ren, Guo-Jian; Chang, Ze; Li, Yun-Wu; Bu, Xian-He

    2015-06-28

    A new lanthanide metal-organic framework was constructed using a tripodal flexible zwitterion ligand (H3LBr3) which takes a chair-shaped configuration. The luminescence of the compound displays highly selective sensing of the Fe(3+) ion and nitrobenzene. PMID:25300876

  15. 30 CFR 57.7032 - Anchoring.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Drilling and Rotary Jet Piercing Drilling-Underground Only § 57.7032 Anchoring...them shall be anchored firmly before and during drilling. Drilling—Surface and...

  16. 30 CFR 57.7032 - Anchoring.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Drilling and Rotary Jet Piercing Drilling-Underground Only § 57.7032 Anchoring...them shall be anchored firmly before and during drilling. Drilling—Surface and...

  17. Immobilized metal affinity chromatography of human growth hormone. Effect of ligand density.

    PubMed

    Liesiene, J; Racaityte, K; Morkeviciene, M; Valancius, P; Bumelis, V

    1997-03-01

    Immobilized metal affinity chromatography was examined as a method for the purification of recombinant human growth hormone, somatotropin. Cellulose-based chelating supports, Chelat-Granocel, of a different content of ligand, charged with Cu(II), were assessed for their ability to bind the protein from both crude extract and solution purified by two chromatography steps. Human growth hormone was found to exhibit high affinity to chelating support charged with Cu(II). One step of immobilized metal affinity chromatography on Chelat-Granocel gives 80% purification of the protein. It was shown that the protein retention depends highly on the ligand density. By regulating sorbent ligand density a favourable desorption was achieved. PMID:9098994

  18. The Calculation of Accurate Metal-Ligand Bond Energies

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Partridge, Harry, III; Ricca, Alessandra; Arnold, James O. (Technical Monitor)

    1997-01-01

    The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

  19. Synthesis and characterization of lanthanide and group 1 metal complexes bearing sulfur-rich ligands

    Microsoft Academic Search

    Likitha Priyanthi Seneviratne

    2006-01-01

    A study has been carried out to synthesize lanthanide and group 1 metal complexes bearing sulfur-rich ligands for use in CVD or ALD. 1H NMR and 13C NMR spectroscopy, IR, melting point measurements, X-ray crystal structure analysis, and elemental analyses were used to characterize the lanthanide and group 1 metal complexes. Volatility and thermal stability were also determined. ^ A

  20. The emergence of sulfoxides as efficient ligands in transition metal catalysis.

    PubMed

    Sipos, Gellért; Drinkel, Emma E; Dorta, Reto

    2015-05-26

    Sulfoxides are capable of forming stable complexes with transition metals and there have been many comprehensive studies into their binding properties. However, the use of sulfoxides, particularly chiral sulfoxides, as ligands in transition metal catalysis is rather less well developed. This review aims to describe these catalytic studies and covers new developments that are showing very promising results and that have led to a renewed interest in this field. PMID:25954773

  1. Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

    NASA Astrophysics Data System (ADS)

    Gavrilov, Konstantin N.; Bondarev, Oleg G.; Polosukhin, Aleksei I.

    2004-07-01

    The data published during the last five years on the application of chiral derivatives of phosphorous acid in coordination chemistry and enantioselective catalysis are summarised and discussed. The effect of the nature of these ligands on the structure of metal complexes and on the efficiency of catalytic organic syntheses is shown. Hydroformylation, hydrogenation, allylic substitution and conjugate addition catalysed by transition metal complexes with optically active phosphites and hydrophosphoranes are considered. The prospects for the development of this field of research are demonstrated.

  2. Complexation of a Ligand with a Surfactant Micelle for Soil Heavy Metal Desorption

    Microsoft Academic Search

    Mari Shin; Suzelle F. Barrington; William D. Marshall; Li Wang

    2005-01-01

    The ligands iodide (I) and thiocyanate (SCN), alone or in admixture, in combination with a non-ionic surfactant, Triton X-100, were evaluated as washing agents for heavy metal desorption from a contaminated soil. After seven successive washings, selective sequential extraction (SSE) was performed to determine the heavy metal content that remained associated with each geo-chemical fraction of the soil. The surfactant

  3. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    PubMed Central

    Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

    2015-01-01

    Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

  4. A mixed-valence copper coordination polymer generated by hydrothermal metal/ligand redox reactions

    E-print Network

    Li, Jing

    A mixed-valence copper coordination polymer generated by hydrothermal metal/ligand redox reactions A novel coordination polymer of mixed-valence copper(I,II) with 4,4A-bipyridine and in situ oxidized and crystallographically char- acterized to be a laminated structure via weak copper(II)­ oxygen interactions. Extended

  5. Synthesis, characterization and biological evaluation of transition metal complexes derived from N, s bidentate ligands.

    PubMed

    Md Yusof, Enis Nadia; S A Ravoof, Thahira Begum; Tiekink, Edward R T; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

    2015-01-01

    Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

  6. The second-shell metal ligands of human arginase affect coordination of the nucleophile and substrate.

    PubMed

    Stone, Everett M; Chantranupong, Lynne; Georgiou, George

    2010-12-14

    The active sites of eukaryotic arginase enzymes are strictly conserved, especially the first- and second-shell ligands that coordinate the two divalent metal cations that generate a hydroxide molecule for nucleophilic attack on the guanidinium carbon of l-arginine and the subsequent production of urea and l-ornithine. Here by using comprehensive pairwise saturation mutagenesis of the first- and second-shell metal ligands in human arginase I, we demonstrate that several metal binding ligands are actually quite tolerant to amino acid substitutions. Of >2800 double mutants of first- and second-shell residues analyzed, we found more than 80 unique amino acid substitutions, of which four were in first-shell residues. Remarkably, certain second-shell mutations could modulate the binding of both the nucleophilic water/hydroxide molecule and substrate or product ligands, resulting in activity greater than that of the wild-type enzyme. The data presented here constitute the first comprehensive saturation mutagenesis analysis of a metallohydrolase active site and reveal that the strict conservation of the second-shell metal binding residues in eukaryotic arginases does not reflect kinetic optimization of the enzyme during the course of evolution. PMID:21053939

  7. Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy.

    PubMed

    Bonhommeau, Sébastien; Pontius, Niko; Cobo, Saioa; Salmon, Lionel; de Groot, Frank M F; Molnár, Gábor; Bousseksou, Azzedine; Dürr, Hermann A; Eberhardt, Wolfgang

    2008-10-14

    A series of thin films of Prussian blue analogues is investigated by X-ray absorption spectroscopy (XAS) at the Fe, Co and Mn L(2,3)-edges. The ligand field multiplet theory enables us to examine accurately the electronic structure of these materials. Experimental XAS spectra of CoFe Prussian blue analogues are successfully reproduced using a ground state configuration including metal-to-ligand (MLCT) and ligand-to-metal charge transfer (LMCT) at the Co and Fe L(2,3)-edges. In particular, a huge improvement is achieved for satellite peaks at the Co(iii) L(2,3)-edges compared to previous calculations in the literature based on LMCT effects only. On the other hand, XAS spectra of MnFe analogues synthesized for the first time, can be reproduced conveniently by taking into account either MLCT or LMCT depending on the conditions of the sample preparation. For each thin film, the proportion of the different oxidation states of Co, Fe and Mn is evaluated. Unexpectedly, this analysis reveals the presence of a significant amount of a reduced phase, which turns out to be strongly dependent on the sample synthesis and storage conditions. PMID:18818842

  8. Electric transport properties of surface-anchored metal-organic frameworks and the effect of ferrocene loading.

    PubMed

    Liu, Jianxi; Wächter, Tobias; Irmler, Andreas; Weidler, Peter G; Gliemann, Hartmut; Pauly, Fabian; Mugnaini, Veronica; Zharnikov, Michael; Wöll, Christof

    2015-05-13

    Understanding of the electric transport through surface-anchored metal-organic frameworks (SURMOFs) is important both from a fundamental perspective as well as with regards to possible future applications in electronic devices. To address this mostly unexplored subject, we integrated a series of representative SURMOF thin films, formed by copper nodes and trimesic acid and known as HKUST-1, in a mercury-drop-based tunneling junction. Although the transport properties of these SURMOFs are analogous to those of hybrid metal-organic molecular wires, manifested by a very low value of the tunneling decay constant (? ? 0.006 Å(-1)), they are at the same time found to be consistent with a linear increase of resistance with film thickness. Upon loading of SURMOF pores with ferrocene (Fc), a noticeable increase in transport current was observed. A transport model and ab initio electronic structure calculations were used to reveal a hopping transport mechanism and to relate the changes upon Fc loading to those of the electronic and vibrational structures of the SURMOF films. PMID:25875419

  9. Tuning of the spin distribution between ligand- and metal-based spin: electron paramagnetic resonance of mixed-ligand molybdenum tris(dithiolene) complex anions.

    PubMed

    Fekl, Ulrich; Sarkar, Biprajit; Kaim, Wolfgang; Zimmer-De Iuliis, Marco; Nguyen, Neilson

    2011-09-19

    Electron paramagnetic resonance spectra of homoleptic and mixed-ligand molybdenum tris(dithiolene) complex anions [Mo(tfd)(m)(bdt)(n)](-) (n + m = 3; bdt = S(2)C(6)H(4); tfd = S(2)C(2)(CF(3))(2)) reveal that the spin density has mixed metal-ligand character with more ligand-based spin for [Mo(tfd)(3)](-) and a higher degree of metal-based spin for [Mo(bdt)(3)](-): the magnitude of the isotropic (95,97)Mo hyperfine interaction increases continuously, by a factor of 2.5, on going from the former to the latter. The mixed complexes fall in between, and the metal character of the spin increases with the bdt content. The experiments were corroborated by density functional theory computations, which reproduce this steady increase in metal-based character. PMID:21853970

  10. Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands.

    PubMed

    Ray, Kallol; Petrenko, Taras; Wieghardt, Karl; Neese, Frank

    2007-04-28

    A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects. PMID:17426855

  11. Pyrene-terminated phenylenethynylene rigid linkers anchored to metal oxide nanoparticles.

    PubMed

    Taratula, Olena; Rochford, Jonathan; Piotrowiak, Piotr; Galoppini, Elena; Carlisle, Rachael A; Meyer, Gerald J

    2006-08-17

    Phenylenethynylene (PE) rigid linkers (para and meta) were used to anchor pyrene to the surface of TiO2 (anatase) and ZrO2 nanoparticle thin films through the two COOH groups of an isophthalic acid (Ipa) unit. Four chromophore-linker models were studied in solution and bound. Two are novel meta-pyrene-PE linker systems: dimethyl 5-(3-(1-pyrenylethynyl)phenylethynyl)-isophthalate, carrying one pyrene, and dimethyl 5-(bis-3,5-(1-pyrenylethynyl)phenylethynyl)-isophthalate, carrying two. These were compared with para rigid-rods dimethyl 5-(1-pyrenylethynyl)isophthalate and dimethyl 5-(4-(1-pyrenylethynyl)phenylethynyl)-isophthalate, each carrying one pyrene but varying in length. The length of the PE linkers and the para or meta substitution influence the photophysical properties of the compounds. The extinction coefficient increased, and the long wavelength absorbance of the pyrene chromophore was shifted to the red with increasing conjugation. Compared to unsubstituted pyrene, the pyrene-linker systems were characterized by short fluorescence lifetimes (tau approximately 2 ns in tetrahydrofuran solutions), but quantum yields were close to unity. ZINDO/S CI calculations attribute this effect to a switching in the order of the two lowest-lying singlet states of pyrene. High surface coverages, approximately 10(-8) mol/cm2, and carboxylate binding modes on nanostructured TiO2 films were obtained in all cases. The appearance of a pyrene excimer emission on ZrO2, an insulator, indicates that the pyrene-linker system is closely packed (Py-Py < 4 A) on the surface. The fluorescence emission on TiO2 was completely quenched, consistent with quantitative and rapid electron injection into the semiconductor indicating that the pyrene excimer acts as a sensitizer. Photoelectrochemical studies in regenerative solar cells with I3-/I- as the redox mediator indicated near-quantitative conversion of absorbed photons into an electrical current. PMID:16898719

  12. Antimicrobial activity studies of the binuclear metal complexes derived from tridentate Schiff base ligands

    Microsoft Academic Search

    Mehmet Tümer; Hüseyin Köksal; M. Kasim Sener; Selahattin Serin

    1999-01-01

    Three novel tridentate Schiff base ligands derived from?the 3-hydroxysalicylaldehyde (H2L1), 4-hydroxysalicylaldehyde (H2L2) and 5-bromosalicylaldehyde (H2L3) with a new amine N-(pyridyl)-2-hydroxy-3-methoxy-5-aminobenzylamine (2) have been prepared. The ligands and their metal complexes have been characterized by elemental analyses, conductivity and magnetic susceptibility measurements, i.r., electronic absorption and 1H and 13C n.m.r. spectroscopy. All complexes are binuclear and, in some, the H2O molecules

  13. Metal complexes of chiral binaphthyl Schiff-base ligands and their application in stereoselective organic transformations

    Microsoft Academic Search

    Chi-Ming Che; Jie-Sheng Huang

    2003-01-01

    Condensations of aromatic aldehydes with 2,2?-diamino-1,1?-binaphthyl or 2-amino-2?-hydroxy-1,1?-binaphthyl afford various chiral binaphthyl Schiff-base ligands, the most common of which are potentially tetradentate with a N2O2 donor set. The chiral binaphthyl Schiff-base ligands have been shown to form stable complexes with metal ions of Al(III), Ti(IV), Cr(III), Mn(II)\\/Mn(III), Fe(II)\\/Fe(III), Co(II)\\/Co(III), Ni(II), Cu(II), Zn(II), Y(III), Zr(IV), Ru(II), and Pd(II); some of such

  14. Kinetic deuterium isotope effects on ligand migrations in metal hydrides

    SciTech Connect

    Bracker-Novak, J.; Hajela, S.; Lord, M.; Zhang, Minsheng; Rosenberg, E. (California State Univ., Northridge (USA)); Gobetto, R.; Milone, L.; Osella, D. (Universita di Torino (Italy))

    1990-05-01

    Variable-temperature (VT) {sup 1}H and {sup 13}C NMR studies of the complexes ({mu}-X){sub 2}Os{sub 3}(CO){sub 9}({mu}{sub 3}-{eta}{sup 2}-(CH{sub 3}CH{sub 2}){sub 2}C{sub 2}) (X = H or D) reveal that alkyne migration over the face of the cluster is directly linked to hydride migrations on the metal core as evidenced by a temperature-independent isotope effect (k{sub HH}/k{sub DD} = 1.7). In a related study of the VT {sup 13}C NMR of ({mu}-X){sub 2}M{sub 3}(CO){sub 9}({mu}{sub 3}-S) (X = H or D; M = Ru, Os) the observation of a k{sub HH}/k{sub DD} = 1.6 for both the osmium and ruthenium complexes demonstrates that the first stage of carbonyl averaging is brought about by hydride migration and not axial-radial exchange of carbonyl groups, a process that occurs only at higher temperatures. The mechanistic implications of these results are discussed in the context of the reactivity of metal clusters and the dynamic properties of the metal-hydrogen bond.

  15. Metal ion oxidation state assignment based on coordinating ligand hyperfine interaction.

    PubMed

    Oyala, Paul H; Stich, Troy A; Britt, R David

    2015-04-01

    In exchange-coupled mixed-valence spin systems, the magnitude and sign of the effective ligand hyperfine interaction (HFI) can be useful in determining the formal oxidation state of the coordinating metal ion, as well as provide information about the coordination geometry. This is due to the fact that the observed ligand HFI is a function of the projection factor (Clebsch-Gordon coefficient) that maps the site spin value S i of the local paramagnetic center onto the total spin of the exchange-coupled system, S T. Recently, this relationship has been successfully exploited in identifying the oxidation state of the Mn ion coordinated by the sole nitrogenous ligand to the oxygen-evolving complex in certain states of photosystem II. The origin and evolution of these efforts is described. PMID:25663565

  16. Supramolecular polymers constructed by orthogonal self-assembly based on host-guest and metal-ligand interactions.

    PubMed

    Wei, Peifa; Yan, Xuzhou; Huang, Feihe

    2015-02-01

    Supramolecular polymers constructed by orthogonal self-assembly based on host-guest and metal-ligand interactions are attracting increasing attention currently because of their interesting properties and potential applications. Host-guest interactions impart these polymers with good selectivity and convenient enviro-responsiveness, and metal-ligand interactions endow them with various coordination geometries, strong yet tunable coordination binding abilities, as well as magnetic, redox, photophysical, and electrochromic properties. Therefore, supramolecular polymers constructed by orthogonal host-guest and metal-ligand interactions have wide applications in the fields of soft matter, fluorescence sensing, heterocatalysis, electronics, gas storage, etc. In this critical review, we will address the recent development of supramolecular polymeric systems involving metal-ligand interactions and host-guest molecular recognition. Specifically, we classify the related supramolecular polymers depending on the types of macrocyclic hosts, and highlight their intriguing properties originating from the elegant combination of host-guest complexation and metal centers. PMID:25423355

  17. Using biotic ligand models to predict metal toxicity in mineralized systems

    USGS Publications Warehouse

    Smith, Kathleen S.; Balistrieri, Laurie S.; Todd, Andrew S.

    2015-01-01

    The biotic ligand model (BLM) is a numerical approach that couples chemical speciation calculations with toxicological information to predict the toxicity of aquatic metals. This approach was proposed as an alternative to expensive toxicological testing, and the U.S. Environmental Protection Agency incorporated the BLM into the 2007 revised aquatic life ambient freshwater quality criteria for Cu. Research BLMs for Ag, Ni, Pb, and Zn are also available, and many other BLMs are under development. Current BLMs are limited to ‘one metal, one organism’ considerations. Although the BLM generally is an improvement over previous approaches to determining water quality criteria, there are several challenges in implementing the BLM, particularly at mined and mineralized sites. These challenges include: (1) historically incomplete datasets for BLM input parameters, especially dissolved organic carbon (DOC), (2) several concerns about DOC, such as DOC fractionation in Fe- and Al-rich systems and differences in DOC quality that result in variations in metal-binding affinities, (3) water-quality parameters and resulting metal-toxicity predictions that are temporally and spatially dependent, (4) additional influences on metal bioavailability, such as multiple metal toxicity, dietary metal toxicity, and competition among organisms or metals, (5) potential importance of metal interactions with solid or gas phases and/or kinetically controlled reactions, and (6) tolerance to metal toxicity observed for aquatic organisms living in areas with elevated metal concentrations.

  18. Competitive metal-ligand binding between CdTe quantum dots and EDTA for free Ca2+ determination.

    PubMed

    Rodrigues, S Sofia M; Prieto, Diego R; Ribeiro, David S M; Barrado, Enrique; Prior, João A V; Santos, João L M

    2015-03-01

    In this work, a fluorometric approach for the selective determination of calcium by using CdTe nanocrystals as chemosensors, was developed. The quantum dots interacted not with the metal, but with a ligand that also bonded the metal. The fluorescence response was modulated by the extension of the competitive metal-ligand binding, and therefore the amount of free ligand. CdTe quantum dots (QDs) with different capping layers were evaluated, as the QDs surface chemistry and capping nature affected recognition, thus the magnitude of the ensuing fluorescence quenching. The developed procedure was automated by using a multipumping flow system. Upon optimization, thioglycolic acid (TGA) and EDTA were selected as capping and ligand, respectively, providing a linear working range for calcium concentrations between 0.80-3.20 mg L(-1), and a detection limit of 0.66 mg L(-1). A quenching mechanism relying on nanocrystal destabilization upon detachment of surface Cd by the ligand was proposed. PMID:25618655

  19. Synthesis and anti-fungicidal activity of some transition metal complexes with benzimidazole dithiocarbamate ligand

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; Ibrahim, Nasser A.; Attia, Hanaa A. E.

    2009-04-01

    Seven transition metal complexes of benzimidazole ligand (HL) are reported and characterized based on elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA and DTA). From the obtained data, the complexes were proposed to have the general formulae [MX 2(HL)(H 2O)]· yH 2O, where M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cr(III); X = Cl -, SO 42- and y = 0-4. The molar conductance data revealed that all the metal chelates were non-electrolytes. From the magnetic and solid reflectance spectra, it was found that the geometrical structure of these complexes is octahedral. The thermal behaviour of these chelates showed that the hydrated complexes loss water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. Fungicidal activity of the prepared complexes and free ligand was evaluated against three soil borne fungi. Data obtained showed the higher biological activity of the prepared complexes than the parent Schiff base ligand. Formulation of the most potent complex was carried out in the form of 25% WP. Fungicidal activity of the new formulation was evaluated and compared with the standard fungicide Pencycuron (Monceren 25% WP). In most cases, the new formulation possessed higher fungicidal activity than the standard fungicide under the laboratory conditions.

  20. K? Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency

    PubMed Central

    2015-01-01

    The mainline feature in metal K? X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of K? mainline XES. Ligand field expressions are derived that describe the behavior of K? mainlines for first row transition metals with any dn count, allowing for a detailed analysis of the factors governing mainline shape. Further, due to limitations associated with existing computational approaches, we have developed a new methodology for calculating K? mainlines using restricted active space configuration interaction (RAS–CI) calculations. This approach eliminates the need for empirical parameters and provides a powerful tool for investigating the effects that chemical environment exerts on the mainline spectra. On the basis of a detailed analysis of the intermediate and final states involved in these transitions, we confirm the known sensitivity of K? mainlines to metal spin state via the 3p–3d exchange coupling. Further, a quantitative relationship between the splitting of the K? mainline features and the metal–ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from K? mainline spectroscopy. PMID:24914450

  1. Bridging-ligand-substitution strategy for the preparation of metal-organic polyhedra

    SciTech Connect

    Li, Jian-Rong; Zhou, Hong-Cai

    2010-01-01

    Metal–organic polyhedra—discrete molecular architectures constructed through the coordination of metal ions and organic linkers—have recently attracted considerable attention due to their intriguing structures, their potential for a variety of applications and their relevance to biological self-assembly. Several synthetic routes have been investigated to prepare these complexes. However, to date, these preparative methods have typically been based on the direct assembly of metal ions and organic linkers. Although these routes are convenient, it remains difficult to find suitable reaction conditions or to control the outcome of the assembly process. Here, we demonstrate a synthetic strategy based on the substitution of bridging ligands in soluble metal–organic polyhedra. The introduction of linkers with different properties from those of the initial metal–organic polyhedra can thus lead to new metal–organic polyhedra with distinct properties (including size and shape). Furthermore, partial substitution can also occur and form mixed-ligand species that may be difficult to access by means of other approaches.

  2. Electrophilic metal alkyl chemistry in new ligand environments

    SciTech Connect

    Jordan, Richard F.

    2002-09-11

    Cationic group 4 and actinide Cp{sub 2}MR{sup +} metallocenes, and isolobal neutral group 3 and lanthanide Cp{sub 2}MR analogs, are exceptionally reactive in insertion and {sigma}-bond metathesis processes, and have been exploited extensively in catalysis and synthesis, most notably single-site olefin polymerization. The objectives of recent work were to design new electrophilic metal alkyls based on non-Cp{sub 2}M structures, and to exploit these systems in fundamental and applied studies related to olefin polymerization and other catalytic reactions. Key results are reported in the following areas: discrete non-metallocene cationic group 4 alkyls, activation of non-metallocene compounds with methylalumoxane, and cationic aluminum alkyl compounds. Numerous structural formulas are included.

  3. Advances in Quantitative Ion Character-Activity Relationships (QICARs): Using Metal-Ligand Binding Characteristics to Predict

    E-print Network

    Newman, Michael C.

    Characteristics to Predict Metal Toxicity David R. Ownbya * and Michael C. Newmanb a Department of Zoology, Life Abstract Environmental toxicologists readily adopted QSARs from pharmacology to predict organic contaminant developed to predict metal toxicity. The QICAR approach, based on metal-ligand binding tendencies, has been

  4. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    SciTech Connect

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  5. An N-heterocyclic carbene phenanthroline ligand: synthesis, multi-metal coordination and spectroscopic studies.

    PubMed

    Webster, Alyssa A; Prasad, Shyamal K K; Hodgkiss, Justin M; Hoberg, John O

    2015-02-28

    Dimetal complexes of a new N-heterocyclic carbene/phenanthroline ligand have been synthesized. Coordination of both ruthenium and rhenium to the phenanthroline moiety in combination with platinum at the carbene moiety are reported. Steady-state and time-resolved optical absorption and photoluminescence spectra were obtained for the complexes. These results illustrate significant changes occur with the incorporation of the second metal, and that the specific metal bound to the phenanthroline moiety is important to the photophysical characteristics of this system. PMID:25604044

  6. Fusogenic supramolecular vesicle systems induced by metal ion binding to amphiphilic ligands

    PubMed Central

    Richard, Antoine; Marchi-Artzner, Valérie; Lalloz, Marie-Noëlle; Brienne, Marie-Josèphe; Artzner, Franck; Gulik-Krzywicki, Thaddée; Guedeau-Boudeville, Marie-Alice; Lehn, Jean-Marie

    2004-01-01

    The incorporation of lipophilic ligands into the bilayer membrane of vesicles offers the possibility to induce, upon binding of suitable metal ions, a variety of processes, in particular vesicle aggregation and fusion and generation of vesicle arrays, under the control of specific metal–ligand recognition events. Synthetic bipyridine lipoligands Bn bearing a bipyridine unit as head group were prepared and incorporated into large unilamellar vesicles. The addition of Ni2+ or Co2+ metal ions led to the formation of complexes MBn and MBn2 followed by spontaneous fusion to generate giant multilamellar vesicles. The metal ion complexation was followed by UV spectroscopy and the progressive fusion could be visualized by optical dark-field and fluorescence microscopies. Vesicle fusion occurred without leakage of the aqueous compartments and resulted in the formation of multilamellar giant vesicles because of the stacking of the lipoligands Bn. The fusion process required a long enough oligoethylene glycol spacer and a minimal concentration of lipoligand within the vesicle membrane. Metallosupramolecular systems such as the present one offer an attractive way to induce selective intervesicular processes, such as vesicle fusion, under the control of molecular recognition between specific metal ions and lipoligands incorporated in the bilayer membrane. They provide an approach to the design of artificial “tissue-mimetics” through the generation of polyvesicular arrays of defined architecture and to the control of their functional properties. PMID:15492229

  7. Synthesis of Ruthenium Boryl Analogues of the Shvo Metal–Ligand Bifunctional Catalyst

    PubMed Central

    Koren-Selfridge, Liza; Query, Ian P.; Hanson, Joel A.; Isley, Nicholas A.; Guzei, Ilia A.; Clark, Timothy B.

    2010-01-01

    Metal boryl complexes have received significant attention in the literature in recent years due to their role as key intermediates in a number of metal-catalyzed borylation reactions. The ligand scaffold is known to have a significant impact on the observed reactivity of these metal boryl complexes. A synthetic strategy to access ruthenium boryl analogues of the Shvo metal–ligand catalysts is described. Heating a precursor to Shvo’s catalyst (1) with bis(catecholato)diboron at 50 °C provided ruthenium boryl complex 3 [2,5-Ph2-3,4-Tol2(?5-C4COBcat)Ru(CO)2Bcat] (Bcat = catecholatoboryl). Addition of bis(catecholato)diboron to complex 1 in the presence of a phenol results in ruthenium boryl complex5 [2,5-Ph2-3,4-Tol2(?5-C4COH)Ru(CO)2Bcat] at 22 °C in 30% isolated yield. A single crystal X-ray analysis of complex 5 confirmed the assigned structure. An improved synthesis of ruthenium boryl complex 5 was developed by the in situ formation of complex 3 [2,5-Ph2-3,4-Tol2(?5-C4COBcat)Ru(CO)2Bcat] followed by addition of the phenol, resulting in a 51% yield. PMID:20835402

  8. Stereochemistry of complexes with double and triple metal-ligand bonds: a continuous shape measures analysis.

    PubMed

    Alvarez, Santiago; Menjón, Babil; Falceto, Andrés; Casanova, David; Alemany, Pere

    2014-11-17

    To each coordination polyhedron we can associate a normalized coordination polyhedron that retains the angular orientation of the central atom-ligand bonds but has all the vertices at the same distance from the center. The use of shape measures of these normalized coordination polyhedra provides a simple and efficient way of discriminating angular and bond distance distortions from an ideal polyhedron. In this paper we explore the applications of such an approach to analyses of several stereochemical problems. Among others, we discuss how to discern the off-center displacement of the metal from metal-ligand bond shortening distortions in families of square planar biscarbene and octahedral dioxo complexes. The normalized polyhedron approach is also shown to be very useful to understand stereochemical trends with the help of shape maps, minimal distortion pathways, and ligand association/dissociation pathways, illustrated by the Berry and anti Berry distortions of triple-bonded [X?ML4] complexes, the square pyramidal geometries of Mo coordination polyhedra in oxido-reductases, the coordination geometries of actinyl complexes, and the tetrahedricity of heavy atom-substituted carbon centers. PMID:25365476

  9. Identification of an altered peptide ligand based on the endogenously presented, rheumatoid arthritis-associated, human cartilage glycoprotein-39(263–275) epitope: an MHC anchor variant peptide for immune modulation

    PubMed Central

    Boots, Annemieke MH; Hubers, Henk; Kouwijzer, Milou; den Hoed-van Zandbrink, Leontien; Westrek-Esselink, Bernice M; van Doorn, Cindy; Stenger, Rachel; Bos, Ebo S; van Lierop, Marie-jose C; Verheijden, Gijs F; Timmers, Cornelis M; van Staveren, Catharina J

    2007-01-01

    We sought to identify an altered peptide ligand (APL) based on the endogenously expressed synovial auto-epitope of human cartilage glycoprotein-39 (HC gp-39) for modulation of cognate, HLA-DR4-restricted T cells. For this purpose we employed a panel of well-characterized T cell hybridomas generated from HC gp-39-immunized HLA-DR4 transgenic mice. The hybridomas all respond to the HC gp-39(263–275) epitope when bound to HLA-DR4(B1*0401) but differ in their fine specificities. First, the major histocompatibility complex (MHC) and T-cell receptor (TCR) contact residues were identified by analysis of single site substituted analogue peptides for HLA-DR4 binding and cognate T cell recognition using both T hybridomas and polyclonal T cells from peptide-immunized HLA-DR4 transgenic mice. Analysis of single site substituted APL by cognate T cells led to identification of Phe265 as the dominant MHC anchor. The amino acids Ala268, Ser269, Glu271 and Thr272 constituted the major TCR contact residues, as substitution at these positions did not affect HLA-DR4(B1*0401) binding but abrogated T cell responses. A structural model for visualisation of TCR recognition was derived. Second, a set of non-classical APLs, modified at the MHC key anchor position but with unaltered TCR contacts, was developed. When these APLs were analysed, a partial TCR agonist was identified and found to modulate the HC gp-39(263–275)-specific, pro-inflammatory response in HLA-DR4 transgenic mice. We identified a non-classical APL by modification of the p1 MHC anchor in a synovial auto-epitope. This APL may qualify for rheumatoid arthritis immunotherapy. PMID:17645792

  10. Guanidinates: a new class of ligands for dimetal units with multiple metal-metal bonds

    E-print Network

    Wilkinson, Chad C.

    2009-05-15

    This dissertation concerns the discovery of the ability of the guanidinate ligand hpp (hpp = anion of 1,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine) to stabilize high oxidation states of dimetal units (particularly dimolybdenum species...

  11. Guanidinates: a new class of ligands for dimetal units with multiple metal-metal bonds 

    E-print Network

    Wilkinson, Chad C.

    2009-05-15

    This dissertation concerns the discovery of the ability of the guanidinate ligand hpp (hpp = anion of 1,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine) to stabilize high oxidation states of dimetal units (particularly dimolybdenum species...

  12. Linear free energy relationships for metal-ligand complexation: Bidentate binding to negatively-charged oxygen donor atoms

    NASA Astrophysics Data System (ADS)

    Carbonaro, Richard F.; Atalay, Yasemin B.; Di Toro, Dominic M.

    2011-05-01

    Stability constants for metal complexation to bidentate ligands containing negatively-charged oxygen donor atoms can be estimated from the following linear free energy relationship (LFER): log KML = ?OO( ?O log KHL,1 + ?O log KHL,2) where KML is the metal-ligand stability constant for a 1:1 complex, KHL,1 and KHL,2 are the proton-ligand stability constants (the ligand p Ka values), and ?O is the Irving-Rossotti slope. The parameter ?OO is metal specific and has slightly different values for five and six membered chelate rings. LFERs are presented for 21 different metal ions and are accurate to within approximately 0.30 log units in predictions of log KML values. Ligands selected for use in LFER development include dicarboxylic acids, carboxyphenols, and ortho-diphenols. For ortho-hydroxybenzaldehydes, ?-hydroxycarboxylic acids, and ?-ketocarboxylic acids, a modification of the LFER where log KHL,2 is set equal to zero is required. The chemical interpretation of ?OO is that it accounts for the extra stability afforded to metal complexes by the chelate effect. Cu-NOM binding constants calculated from the bidentate LFERs are similar in magnitude to those used in WHAM 6. This LFER can be used to make log KML predictions for small organic molecules. Since natural organic matter (NOM) contains many of the same functional groups (i.e. carboxylic acids, phenols, alcohols), the LFER log KML predictions shed light on the range of appropriate values for use in modeling metal partitioning in natural systems.

  13. Photoinduced charge, ion & energy transfer processes at transition-metal coordination compounds anchored to mesoporous, nanocrystalline metal-oxide thin films

    NASA Astrophysics Data System (ADS)

    Ardo, Shane

    Photovoltaics provide a direct means of converting photons into useful, electric power; however traditional silicon-based technologies are too expensive for global commercialization. Dye-sensitized mesoporous semiconducting thin films, when utilized in regenerative photoelectrochemical cells, are one category of next generation photovoltaics that could eventually circumvent this issue. In fact, their architecture also affords a clear platform for implementation of a direct, solar fuel-forming system. The mechanisms involved in the myriad of molecular processes that occur in these molecular--solid-state hybrid materials are poorly understood. Thus, the overriding goal of this dissertation was to evaluate sensitized mesoporous, nanocrystalline metal-oxide thin films critically so as to elucidate mechanistic phenomena. Using transient and steady-state absorption and emission spectroscopies as well as (photo)electrochemistry, various previously unobserved processes have been identified. Chapter 2 demonstrates for the first time that the electric fields emanating from these charged thin films affect surface-anchored molecular sensitizers via a Stark effect. In most cases, further, but incomplete, ionic screening of the charged nanoparticles from the sensitizers, as non-Faradaic electrolyte redistribution, was spectroscopically inferred after rapid semiconductor charging. Chapter 3 highlights the reactivity of Co(I) coordination-compound catalysts anchored to anatase TiO2 thin-film electrodes. Visible-light excitation resulted in prompt excited-state electron injection into TiO2 while introduction of benzylbromide into the fluid solution surrounding the thin film led to a 2e--transfer, oxidative-addition reaction to Co1 forming a stable Co--benzyl product. Subsequent visible-light excitation initiated a photocatalytic cycle for C--C bond formation. Unique to the nanocrystalline thin films employed here, Chapter 4 demonstrates that traditional time-resolved polarization spectroscopy can be employed to monitor lateral self-exchange energy- and hole-transfer reactions across the sensitized TiO2 surface. Under conditions of poor excited-state injection, support for Ru*/II self exchange was obtained, while subsequent to electron injection, the resulting RuIII state of the sensitizer was often capable of RuIII/II self-exchange reactions. The kinetics for many processes associated with mesoporous, nanocrystalline TiO2 thin films can be modeled by a stretched-exponential function, which possesses an underlying distribution of rate constants. In Chapter 5, we provide the first implementation of an Arrhenius analysis for the temperature dependence of these distributions.

  14. Excitation of the ligand-to-metal charge transfer band induces electron tunnelling in azurin

    SciTech Connect

    Baldacchini, Chiara [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy); Institute of Agro-environmental and Forest Biology, National Research Council, I-05010 Porano (Italy); Bizzarri, Anna Rita; Cannistraro, Salvatore, E-mail: cannistr@unitus.it [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy)

    2014-03-03

    Optical excitation of azurin blue copper protein immobilized on indium-tin oxide, in resonance with its ligand-to-metal charge transfer absorption band, resulted in a light-induced current tunnelling within the protein milieu. The related electron transport rate is estimated to be about 10{sup 5}?s{sup ?1}. A model based on resonant tunnelling through an azurin excited molecular state is proposed. The capability of controlling electron transfer processes through light pulses opens interesting perspectives for implementation of azurin in bio-nano-opto-electronic devices.

  15. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand

    PubMed Central

    Noro, Shin-ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. PMID:25592677

  16. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand

    NASA Astrophysics Data System (ADS)

    Noro, Shin-Ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs.

  17. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand.

    PubMed

    Noro, Shin-ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. PMID:25592677

  18. Labeling of fatty acid ligands with the strong electrophilic metal fragment [99mTc(N)(PNP)]2+ (PNP=diphosphane ligand).

    PubMed

    Cazzola, Emiliano; Benini, Elisa; Pasquali, Micol; Mirtschink, Peter; Walther, Martin; Pietzsch, Hans-Jurgen; Uccelli, Licia; Boschi, Alessandra; Bolzati, Cristina; Duatti, Adriano

    2008-02-01

    The electrophilic metal fragment [(99m)Tc(N)(PNP)](2+) (PNP=diphosphane ligand) has been employed for the labeling of fatty acid chains of different lengths. To provide a site-specific group for the attachment of the metallic moiety, the fatty acid derivatives were functionalized by appending a bis-mercapto or, alternatively, a dithiocarbamato pi-donor chelating systems to one terminus of the carbon chain to yield both dianionic and monoanionic bifunctional ligands (L). The resulting complexes, [(99m)Tc(N)(PNP)(L)] (0/+), exhibited the usual asymmetrical structure in which a Tc(triple bond)N group was surrounded by two different bidentate chelating ligands. Dianionic ligands gave rise to neutral complexes, while monoanionic ligands afforded monocationic species. Biodistribution studies were carried out in rats. An isolated perfused rat heart model was employed to assess how structural changes in the radiolabeled fatty acid compound affect the myocardial first pass extraction. Results showed that only monocationic complexes accumulated in myocardium to a significant extent. Conversely, neutral complexes were not efficiently retained into the heart region and rapidly washed out. In isolated perfused rat heart experiments, monocationic complexes exhibited a behavior similar to that of the monocationic flow tracers (99m)Tc-MIBI and (99m)Tc-DBODC with almost identical extraction values, a result that could be attributed to the presence of the monopositive charge. Instead, a slightly lower myocardial extraction was found for neutral complexes. Comparison of the observed kinetic behavior of neutral complexes in the isolated perfused rat heart model with that of the myocardial metabolic tracer [(123)I]IPPA revealed that the introduction of the metallic moiety partially hampers recognition of the labeled fatty acids by cardiac enzymes, and consequently, their behavior did not completely reflect myocardial metabolism. PMID:18205326

  19. Metal-Organic Frameworks (MOFs) as Multivalent Materials: Size Control and Surface Functionalization by Monovalent Capping Ligands.

    PubMed

    Rijnaarts, Timon; Mejia-Ariza, Raquel; Egberink, Richard J M; van Roosmalen, Wies; Huskens, Jurriaan

    2015-07-13

    Control over particle size and composition are pivotal to tune the properties of metal organic frameworks (MOFs), for example, for biomedical applications. Particle-size control and functionalization of MIL-88A were achieved by using stoichiometric replacement of a small fraction of the divalent fumarate by monovalent capping ligands. A fluorine-capping ligand was used to quantify the surface coverage of capping ligand at the surface of MIL-88A. Size control at the nanoscale was achieved by using a monovalent carboxylic acid-functionalized poly(ethylene glycol) (PEG-COOH) ligand at different concentrations. Finally, a biotin-carboxylic acid capping ligand was used to functionalize MIL-88A to bind fluorescently labeled streptavidin as an example towards bioapplications. PMID:26096150

  20. Ligand-controlled syntheses of copper(I) complexes with metal-metal interactions: crystal structure and relativistic density functional theory investigation.

    PubMed

    Liu, Jun-Feng; Min, Xue; Lv, Jin-Yu; Pan, Fu-Xing; Pan, Qing-Jiang; Sun, Zhong-Ming

    2014-10-20

    A family of di-, tri-, and tetranuclear copper(I) complexes supported by length-controlled silaamidinate ligands have been synthesized to show short Cu(I)-Cu(I) distances (2.43-2.62 Å) and feature a linear or bent metal-metal arrangement, which is elucidated by a relativistic density functional theory calculation. PMID:25278439

  1. Metal-pyrazolyl diazine interaction: Synthesis, structure and electrochemistry of binuclear transition metal(II) complexes derived from an `end-off' compartmental Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Budagumpi, Srinivasa; Revankar, Vidyanand K.

    2010-09-01

    Pyrazolyl diazine (?-NN) bridged late first row transition metal(II) complexes have been prepared by the interaction of metal(II) chlorides with an 'end-off' compartmental Schiff base ligand. The ligand system has a strong diazine bridging component and obtained as a condensation product between 1 H-pyrazole-3,5-dicarbohydrazide and 3-acetylcoumarin in absolute ethanol. All synthesized compounds are characterized on the basis of various spectral and analytical techniques. Complexes are found to be non-electrolytes and monomeric in nature. The magnetic exchange interactions are very weak because of the more electronegative exogenous chloride, though diazine bridging group bring metal centers in a close proximity.

  2. Room temperature rapid functionalization of E-H bonds (E = O, N, S) via the metal-ligand cooperation mechanism.

    PubMed

    Scharf, Adam; Goldberg, Israel; Vigalok, Arkadi

    2014-01-01

    An arylpalladium PNF-type pincer complex reacts with water and anilines under very mild conditions, providing access to new PNO- and PNN-pincer complexes with concomitant hydrogen transfer to the ligand core. Such a metal-ligand cooperation mode allows for the irreversible double activation of even highly sterically hindered aniline molecules. With thiols, the activation mode depends on the nature of the substituent at the sulfur atom, with thiophenols giving products of C-S elimination. PMID:24344770

  3. Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

    Microsoft Academic Search

    Oleg S. Pokrovsky; Jacques Schott; Alain Castillo

    2005-01-01

    Brucite (Mg(OH)2) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked

  4. Metal-Containing Ligands for Mixed-Metal Polymers: Novel Cu(II)-Ag(I) Mixed-Metal Coordination Polymers Generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)],3H2O

    E-print Network

    zur Loye, Hans-Conrad

    -dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 wereMetal-Containing Ligands for Mixed-Metal Polymers: Novel Cu(II)-Ag(I) Mixed-Metal Coordination Polymers Generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)],3H2O and Silver(I) Salts Yu-Bin Dong

  5. New metal complexes of N3 tridentate ligand: Synthesis, spectral studies and biological activity

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Abbas Ali Salih; Al Zoubi, Wail

    2015-02-01

    New tridentate ligand 3-amino-4-{1,5-dimethyl-3-[2-(5-methyl-1H-indol-3-yl)-ethylimino]-2phenyl-2,3-dihydro-1H-pyrazol-4-ylazo}-phenol L was synthesized from the reaction of 1,5-dimethyl-3-[2-(5-methyl-1H-indol-3-yl)-ethylimino]-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylamine and 3.4-amino phenol. A complexes of these ligand [Ni(II)(L)(H2O)2 Cl]Cl, [pt(IV)(L)Cl3]Cl and [M(II)(L)Cl]Cl (M = Pd (II), Zn (II), Cd (II) and Hg (II) were synthesized. The complexes were characterized by spectroscopic methods and magnetic moment measurements, elemental analysis, metal content, Chloride containing and conductance. These studies revealed octahedral geometries for the Ni (II), pt (IV) complexes, square planar for Pd (II) complex and tetrahedral for the Zn (II), Cd(II) and Hg (II) complexes. The study of complexes formation via molar ratio and job method in DMF solution has been investigated and results were consistent to those found in the solid complexes with a ratio of (M:L) as (1:1). The thermodynamic parameters, such as ?E*, ?H*, ?S* ?G* and K are calculated from the TGA curve using Coats-Redfern method. Hyper Chem-8 program has been used to predict structural geometries of compounds in gas phase. The synthesized ligand and its metal complexes were screened for their biological activity against bacterial species, two Gram positive bacteria (Bacillus subtilis and Staphylococcus aureus) and two Gram negative bacteria (Escherichia coli and Pseudomonasaeruginosa).

  6. Anchor Modeling

    NASA Astrophysics Data System (ADS)

    Regardt, Olle; Rönnbäck, Lars; Bergholtz, Maria; Johannesson, Paul; Wohed, Petia

    Maintaining and evolving data warehouses is a complex, error prone, and time consuming activity. The main reason for this state of affairs is that the environment of a data warehouse is in constant change, while the warehouse itself needs to provide a stable and consistent interface to information spanning extended periods of time. In this paper, we propose a modeling technique for data warehousing, called anchor modeling, that offers non-destructive extensibility mechanisms, thereby enabling robust and flexible management of changes in source systems. A key benefit of anchor modeling is that changes in a data warehouse environment only require extensions, not modifications, to the data warehouse. This ensures that existing data warehouse applications will remain unaffected by the evolution of the data warehouse, i.e. existing views and functions will not have to be modified as a result of changes in the warehouse model.

  7. Isolation of naturally occurring aluminium ligands using immobilized metal affinity chromatography for analysis by ESI-MS.

    PubMed

    Baldwin, Carson; Cumming, Jonathan; Timperman, Aaron T

    2005-03-01

    Aluminium (iii) is one of the most abundant metal ions found in soil. Typically, Al(+3) is bound to minerals, but its bioavailability and toxicity toward vascular plants increases with increasing soil acidity. Ectomycorrhizal fungi, which live symbiotically on the roots of numerous woody plants, often confer Al(+3) resistance to host plants by reducing metal availability to the plant by unknown mechanisms. A potential mechanism of detoxification is binding of the Al(+3) by organic compounds that are exuded by the fungi into the surrounding soil and solution. A novel method has been developed to purify and characterize Al(+3) binding ligands from Pisolithus tinctorius exudate solutions using Al(+3) immobilized metal affinity chromatography (IMAC), reversed phase chromatography, and mass spectrometry. Fungal exudates produced by P. tinctorius exhibit a strong binding capacity for Al(+3), allowing their selective enrichment and collection using this IMAC method. Elution of the ligands requires the use of high pH. RP-HPLC separation and elemental analysis of the IMAC elutent indicates that the Al(+3) and the exudate ligands both elute from the column but are not bound in a complex. Thus, reversed phase HPLC at pH 10 is used for separation of the ligands and Al(+3) prior to MS analysis. The strongest binding IMAC fraction is analyzed by electrospray ionization mass spectrometry in positive and negative ion modes. This report provides new methods for the direct purification and analysis of naturally occurring ligands that bind hard metal ions. PMID:15724160

  8. Synthesis, crystal structures and properties of three new mixed-ligand d{sup 10} metal complexes constructed from pyridinecarboxylate and in situ generated amino-tetrazole ligand

    SciTech Connect

    Liu Dongsheng [State Key Laboratory Breeding Base of Photocatalysis, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); College of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an, Jiangxi 343009 (China); Huang, Xihe [State Key Laboratory Breeding Base of Photocatalysis, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); Huang Changcang, E-mail: changcanghuang@hotmail.co [State Key Laboratory Breeding Base of Photocatalysis, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); Huang Gansheng [State Key Laboratory Breeding Base of Photocatalysis, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); College of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an, Jiangxi 343009 (China); Chen Jianzhong, E-mail: j.z.chen@fzu.edu.c [State Key Laboratory Breeding Base of Photocatalysis, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China)

    2009-07-15

    Three new metal-organic frameworks, [Zn(atz)(nic)]{sub n}(1), [Zn(atz)(isonic)]{sub n}.nHisonic(2) and [Cd(atz)(isonic)]{sub n}(3) (Hnic=nicotinic acid, Hisonic=isonicotinic acid), have been firstly synthesized by employing mixed-ligand of pyridinecarboxylate with the in situ generated ligand of 5-amino-tetrazolate(atz{sup -}), and characterized by elemental analysis, IR spectroscopy, TGA and single crystal X-ray diffraction. The results revealed that 1 presents a two-dimensional (2D) 'sql' topological network constructed from the linear chain subunit of Zn(nic){sub 2} and atz{sup -} ligand. A remarkable feature of 2 is a 2-fold interpenetrated diamondoid network with free Hisonic molecules locating in the channels formed by the zigzag chain subunits of Zn(isonic){sub 2}. Complex 3 is a 3D non-interpenetrated pillared framework constructed from the double chain subunits of Cd-COO{sup -}Cd. It possesses a rarely observed (4,6)-connected 'fsc' topology. The thermal stabilities and fluorescent properties of the complexes were investigated. All of these complexes exhibited intense fluorescent emissions in the solid state at room temperature. - Graphical abstract: Three new mixed-ligand d{sup 10} metal complexes have been synthesized by employing mixed-ligand synthetic approach. Complex 1 presents a 2D 'sql' topological network. Complex 2 is a 2-fold interpenetrated diamondoid network with microporous channels. Rarely observed (4,6)-connected 'fsc' topological network was found in complex 3.

  9. Testing an application of a biotic ligand model to predict acute toxicity of metal mixtures to rainbow trout.

    PubMed

    Iwasaki, Yuichi; Kamo, Masashi; Naito, Wataru

    2015-04-01

    The authors tested the applicability of a previously developed biotic ligand model (BLM) to predict acute toxicity of single metals and metal mixtures (cadmium, lead, and zinc) to rainbow trout fry (Oncorhynchus mykiss) from a single available dataset. The BLM used in the present study hypothesizes that metals inhibit an essential cation (calcium) and organisms die as a result of its deficiency, leading to an assumption that the proportion of metal-binding ligand (f) is responsible for the toxic effects of metals on the survival of rainbow trout. The f value is a function of free-ion concentrations of metals computed by a chemical speciation model, and the function has affinity constants as model parameters. First, the survival effects of single metals were statistically modeled separately (i.e., f-survival relationship) by using the generalized linear mixed model with binomial distribution. The modeled responses of survival rates to f overlapped reasonably irrespective of metals tested, supporting the theoretical prediction from the BLM that f-survival relationships are comparable regardless of metal species. The authors thus developed the generalized linear mixed model based on all data pooled across the single-metal tests. The best-fitted model well predicted the survival responses observed in mixture tests (r?=?0.97), providing support for the applicability of the BLM to predict effects of metal mixtures. PMID:25323464

  10. Synthesis of metal complexes involving Schiff base ligand with methylenedioxy moiety: Spectral, thermal, XRD and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Sundararajan, M. L.; Jeyakumar, T.; Anandakumaran, J.; Karpanai Selvan, B.

    2014-10-01

    Metal complexes of Zn(II), Cd(II), Ni(II), Cu(II), Fe(III), Co(II), Mn(II) Hg(II), and Ag(I) have been synthesized from Schiff base ligand, prepared by the condensation of 3,4-(methylenedioxy)aniline and 5-bromo salicylaldehyde. All the compounds have been characterized by using elemental analysis, molar conductance, FT-IR, UV-Vis, 1H NMR, 13C NMR, mass spectra, powder XRD and thermal analysis (TG/DTA) technique. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). The FT-IR, 1H NMR, 13C NMR and UV-Vis spectral data suggest that the ligand coordinate to the metal atom by imino nitrogen and phenolic oxygen as bidentate manner. Mass spectral data further support the molecular mass of the compounds and their structure. Powder XRD indicates the crystalline state and morphology of the ligand and its metal complexes. The thermal behaviors of the complexes prove the presence of lattice as well as coordinated water molecules in the complexes. Melting point supports the thermal stability of all the compounds. The in vitro antimicrobial effects of the synthesized compounds were tested against five bacterial and three fungal species by well diffusion method. Antioxidant activities have also been performed for all the compounds. Metal complexes show more biological activity than the Schiff base.

  11. Anchor connector

    SciTech Connect

    Quigg, D.F.; Bell, J.L. Jr.; Jones, D.L.; McFerron, R.G.

    1984-03-27

    An anchor connector incorporating a flexible joint for securing the tension legs of a tensioned leg platform. A latch dog head engages a first recess on the fixed member of the flexible joint and a template recess to prevent disconnection when the dog heads and latch carrier are in a lower position. With the latch carrier (40) in an upper position the latch dog heads fit within a second recess (44) in the fixed member with the dog heads clearing shoulder of template recess, whereby the connector may be released.

  12. Multicomponent assembly of fluorescent-tag functionalized ligands in metal-organic frameworks for sensing explosives.

    PubMed

    Gole, Bappaditya; Bar, Arun Kumar; Mukherjee, Partha Sarathi

    2014-10-01

    Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal-organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by single-crystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of explosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT). PMID:25164426

  13. A photoluminescent interpenetrating metal-organic frame work based on Cu4I4 and novel azino-quinoline ligand

    NASA Astrophysics Data System (ADS)

    Pal, Pankaj K.; Mukherjee, Anindita; Ghosh, Anindya; Patra, Goutam K.

    2014-02-01

    Synthesis of a novel, triply-interpenetrating metal-organic framework 1.H2O is described here. The coordination polymer was synthesized by simple reaction of Cu2I2 with an azino-quinoline ligand (L1). The X-ray crystal structure analysis reveals that the complex 1.H2O is a 2-D coordination polymer having (4,4?) grid network architecture. The ligand L1 possesses quinoline group and the 2-D structure of 1.H2O contains distorted cubane type Cu4I4 SBU unit. Each of the four Cu(I) ions posses tetrahedral coordination environment. Metal-organic framework in 1.H2O shows strong photoluminescence property at room temperature in solid state and emission spectra shows a blue shift of the peak in comparison to the free azino-quinoline ligand (L1). The coordination polymer 1.H2O was found to be stable up to 290 °C.

  14. Liquid chromatographic separation of metal-tetraphenylporphine complexes based on coordination interaction with immobilized neutral ligand in stationary phase

    Microsoft Academic Search

    Tomohiro Suzuki; Koichi Matsumoto; Kin-ichi Tsunoda; Hideo Akaiwa

    1997-01-01

    Proposed is a novel liquid chromatographic system for metal chelates based on the coordination interaction between the central metal in a complex and immobilized neutral ligand in the stationary phase. For this purpose, a 2-(4-pyridyl)ethyl bonded silica gel (4-PES) column was newly prepared, and cobalt(II)-, nickel(II)-, copper(II)-, and zinc(II)-tetraphenylporphine (TPP) complexes were separated on the 4-PES column as well as

  15. Ligand-Assisted Co-Assembly Approach toward Mesoporous Hybrid Catalysts of Transition-Metal Oxides and Noble Metals: Photochemical Water Splitting.

    PubMed

    Liu, Ben; Kuo, Chung-Hao; Chen, Jiejie; Luo, Zhu; Thanneeru, Srinivas; Li, Weikun; Song, Wenqiao; Biswas, Sourav; Suib, Steven L; He, Jie

    2015-07-27

    A bottom-up synthetic approach was developed for the preparation of mesoporous transition-metal-oxide/noble-metal hybrid catalysts through ligand-assisted co-assembly of amphiphilic block-copolymer micelles and polymer-tethered noble-metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble-metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble-metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (?0.1?wt?%) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble-metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems. PMID:26073465

  16. Synthesis, characterization, biological activity and equilibrium studies of metal(II) ion complexes with tridentate hydrazone ligand derived from hydralazine

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Shoukry, Mohamed M.; Abd-Elgawad, Mohamed M. A.

    2012-12-01

    In the present study, a new hydrazone ligand (2-((2-phthalazin-1-yl)hydrazono)methyl)phenol) prepared by condensation of hydralazine (1-Hydralazinophthalazine) with salicylaldehyde (SAH). The synthesized SAH-hydrazone and its metal complexes have been characterized by elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, UV-vis and thermal analysis (TGA). The analytical data of the complexes show the formation of 1:1 [M:L] ratio, where M represents Ni(II), Co(II) and Cu(II) ions, while L represents the deprotonated hydrazone ligand. IR spectra show that SAH is coordinated to the metal ions in a tridentate manner through phthalazine-N, azomethine-N and phenolic-oxygen groups. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. Proton-ligand association constants of (SAH) and the stepwise stability constants of its metal complexes are determined potentiometrically in 0.1 M NaNO3 at different temperatures and the corresponding thermodynamic parameters were derived and discussed. The order of -?G° and -?H° were found to obey Mn2+ < Co2+ < Ni2+ < Cu2+, in accordance with the Irving-Williams order. The complexes were stabilized by enthalpy changes and the results suggest that the complexation is an enthalpy-driven process. The concentration distribution diagrams of the complexes are evaluated.

  17. Factors affecting the removal of metals during activated sludge wastewater treatment I. The role of soluble ligands

    Microsoft Academic Search

    P. S. Lawson; R. M. Sterritt; J. N. Lester

    1984-01-01

    Samples of mixed liquor were withdrawn from a laboratory-scale activated sludge simulation operated at a range of sludge ages from 3 to 12 days in order to examine the difference in metal uptake by the mixed liquor biomass in the absence and presence of soluble ligands. One half of the samples were centrifuged, washed, and resuspended in physiological saline solution,

  18. Reevaluation of metal bioaccumulation and chronic toxicity in Hyalella azteca using saturation curves and the biotic ligand model

    Microsoft Academic Search

    U. Borgmann; W. P. Norwood; D. G. Dixon

    2004-01-01

    Bioaccumulation by Hyalella of all metals studied so far in our laboratory was re-evaluated to determine if the data could be explained satisfactorily using saturation models. Saturation kinetics are predicted by the biotic ligand model (BLM), now widely used in modelling acute toxicity, and are a pre-requisite if the BLM is to be applied to chronic toxicity. Saturation models provided

  19. Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

  20. Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

    SciTech Connect

    Byrne, Lindsay T.; Hondow, Nicole S.; Koutsantonis, George A.; Skelton, Brian W.; Torabi, A. Asgar; White, Allan H.; Wild, S. Bruce (UWA); (ANU)

    2008-11-03

    The trimetallic clusters [Ru{sub 3}(CO){sub 10}(dppm)], [Ru{sub 3}(CO){sub 12}] and [RuCo{sub 2}(CO){sub 11}] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH{sub 2}CH{sub 2}PHPh ({double_bond}LH{sub 2}), gave two products under various conditions which have been characterized by spectroscopic and crystallographic means. These two complexes [Ru{sub 3}({mu}dppm)(H)(CO){sub 7}(LH)] and [Ru{sub 3}({mu}-dppm)(H)(CO){sub 8}(LH)Ru{sub 3}({mu}-dppm)(CO){sub 9}], show the versatility of the ligand, with it chelating in the former and bridging two Ru{sub 3} units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru{sub 3}(CO){sub 12}] the reaction with LH{sub 2} gave a poor yield of a tetranuclear butterfly cluster, [Ru{sub 4}(CO){sub 10}(L){sub 2}], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe), reacted with [RuCo{sub 2}(CO){sub 11}] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO){sub 6}(SCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe))], which appears to be the only one of its type so far structurally characterized. The secondary phosphine, HPMe(C{sub 6}H{sub 4}(CH{sub 2}OMe)) and its oxide HP(O)Me(C{sub 6}H{sub 4}(CH{sub 2}OMe)) also react with the cluster [Ru{sub 3}(CO){sub 10}(dppm)] to give carbonyl substitution products, [Ru{sub 3}(CO){sub 5}(dppm)({mu}{sub 2}-PMe(C{sub 6}H{sub 4}CH{sub 2}OMe)){sub 4}], and [Ru{sub 3}H(CO){sub 7}(dppm)({mu}{sub 2},{eta}{sup 1}P({double_bond}O)Me(C{sub 6}H{sub 4}CH{sub 2}OMe))]. The former consists of an open Ru{sub 3} triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom.

  1. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    NASA Astrophysics Data System (ADS)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  2. Electrochemically triggered double translocation of two different metal ions with a ditopic calix[6]arene ligand.

    PubMed

    Colasson, Benoit; Le Poul, Nicolas; Le Mest, Yves; Reinaud, Olivia

    2010-03-31

    A ditopic ligand based on a calix[6]arene with three imidazoles (Im) appended at the small rim and three triazoles (Tria) at the large one is able to form selectively two stable heterodinuclear complexes with Zn(II)(Im)/Cu(I)(Tria) and Cu(II)(Im)/Zn(II)(Tria). In the Cu(I) case, the zinc cation is preferentially coordinated at the Im site while the copper is bound at the Tria site. The situation is the opposite when Cu(II) is used. The position of the two cations within the complex can be electrochemically switched via the oxidation-reduction of the copper cation between oxidation states +I and +II. The presence of the zinc cation is crucial (i) to control the bistability of the system by an allosteric structuring role and (ii) to promote the metal switch since the monocopper complex exhibits reversible behavior with Cu located at the imidazole site in both oxidation states. This represents the first example of a double translocation of two different metal cations. PMID:20210313

  3. Gold complexes with dithiothiophene ligands: a metal based on a neutral molecule.

    PubMed

    Belo, D; Alves, H; Lopes, E B; Duarte, M T; Gama, V; Henriques, R T; Almeida, M; Pérez-Benítez, A; Rovira, C; Veciana, J

    2001-01-19

    The gold complexes n-Bu4N[Au(alpha-tpdt)2] (5), n-Bu4N[Au(dtpdt)2] (4) and n-Bu4N[Au(tpdt)2] (6) based on new dithiothiophene ligands (alpha-tpdt= 2,3-thiophenedithiolate, dtpdt=2,3-dihydro-5,6-thiophenedithiolate and tpdt = 3,4-thiophenedithiolate) have been prepared and characterised. These gold(III) complexes are diamagnetic, but they can be oxidised with iodine to the paramagnetic compounds [Au(alpha-tpdt)2] (8), [Au(dtpdt)2] (7) and n-Bu4N[[Au(tpdt)2]n-2] (9), which were isolated as fine powders and which exhibit paramagnetic susceptibilities that are almost temperature independent with room temperature values of 2.5 x 10(-4), 2.0 x 10(-4) and 5 x 10(-4) emu x mol(-1), respectively. Interestingly, the neutral complex [Au(alpha-tpdt)2] (8) as a polycrystalline sample displays the properties of a metallic system with a room temperature electrical conductivity of 6 S x cm(-1) and a thermoelectric power of 5.5 microVK(-1); this is the first time that this metallic property has been observed in a molecular system based on a neutral species. PMID:11271537

  4. Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand

    NASA Astrophysics Data System (ADS)

    Shankarwar, Sunil G.; Nagolkar, Bhagwat B.; Shelke, Vinod A.; Chondhekar, Trimbak K.

    2015-06-01

    A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been synthesized with newly synthesized biologically active macrocyclic ligand. The ligand was synthesized by condensation of ?-diketone 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)propane-1,3-dione and o-phenylene diamine. All the complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV-Vis spectroscopy and mass spectroscopy. From the analytical data, stoichiometry of the complexes was found to be 1:2 (metal:ligand). Thermal behavior (TG/DTA) and kinetic parameters suggest more ordered activated state in complex formation. All the complexes are of high spin type and six coordinated. On the basis of IR, electronic spectral studies and magnetic behavior, an octahedral geometry has been assigned to these complexes. The antibacterial and antifungal activities of the ligand and its metal complexes, has been screened in vitro against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma respectively.

  5. Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand.

    PubMed

    Shankarwar, Sunil G; Nagolkar, Bhagwat B; Shelke, Vinod A; Chondhekar, Trimbak K

    2015-06-15

    A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been synthesized with newly synthesized biologically active macrocyclic ligand. The ligand was synthesized by condensation of ?-diketone 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)propane-1,3-dione and o-phenylene diamine. All the complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, (1)H-NMR, UV-Vis spectroscopy and mass spectroscopy. From the analytical data, stoichiometry of the complexes was found to be 1:2 (metal:ligand). Thermal behavior (TG/DTA) and kinetic parameters suggest more ordered activated state in complex formation. All the complexes are of high spin type and six coordinated. On the basis of IR, electronic spectral studies and magnetic behavior, an octahedral geometry has been assigned to these complexes. The antibacterial and antifungal activities of the ligand and its metal complexes, has been screened in vitro against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma respectively. PMID:25775943

  6. Crystal structures, spectroscopic and nonlinear optical properties of metal complexes of Schiff-base ligands containing nitrogen and sulfur donors

    Microsoft Academic Search

    Yu-Peng Tian; Chun-Ying Duan; Xiao-Zeng You; Thomas C. W. Mak; Qing Luo; Jian-Ying Zhou

    1997-01-01

    ML2 type CuII chelates with the Schiff base ligands R-C6H4CHNNHC(S)SCH2Ph (R=NMe2 or -OMe) have been prepared and characterized.\\u000a Spectroscopic data suggest that the Schiff bases act as singly charged anionic bidentate ligands, forming stable neutral metal\\u000a complexes. Magnetic and e.s.r. data support a square-planar coordination geometry for both complexes. Single crystal X-ray\\u000a diffraction analysis of the complexes has established that

  7. Studies on antimicrobial effects of four ligands and their transition metal complexes with 8-mercaptoquinoline and pyridine terminal groups.

    PubMed

    Zhang, Li-Jie; Zhang, Jing-An; Zou, Xun-Zhong; Liu, Ya-Jie; Li, Ning; Zhang, Zi-Jie; Li, Yu

    2015-04-15

    Four types of ligands (Q1-Q4) and their complexes (1-36) with transition metal ions have been synthesized, in which two new complexes (15 and 20) have been prepared and tested. In vitro antimicrobial activities of the ligands and their complexes were investigated against a representative panel of strains including two Gram positive bacteria (Sarcina ureae, Staphylococcus aureus), two Gram negative bacteria (Escherichia coli, Pseudomonas aeruginosa) and three fungi (Aspergillus niger, Saccharomyces cerevisiae, Fusarium oxysporum f. sp. cubense). The relationship between the structure and the antibacterial activities was discussed. Our study results indicated that some compounds have preferred antibacterial activities that may have potential pharmaceutical applications. PMID:25791454

  8. Metal speciation dynamics in dispersions of soft colloidal ligand particles under steady-state laminar flow condition.

    PubMed

    Duval, Jérôme F L; Qian, Shizhi

    2009-11-19

    A theory is presented for metal speciation dynamics in a swarm of soft, spherical core-hell colloidal ligand particles under steady-state laminar flow condition. Mass transfer and subsequent complexation of metal species within the reactive, permeable particle shell are governed by the interplay between (i) convective-diffusion of free metal ions M within and around the shell where ligands L are distributed, and (ii) kinetics of ML complex formation/dissociation in the shell. The local concentrations of metal M and complex ML are determined by the convective-diffusion equations with appropriate chemical source term and full account of radial and angular concentration polarization contributions. The steady-state flow field is determined from the solution of Navier-tokes equation including convective acceleration term for the fluid external to the particle, and from Brinkman equation for the internal fluid flow. The confined location of ligands within the particle shell leads to ML formation/dissociation rate constants (denoted as ka* and kd*, respectively) that differ significantly from their counterparts (ka and kd) defined for homogeneous ligand distribution throughout the solution. The relationship between ka,d* and ka,d is derived from the numerical evaluation of the spatial, time-dependent distributions of free and bound metal within and/or outside the particle. The dramatic dependence of ka,d* on hydrodynamic particle softness, Péclet number, soft surface layer thickness, and particle radius are analyzed in the steady-state nonequilibrium chemical regime within the context of dynamic features for colloidal complexes. The analysis covers the limiting cases of hydrodynamically impermeable, hard particles where binding sites are located at the very surface of the particle core (e.g., functionalized latex colloids) and free draining, polymeric ligand particles devoid of a hard core (e.g., porous gel particles). The formalism further applies to any values of the Péclet number, that is, for speciation dynamics determined by kinetic processes coupled to diffusion and/or convection metal mass transfer(s). A discussion is provided for the comparison between the exact numerical results and the analytical formulation based on the approximate Levich expression for convective-diffusion metal flux at the surface of hard ligand particles. PMID:19810749

  9. Photoemission mechanism of water-soluble silver nanoclusters: ligand-to-metal-metal charge transfer vs strong coupling between surface plasmon and emitters.

    PubMed

    Chen, Yuting; Yang, Taiqun; Pan, Haifeng; Yuan, Yufeng; Chen, Li; Liu, Mengwei; Zhang, Kun; Zhang, Sanjun; Wu, Peng; Xu, Jianhua

    2014-02-01

    Using carboxylate-protected silver nanoclusters (Ag-carboxylate NCs) as a model, we separately investigated the contribution of the ligand shell and the metal core to understand the nature of photoluminescence of Ag NCs. A new Ag(0)NCs@Ag(I)-carboxylate complex core-shell structural model has been proposed. The emission from the Ag-carboxylate NCs could be attributed to ligand-to-metal-metal charge transfer from Ag(I)-carboxylate complexes (the oxygen atom in the carboxylate ligands to the Ag(I) ions) to the Ag atoms and subsequent radiative relaxation. Additionally, we found that the emission wavelength of the Ag NCs depends on the excitation wavelength implying a strong coupling between surface plasmon and emitter in Ag NCs. The strong coupling between the surface plasmon and the emitter determines the quantum yield and lifetime. The emission mechanism of Ag NCs and its relation to the organic templates and metal cores were clearly clarified. The results should stimulate additional experimental and theoretical research on the molecular-level design of luminescent metal probes for optoelectronics and other applications. PMID:24437963

  10. Ultrasonic/Sonic Anchor

    NASA Technical Reports Server (NTRS)

    Bar-Cohen, Yoseph; Sherrit, Stewart

    2009-01-01

    The ultrasonic/sonic anchor (U/S anchor) is an anchoring device that drills a hole for itself in rock, concrete, or other similar material. The U/S anchor is a recent addition to a series of related devices, the first of which were reported in "Ultrasonic/Sonic Drill/Corers With Integrated Sensors"

  11. Phosphinite-Ni(0) Mediated Formation of a Phosphide-Ni(II)-OCOOMe Species via Uncommon Metal-Ligand Cooperation.

    PubMed

    Kim, Yeong-Eun; Oh, Seohee; Kim, Seji; Kim, Onnuri; Kim, Jin; Han, Sang Woo; Lee, Yunho

    2015-04-01

    Reversible transformations are observed between a phosphide-nickel(II) alkoxide and a phosphinite-nickel(0) species via a P-O bond formation coupled with a 2-e(-) redox change at the nickel center. In the forward reaction, the nickel(0) dinitrogen species (PP(OMe)P)Ni(N2) (2) and {(PP(OMe)P)Ni}2(?-N2) (3) were formed from the reaction of (PPP)NiCl (1) with a methoxy anion. In the backward reaction, a (PPP)Ni(II) moiety was regenerated from the CO2 reaction of 3 with the concomitant formation of a methyl carbonate ligand in (PPP)Ni(OCOOMe) (7). Thus, unanticipated metal-ligand cooperation involving a phosphide based ligand is reported. PMID:25798737

  12. Investigation of the ligand shells of homo-ligand and mixed-ligand monolayer protected metal nanoparticles : a scanning tunneling microscopy study

    E-print Network

    Jackson, Alicia M

    2007-01-01

    Monolayer Protected Metal Nanoparticles have recently found widespread use in and are the focus of intensive study in many areas of scientific research ranging from biology to physics to medicine. Consisting of a nanoscale, ...

  13. Experimental and calculated complex formation curves for a labile metal-ligand system a differential pulse polarographic study of the Pb(II)-( N, N, N?, N?-tetramethylethylenediamine-OH system at fixed ligand to metal ratio and varied pH

    Microsoft Academic Search

    Ignacy Cukrowski; Michael Adsetts

    1997-01-01

    Experimental and calculated complex formation curves (ECFC and CCFC) for a labile metal-ligand system are defined and used for the speciation study by differential pulse polarography (DPP) at fixed total ligand (LT) to total metal (MT) concentration ratio and varied pH. The CCFC is used for the modeling of species formed in a solution and optimization of formation constants for

  14. Synthesis and characterisation of group nine transition metal complexes containing new mesityl and naphthyl based azaindole scorpionate ligands.

    PubMed

    Owen, Gareth R; Tsoureas, Nikolaos; Hope, Rebecca F; Kuo, Yu-Ying; Haddow, Mairi F

    2011-06-14

    Two novel boron-based flexible scorpionate ligands based on 7-azaindole, Li[HB(azaindolyl)(2)(1-naphthyl)] and Li[HB(azaindolyl)(2)(mesityl)] {Li[(Naphth)Bai] and Li[(Mes)Bai] respectively}, have been prepared (mesityl = 2,4,6-trimethylphenyl). These salts have been isolated in two forms, either as dimeric structures which contain bridging hydride interactions with the lithium centres or as crystalline material containing mono nuclear bis-acetonitrile solvates. The newly formed ligands have been utilised to prepare a range of group nine transition metal complexes with the general formula [M(COD){?(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where M = rhodium, iridium; Ar = 1-naphthyl, mesityl; COD = 1,5-cyclooctadiene) and [Rh(NBD){?(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where NBD = 2,5-norbornadiene; Ar = 1-naphthyl, mesityl). These new complexes have been compared to the previously reported compounds which contain the related scorpionate ligands Li[HB(azaindolyl)(2)(phenyl)] and K[HB(azaindolyl)(3)] {Li[(Ph)Bai] and K[Tai] respectively}. Structural characterisation of the complexes [Rh(COD){?(3)-NNH-HB (azaindolyl)(2)(mesityl)}], [Ir(COD){?(3)-NNH-HB (azaindolyl)(2)(mesityl)}] and [Rh(NBD){?(3)-NNH-HB (azaindolyl)(2)(naphthyl)}] confirm the expected ?(3)-NNH coordination mode for these new ligands. Spectroscopic analysis suggests strong interactions of the B-H functional group with the metal centres in all cases. PMID:21528139

  15. Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies.

    PubMed

    El-Boraey, Hanaa A; Serag El-Din, Azza A

    2014-11-11

    Novel penta-azamacrocyclic 15-membered [N5] ligand [L] i.e. 1,5,8,12-tetetraaza-3,4: 9,10-dibenzo-6-ethyl-7-methyl-1,12-(2,6-pyrido)cyclopentadecan-5,7 diene-2,11-dione and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and structurally characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On basis of IR, MS, UV-Vis 1H NMR and EPR spectral studies an octahedral geometry has been proposed for all complexes except Co(II), Cu(II) nitrate complexes and Pd(II) chloride complex that adopt tetrahedral, square pyramidal and square planar geometries, respectively. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50=2.04-9.7, 2.5-3.7 ?g/mL) showed potent antitumor activity comparable with their ligand (IC50=11.7, 3.45 ?g/mL) against the above mentioned cell lines, respectively. The results evidently show that the activity of the ligand becomes more pronounced and significant when coordinated to the metal ion. PMID:24892547

  16. New 15-membered tetraaza (N4) macrocyclic ligand and its transition metal complexes: Spectral, magnetic, thermal and anticancer activity

    NASA Astrophysics Data System (ADS)

    El-Boraey, Hanaa A.; EL-Gammal, Ohyla A.

    2015-03-01

    Novel tetraamidemacrocyclic 15-membered ligand [L] i.e. naphthyl-dibenzo[1,5,9,12]tetraazacyclopentadecine-6,10,11,15-tetraoneand its transition metal complexes with Fe(II), Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On the basis of analytical, spectral (IR, MS, UV-Vis, 1H NMR and EPR) and thermal studies distorted octahedral or square planar geometry has been proposed for the complexes. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50 = 2.27-2.7, 8.33-31.1 ?g/mL, respectively) showed potent antitumor activity, towards the former cell lines comparable with their ligand (IC50 = 13, 26 ?g/mL, respectively). The results show that the activity of the ligand towards breast cancer cell line becomes more pronounced and significant when coordinated to the metal ion.

  17. Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies

    NASA Astrophysics Data System (ADS)

    El-Boraey, Hanaa A.; Serag El-Din, Azza A.

    2014-11-01

    Novel penta-azamacrocyclic 15-membered [N5] ligand [L] i.e. 1,5,8,12-tetetraaza-3,4: 9,10-dibenzo-6-ethyl-7-methyl-1,12-(2,6-pyrido)cyclopentadecan-5,7 diene-2,11-dione and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and structurally characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On basis of IR, MS, UV-Vis 1H NMR and EPR spectral studies an octahedral geometry has been proposed for all complexes except Co(II), Cu(II) nitrate complexes and Pd(II) chloride complex that adopt tetrahedral, square pyramidal and square planar geometries, respectively. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50 = 2.04-9.7, 2.5-3.7 ?g/mL) showed potent antitumor activity comparable with their ligand (IC50 = 11.7, 3.45 ?g/mL) against the above mentioned cell lines, respectively. The results evidently show that the activity of the ligand becomes more pronounced and significant when coordinated to the metal ion.

  18. New 15-membered tetraaza (N4) macrocyclic ligand and its transition metal complexes: spectral, magnetic, thermal and anticancer activity.

    PubMed

    El-Boraey, Hanaa A; EL-Gammal, Ohyla A

    2015-03-01

    Novel tetraamidemacrocyclic 15-membered ligand [L] i.e. naphthyl-dibenzo[1,5,9,12]tetraazacyclopentadecine-6,10,11,15-tetraoneand its transition metal complexes with Fe(II), Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and characterized by elemental analysis, spectral, thermal as well as magnetic and molar conductivity measurements. On the basis of analytical, spectral (IR, MS, UV-Vis, (1)H NMR and EPR) and thermal studies distorted octahedral or square planar geometry has been proposed for the complexes. The antitumor activity of the synthesized ligand and some complexes against human breast cancer cell lines (MCF-7) and human hepatocarcinoma cell lines (HepG2) has been studied. The complexes (IC50=2.27-2.7, 8.33-31.1?g/mL, respectively) showed potent antitumor activity, towards the former cell lines comparable with their ligand (IC50=13, 26?g/mL, respectively). The results show that the activity of the ligand towards breast cancer cell line becomes more pronounced and significant when coordinated to the metal ion. PMID:25531404

  19. Group 4 metal complexes with new chiral pincer NHC-ligands: synthesis, structure and catalytic activity.

    PubMed

    Zhao, Ning; Hou, Guohua; Deng, Xuebin; Zi, Guofu; Walter, Marc D

    2014-06-14

    Chiral group 4 NHC-metal complexes were prepared in good yields by amine elimination from M(NR2)4 (M = Ti, Zr, Hf; R = Me, Et) and chiral pincer NHC-ligands, L4(L4a and L4b), L5 and L6, which are derived from (S,S)-diphenyl-1,2-ethanediamine. Treatment of M(NR2)4 with 1 equiv. of L4 in THF gives, after recrystallization from a benzene solution, the chiral titanium amides (L4)Ti(NMe2)(Br)(THF) (7) and (L4)Ti(NMe2)(Cl)(THF) (11), zirconium amides (L4)Zr(NMe2)(Br)(THF) (8), (L4)Zr(NEt2)(Br)(THF) (10), (L4)Zr(NMe2)(Cl)(THF) (12) and (L4)Zr(NEt2)(Cl)(THF) (14), and hafnium amides (L4)Hf(NMe2)(Br)(THF) (9) and (L4)Hf(NMe2)(Cl)(THF) (13), respectively. Similarly, the reactions of L5 or L6 with 1 equiv. of M(NR2)4 yield the titanium amide (L6)Ti(NMe2)(Cl)(THF) (16), the zirconium amides (L5)Zr(NMe2)(Cl)(THF) (15), (L6)Zr(NMe2)(Cl)(THF) (17) and (L6)Zr(NEt2)(Cl)(THF) (19), and the hafnium amide (L6)Hf(NMe2)(Cl)(THF) (18), respectively. Complexes 7 - 19 were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 10 and 14 - 19 were also established by X-ray diffraction analyses, which represent the first example of the structurally characterized group 4 chiral NHC-metal complex. Furthermore, 7 - 19 are active catalysts for the polymerization of rac-lactide in the presence of isopropanol, leading to the heterotactic-rich polylactides. PMID:24710509

  20. Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

    NASA Astrophysics Data System (ADS)

    Ma, Zhiya; Guan, Yueping; Liu, Huizhou

    2006-06-01

    Superparamagnetic silica-coated magnetite (Fe 3O 4) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe 2+ and Fe 3+ in an ammonia solution. Then silica was coated on the Fe 3O 4 nanoparticles using a sol-gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu 2+, the magnetic silica nanoparticles with immobilized Cu 2+ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.

  1. Rare earth metal bis(alkyl) complexes bearing a monodentate arylamido ancillary ligand: Synthesis, structure, and Olefin polymerization catalysis

    Microsoft Academic Search

    Yunjie Luo; Masayoshi Nishiura; Zhaomin Hou

    2007-01-01

    The reaction of Ln(CH2SiMe3)3(thf)2 with 1 equiv. of the amine ligand 2,6-iPr2C6H3NH(SiMe3) gave the corresponding amido-ligated rare earth metal bis(alkyl) complexes [2,6-iPr2C6H3N(SiMe3)]Ln(CH2SiMe3)2(thf) (Ln=Sc (1), Y (2), Ho (3), Lu (4)), which represent rare examples of bis(alkyl) rare earth metal complexes bearing a monodentate anionic ancillary ligand. In the case of Gd, a similar reaction gave the bimetallic complex Gd2(?-CH2SiMe2NC6H3iPr2-2,6)3(thf)3 (5)

  2. Anchoring noble metal nanoparticles on CeO2 modified reduced graphene oxide nanosheets and their enhanced catalytic properties.

    PubMed

    Ji, Zhenyuan; Shen, Xiaoping; Xu, Yuling; Zhu, Guoxing; Chen, Kangmin

    2014-10-15

    The strategy of structurally integrating noble metal, metal oxide, and graphene is expected to offer prodigious opportunities toward emerging functions of graphene-based nanocomposites. In this study, we develop a facile two-step approach to disperse noble metal (Pt and Au) nanoparticles on the surface of CeO2 functionalized reduced graphene oxide (RGO) nanosheets. It is shown that Pt and Au with particle sizes of about 5 and 2nm are well dispersed on the surface of RGO/CeO2. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by NaBH4 was used as a model reaction to quantitatively evaluate the catalytic properties of the as-synthesized RGO/Pt/CeO2 and RGO/Au/CeO2 ternary nanocomposites. In such triple-component catalysts, CeO2 nanocrystals provide unique and critical roles for optimizing the catalytic performance of noble metallic Pt and Au, allowing them to express enhanced catalytic activities in comparison with RGO/Pt and RGO/Au catalysts. In addition, a possible mechanism for the enhanced catalytic activities of the RGO/Pt/CeO2 and RGO/Au/CeO2 ternary catalysts in the reduction of 4-NP is proposed. It is expected that our prepared graphene-based triple-component composites, which inherit peculiar properties of graphene, metal oxide, and noble metal, are attractive candidates for catalysis and other applications. PMID:25080384

  3. Metal-ligand cooperation on a diruthenium platform: selective imine formation through acceptorless dehydrogenative coupling of alcohols with amines.

    PubMed

    Saha, Biswajit; Rahaman, S M Wahidur; Daw, Prosenjit; Sengupta, Gargi; Bera, Jitendra K

    2014-05-19

    Metal-metal singly-bonded diruthenium complexes, bridged by naphthyridine-functionalized N-heterocyclic carbene (NHC) ligands featuring a hydroxy appendage on the naphthyridine unit, are obtained in a single-pot reaction of [Ru2(CH3COO)2(CO)4] with 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (BIN?HBr) or 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (PIN?HBr), TlBF4, and substituted benzaldehyde containing an electron-withdrawing group. The modified NHC-naphthyridine-hydroxy ligand spans the diruthenium unit in which the NHC carbon and hydroxy oxygen occupy the axial sites. All the synthesized compounds catalyze acceptorless dehydrogenation of alcohols to the corresponding aldehydes in the presence of a catalytic amount of weak base 1,4-diazabicyclo[2.2.2]octane (DABCO). Further, acceptorless dehydrogenative coupling (ADHC) of the alcohol with amines affords the corresponding imine as the sole product. The substrate scope is examined with 1 (BIN, p-nitrobenzaldehyde). A similar complex [Ru2(CO)4(CH3COO)(3-PhBIN)][Br], that is devoid of a hydroxy arm, is significantly less effective for the same reaction. Neutral complex 1?a, obtained by deprotonation of the hydroxy arm in 1, is found to be active for the ADHC of alcohols and amines under base-free conditions. A combination of control experiments, deuterium labeling, kinetic Hammett studies, and DFT calculations support metal-hydroxyl/hydroxide and metal-metal cooperation for alcohol activation and dehydrogenation. The bridging acetate plays a crucial role in allowing ?-hydride elimination to occur. The ligand architecture on the diruthenium core causes rapid aldehyde extrusion from the metal coordination sphere, which is responsible for exclusive imine formation. PMID:24715433

  4. Structural Investigations of Silica Polyamine Composites: Surface Coverage, Metal Ion Coordination, and Ligand Modification

    SciTech Connect

    Hughes, Mark; Nielsen, Daniel; Rosenberg, Edward; Gobetto, Roberto; Viale, Alessandra; Burton, Sarah D.; Ferel, Joseph

    2006-09-13

    Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)-trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of ''free amines''. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake studies show increases in Cu(II) capacity and/or an improvement in Cu(II) mass-transfer kinetics. The effect of polymer molecular weight upon Cu(II) capacity was investigated for each polyamine. Substantial differences in Cu(II) capacity between 50,000 MW poly(vinylamine) (PVA) and >1000 MW PVA were evident. Similar differences between 25,000 MW poly(ethyleneimine) (PEI) and 1200 MW PEI were found. The mass-transfer kinetics was shown to be improved for composites prepared using a large fraction of MTCS in the reagent silane mixture. This resulted in substantial improvements in the 10% breakthrough Cu(II) capacity for PVA (50 000 MW). PEI composites were further modified to form an amino-acetate ligand. The impact of the MTCS:CPTCS silane ratio on the acetate ligand loading and ultimately on the Cu(II) capacity at pH 2 was investigated. A ratio of 12.5:1 was shown to result in an acetate modified PEI composite with a Cu(II) capacity 140% of the Cu(II) capacity of the same composite prepared with ''CPTCS only''.

  5. Microwave Measurements of Structure Changes for Ligand Molecules Bound to Transition Metals

    NASA Astrophysics Data System (ADS)

    Kukolich, Stephen G.

    2010-06-01

    Precise values for structural parameters for transition metal complexes have been obtained from high-resolution PBFT microwave measurements. The changes in structural parameters for the small organic molecule ligands are relatively large and well-determined. Results for C_2H_4-Os-(CO)_4, C_2H_4-Fe-(CO)_4, C_2H_2-Re-(O)_2CH_3, C_6H_6-Cr-(CO)_3 and C_4H_6-Fe-(CO)_3 will be discussed and compared. For the Ethylene Osmium Tetracarbonyl complex, the experimental ethylene C-C bond length is 1.432 Å, which falls between the free ethylene value of 1.339 Å { } and the ethane value of 1.534 Å. The angle between the plane of the CH_2 group and the extended ethylene C-C bond (out-of-plane angle) is 26 °. Ethylene structural changes are larger for the Os complex than for the similar Fe complex. For Acetylene Methyl dioxoRhenium, the C-C bond length is increased by 0.08 Å { } to 1.29 Å. The H-C-C interbond angles are reduced from 180 ° to 146 °, and 147 °. The planar, D_6_h structure of free benzene is changed to a C_3_v structure with alternating C-C bond lengths due to interaction with Cr-(CO)_3 in the complex. The structural changes are small but significant, since the benzene reactivity is changed. For Butadiene Iron Tricarbonyl, the terminal CH_2 groups are rotated by 28 ° out of the butadiene plane and the CH_2 plane is folded away from the butadiene C1-C2 axis by 27 ° in a direction away from the iron atom. Free butadiene has a trans planar conformation, much different from the distorted cis conformation in the complex. These structural changes are usually accompanied by significant changes in reactivity, which has proved useful for transition metal catalysts and metal containing enzymes.

  6. The in vivo histology of an absorbable suture anchor: a preliminary report

    Microsoft Academic Search

    F. Alan Barber; Michael A. Deck

    1995-01-01

    Suture anchors are playing an increasingly important role in attaching tendons or ligaments to bone. Anchors are usually made of metallic or other nonbioabsorbable materials. The development of an absorbable suture anchor would provide a valuable tool for the surgeon; this characteristic would minimize the problems of anchor loosening, migration, interference with imaging studies, and the potential requirement for later

  7. Tin, Antimony, Bismuth, and Tellurium Lewis Acids in sigma-Accepting Ligands for Transition Metals

    E-print Network

    Lin, Tzu-Pin

    2012-10-19

    shown to activate small molecules such as H2, CO2, and CHCl3. Further, the concept of Z-ligand has been extended to s- and d-block Lewis acids. In spite of these achievements, Z-ligands that contain Group 14-16 elements as Lewis acids remain scarce...

  8. Rare-earth-metal methyl, amide, and imide complexes supported by a superbulky scorpionate ligand.

    PubMed

    Schädle, Dorothea; Maichle-Mössmer, Cäcilia; Schädle, Christoph; Anwander, Reiner

    2015-01-01

    The reaction of monomeric [(Tp(tBu,Me) )LuMe2 ] (Tp(tBu,Me) =tris(3-Me-5-tBu-pyrazolyl)borate) with primary aliphatic amines H2 NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(Tp(tBu,Me) )LuMe(NHR)], the solid-state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(Tp(tBu,Me) )LnMe({?2 -Me}AlMe3 )] (Ln=Y, Ho) reacted selectively and in high yield with H2 NR, according to methane elimination, to afford heterobimetallic complexes: [(Tp(tBu,Me) )Ln({?2 -Me}AlMe2 )(?2 -NR)] (Ln=Y, Ho). X-ray structure analyses revealed that the monomeric alkylaluminum-supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by (1) H and (13) C?NMR spectroscopic studies at variable temperatures and (1) H-(89) Y HSQC NMR spectroscopy. Treatment of [(Tp(tBu,Me) )LnMe(AlMe4 )] with H2 NtBu gave dimethyl compounds [(Tp(tBu,Me) )LnMe2 ] as minor side products for the mid-sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative-scale amounts of complexes [(Tp(tBu,Me) )LnMe2 ] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(Tp(tBu,Me) )LnMe(AlMe4 )] with N,N,N',N'-tetramethylethylenediamine (tmeda). The solid-state structures of [(Tp(tBu,Me) )HoMe(AlMe4 )] and [(Tp(tBu,Me) )HoMe2 ] were analyzed by XRD. PMID:25392940

  9. Synthesis, spectral characterization, molecular modeling, thermal study and biological evaluation of transition metal complexes of a bidentate Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Bargujar, Savita; Nirwal, Rita; Qanungo, Kushal; Sharma, Saroj K.

    2013-09-01

    Complexes of copper(II) and nickel(II) of general composition M(L)2X2, have been synthesized [where L = 3-Bromoacetophenone thiosemicarbazone and X = CH3COO-, Cl- and NO3-]. All the complexes were characterized by elemental analysis, magnetic moments, IR, electronic and EPR spectral studies. The ligand behaved as bidentate and coordinated through sulfur of sbnd Cdbnd S group and nitrogen atoms of sbnd Cdbnd N group. The copper(II) and nickel(II) complexes were found to have magnetic moments 1.94-2.02 BM, 2.96-3.02 BM respectively which was corresponding to one and two unpaired electrons respectively. The molar conductance of the complexes in solution of DMSO lies in the range of 10-20 ?-1 cm2 mol-1 indicating their non-electrolytic behavior. On the basis of EPR, electronic and infrared spectral studies, tetragonal geometry has been assigned for copper(II) complexes and an octahedral geometry for nickel(II) complexes. The values of Nephelauxetic parameter ? lie in the range 0.19-0.37 which indicated the covalent character in metal ligand ‘?' bond. Synthesized ligand and its copper(II) and nickel(II) complexes have also been screened against different bacterial and fungal species which suggested that complexes are more active than the ligands in antimicrobial activities.

  10. Synthesis, spectral characterization, molecular modeling, thermal study and biological evaluation of transition metal complexes of a bidentate Schiff base ligand.

    PubMed

    Chandra, Sulekh; Bargujar, Savita; Nirwal, Rita; Qanungo, Kushal; Sharma, Saroj K

    2013-09-01

    Complexes of copper(II) and nickel(II) of general composition M(L)2X2, have been synthesized [where L=3-Bromoacetophenone thiosemicarbazone and X=CH3COO(-), Cl(-) and NO3(-)]. All the complexes were characterized by elemental analysis, magnetic moments, IR, electronic and EPR spectral studies. The ligand behaved as bidentate and coordinated through sulfur of -C=S group and nitrogen atoms of -C=N group. The copper(II) and nickel(II) complexes were found to have magnetic moments 1.94-2.02 BM, 2.96-3.02 BM respectively which was corresponding to one and two unpaired electrons respectively. The molar conductance of the complexes in solution of DMSO lies in the range of 10-20 ?(-1) cm(2) mol(-1) indicating their non-electrolytic behavior. On the basis of EPR, electronic and infrared spectral studies, tetragonal geometry has been assigned for copper(II) complexes and an octahedral geometry for nickel(II) complexes. The values of Nephelauxetic parameter ? lie in the range 0.19-0.37 which indicated the covalent character in metal ligand '?' bond. Synthesized ligand and its copper(II) and nickel(II) complexes have also been screened against different bacterial and fungal species which suggested that complexes are more active than the ligands in antimicrobial activities. PMID:23727669

  11. Zinc(II) Thiosemicarbazone Complex As a Ligand Towards Some Transition Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies.

    PubMed

    Khalil, Saied M E; Shebl, Magdy; Al-Gohani, Faizah S

    2010-09-01

    Heterobinuclear complexes have been synthesized by stepwise reactions using the mononuclear complex, [Zn(Tsc)2] • H2O, as a complex ligand towards the metal ions, vanadyl(IV), manganese(II), iron(III), cobalt(II), nickel(II) and copper(II). The complex ligand was synthesized by the reaction of zinc acetate dihydrate with salicylaldehyde followed by the condensation with thiosemicarbazide. The structures of the complex ligand and the prepared complexes were elucidated by elemental analyses, IR, electronic, mass, 1H and 13C NMR spectra as well as molar conductivity and magnetic susceptibility measurements. All the complexes exhibited octahedral geometrical arrangements formulated as [Zn(Tsc)2VO(SO4)(H2O)], [Zn(Tsc)2MCl2(H2O)2] (M = Mn, Fe and Co) and [Zn(Tsc)2Fe(ox)Cl2] except the nickel(II) and copper(II) complexes, [Zn(Tsc)2CuCl(H2O)], [Zn(Tsc)2NiCl2], which have square planar geometries. The complex ligand and some of its heterobinuclear complexes showed antibacterial activity against the sensitive organisms Staphylococcus aureus as Gram-positive bacteria, Escherichia coli as Gram-negative bacteria and antifungal activity against the fungi Candida albicans and Aspergillus flavus. PMID:24061821

  12. Site-selective growth of surface-anchored metal-organic frameworks on self-assembled monolayer patterns prepared by AFM nanografting

    PubMed Central

    Ladnorg, Tatjana; Welle, Alexander; Heißler, Stefan; Wöll, Christof

    2013-01-01

    Summary Surface anchored metal-organic frameworks, SURMOFs, are highly porous materials, which can be grown on modified substrates as highly oriented, crystalline coatings by a quasi-epitaxial layer-by-layer method (liquid-phase epitaxy, or LPE). The chemical termination of the supporting substrate is crucial, because the most convenient method for substrate modification is the formation of a suitable self-assembled monolayer. The choice of a particular SAM also allows for control over the orientation of the SURMOF. Here, we demonstrate for the first time the site-selective growth of the SURMOF HKUST-1 on thiol-based self-assembled monolayers patterned by the nanografting technique, with an atomic force microscope as a structuring tool. Two different approaches were applied: The first one is based on 3-mercaptopropionic acid molecules which are grafted in a 1-decanethiolate SAM, which serves as a matrix for this nanolithography. The second approach uses 16-mercaptohexadecanoic acid, which is grafted in a matrix of an 1-octadecanethiolate SAM. In both cases a site-selective growth of the SURMOF is observed. In the latter case the roughness of the HKUST-1 is found to be significantly higher than for the 1-mercaptopropionic acid. The successful grafting process was verified by time-of-flight secondary ion mass spectrometry and atomic force microscopy. The SURMOF structures grown via LPE were investigated and characterized by atomic force microscopy and Fourier-transform infrared microscopy. PMID:24205458

  13. Synthesis, spectra and DNA interactions of certain mononuclear transition metal(II) complexes of macrocyclic tetraaza diacetyl curcumin ligand

    NASA Astrophysics Data System (ADS)

    Rajesh, Jegathalaprathaban; Gubendran, Ammavasi; Rajagopal, Gurusamy; Athappan, Periyakaruppan

    2012-02-01

    A series of mononuclear transition metal(II) complexes of type [M(LL)]2+ (LL = the template condensate of orthophenylene diamine and benzilidene diacetyl curcumin (ben-diacecur) and M = Cu(II) (1) or Co(II) (2) or Ni(II) (3) or Mn(II) (4)), have been isolated and the spectral behaviors are discussed. The ligand and complexes have also been characterized by the analytical and spectral methods like UV-Visible, FT-IR, NMR and EPR. Further, the interaction of the transition metal complexes with Calf thymus (CT) DNA have also been studied by the use of physical methods like UV-Visible, emission and CD spectroscopic techniques. The electrochemical responses of these metal complexes both in presence and absence of DNA have also been demonstrated. All these findings support the hypothesis of DNA interactions of all these metal complexes through the grooves with a higher degree of interaction by complex 1 (Kb = 1.4 × 105) possibly through the interposition of the aromatic rings of the ligand compared to complexes, 2-4. The complex 1 display significant oxidative cleavage of circular plasmid pUC18 DNA in the presence of H2O2 using the singlet oxygen as a reactive species. The spectral and electrochemical response of these complexes designate that the square-planar Cu(II), Ni(II) and Co(II) complexes interact much better than the axially coordinated octahedral Mn(II) complex.

  14. Chelating ligands for nanocrystals' surface functionalization.

    PubMed

    Querner, Claudia; Reiss, Peter; Bleuse, Joël; Pron, Adam

    2004-09-22

    A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild conditions; they significantly improve the resistance of nanocrystals against photooxidation because of their ability of strong chelate-type binding to metal atoms; their relatively simple preparation via Grignard intermediates facilitates the development of new bifunctional ligands containing, in addition to the anchoring carbodithioate group, a second function, which enables the grafting of molecules or macromolecules of interest on the nanocrystal surface. To give an example of this approach, we report, for the first time, the grafting of an electroactive oligomer from the polyaniline family-aniline tetramer-on CdSe nanocrystals after their functionalization with 4-formyldithiobenzoic acid. The grafting proceeds via a condensation reaction between the aldehyde group of the ligand and the terminal primary amine group of the tetramer. The resulting organic/inorganic hybrid exhibits complete extinction of the fluorescence of its constituents, indicating efficient charge or energy transfer between the organic and the inorganic semiconductors. PMID:15366904

  15. Synthesis and characterization of metal complexes of Schiff base ligand derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine.

    PubMed

    Selwin Joseyphus, R; Shiju, C; Joseph, J; Justin Dhanaraj, C; Arish, D

    2014-12-10

    The Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine were synthesized. These compounds were characterized by elemental analysis, IR, mass, (1)H NMR, electronic spectra, magnetic moment, molar conductance, thermal analysis, powder XRD and SEM. The analytical data show that the metal to ligand ratio is 1:1. The IR results show that the ligand acts as a bidentate donor coordinating through the azomethine nitrogen and imidazole nitrogen atoms. From the electronic spectra and magnetic moment value predicts the geometry of the complexes. The surface morphology of the compounds was studied by SEM. The compounds were screened for their antibacterial activity and antifungal activity using Kirby Bayer disc diffusion method. The DNA cleavage and superoxide dismutase activities of the compounds were investigated. The anticancer activities of the complexes have been carried out towards HeLa and HCT116 cancer cells. PMID:24934973

  16. Synthesis and characterization of metal complexes of Schiff base ligand derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine

    NASA Astrophysics Data System (ADS)

    Selwin Joseyphus, R.; Shiju, C.; Joseph, J.; Justin Dhanaraj, C.; Arish, D.

    2014-12-01

    The Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine were synthesized. These compounds were characterized by elemental analysis, IR, mass, 1H NMR, electronic spectra, magnetic moment, molar conductance, thermal analysis, powder XRD and SEM. The analytical data show that the metal to ligand ratio is 1:1. The IR results show that the ligand acts as a bidentate donor coordinating through the azomethine nitrogen and imidazole nitrogen atoms. From the electronic spectra and magnetic moment value predicts the geometry of the complexes. The surface morphology of the compounds was studied by SEM. The compounds were screened for their antibacterial activity and antifungal activity using Kirby Bayer disc diffusion method. The DNA cleavage and superoxide dismutase activities of the compounds were investigated. The anticancer activities of the complexes have been carried out towards HeLa and HCT116 cancer cells.

  17. Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole

    NASA Astrophysics Data System (ADS)

    Chen, Zhimin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

    2007-11-01

    A new chelating ligand, 2-(2-(5- tert-butylisoxazol-3-yl)hydrazono)- N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M 2(L) 2 (?-OCH 3) 2 [M = Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, 1H NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Different thermodynamic and kinetic parameters namely activation energy ( E*), enthalpy of activation (? H*), entropy of activation (? S*) and free energy change of activation (? G*) are calculated using Coats-Redfern (CR) equation.

  18. Carboxylic-Acid-passivated metal oxide nanocrystals: ligand exchange characteristics of a new binding motif.

    PubMed

    De Roo, Jonathan; Justo, Yolanda; De Keukeleere, Katrien; Van den Broeck, Freya; Martins, José C; Van Driessche, Isabel; Hens, Zeger

    2015-05-26

    Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO2 and ZrO2 NCs using (1) H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self-adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X-type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X-type ligands yielding a combined X2 binding motif that allows for self-adsorption and exchange for L-type ligands. PMID:25866095

  19. Transition metal complexes with 2-methyl-, 3-methyl-, and 4-methyl-piperidine dithiocarbamate as ligands

    Microsoft Academic Search

    Antonio C. Fabretti; Gian C. Franchini; Carlo Preti; Giuseppe Tosi; Paolo Zannini

    1985-01-01

    A new series of manganese(III), cobalt(II), nickel(II), zinc(II), cadmium(II) and mercury(II) complexes with monomethylsubstituted dithiocarbamates as ligands has been synthesized and studied. Their structures are discussed in relation to their spectroscopic, magnetic and thermal properties. The dithio-ligands exhibit bidentate behaviour acting as S,S'donors in all the complexes. In the far i.r. region particular attention is paid to a comparison of

  20. Metal chelates anchored to poly-L-peptides and linear D,L-?-peptides with promising nanotechnological applications.

    PubMed

    Punzi, P; Giordano, C; Marino, F; Morosetti, S; De Santis, P; Scipioni, A

    2012-10-01

    Regular configurationally alternating amino acid sequences generate cyclic and linear helical peptides with a local ?-conformation able to self-assemble in nanowires and nanoscaffolds directed and stabilized by hydrogen bonds. The possibility of modulating the chemical profile of the various amino acid residues containing reactive side chains means that peptides could be flexible templates for creating various building blocks. A method for the design of molecules with potential spintronic properties is described. Peptides containing lysine residues, the side chains of which are bridged through the formation of metal chelates via Schiff bases, could provide stable molecular channels. When metal chelates with high electron spin states are used, their coupling could generate materials that are interesting due to their magnetic properties as well as for the patterning of nanometric lattices driven by their orientation under a magnetic field. With this aim, three alternating D- and L-lysine-containing octapeptides are synthesized and the formation of their bis(pyridoxalaldimine) copper(II) chelate derivatives is shown by absorption and circular dichroism spectroscopies. PMID:22972390

  1. Metal chelates anchored to poly-l-peptides and linear d,l-?-peptides with promising nanotechnological applications

    NASA Astrophysics Data System (ADS)

    Punzi, P.; Giordano, C.; Marino, F.; Morosetti, S.; De Santis, P.; Scipioni, A.

    2012-10-01

    Regular configurationally alternating amino acid sequences generate cyclic and linear helical peptides with a local ?-conformation able to self-assemble in nanowires and nanoscaffolds directed and stabilized by hydrogen bonds. The possibility of modulating the chemical profile of the various amino acid residues containing reactive side chains means that peptides could be flexible templates for creating various building blocks. A method for the design of molecules with potential spintronic properties is described. Peptides containing lysine residues, the side chains of which are bridged through the formation of metal chelates via Schiff bases, could provide stable molecular channels. When metal chelates with high electron spin states are used, their coupling could generate materials that are interesting due to their magnetic properties as well as for the patterning of nanometric lattices driven by their orientation under a magnetic field. With this aim, three alternating d- and l-lysine-containing octapeptides are synthesized and the formation of their bis(pyridoxalaldimine) copper(II) chelate derivatives is shown by absorption and circular dichroism spectroscopies.

  2. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.

    PubMed

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(?-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M2(?2-NO)]; (c) threefold nitrosyl bridges, [M3(?3-NO)]; (d) ?/?-dihaptonitrosyls or "side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 ?/1.60-1.90 ?/180-160° and for bent nitrosyls are 1.16-1.22 ?/1.80-2.00 ?/140-110°. The [M2(?2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M?M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 ?/1.18-1.22 ?/1.80-2.00 ?/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 ?/1.20-1.24 ?/1.90-2.10 ?/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M?M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 ?/1.80-1.90 ?, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the "effective atomic number (EAN)" or "18-electron" rule. In the paucity of enough vibrational spectroscopic data from complexes with only nitrosyl ligands, it turned out to be very advantageous to use wavenumbers from the spectra of uncharged and saturated nitrosyl/carbonyl metal complexes as references, because the presence of a carbonyl ligand was found to be neutral in its effect on the ?(NO)-values. The wide wavenumber range found for the ?(NO) values of linear MNO complexes are then presented in terms of the estimated effects of net ionic charges, or of electron-withdrawing or electron-donating ligands bonded to the same metal atom. Using this approach we have found that: (a) the effect for a unit positive charge is [plus 100 cm(-1)] whereas for a unit negative charge it is [minus 145 cm(-1)]. (b) For electron-withdrawing co-ligands the estimated effects are: terminal CN [plus 50 cm(-1)]; terminal halogens [plus 30 cm(-1)]; bridging or quasi-bridging halogens [plus 15 cm(-1)]. (c) For electro donating co-ligands they are: PF3 [plus 10 cm(-1)]; P(OPh)3 [-30 cm(-1)]; P(OR)3 (R=alkyl group) [-40 cm(-1)]; PPh3 [-55 cm(-1)]; PR3 (R=alkyl group) [-70 cm(-1)]; and ?5-C5H5 [-60 cm(-1)]; ?5-C5H4Me [-70 cm(-1)]; ?5-C5Me5 [-80 cm(-1)]. These values were mostly derived from the spectra of nitrosyl complexes that have been corrected for the presence of only a single electronically-active co-ligand. After making allowance for ionic charges or strongly-perturbing ligands on the same metal atom, the adjusted 'neutral-co-ligand' ?(NO)*-values (in cm(-1)) are for linear nitrosyl complexes with transition metals of Period 4 of the Periodic Table, i.e. those with atomic orbitals (…4s3d4p): [ca. 1750, Cr(NO)]; [1775,Mn(NO)]; [1796,Fe(NO)]; [1817,Co(NO)]; [ca. 1840, Ni(NO)]. Period 5 (…5s4d5p): [1730 Mo(NO)]; [-, Tc(NO)]; [1745,Ru(NO)]; [1790,Rh(NO)]; [ca. 1845, Pd(NO)]. Period 6 (…6s4f5d6p), [1720,W(NO)]; [1730,Re(NO)]; [1738,Os(NO)]; [1760,Ir(NO)]; [-, Pt] respectively. Environmental differences to these values, e.g. data taken in polar solu

  3. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters

    NASA Astrophysics Data System (ADS)

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(?-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M 2(? 2-NO)]; (c) threefold nitrosyl bridges, [M 3(? 3-NO)]; (d) ?/?-dihaptonitrosyls or " side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M 2(? 2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M 3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the " effective atomic number (EAN)" or "18-electron" rule. In the paucity of enough vibrational spectroscopic data from complexes with only nitrosyl ligands, it turned out to be very advantageous to use wavenumbers from the spectra of uncharged and saturated nitrosyl/carbonyl metal complexes as references, because the presence of a carbonyl ligand was found to be neutral in its effect on the ?(NO)-values. The wide wavenumber range found for the ?(NO) values of linear MNO complexes are then presented in terms of the estimated effects of net ionic charges, or of electron-withdrawing or electron-donating ligands bonded to the same metal atom. Using this approach we have found that: (a) the effect for a unit positive charge is [plus 100 cm -1] whereas for a unit negative charge it is [minus 145 cm -1]. (b) For electron-withdrawing co-ligands the estimated effects are: terminal CN [plus 50 cm -1]; terminal halogens [plus 30 cm -1]; bridging or quasi-bridging halogens [plus 15 cm -1]. (c) For electro donating co-ligands they are: PF 3 [plus 10 cm -1]; P(OPh) 3 [-30 cm -1]; P(OR) 3 (R = alkyl group) [-40 cm -1]; PPh 3 [-55 cm -1]; PR 3 (R = alkyl group) [-70 cm -1]; and ? 5-C 5H 5 [-60 cm -1]; ? 5-C 5H 4Me [-70 cm -1]; ? 5-C 5Me 5 [-80 cm -1]. These values were mostly derived from the spectra of nitrosyl complexes that have been corrected for the presence of only a single electronically-active co-ligand. After making allowance for ionic charges or strongly-perturbing ligands on the same metal atom, the adjusted 'neutral-co-ligand' ?(NO)*-values (in cm -1) are for linear nitrosyl complexes with transition metals of Period 4 of the Periodic Table, i.e. those with atomic orbitals (…4s3d4p): [ca. 1750, Cr(NO)]; [1775,Mn(NO)]; [1796,Fe(NO)]; [1817,Co(NO)]; [ca. 1840, Ni(NO)]. Period 5 (…5s4d5p): [1730 Mo(NO)]; [—, Tc(NO)]; [1745,Ru(NO)]; [1790,Rh(NO)]; [ca. 1845, Pd(NO)]. Period 6 (…6s4f5d6p), [1720,W(NO)]; [1730,Re(NO)]; [1738,Os(NO)]; [1760,Ir(NO)]; [—, Pt] respectively. Environmental differences to these values, e.g. data taken

  4. Synthesis, structure and magnetism of new polynuclear transition metal aggregates assembled with Schiff-base ligand and anionic N-donor ligands

    NASA Astrophysics Data System (ADS)

    Li, Yangguang; Wu, Qiong; Lecren, Lollita; Clérac, Rodolphe

    2008-11-01

    Three new polynuclear aggregates [Co 6(sae) 4(N 3) 6(MeO) 2(MeOH) 2]·0.5H 2O ( 1), [Mn 4O(sae) 4(C(CN) 3)(MeOH) 3](NO 3)·MeOH ( 2) and [NaFe 6(sae) 6(MeO) 6] (N(CN) 2)·H 2O ( 3) have been synthesized with mixed ligands of Schiff-base (salicylidene-2-ethanolamine, H 2sae) and various anionic N-donor ligands (N 3-, N(CN) 2- or C(CN) 3-) and transition metal salts in methanol solution. Crystallographic data for 1: trigonal, R3¯, a = 26.113(4) Å, b = 26.113(4) Å, c = 20.689(4) Å, ? = 120°, V = 12,218(3) Å 3, Z = 9, R1( wR2) = 0.0753(0.2176); for 2: orthorhombic, Pna2 1, a = 20.746(4) Å, b = 13.357(3) Å, c = 17.992(4) Å, V = 4985.6(2) Å 3, Z = 4, R1( wR2) = 0.0357(0.0969); for 3: monoclinic, C2/ c, a = 30.311(6) Å, b = 12.452(3) Å, c = 20.789(4) Å, ? = 94.75(3)°, V = 7820(3) Å 3, Z = 4, R1( wR2) = 0.0773(0.2299). Compound 1 exhibits a new rod-like [Co III4Co II2] structural feature. Compound 2 contains an unusual tetranuclear [Mn III4] cationic core. Compound 3 possesses a well-known circle-like [Fe III6] unit encapsulated a central sodium cation. Magnetic properties of these compounds have been studied revealing the presence of (i) intra-molecular antiferromagnetic interactions in 2 and 3 that induce an overall ST = 0 ground state and (ii) Co II-Co II ferromagnetic interactions in complex 1.

  5. Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals

    E-print Network

    Pinder, Tiffany

    2013-12-09

    transition metals, a library of well-characterized synthetic analogues has been established. These metal-bound cis-dithiolates, display a wide range of reactivity, including S-based metallation, oxygenation, and alkylation. Sulfur’s affinity for gold...

  6. Synthesis, spectroscopic studies and inhibitory activity against bactria and fungi of acyclic and macrocyclic transition metal complexes containing a triamine coumarine Schiff base ligand.

    PubMed

    Abou-Hussein, A A; Linert, Wolfgang

    2015-04-15

    Two series of new mono and binuclear complexes with a Schiff base ligand derived from the condensation of 3-acetylcoumarine and diethylenetriamine, in the molar ratio 2:1 have been prepared. The ligand was characterized by elemental analysis, IR, UV-visible, (1)H-NMR and mass spectra. The reaction of the Schiff base ligand with cobalt(II), nickel(II), copper(II), zinc(II) and oxovanadium(IV) lead to mono or binuclear species of cyclic or macrocyclic complexes, depending on the mole ratio of metal to ligand and as well as on the method of preparation. The Schiff base ligand behaves as a cyclic bidentate, tetradendate or pentaentadentae ligand. The formation of macrocyclic complexes depends significantly on the dimension of the internal cavity, the rigidity of the macrocycles, the nature of its donor atoms and on the complexing properties of the anion involved in the coordination. Electronic spectra and magnetic moments of the complexes indicate that the geometries of the metal centers are either square pyramidal or octahedral for acyclic or macro-cyclic complexes. The structures are consistent with the IR, UV-visible, ESR, (1)H-NMR, mass spectra as well as conductivity and magnetic moment measurements. The Schiff base ligand and its metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi. Most of the complexes exhibit mild antibacterial and antifungal activities against these organisms. PMID:25681806

  7. Synthesis, spectroscopic studies and inhibitory activity against bactria and fungi of acyclic and macrocyclic transition metal complexes containing a triamine coumarine Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Abou-Hussein, A. A.; Linert, Wolfgang

    2015-04-01

    Two series of new mono and binuclear complexes with a Schiff base ligand derived from the condensation of 3-acetylcoumarine and diethylenetriamine, in the molar ratio 2:1 have been prepared. The ligand was characterized by elemental analysis, IR, UV-visible, 1H-NMR and mass spectra. The reaction of the Schiff base ligand with cobalt(II), nickel(II), copper(II), zinc(II) and oxovanadium(IV) lead to mono or binuclear species of cyclic or macrocyclic complexes, depending on the mole ratio of metal to ligand and as well as on the method of preparation. The Schiff base ligand behaves as a cyclic bidentate, tetradendate or pentaentadentae ligand. The formation of macrocyclic complexes depends significantly on the dimension of the internal cavity, the rigidity of the macrocycles, the nature of its donor atoms and on the complexing properties of the anion involved in the coordination. Electronic spectra and magnetic moments of the complexes indicate that the geometries of the metal centers are either square pyramidal or octahedral for acyclic or macro-cyclic complexes. The structures are consistent with the IR, UV-visible, ESR, 1H-NMR, mass spectra as well as conductivity and magnetic moment measurements. The Schiff base ligand and its metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi. Most of the complexes exhibit mild antibacterial and antifungal activities against these organisms.

  8. How Innocent are Potentially Redox Non-Innocent Ligands? Electronic Structure and Metal Oxidation States in Iron-PNN Complexes as a Representative Case Study.

    PubMed

    Butschke, Burkhard; Fillman, Kathlyn L; Bendikov, Tatyana; Shimon, Linda J W; Diskin-Posner, Yael; Leitus, Gregory; Gorelsky, Serge I; Neidig, Michael L; Milstein, David

    2015-05-18

    Herein we present a series of new ?-iminopyridine-based iron-PNN pincer complexes [FeBr2LPNN] (1), [Fe(CO)2LPNN] (2), [Fe(CO)2LPNN](BF4) (3), [Fe(F)(CO)2LPNN](BF4) (4), and [Fe(H)(CO)2LPNN](BF4) (5) with formal oxidation states ranging from Fe(0) to Fe(II) (LPNN = 2-[(di-tert-butylphosphino)methyl]-6-[1-(2,4,6-mesitylimino)ethyl]pyridine). The complexes were characterized by a variety of methods including (1)H, (13)C, (15)N, and (31)P NMR, IR, Mössbauer, and X-ray photoelectron spectroscopy (XPS) as well as electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy, SQUID magnetometry, and X-ray crystallography, focusing on the assignment of the metal oxidation states. Ligand structural features suggest that the ?-iminopyridine ligand behaves as a redox non-innocent ligand in some of these complexes, particularly in [Fe(CO)2LPNN] (2), in which it appears to adopt the monoanionic form. In addition, the NMR spectroscopic features ((13)C, (15)N) indicate the accumulation of charge density on parts of the ligand for 2. However, a combination of spectroscopic measurements that more directly probe the iron oxidation state (e.g., XPS), density functional theory (DFT) calculations, and electronic absorption studies combined with time-dependent DFT calculations support the description of the metal atom in 2 as Fe(0). We conclude from our studies that ligand structural features, while useful in many assignments of ligand redox non-innocence, may not always accurately reflect the ligand charge state and, hence, the metal oxidation state. For complex 2, the ligand structural changes are interpreted in terms of strong back-donation from the metal center to the ligand as opposed to electron transfer. PMID:25918944

  9. Metal-organic architectures of silver(I), cadmium(II), and copper(II) with a flexible tricarboxylate ligand.

    PubMed

    Zhu, Hui-Fang; Fan, Jian; Okamura, Taka-aki; Zhang, Zheng-Hua; Liu, Guang-Xiang; Yu, Kai-Bei; Sun, Wei-Yin; Ueyama, Norikazu

    2006-05-15

    Three novel metal-organic architectures, [Ag3(bta)].1.5H2O (1), [Cd3(bta)2(H2O)7].5H2O (2), and [Cu11(bta)6(Hbta)2(H2O)10].29H2O (3), were obtained by reactions of the corresponding metal salts with a flexible tripodal ligand, benzene-1,3,5-triacetic acid (H3bta), and their structures were determined by single-crystal X-ray diffraction studies. The results revealed that, in complexes 1 and 2, the carboxylate groups of the bta3- ligand adopted varied coordination modes to link metal atoms and further to form three-dimensional structures with open channels occupied by water molecules, while in complex 3, for the first time, the flexible H3bta acted as a secondary building unit to generate a novel nanometer-sized metallocage, which is composed of a Cu(II) paddle wheel (square secondary building units) and bta3-/Hbta2- organic links (triangular secondary building units). The photoluminescence properties of complexes 1 and 2 were investigated, and the results showed that 2 exhibited photoluminescence in the solid state at room temperature. PMID:16676952

  10. Spectroscopic and thermal properties of short wavelength metal (II) complexes containing ?-isoxazolylazo-?-diketones as co-ligands

    NASA Astrophysics Data System (ADS)

    Huang, Fuxin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

    2005-10-01

    Two new azo dyes of ?-isoxazolylazo-?-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni 2+ and Cu 2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl 3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.

  11. GPI-anchor and GPI-anchored protein expression in PMM2-CDG patients

    PubMed Central

    2013-01-01

    Background Mutations in PMM2 impair phosphomannomutase-2 activity and cause the most frequent congenital disorder of glycosylation, PMM2-CDG. Mannose-1-phosphate, that is deficient in this disorder, is also implicated in the biosynthesis of glycosylphosphatidyl inositol (GPI) anchors. Objective To evaluate whether GPI-anchor and GPI-anchored proteins are defective in PMM2-CDG patients. Methods The expression of GPI-anchor and seven GPI-anchored proteins was evaluated by flow cytometry in different cell types from twelve PMM2-CDG patients. Additionally, neutrophil CD16 and plasma hepatic proteins were studied by Western blot. Transferrin glycoforms were evaluated by HPLC. Results Patients and controls had similar surface expression of GPI-anchor and most GPI-anchored proteins. Nevertheless, patients displayed a significantly diminished binding of two anti-CD16 antibodies (3G8 and KD1) to neutrophils and also of anti-CD14 (61D3) to monocytes. Interestingly, CD16 immunostaining and asialotransferrin levels significantly correlated with patients’ age. Analysis by flow cytometry of CD14 with M?P9, and CD16 expression in neutrophils by Western blot using H-80 ruled out deficiencies of these antigens. Conclusions PMM2 mutations do not impair GPI-anchor or GPI-anchored protein expression. However, the glycosylation anomalies caused by PMM2 mutations might affect the immunoreactivity of monoclonal antibodies and lead to incorrect conclusions about the expression of different proteins, including GPI-anchored proteins. Neutrophils and monocytes are sensitive to PMM2 mutations, leading to abnormal glycosylation in immune receptors, which might potentially affect their affinity to their ligands, and contribute to infection. This study also confirms less severe hypoglycosylation defects in older PMM2-CDG patients. PMID:24139637

  12. Photophysical Studies of Bioconjugated Ruthenium Metal-Ligand Complexes Incorporated in Phospholipid Membrane Bilayers

    PubMed Central

    Sharmin, Ayesha; Salassa, Luca; Rosenberg, Edward; Ross, J. B. Alexander; Abbott, Geoffrey; Black, Labe; Terwilliger, Michelle; Brooks, Robert

    2013-01-01

    Luminescent, mono-diimine, ruthenium complexes, [(H)Ru(CO)(PPh3)2(dcbpy)][PF6] (1, dcbpy = 4,4?-dicarboxy bipyridyl) and [(H)Ru(CO)(dppene)(5-amino-1,10-phen)][PF6] (2, dppene = bis diphenylphosphino-ethylene, phen = 9,10-phenanthroline), have been conjugated with 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine (DPPE) and with cholesterol in the case of 2. Compound 1 gives the bis-lipid derivative [(H)Ru(CO)(PPh3)2(dcbpy-N-DPPE2)][PF6] (3), while 2 provides the mono-lipid conjugate [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(S)-N-DPPE)][ PF6] (4), and the cholesterol derivative [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(O)OChol)][PF6] (5, Chol = cholesteryl), using standard conjugation techniques. These compounds were characterized by spectroscopic methods, and their photophysical properties were measured in organic solvents. The luminescence of lipid conjugates 3 and is quenched in organic solvents while compound 4 a weak, short-lived, blue-shifted emission in solution. The cholesterol conjugate shows the long-lived, microsecond-timescale emission associated with triplet metal-to-ligand charge-transfer (3MLCT) excited states. Incorporation of conjugate 3 in lipid bilayer vesicles restores the luminescence, but with blue shifts (~80 nm) accompanied by nanosecond-timescale lifetimes. In the vesicles conjugate 4 shows a similar short-lived and blue-shifted emission to that observed in solution but with increased intensity. Conjugation of the complex [(H)Ru(CO)(PhP2C2H4C(O)O-N-succinimidyl)2(bpy)][PF6] (6”) with DPPE gives the phosphine-conjugated complex [(H)Ru(CO)(PhP2C2H4C(O)-N-DPPE)2(bpy)][PF6] (7). Complex 7 also exhibits a short-lived and blue-shifted emission in solution and in vesicles as observed for 3 and 4. We have also conjugated the complex [Ru(bpy)2(5-amino-1,10-phenanthroline)][PF6]2 (8) with both cholesterol (9) and DPPE (10). Neither 9 nor the previously reported 10 exhibited the blue shifts observed for 3 and 4 when incorporated into LUVs. The anisotropies of the emissions of 3, 4 and 7 were also measured in LUVs and of 5 in both glycerol and LUVs. High fundamental anisotropies were observed for 3 and 4 and 7. PMID:24063694

  13. Quest for highly porous metal?metalloporphyrin framework based upon a custom-designed octatopic porphyrin ligand

    SciTech Connect

    Wang, Xi-Sen; Chrzanowski, Matthew; Kim, Chungsik; Gao, Wen-Yang; Wojtas, Lukasz; Chen, Yu-Sheng; Zhang, X. Peter; Ma, Shengqian (USF); (UC)

    2012-12-13

    A porous metal-metalloporphyrin framework, MMPF-2, has been constructed from a custom-designed octatopic porphyrin ligand, tetrakis(3,5-dicarboxyphenyl)porphine, that links a distorted cobalt trigonal prism secondary building unit. MMPF-2 possesses permanent microporosity with the highest surface area of 2037 mg{sup 2} g{sup -1} among reported porphyrin-based MOFs, and demonstrates a high uptake capcity of 170 cm{sup 3} g{sup -1} CO{sub 2} at 273 K and 1 bar.

  14. A comparative study of cytotoxicity and interaction with DNA/protein of five transition metal complexes with Schiff base ligands.

    PubMed

    Niu, Meiju; Hong, Min; Chang, Guoliang; Li, Xiao; Li, Zhen

    2015-07-01

    Five transition metal complexes NiL(1)2 (1), CuL(1)2 (2), ZnL(1)2 (3), [MnL(1)2(N3)]n·nCH2Cl2 (4), CuL(2)2 (5) {HL(1)=3-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-naphthalen-2-ol, HL(2)=2-{[2-(2-hydroxy-ethoxy)-ethylimino]-methyl}-phenol} have been synthesized and fully characterized. In all of the complexes, the ligands coordinated to the metal ion in a negative fashion via O and N donor atoms. The X-ray structures of nickel complex 1 and copper complexes 2 and 5 are four-coordinated monomers and show slightly distorted square-planar geometry in the vicinity of the central metal atom. Zinc complex 3 exhibits a four-coordinated tetrahedral structure. Differently, manganese complex 4 reveals a six-coordinated octahedral structure, one-dimensional chain is linked by azide in the end-to-end mode. In vitro cytotoxicity of these complexes to various tumor cell lines was assayed by the MTT method. The results showed that most of these metal-Schiff base complexes exhibited enhanced cytotoxicity than Schiff base ligands, which clearly implied a positive synergistic effect. Moreover, these complexes appeared to be selectively active against certain cell lines. The interactions of these metal complexes with CT-DNA were investigated by UV-vis, fluorescence and CD spectroscopy, the results indicated that these complexes are metallointercalators and can interact with CT-DNA. The study of interaction between complexes and BSA indicated that all of the complexes could quench the intrinsic fluorescence of BSA in a static quenching process. PMID:25974907

  15. DNA binding, anti-inflammatory and analgesic evaluation of metal complexes of N/S/O donor ligands; Synthesis, spectral characterization

    NASA Astrophysics Data System (ADS)

    Kumar Naik, K. H.; Ashok, B.; Naik, Nagaraja; Mulla, Jameel Ahmed S.; Prakasha, Avinash

    2015-04-01

    Transition metal complexes containing tri-dentate NSN donor ligands i.e., 5-((1(aminomethyl)cyclohexyl)methyl)-1,3,4-thiadiazol-2-amine (AMTA) (2) and 5-(2-aminophenyl)-1,3,4-thiadiazol-2-amine (ATA) (4i-ii) have been synthesized. The newly synthesized ligands and their respective complexes were characterized by elemental analysis, molar conductance measurement and various spectral studies [infrared (IR), electronic, and NMR (for ligands only)]. Metal complexes are like [M(AMTA)2], [M(ATA)2] type, where M = Mn(II), Co(II) and Cu(II). The proposed geometries of the complexes are octahedral in nature. The synthesized ligands and their complexes were exhibits effective anti-inflammatory, analgesic and DNA binding activities. All the tested compounds exhibited significant analgesic activity, whereas the compound 4i, 4(ia) and 4(iib) is equipotent with Diclofenac sodium.

  16. DNA binding, anti-inflammatory and analgesic evaluation of metal complexes of N/S/O donor ligands; synthesis, spectral characterization.

    PubMed

    Kumar Naik, K H; Ashok, B; Naik, Nagaraja; Mulla, Jameel Ahmed S; Prakasha, Avinash

    2015-04-15

    Transition metal complexes containing tri-dentate NSN donor ligands i.e., 5-((1(aminomethyl)cyclohexyl)methyl)-1,3,4-thiadiazol-2-amine (AMTA) (2) and 5-(2-aminophenyl)-1,3,4-thiadiazol-2-amine (ATA) (4i-ii) have been synthesized. The newly synthesized ligands and their respective complexes were characterized by elemental analysis, molar conductance measurement and various spectral studies [infrared (IR), electronic, and NMR (for ligands only)]. Metal complexes are like [M(AMTA)2], [M(ATA)2] type, where M=Mn(II), Co(II) and Cu(II). The proposed geometries of the complexes are octahedral in nature. The synthesized ligands and their complexes were exhibits effective anti-inflammatory, analgesic and DNA binding activities. All the tested compounds exhibited significant analgesic activity, whereas the compound 4i, 4(ia) and 4(iib) is equipotent with Diclofenac sodium. PMID:25666328

  17. Antifungal activity of ?-methyl trans cinnamaldehyde, its ligand and metal complexes: promising growth and ergosterol inhibitors.

    PubMed

    Shreaz, Sheikh; Sheikh, Rayees A; Bhatia, Rimple; Neelofar, Khan; Imran, Sheikh; Hashmi, Athar A; Manzoor, Nikhat; Basir, Seemi F; Khan, Luqman A

    2011-10-01

    Antifungal effectivity and utility of cinnamaldehyde is limited because of its high MIC and skin sensitivity. In this study, ?-methyl trans cinnamaldehyde, a less irritating derivative, have been self coupled and complexed with Co(II) and Ni(II) to generate N, N'-Bis (?-methyl trans cinnamadehyde) ethylenediimine [C(22)H(24)N(2)], [Co(C(44)H(48)N(4))Cl(2)] and [Ni(C(44)H(48)N(4))Cl(2)]. Ligand and complexes were characterized on the basis of FTIR, ESI-MS, IR and (1)HNMR techniques. Synthesized ligand [L] and complexes were investigated for their MICs, inhibition of ergosterol biosynthesis and H(+) extrusion against three strains of Candida: C. albicans 44829, C. tropicalis 750 and C. krusei 6258. Average of three species MIC of methyl cinnamaldehyde is 317 ?g/ml (2168 ?M). Compared to methyl cinnamaldehyde ligand [L], Co(II) and Ni(II) complex are found to be 4.48, 17.78 and 21.46 times more effective in liquid medium and 2.73, 8.93 and 10.38 times more effective in solid medium. At their respective MIC(90) average inhibition of ergosterol biosynthesis caused by methyl cinnamaldehyde, ligand [L], Co(II) and Ni(II) complex, respectively was 80, 78, 90 and 93%. H(+) extrusion was also significantly inhibited but did not co-relate well with MIC(90). Results indicate ergosterol biosynthesis as site of action of ?-methyl cinnamaldehyde, synthesized ligand and complexes. ?-methyl cinnamaldehyde and ligand did not show any toxicity against H9c2 rat cardiac myoblast cell, whereas Co(II) and Ni(II) complexes on an average produced 19% cellular toxicity. PMID:21476019

  18. Heterometallic 3d-4f single-molecule magnets: ligand and metal ion influences on the magnetic relaxation.

    PubMed

    Langley, Stuart K; Le, Crystal; Ungur, Liviu; Moubaraki, Boujemaa; Abrahams, Brendan F; Chibotaru, Liviu F; Murray, Keith S

    2015-04-01

    Six tetranuclear 3d–4f single-molecule magnet (SMM) complexes formed using N-n-butyldiethanolamine and N-methyldiethanolamine in conjunction with ortho- and para-substituted benzoic acid and hexafluoroacetoacetone ligands yield two families, both having a butterfly metallic core. The first consists of four complexes of type {Co2(III)Dy2(III)} and {Co2(III)Co(II)Dy(III)} using N-n-butyldiethanolamine with variation of the carboxylate ligand. The anisotropy barriers are 80 cm–1, (77 and 96 cm–1—two relaxation processes occur), 117 and 88 cm–1, respectively, each following a relaxation mechanism from a single DyIII ion. The second family consists of a {Co2(III)Dy2(III)} and a {Cr2(III)Dy2(III)} complex, from the ligand combination of N-methyldiethanolamine and hexafluoroacetylacetone. Both show SMM behavior, the Co(III) example displaying an anisotropy barrier of 23 cm–1. The Cr(III) complex displays a barrier of 28 cm–1, with longer relaxation times and open hysteresis loops, the latter of which is not seen in the Co(III) case. This is a consequence of strong Dy(III)–Cr(III) magnetic interactions, with the relaxation arising from the electronic structure of the whole complex and not from a single DyIII ion. The results suggest that the presence of strong exchange interactions lead to significantly longer relaxation times than in isostructural complexes where the exchange is weak. The study also suggests that electron-withdrawing groups on both bridging (carboxylate) and terminal (?-diketonate) ligands enhance the anisotropy barrier. PMID:25796958

  19. MOF crystal growth: UV resonance Raman investigation of metal-ligand binding in solution and accelerated crystal growth methods.

    PubMed

    Petersen, Thomas D; Balakrishnan, Gurusamy; Weeks, Colin L

    2015-07-01

    Determining the mechanism of metal-organic framework (MOF) crystal growth is important for the development of more efficient and reliable synthetic methods. Resonance Raman spectroscopy has been used for the first time to detect interactions in solution between metal ions and bridging ligands as MOFs form. UV excitation (229 nm) produced strong resonance enhancement of 4,4'-bipyridine (bpy) vibrational bands and showed that soluble Co(2+)-bpy species formed in solution prior to the growth of MOF crystals from bpy and Co(NO3)2. The results of the Raman experiments informed the development of faster methods for synthesizing [Co2(bpy)3(NO3)4]n 2D bilayer and [Co(bpy)(NO3)2(H2O)2]n 1D chain MOFs. PMID:26100962

  20. Manipulating the Lateral Diffusion of Surface-Anchored EGF Demonstrates that Receptor Clustering Modulates its Phosphorylation Levels

    SciTech Connect

    Stabley, Daniel [Emory University; Retterer, Scott T [ORNL; Marshal, Stephen [Emory University; Salaita, Khalid [Emory University

    2013-01-01

    Upon activation, the epidermal growth factor (EGF) receptor becomes phosphorylated and triggers a vast signaling network that has profound effects on cell growth. The EGF receptor is observed to assemble into clusters after ligand binding and tyrosine kinase autophosphorylation, but the role of these assemblies in the receptor signaling pathway remains unclear. To address this question, we measured the phosphorylation of EGFR when the EGF ligand was anchored onto laterally mobile and immobile surfaces. We found that cells generated clusters of ligand-receptor complex on mobile EGF surfaces, and generated a lower ratio of phosphorylated EGFR to EGF than when compared to immobilized EGF that is unable to cluster. This result was verified by tuning the lateral assembly of ligand-receptor complexes on the surface of living cells using patterned supported lipid bilayers. Nanoscale metal lines fabricated into the supported membrane constrained lipid diffusion and EGF receptor assembly into micron and sub-micron scale corrals. Single cell analysis indicated that clustering impacts EGF receptor activation, and larger clusters (> 1 m2) of ligand-receptor complex generated lower EGF receptor phosphorylation per ligand than smaller assemblies (< 1 m2) in HCC1143 cells that were engaged to ligand-functionalized surfaces. We investigated EGFR clustering by treating cells with compounds that disrupt the cytoskeleton (Latrunculin-B), clathrin-mediated endocytosis (Pitstop2), and inhibit EGFR activation (Gefitinib). These results help elucidate the nature of large-scale EGFR clustering, thus underscoring the general significance of receptor spatial organization in tuning function.

  1. Spectroscopic and biological studies of new mononuclear metal complexes of a bidentate NN and NO hydrazone-oxime ligand derived from egonol.

    PubMed

    Babahan, Ilknur; Emirda?-Öztürk, Safiye; Poyrazo?lu-Çoban, Esin

    2015-04-15

    A novel ligand, vicinal dioxime ligand (egonol-hydrazone glyoxime) (LH2) was synthesized and characterized using (1)H NMR, (13)C NMR, MS, AAS, infrared spectroscopy, and magnetic susceptibility measurements. Mononuclear nickel (II), copper (II) and cobalt (II) complexes with a metal:ligand ratio of 1:2 for LH2 were also synthesized. Zn(II) forms complex [Zn(LH)Cl2] with a metal to ligand ratio of 1:1. IR spectrum shows that the ligand act in a bidentate manner and coordinates N4 donor groups of the ligands to Ni(II), Cu(II), Co(II) and Zn(II) ions. The detection of H-bonding (OH?O) in the [M(LH)2] metal complexes by IR spectra supported the square-planar MN4 coordination of Ni(II), Cu(II) and Co(II) complexes. The antimicrobial activities of compounds LH2 and their Ni(II), Cu(II), Co(II) and Zn(II) complexes were evaluated using the disc diffusion method against 16 bacteria and 5 yeasts. The minimal inhibitory concentrations (MICs) against all the bacteria and yeasts were also determined. Among the attempted test compounds, it is showed that all the compounds (L, LH2, [Ni(LH)2], [Cu(LH)2], [Co(LH)2(H2O)2], [Zn(LH)Cl2]) were effective against used test microorganisms. PMID:25686861

  2. Synthesis, Characterization, Antimicrobial, DNA Cleavage, and In Vitro Cytotoxic Studies of Some Metal Complexes of Schiff Base Ligand Derived from Thiazole and Quinoline Moiety

    PubMed Central

    Yernale, Nagesh Gunvanthrao; Bennikallu Hire Mathada, Mruthyunjayaswamy

    2014-01-01

    A novel Schiff base ligand N-(4-phenylthiazol-2yl)-2-((2-thiaxo-1,2-dihydroquinolin-3-yl)methylene)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-thioxo-1,2-dihydroquinoline-3-carbaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), and Zn(II) complexes have been characterized by elemental analysis and various spectral studies like FT-IR, 1H NMR, ESI mass, UV-Visible, ESR, TGA/DTA, and powder X-ray diffraction studies. The Schiff base ligand (L) behaves as tridentate ONS donor and forms the complexes of type [ML(Cl)2] with square pyramidal geometry. The Schiff base ligand (L) and its metal complexes have been screened in vitro for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activity of ligand and its metal complexes were studied using plasmid DNA pBR322 as a target molecule by gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties for the ligand and its metal complexes against Artemia salina. The results showed that the biological activities of the ligand were found to be increased on complexation. PMID:24729778

  3. The development of N2S2 metal complexes as bidentate ligands for organometallic chemistry 

    E-print Network

    Rampersad, Marilyn Vena

    2007-04-25

    , indicating that the remaining W-S bond is considerably strengthened upon ring-opening. Several new cluster compounds based on the NiN2S2 ligands bound to CuI, RhI, PdII and W0 are reported. Structural analysis of (NiN2S2)MLn complexes show a unique structural...

  4. Synthesis and Characterization of Transition Metal Complexes of Multidentate Ligands Containing a Pyridine Ring

    Microsoft Academic Search

    2005-01-01

    Several mono? or bi?nuclear nickel, copper, and zinc complexes of some multidentate ligands containing a pyridine ring have been synthesized and characterized by elemental analyses, molar conductivity, IR, UV, H NMR and TG?DTA. The deprotonation behavior upon coordination is discussed.

  5. Protonation of metal-bound ?-hydroxycarboxylate ligand and implication for the role of homocitrate in nitrogenase: Computational study of the oxy-bidentate chelate ring opening

    NASA Astrophysics Data System (ADS)

    Cao, Zexing; Jin, Xi; Zhou, Zhaohui; Zhang, Qianer

    Protonation of the metal-bound oxy-bidentate ligand in the model complexes of [(HS)3(NH3)M(OCH2COO)]q (M = Mo, Fe, V, Co; q = -2, -1) in the gas phase and in solutions of water and acetonitrile has been explored by the density functional approach. Calculations show that protonation of the carboxyl oxygen can open the ?-hydroxycarboxylate chelate ring ligated to a transition-metal center under specific oxidation and spin states. The feasibility of the chelate ring opening by protonation depends on the electronic nature of the metal site in tune with conversion of a six-coordinate with a five-coordinate metal atom. Such selective dissociation of the metal-bound chelate ligand manipulates the availability of an empty site at the metal center and significantly affects reactivity of the metal-mediated chemical processes. Protonation changes the stability of species with different spin multiplicities and impels spin transition at the metal center in dissociation of the oxy-bidentate ligand. Solvent environments of water and acetonitrile play an important role in stabilizing the negatively charged species.

  6. Late first-row transition metal complexes of a tetradentate pyridinophane ligand: electronic properties and reactivity implications.

    PubMed

    Khusnutdinova, Julia R; Luo, Jia; Rath, Nigam P; Mirica, Liviu M

    2013-04-01

    The synthesis and structural comparison are reported herein for a series of late first-row transition metal complexes using a macrocyclic pyridinophane ligand, N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane ((tBu)N4). The (tBu)N4 ligand enforces a distorted octahedral geometry in complexes [((tBu)N4)M(II)(MeCN)2](OTf)2 (M = Fe(II), Co(II), Ni(II), Cu(II)), [((tBu)N4)Zn(II)(MeCN)(OTf)](OTf), and [((tBu)N4)Fe(III)(OMe)2](OTf), with elongated axial M-N(amine) distances compared to the equatorial M-N(py) distances. The geometry of [((tBu)N4)Cu(I)(MeCN)](OTf) is pentacoordinate with weak axial interactions with the amine N-donors of (tBu)N4. Complexes [((tBu)N4)M(MeCN)2](OTf)2 (M = Fe, Co) exhibit magnetic properties that are intermediate between those expected for high spin and low spin complexes. Electrochemical studies of ((tBu)N4)M complexes suggest that (tBu)N4 is suitable to stabilize Co(I), Ni(I), Co(III), Fe(III) solvato-complexes, while the electrochemical oxidation of ((tBu)N4)NiCl2 complex leads to formation of a Ni(III) species, supporting the ability of the (tBu)N4 ligand to stabilize first row transition metal complexes in various oxidation states. Importantly, the [((tBu)N4)M(II)(MeCN)2](2+) complexes exhibit two available cis coordination sites and thus can mediate reactions involving exogenous ligands. For example, the [((tBu)N4)Cu(II)(MeCN)2](2+) species acts as an efficient Lewis acid and promotes an uncommon hydrolytic coupling of nitriles. In addition, initial UV-vis and electron paramagnetic resonance (EPR) studies show that the [((tBu)N4)Fe(II)(MeCN)2](2+) complex reacts with oxidants such as H2O2 and peracetic acid to form high-valent Fe transient species. Overall, these results suggest that the ((tBu)N4)M(II) systems should be able to promote redox transformations involving exogenous substrates. PMID:23517006

  7. Anchored periplasmic expression, a versatile technology for the isolation of high-affinity antibodies from Escherichia coli-expressed libraries

    Microsoft Academic Search

    Barrett R. Harvey; George Georgiou; Andrew Hayhurst; Ki Jun Jeong; Brent L. Iverson; Geoffrey K. Rogers

    2004-01-01

    Anchored periplasmic expression (APEx) is a technology for the isolation of ligand-binding proteins from combinatorial libraries anchored on the periplasmic face of the inner membrane of Escherichia coli. After disruption of the outer membrane by Tris-EDTA-lysozyme, the inner-membrane-anchored proteins readily bind fluorescently labeled ligands as large as 240 kDa. Fluorescently labeled cells are isolated by flow cytometry, and the DNA

  8. DNA interaction studies of d and d metal complexes having Schiff base and polypyridyl ligands

    Microsoft Academic Search

    Krishnan Pothiraj; Thanasekaran Baskaran; Natarajan Raman

    2012-01-01

    Four mononuclear complexes of Cu(II) and Zn(II) having a Schiff base ligand and 1,10-phenanthroline\\/2,2'-bipyridine have been synthesized and characterized. From electronic spectral and magnetic susceptibility data, octahedral geometry has been proposed for the complexes. DNA binding behaviors of these complexes are studied by absorption titration, electrochemical and viscosity methods. The results indicate that the complexes bind to calf thymus DNA

  9. Some Metal Complexes of Schiff Base Ligands Derived from Ninhydrin and Some Amino Acids

    Microsoft Academic Search

    Aly M. A. Hassaan

    1997-01-01

    The Fe(III), Cr(III) and Al(III) complexes of Schiff base ligands derived from ninhydrin with some amino acids (glycine, ?-alanine, serine) have been prepared and characterized by means of elemental analyses, IR, electronic spectra as well as conductivity and magnetic measurements. Modes of bonding and geometrical structures for these chelates are proposed.Referee I: M. S. ChinnReferee II: J. W. Fitch III

  10. Using low-frequency IR spectra for the unambiguous identification of metal ion-ligand coordination sites in purpose-built complexes

    NASA Astrophysics Data System (ADS)

    Varga, Gábor; Csendes, Zita; Peintler, Gábor; Berkesi, Ottó; Sipos, Pál; Pálinkó, István

    2014-03-01

    One of the aims of our long-term research is the identification of metal ion-ligand coordination sites in bioinspired metal ion-C- or N-protected amino acid (histidine, tyrosine, cysteine or cystine) complexes immobilised on the surface of chloropropylated silica gel or Merrifield resin. In an attempt to reach this goal, structurally related, but much simpler complexes have been prepared and their metal ion-ligand vibrations were determined from their low-frequency IR spectra. The central ions were Mn(II), Co(II), Ni(II) or Cu(II) and the ligands (imidazole, isopropylamine, monosodium malonate) were chosen to possess only one-type of potential donor group. The low-frequency IR spectra were taken of the complexes for each ion-ligand combination and the typical metal ion-functional group vibration bands were selected and identified. The usefulness of the obtained assignments is demonstrated on exemplary immobilised metal ion-protected amino acid complexes.

  11. Anchoring pipelines prevents damage

    SciTech Connect

    Odusch, J.M.

    1980-11-24

    Pinning the pipeline to the trench or seafloor by tensioned mechanical anchors is one solution to resisting water and soil forces either offshore or onshore on swampy or frequently flooded land. Furthermore, it reduces concrete-coating requirements, thus lowering the stress on pipe during laying. Anchoring also permits designing the pipe to withstand 100-year storms without excessive costs, eliminates lift and drag effects on the pipe by wave and current forces, and ensures that the line will remain where originally placed. For later maintenance, an anchored line is easier to find and less brittle than an unanchored pipe. Based on the pressure-distribution theory of mechanical anchoring, the system uses helical anchors on long anchor rods screwed into the subsoil on either side of the pipeline. Flanges at the head of the anchors engage a bracket between them that maintains tension on the pipeline, pinning it to the trench bottom. Measurements of the soil's load resistance - obtained by a portable soil-test probe - are essential to the design of an effective anchoring system.

  12. Syntheses, crystal structures, and optical properties of five metal complexes constructed from a V-shaped thiophene-containing ligand and different dicarboxylate ligands.

    PubMed

    Shi, Zhi-Qiang; Guo, Zi-Jian; Zheng, He-Gen

    2014-09-21

    Five new metal complexes, {[Ni(DIDP)(m-bdc)(H2O)]·5H2O}n (1), {[Zn(DIDP)(hfipbb)]·2DMA}n (2), {[Zn(DIDP)(4,4'-sdb)]·H2O}n (3), {[Co(DIDP)(p-bdc)]}n (4), and {[Co2(DIDP)(hfipbb)2]·H2O}n (5), have been synthesized by reactions of the corresponding metal ions with a V-shaped ligand 2,8-di(1H-imidazol-1-yl)dibenzothiophene (DIDP) and different aromatic dicarboxylic acids, namely isophthalic acid (m-H2bdc), terephthalic acid (p-H2bdc), 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), and 4,4'-sulfonyldicarboxylic acid (4,4'-H2sdb), respectively. The structures of the complexes were determined by X-ray single-crystal diffraction. Complex 1 is a 1D chain structure containing a one-dimensional channel along the a direction and is further extended via O-H···S hydrogen bonds and C-H···? stacking interactions into a 3D framework. Complex 2 exhibits a quasi 2D + 2D ? 2D with parallel polycatenation of 2D (4, 4) nets. Complex 3 displays an unusual 2D + 2D ? 3D parallel polycatenated framework based on a 2D 6(3)-hcb network. Complex 4 shows a 2D 4-connected {4(4)·6(2)}-sql network containing a one-dimensional channel along the b direction. The adjacent 2D networks are further extended via C-H···O hydrogen bonds into a 3D supramolecular framework. Complex 5 features a 2-fold interpenetrating 3D framework with a 6-connected {4(12)·6(3)} pcu topology. Furthermore, the thermal stability for 1-5 and luminescence properties of 2 and 3 have been studied. Moreover, the solid-state UV-visible spectroscopy experiments show that complexes 1-5 are all optical semiconductors with band gaps of 3.06, 3.18, 3.23, 2.98, and 3.17 eV, respectively. PMID:25050987

  13. Red electroluminescence of ruthenium sensitizer functionalized by sulfonate anchoring groups.

    PubMed

    Shahroosvand, Hashem; Abbasi, Parisa; Mohajerani, Ezeddin; Janghouri, Mohammad

    2014-06-28

    We have synthesized five novel Ru(ii) phenanthroline complexes with an additional aryl sulfonate ligating substituent at the 5-position [Ru(L)(bpy)2](BF4)2 (1), [Ru(L)(bpy)(SCN)2] (2), [Ru(L)3](BF4)2 (3), [Ru(L)2(bpy)](BF4)2 (4) and [Ru(L)(BPhen)(SCN)2] (5) (where L = 6-one-[1,10]phenanthroline-5-ylamino)-3-hydroxynaphthalene 1-sulfonic, bpy = 2,2'-bipyridine, BPhen = 4,7-diphenyl-1,10-phenanthroline), as both photosensitizers for oxide semiconductor solar cells (DSSCs) and light emitting diodes (LEDs). The absorption and emission maxima of these complexes red shifted upon extending the conjugation of the phenanthroline ligand. Ru phenanthroline complexes exhibit broad metal to ligand charge transfer-centered electroluminescence (EL) with a maximum near 580 nm. Our results indicated that a particular structure (2) can be considered as both DSSC and OLED devices. The efficiency of the LED performance can be tuned by using a range of ligands. Device (2) has a luminance of 550 cd m(-2) and maximum efficiency of 0.9 cd A(-1) at 18 V, which are the highest values among the five devices. The turn-on voltage of this device is approximately 5 V. The role of auxiliary ligands in the photophysical properties of Ru complexes was investigated by DFT calculation. We have also studied photovoltaic properties of dye-sensitized nanocrystalline semiconductor solar cells based on Ru phenanthroline complexes and an iodine redox electrolyte. A solar energy to electricity conversion efficiency (?) of 0.67% was obtained for Ru complex (2) under standard AM 1.5 irradiation with a short-circuit photocurrent density (Jsc) of 2.46 mA cm(-2), an open-circuit photovoltage (Voc) of 0.6 V, and a fill factor (ff) of 40%, which are all among the highest values for ruthenium sulfonated anchoring groups reported so far. Monochromatic incident photon to current conversion efficiency was 23% at 475 nm. Photovoltaic studies clearly indicated dyes with two SCN substituents yielded a higher Jsc for the cell than dyes with a tris-homoleptic anchor substituent. PMID:24818219

  14. High current density electrodeposition of silver from silver-containing liquid metal salts with pyridine-N-oxide ligands.

    PubMed

    Sniekers, Jeroen; Brooks, Neil R; Schaltin, Stijn; Van Meervelt, Luc; Fransaer, Jan; Binnemans, Koen

    2014-01-28

    New cationic silver-containing ionic liquids were synthesized and used as non-aqueous electrolytes for the electrodeposition of silver layers. In the liquid state of these ionic liquids, a silver (i) cation is coordinated by pyridine-N-oxide (py-O) ligands in a 1?:?3 metal-to-ligand ratio, although in some cases a different stoichiometry of the silver center crystallized out. As anions, bis(trifluoromethanesulfonyl)imide (Tf2N), trifluoromethanesulfonate (OTf), methanesulfonate (OMs) and nitrate were used, yielding compounds with the formulae [Ag(py-O)3][Tf2N], [Ag(py-O)3][OTf], [Ag(py-O)3][OMs] and [Ag(py-O)3][NO3], respectively. The compounds were characterized by CHN analysis, FTIR, NMR, DSC, TGA and the electrodeposition of silver was investigated by cyclic voltammetry, linear potential scans, scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDX). With the exception of [Ag(py-O)3][Tf2N], which melts at 108 °C, all the silver(i) compounds have a melting point below 80 °C and were tested as electrolytes for silver electrodeposition. Interestingly, very high current densities were observed at a potential of -0.5 V vs. Ag/Ag(+) for the compounds with fluorine-free anions, i.e. [Ag(py-O)3][NO3] (current density of -10 A dm(-2)) and [Ag(py-O)3][OMs] (-6.5 A dm(-2)). The maximum current density of the compound with the fluorinated anion trifluoromethanesulfonate, [Ag(py-O)3][OTf], was much lower: -2.5 A dm(-2) at -0.5 V vs. Ag/Ag(+). Addition of an excess of ligand to [Ag(py-O)3][OTf] resulted in the formation of the room-temperature ionic liquid [Ag(py-O)6][OTf]. A current density of -5 A dm(-2) was observed at -0.5 V vs. Ag/Ag(+) for this low viscous silver salt. The crystal structures of several silver complexes could be determined by X-ray diffraction, and it was found that several of them had a stoichiometry different from the 1?:?3 metal-to-ligand ratio used in their synthesis. This indicates that the compounds form crystals with a composition different from that of the molten state. The electrochemical properties were measured in the liquid state, where the metal-to-ligand ratio was 1?:?3. Single crystal X-ray diffraction measurements showed that silver(i) is six coordinate in [Ag(py-O)3][Tf2N] and [Ag(py-O)3][OTf], while it is five coordinate in the other complexes. In [Ag3(py-O)8][OTf]3, there are two different coordination environments for silver ions: six coordinate central silver ions and five coordinate for the outer silver ions. In some of the silver(i) complexes, silver-silver interactions were observed in the solid state. PMID:24217798

  15. Transition metal complexes with Schiff-base ligands: 4-aminoantipyrine based derivatives–a review

    Microsoft Academic Search

    N. Raman; S. Johnson Raja; A. Sakthivel

    2009-01-01

    The survey highlights structural properties and biological studies of transition metal complexes derived from 4-aminoantipyrine. The most important results of extensive studies (syntheses, spectral, magnetic, redox, structural characteristics, antimicrobial and DNA cleavage) of the metal complexes with heterocyclic Schiff bases of 4-aminoantipyrine with some aldehydes and oximes are reviewed.

  16. Schiff base ligands and their transition metal complexes in the mixtures of ionic liquid + organic solvent: a thermodynamic study.

    PubMed

    Shekaari, Hemayat; Kazempour, Amir; Khoshalhan, Maryam

    2015-01-21

    Schiff bases and their metal complexes in the mixtures of ionic liquid (IL) + organic solvent have shown great potential in attractive oxidation catalytic processes. The efficiency of such a process is strongly dependent on the various molecular interactions occurring between components. Thermodynamic properties of these systems can provide valuable information about structural interactions. Therefore, in this work, the interactions of the IL 1-hexyl-3-methylimidazolium chloride ([HMIm]Cl) with Schiff bases in organic solvents were studied through the measurements of density, viscosity, and electrical conductivity. The effect of solvent on the interactions was examined by the solutions of IL + BPIC Schiff base + solvent (C2H6O-C3H8O-C4H10O). Moreover, the influence of Schiff base ligand and Schiff base complex structures was probed by the solutions of IL + DMA + ligand (salcn/salpr/salen) and IL + DMA + complex (VO(3-OMe-salen)/VO(salophen)/VO(salen)), respectively. Using the experimental data, some important thermodynamic properties, such as standard partial molar volume (V(0)(?,IL)), experimental slope (Sv), viscosity B-coefficient, solvation number (B/V(0)(?,IL) and limiting molar conductivity (?0) were calculated and discussed in terms of solute-solvent (IL-DMF/alcohol) and solute-cosolute (IL-Schiff base) interactions. PMID:25482659

  17. Antifungal activity of ?-methyl trans cinnamaldehyde, its ligand and metal complexes: promising growth and ergosterol inhibitors

    Microsoft Academic Search

    Sheikh Shreaz; Rayees A. Sheikh; Rimple Bhatia; Khan Neelofar; Sheikh Imran; Athar A. Hashmi; Nikhat Manzoor; Seemi F. Basir; Luqman A. Khan

    Antifungal effectivity and utility of cinnamaldehyde is limited because of its high MIC and skin sensitivity. In this study,\\u000a ?-methyl trans cinnamaldehyde, a less irritating derivative, have been self coupled and complexed with Co(II) and Ni(II) to\\u000a generate N, N?–Bis (?-methyl trans cinnamadehyde) ethylenediimine [C22H24N2], [Co(C44H48N4)Cl2] and [Ni(C44H48N4)Cl2]. Ligand and complexes were characterized on the basis of FTIR, ESI–MS, IR

  18. Isospecific polymerization of 1-hexene by C1-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands.

    PubMed

    Yasumoto, Takahiro; Yamamoto, Keishi; Tsurugi, Hayato; Mashima, Kazushi

    2013-07-01

    Non-bridged half-metallocene dimethyl complexes of group 4 metals 2a-4a with an N-4-methoxyphenyl(iminomethyl)pyrrolyl ligand 1a were synthesized and characterized by NMR spectroscopy and X-ray analysis. Upon activation with [Ph3C][B(C6F5)4], these complexes became active catalysts for the polymerization of 1-hexene. A series of hafnium complexes with various N-substituents on the imine group of ligands 1b-1g were also prepared and applied as catalysts for 1-hexene polymerization. The activation parameters for the exchange process between the two methyl groups bound to the metal for Cp*MMe2(R-pyr) complexes were estimated by NMR shape analysis at various temperatures. The findings indicated that the transition state of the ligand flipping process might be associated with the isoselectivity of the polymerization reaction. PMID:23235804

  19. Highly sensitive and selective fluorescence detection of copper (II) ion based on multi-ligand metal chelation.

    PubMed

    Zhang, Shan; Yu, Tao; Sun, Mingtai; Yu, Huan; Zhang, Zhongping; Wang, Suhua; Jiang, Hui

    2014-08-01

    A fluorescent probe was synthesized and demonstrated to be highly selective and sensitive in the reaction with copper (II) ion, generating a large variation of the fluorescence intensity in a dose-response manner. The probe contains a dansyl moiety as fluorophore and a multidentate ligand for copper (II) ion recognition. The reaction of the molecular probe with copper (II) ion proceeds rapidly and irreversibly in a 1 to 1 stoichiometric way, leading to the production of stable copper (II) complex, which subsequently results in the quenching of fluorescence. The detection limit for copper (II) ion was measured to be about 2ppb. It was also shown that the probe has high selectivity for copper (II) ion and good anti-interference ability against other transition metal ions. The herein reported very simple and reliable fluorescence probe could be employed for copper (II) ion detection in many aspects. PMID:24881551

  20. Metal-assisted synthesis of unsymmetrical magnolol and honokiol analogs and their biological assessment as GABAA receptor ligands.

    PubMed

    Rycek, Lukas; Puthenkalam, Roshan; Schnürch, Michael; Ernst, Margot; Mihovilovic, Marko D

    2015-01-15

    We present the synthesis of new derivatives of natural products magnolol (1) and honokiol (2) and their evaluation as allosteric ligands for modulation of GABAA receptor activity. New derivatives were prepared via metal assisted cross-coupling reactions in two consecutive steps. Compounds were tested by means of two-electrode voltage clamp electrophysiology at the ?1?2?2 receptor subtype at low GABA concentrations. We have identified several compounds enhancing GABA induced current (IGABA) in the range similar or even higher than the lead structures. At 3?M, compound 8g enhanced IGABA by factor of 443, compared to 162 and 338 of honokiol and magnolol, respectively. Furthermore, 8g at EC10-20 features a much bigger window of separation between the ?1?2?2 and the ?1?1?2 subtypes compared to honokiol, and thus improved subtype selectivity. PMID:25510374

  1. Metal-assisted synthesis of unsymmetrical magnolol and honokiol analogs and their biological assessment as GABAA receptor ligands

    PubMed Central

    Rycek, Lukas; Puthenkalam, Roshan; Schnürch, Michael; Ernst, Margot; Mihovilovic, Marko D.

    2015-01-01

    We present the synthesis of new derivatives of natural products magnolol (1) and honokiol (2) and their evaluation as allosteric ligands for modulation of GABAA receptor activity. New derivatives were prepared via metal assisted cross-coupling reactions in two consecutive steps. Compounds were tested by means of two-electrode voltage clamp electrophysiology at the ?1?2?2 receptor subtype at low GABA concentrations. We have identified several compounds enhancing GABA induced current (IGABA) in the range similar or even higher than the lead structures. At 3 ?M, compound 8g enhanced IGABA by factor of 443, compared to 162 and 338 of honokiol and magnolol, respectively. Furthermore, 8g at EC10–20 features a much bigger window of separation between the ?1?2?2 and the ?1?1?2 subtypes compared to honokiol, and thus improved subtype selectivity. PMID:25510374

  2. Quadruple metal-metal bonds with strong donor ligands. Ultraviolet photoelectron spectroscopy of M{sub 2}(form){sub 4} (M = Cr, Mo, W; form = N,N{prime}-diphenylformamidinate)

    SciTech Connect

    Lichtenberger, D.L.; Lynn, M.A.; Chisholm, M.H.

    1999-12-29

    The He I photoelectron spectra of M{sub 2}(form){sub 4}(M = Cr, Mo, W; form - N,N{prime}-diphenylformamidinate) and Mo{sub 2}(cyform){sub 4} (cyform = N,N{prime}-dicyclohexylformamidinate) are presented. For comparison, the Ne I, He I, and He II photoelectron spectra of Mo{sub 2}(p-CH{sub 3}-form){sub 4} have also been obtained. The valence ionization features of these molecules are interpreted based on (1) the changes that occur with the metal and ligand substitutions, (2) the changes in photoelectron cross sections with excitation source, and (3) the changes from previously studied dimetal complexes. These photoelectron spectra are useful for revealing the effects that better electron donor ligands have on the valence electronic structure of M{sub 2}(L-L){sub 4} systems. Comparison with the He I spectra of the isoelectronic M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} compounds is particularly revealing. Unlike with the more electron-withdrawing acetate ligand, several formamidinate-based ionizations derived from the nitrogen p{sub {pi}} orbitals occur among the metal-metal {sigma}, {pi}, and {delta} ionization bands. Although these formamidinate-based levels are close in energy to the occupied metal-metal bonds, they have little direct mixing interaction with them. The shift of the metal-metal bond ionizations to lower ionization energies for the formamidinate systems is primarily a consequence of the lower electronegativity of the ligand and the better {pi} donation into empty metal levels. The metal-metal {delta} orbital experiences some additional net bonding interaction with ligand orbitals of the same symmetry. Also, an additional bonding interaction from ligand-to-metal electron donation to the {delta}* orbital is identified. These spectra suggest a greater degree of metal-ligand covalency than in the related M{sub 2}(O{sub 2}CCH{sub 3}){sub 4} systems. Fenske-Hall molecular orbital and density functional (ADF) calculations agree with the assignment and interpretation of these spectra. Calculated ionization energies are reported for M{sub 2}(form){sub 4} based on several different density functionals and with different orientations and substitutions for the phenyl rings. It is found that good estimates of the ionization energies are obtained when the truncated system M{sub 2}(HN-(CH)NH){sub 4}, in which the phenyl groups are replaced by hydrogen atoms, is employed.

  3. Ligand-stabilized Au13Cu(x) (x = 2, 4, 8) bimetallic nanoclusters: ligand engineering to control the exposure of metal sites.

    PubMed

    Yang, Huayan; Wang, Yu; Lei, Jing; Shi, Lei; Wu, Xiaohu; Mäkinen, Ville; Lin, Shuichao; Tang, Zichao; He, Jian; Häkkinen, Hannu; Zheng, Lansun; Zheng, Nanfeng

    2013-07-01

    Three novel bimetallic Au-Cu nanoclusters stabilized by a mixed layer of thiolate and phosphine ligands bearing pyridyl groups are synthesized and fully characterized by X-ray single crystal analysis and density functional theory computations. The three clusters have an icosahedral Au13 core face-capped by two, four, and eight Cu atoms, respectively. All face-capping Cu atoms in the clusters are triply coordinated by thiolate or pyridyl groups. The surface ligands control the exposure of Au sites in the clusters. In the case of the Au13Cu8 cluster, the presence of 12 2-pyridylthiolate ligands still leaves open space for catalysis. All the 3 clusters are 8-electron superatoms displaying optical gaps of 1.8-1.9 eV. The thermal decomposition studies suggest that the selective release of organic ligands from the clusters is possible. PMID:23789787

  4. Synthesis, spectral and thermal studies of some transition metal mixed ligand complexes: Modeling of equilibrium composition and biological activity

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Sundaram, M.; Nair, M. Sivasankaran

    2011-09-01

    Several mixed ligand Ni(II), Cu(II) and Zn(II) complexes of 2-amino-3-hydroxypyridine (AHP) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) have been synthesized and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as by magnetic moment values. On the basis of elemental analysis and molar conductance values, all the complexes can be formulated as [MAB]Cl except histidine complexes as MAB. Thermogravimetric studies reveal the presence of coordinated water molecules in most of the complexes. From the magnetic measurements and electronic spectral data, octahedral structure was proposed for Ni(II) and Cu(II)-AHP-his, tetrahedral for Cu(II)-AHP-him/bim/hist, but square planar for the Cu(II)-AHP complex. The g?/ A? calculated supports tetrahedral environment around the Cu(II) in Cu(II)-AHP-him/bim/hist and distorted octahedral for Cu(II)-AHP-his complexes. The morphology of the reported metal complexes was investigated by scanning electron micrographs (SEM). The potentiometric study has been performed in aqueous solution at 37 °C and I = 0.15 mol dm -3 NaClO 4. MABH, MAB and MAB 2 species has been identified in the present systems. Proton dissociation constants of AHP and stability constants of metal complexes were determined using MINIQUAD-75. The most probable structure of the mixed ligand species is discussed based upon their stability constants. The in vitro biological activity of the complexes was tested against the Gram positive and Gram negative bacteria, fungus and yeast. The oxidative DNA cleavage studies of the complexes were performed using gel electrophoresis method. Cu(II) complexes have been found to promote DNA cleavage in presence of biological reductant such as ascorbate and oxidant like hydrogen peroxide.

  5. Ligand self-assembling through complementary hydrogen-bonding in the coordination sphere of a transition metal center: the 6-diphenylphosphanylpyridin-2(1H)-one system.

    PubMed

    Gellrich, Urs; Huang, Jing; Seiche, Wolfgang; Keller, Manfred; Meuwly, Markus; Breit, Bernhard

    2011-02-01

    Motivated by previous findings which had shown that transition metal catalysts based on the 6-diphenylphosphanylpyridone ligand (6-DPPon, 2) display properties as a self-assembling bidentate ligand-metal complex, we have performed a thorough study on the bonding situation of this ligand, alone and in the coordination sphere of a late transition metal. Thus, combining a number of spectroscopic methods (UV-vis, IR, NMR, X-ray), we gained insights into the unique structural characteristics of 2. These experimental studies were corroborated by DFT calculations, which were in all cases in good agreement with the experimental results. The free ligand 2 prefers to exist as the pyridone tautomer 2A and dimerizes to the pyridone-pyridone dimer 4A in solution as well as in the crystal state. The corresponding hydroxypyridine tautomer 2B is energetically slightly disfavored (ca. 0.9 kcal/mol within the up-conformer relevant for metal coordination); hence, hydrogen bond formation within the complex may easily compensate this small energy penalty. Coordination properties of 2 were studied in the coordination sphere of a platinum(II) center. As a model complex, [Cl(2)Pt(6-DPPon)(2)] (11) was prepared and investigated. All experimental and theoretical methods used prove the existence of a hydrogen-bonding interligand network in solution as well as in the crystal state of 11 between one 6-DPPon ligand existing as the pyridone tautomer 2A and the other ligand occupying the complementary hydroxypyridine form 2B. Dynamic proton NMR allowed to determine the barrier for interligand hydrogen bond breaking and, in combination with theory, enabled us to determine the enthalpic stabilization through hydrogen-bonding to contribute 14-15 kcal/mol. PMID:21142007

  6. Interplay of coordinative and supramolecular interactions in engineering unusual crystalline architectures of low-dimensional metal–pamoate complexes under co-ligand intervention

    Microsoft Academic Search

    Miao Du; Cheng-Peng Li; Xiao-Jun Zhao; Qian Yu

    2007-01-01

    This work presents a systematic investigation on coordination chemistry of a pharmaceutical agent pamoic acid (H2PA), and also reveals the significant function of supramolecular interactions in managing the resultant crystalline networks with the incorporation of secondary co-ligands. Assemblies of pamoic acid with transition metal ions under similar conditions yield a series of eleven Mn II ,C u II ,Z n

  7. Transition metal(II) complexes of vitamin B13 with monodentate orotate(1-) ligands

    NASA Astrophysics Data System (ADS)

    Köse, Dursun Ali; Zümreoglu-Karan, Birgül; ?ahin, Onur; Büyükgüngör, Orhan

    2006-05-01

    The formation of bisorotate(1-) complexes of the type [M(C 5H 3N 2O 4) 2(H 2O) 4]· nH 2O (M=Co, Ni, Zn and n=2, 4) was achieved by the reaction of ammonium orotate with the corresponding M(II) ions. The crystal structure of [Co(C 5H 3N 2O 4) 2(H 2O) 4]·2H 2O was determined by single crystal X-ray diffraction analysis. Each Co(II) ion in the monomeric Co(C 5H 3N 2O 4) 2(H 2O) 4 units adapts a slightly distorted octahedral geometry comprised of two monodentate orotate anions and four H 2O ligands. Columnar packing of pyrimidine rings along the c axis leads to the formation of layers that propagate parallel to the b axis and the adjacent layers are linked by hydrogen bonds forming a 3D lattice. Complexes of nickel and zinc were assumed to contain monodentate bound orotate ligands as well on the basis of physical and spectroscopic data.

  8. Metal Complexes with Schiff Base Ligands: Pyridoxal and Semicarbazide-Based Derivatives

    Microsoft Academic Search

    Vukadin M. Leovac; Violeta S. Jevtovic; Ljiljana S. Jovanovic; Goran A. Bogdanovic

    2005-01-01

    The most important results of extensive studies (syntheses, spectral, mag- netic, voltammetric and structural characteristics and biological activity) of metal complexes with pyridoxal semi-, thiosemi- and isothiosemicarbazones are reviewed.

  9. Zwitterionic late transition metal alkene polymerisation catalysts containing aminofulvene-aldiminate (AFA) ligands 

    E-print Network

    Rahman, Mohammed Mahmudur

    2010-01-01

    Over recent years significant progress has been made in the design and development of late transition metal cationic catalysts for olefin polymerisation. Never-the-less, the activation of catalyst precursors and generation ...

  10. Heat-Conducting Anchors for Thermocouples

    NASA Technical Reports Server (NTRS)

    Macdavid, Kenton S.

    1987-01-01

    Metal particles in adhesive aid heat transfer. Aluminum caps containing silver-filled epoxy used as high-thermal-conductance anchors for thermocouples, epoxy providing thermal path between mounting surfaces and thermocouple measuring junctions. Normally, epoxy-filled aluminum caps used when measuring steady-state temperatures. Silver-filled epoxy used when thermocouple not isolated electrically from surface measured.

  11. Development and Assessment of a New CFRP Rod–Anchor System for Prestressed Concrete

    Microsoft Academic Search

    A. Al-Mayah; K. Soudki; A. Plumtree

    2006-01-01

    Design concepts and experimental assessment of a new wedge anchor system for prestressing CFRP rods are presented. This compact and reusable anchor consists of an outer cylinder (barrel), a number of wedges, and a soft metal sleeve. The contacting surfaces of the wedges and barrel have a circular profile along the length of the anchor. Tensile testing using different presetting

  12. Paramagnetic metal effect on the ligand localized S/sub 1/. -->. T/sub 1/ intersystem crossing in the rare-earth-metal complexes and methyl salicylate

    SciTech Connect

    Tobita, S.; Arakawa, M.; Tanaka, I.

    1985-01-01

    The electronic relaxation processes in the chelates of La/sup 3 +/, Gd/sup 3 +/, Tb/sup 3 +/, and Lu/sup 3 +/ with methyl salicylate have been investigated by measurements of picosecond fluorescence, nanosecond transient absorptions, and quantum yields. The quantum yields of the S/sub 1/ ..-->.. T/sub 1/ intersystem crossing are not appreciably altered by a change in the central metal ions. However, the fluorescence lifetimes are decreased dramatically in the paramagnetic Gd/sup 3 +/ (240 ps) and Tb/sup 3 +/ (<10 ps) complexes compared with those in the diamagnetic La/sup 3 +/ (2.2 ns) and Lu/sup 3 +/ (2.4 ns) complexes. The rate constants derived from these results for the S/sub 1/ ..-->.. T/sub 1/ intersystem crossing, k/sub TM/, in ligands are 5.5 x 10/sup 7/, 7.5 x 10/sup 8/, and 7.9 x 10/sup 7/ s/sup -1/ for the La/sup 3 +/, Gd/sup 3 +/, and Lu/sup 3 +/ complexes, respectively. A large increase of k/sub TM/ is observed in the paramagnetic Gd/sup 3 +/ complexes, which can be attributed to the electron exchange mechanism with ligand ..pi.. electrons. 27 references, 8 figures, 3 tables.

  13. Dinuclear metal complexes of Schiff base ligands as catalysts for oxidation and epoxidation reactions

    Microsoft Academic Search

    P. S. Zacharias; B. Srinivas; H. Aneetha

    1995-01-01

    Dinuclear copper(II) complexes (Cu2 LnCl3), nickel(II) complexes (Ni2 LnCl3) and cobalt(II) complexes (Co2L\\u000a 2\\u000a n\\u000a Cl2) from Schiff base ligands are synthesised, characterised and used as catalysts for oxidation of 3,5-DTBC to 3,5-DTBQ. (Cu2LnCl3) are found to be more efficient than the other complexes. Dinuclear iron(III) complexes of composition (Fe2L2Cl2) and ruthenium (III) complexes of composition Ru2L\\u000a 2\\u000a n\\u000a Cl6(PPh3)2

  14. Mixed ligand complexation of some transition metal ions in solution and solid state: Spectral characterization, antimicrobial, antioxidant, DNA cleavage activities and molecular modeling

    NASA Astrophysics Data System (ADS)

    Shobana, Sutha; Dharmaraja, Jeyaprakash; Selvaraj, Shanmugaperumal

    2013-04-01

    Equilibrium studies of Ni(II), Cu(II) and Zn(II) mixed ligand complexes involving a primary ligand 5-fluorouracil (5-FU; A) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) as co-ligands(B) were carried out pH-metrically in aqueous medium at 310 ± 0.1 K with I = 0.15 M (NaClO4). In solution state, the stoichiometry of MABH, MAB and MAB2 species have been detected. The primary ligand(A) binds the central M(II) ions in a monodentate manner whereas him, bim, hist and his co-ligands(B) bind in mono, mono, bi and tridentate modes respectively. The calculated ? log K, log X and log X' values indicate higher stability of the mixed ligand complexes in comparison to binary species. Stability of the mixed ligand complex equilibria follows the Irving-Williams order of stability. In vitro biological evaluations of the free ligand(A) and their metal complexes by well diffusion technique show moderate activities against common bacterial and fungal strains. Oxidative cleavage interaction of ligand(A) and their copper complexes with CT DNA is also studied by gel electrophoresis method in the presence of oxidant. In vitro antioxidant evaluations of the primary ligand(A), CuA and CuAB complexes by DPPH free radical scavenging model were carried out. In solid, the MAB type of M(II)sbnd 5-FU(A)sbnd his(B) complexes were isolated and characterized by various physico-chemical and spectral techniques. Both the magnetic susceptibility and electronic spectral analysis suggest distorted octahedral geometry. Thermal studies on the synthesized mixed ligand complexes show loss of coordinated water molecule in the first step followed by decomposition of the organic residues subsequently. XRD and SEM analysis suggest that the microcrystalline nature and homogeneous morphology of MAB complexes. Further, the 3D molecular modeling and analysis for the mixed ligand MAB complexes have also been carried out.

  15. Polymer pendant ligand chemistry. 3. A biomimetic approach to selective metal ion removal and recovery from aqueous solution with polymer-supported sulfonated catechol and linear catechol amide ligands

    SciTech Connect

    Huang, Song-Ping; Li, Wei; Franz, K.J.; Albright, R.L.; Fish, R.H. [Univ. of California, Berkeley, CA (United States)

    1995-05-24

    The design of organic ligands to selectively remove and recover metal ions from aqueous solution is a new and important area of environmental inorganic chemistry. One approach to designing organic ligands for these purposes is to use biological systems as examples for selective metal ion complexation. Thus, the authors report results on the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis(catechol) linear amide (PS-2-6-LICAMS), and sulfonated 3.3-linear tris(catechol) amide (PS-3,3-LICAMS) ligands that are chemically bonded to modified 6% cross-linked macroporous polystyrene-divinylbenzene beads (PS-DVB) for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity was dramatically shown for PS-CATS, PS-2-6-LICAMS and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1-3, while metal ion selectivity could be changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). Rates of removal and recovery of the Fe{sup 3+} ion with the PS-CATS, PS-2-6LICAMS and PS-3,3-LICAMS polymer beads were also studied as well as relative equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies.

  16. Stabilizing coordinated radicals via metal-ligand covalency: a structural, spectroscopic, and theoretical investigation of group 9 tris(dithiolene) complexes.

    PubMed

    Morsing, Thorbjørn J; MacMillan, Samantha N; Uebler, Jacob W H; Brock-Nannestad, Theis; Bendix, Jesper; Lancaster, Kyle M

    2015-04-01

    Proper assignment of redox loci in coordination complexes with redox-active ligands to either the metal or the ligand is essential for rationalization of their chemical reactivity. However, the high covalency endemic to complexes of late, third-row transition metals complicates such assignments. Herein, we systematically explore the redox behavior of a series of group 9 tris(dithiolene) complexes, [M(mnt)3]3– (M = Ir, Rh, Co; mnt = maleonitriledithiolate). The Ir species described comprise the first examples of homoleptic Ir dithiolene complexes. The enhanced metal–ligand covalency of the Ir–S interaction leads to remarkable reactivity of [Ir(mnt)3]3– and stabilization of mononuclear [Ir(mnt)3]2– complex ions as well as dimerized versions featuring weak, covalent, intermolecular S–S bonds. The dianionic Rh and Co analogues are, in contrast, highly unstable, resulting in the rapid formation of [Rh2(mnt)5]4– and [Co(mnt)2]22–, respectively. The synthesized complexes were studied by single-crystal X-ray diffraction, X-ray absorption spectroscopy, optical spectroscopy, magnetometry, density functional theory, and spectroscopy-oriented configuration interaction calculations. Spectroscopic and theoretical analyses suggest that the stability of [Ir(mnt)3]2– may be attributed to dilution of ligand radical character by a high degree of Ir 5d character in the singly occupied molecular orbital. PMID:25756298

  17. Progress in the study of metal–organic materials applying naphthalene diimide (NDI) ligands

    Microsoft Academic Search

    Mei Pan; Xiao-Ming Lin; Guo-Bi Li; Cheng-Yong Su

    2011-01-01

    1,4,5,8-naphthalenediimide (NDI) derivatives are versatile in coordination and material chemistry due to their large conjugated planar structure and special electron transfer properties. This review presents an overview of metal–organic materials derived from NDIs with their structural models, analytical techniques and potential applications outlined.

  18. Tin, Antimony, Bismuth, and Tellurium Lewis Acids in sigma-Accepting Ligands for Transition Metals 

    E-print Network

    Lin, Tzu-Pin

    2012-10-19

    reversible two-electron redox processes including the photo-reductive elimination of chlorine. Other noteworthy outcomes of this research include the isolation of the first telluroxanyl-metal complex as well as the discovery of complexes with HgII ? Sb...

  19. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2014-09-01

    Schiff base ligand 3-chloro-N?-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

  20. Influence of vanadium-organic ligands treatment on selected metal levels in kidneys of STZ rats.

    PubMed

    Kro?niak, Miros?aw; Kowalska, Joanna; Francik, Renata; Grybo?, Ryszard; Blusz, Magdalena; Kwiatek, Wojciech M

    2013-06-01

    The objective of the study was to investigate the effects of five organic vanadium complexes supplement and a small dose of insulin injection on V, Fe, Cu, Zn, Mn, Ca, and K level in the streptozotocin diabetic rat's kidney during a 5-week treatment with the tested complexes. In all groups of animals, metal level in the lyophilized kidney organs was investigated by means of the proton induced X-ray emission method. Tissue vanadium level was naturally higher in vanadium-treated rats. The maximum level of vanadium was observed in the kidney (x(mean) = 16.6 ?g/g). The influence of vanadium administration on other metal level in rat's tissue was also investigated. Spectacular influence of vanadium action was observed on copper and zinc level in examined tissue. PMID:23661329

  1. Metal Complexes of Phenylpiperazine?Based Dithiocarbamate Ligands. Synthesis, Characterization, Spectroscopic, Thermal, and Antimicrobial Activity Studies

    Microsoft Academic Search

    Veysel T. Yilmaz; Turan K. Yaz?c?lar; Hasan Cesur; Resit Ozkanca; Fatma Z. Maras

    2003-01-01

    Potassium salts of phenylpiperazine (Phpzdtc), fluorophenylpiperazine (F?Phpzdtc) and nitrophenylpiperazine (N?Phpzdtc) dithiocarbamates and their manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by elemental analyses, IR, UV?VIS, magnetic moment measurements and thermal analysis techniques. On the basis of experimental data, the dithiocarbamates (dtcs) have been observed to coordinate to the metal ions via both sulphur atoms

  2. Organoantimony Lewis Acid as Flouride Receptors and Ligands towards Transition Metals 

    E-print Network

    Ke, Iou-Sheng

    2013-08-08

    that the redox state of the metal could be used to control anion binding at antimony. Reaction of (o-(Ph_(2)P)C_(6)H_(4))_(2)SbPh with (Et_(2)S)_(2)PtCl_(2) affords [ClSb(Ph)PtCl(o-dppp)_(2)] (o-dppp = o-(Ph_(2)P)C_(6)H_(4)) which further reacts with PhICl_(2...

  3. Concentration, Complexation and Chemical Speciation of Zinc and Cadmium in the Western North Pacific Ocean : Exploring Sources and Transport of Trace Metals and Complexing Ligands.

    NASA Astrophysics Data System (ADS)

    Carrasco, G. G.; Morton, P. L.; Donat, J. R.

    2008-12-01

    We determined Zn and Cd total dissolved (0.45 µm-filtered) concentrations, organic complexation and chemical speciation in surface water samples collected along the transect of the 2002 IOC Baseline Contaminant Survey expedition in the Western North Pacific and in vertical profile water samples at nine stations. The goals of this work were (1) to compare and contrast various trace metal sources, including both natural and anthropogenic atmospheric deposition, upwelling, marginal seas and others; (2) to study the organic ligand sources, generally thought to be phytoplankton; and (3) to investigate metal and ligand transport mechanisms, residence times and eventual upwelling in the Eastern North Pacific. Total dissolved (TD) Zn and Cd values were obtained using a combination of differential pulse stripping anodic voltammetry (DPASV), preconcentration with 8-HQ or APDC/DDC and quantification at ICPMS or AA. Organic complexation and chemical speciation of Zn and Cd were determined simultaneously using DPASV at a thin-mercury-film, glassy-carbon-disk-electrode. Surface transect TDZn and TDCd concentrations were low in the Subtropical Gyre (STG), in contrast with high values in the Western Subarctic Gyre (WSG). Zn and Cd were organically complexed in most surface samples: at least one ligand class was detected for Zn and Cd, whose conditional stability constants (log K') averaged 10.2 and 10.5, respectively. These ligands were found in excess of the total dissolved metal throughout the region of study except in the WSG for Cd. Vertical distributions of TDZn and TDCd exhibited nutrient-type profiles for all the STG stations. While constant Zn/Si and Cd/P values were observed throughout the water column in the WSG, some deviations were observed within the STG. In addition, the mode and intermediate water masses of the STG displayed very high concentrations of a Zn-complexing ligand (log K' 10.0) in excess of TDZn. As these water masses moved eastward, we observed that the ligand concentrations decreased. In contrast to the STG, the upper 1000m of the WSG showed elevated concentrations of both metals. Despite elevated surface (0-200m) Zn concentrations (~2nM), a Zn-complexing ligand (log K' 9.8) was found in excess of TDZn; below the photic layer, even higher TDZn concentrations might have saturated the ligand. A ligand for Cd was present in lower-than-TDCd concentrations in the same surface waters; below them, organic complexation of Cd was observed rarely in both STG and WSG regions. By studying the geographic distribution of the total dissolved metals and ligands, along with other dissolved and particulate tracers, possible sources and transport mechanisms can be contrasted and evaluated. Furthermore, the influence of these sources and transport mechanisms on the distribution of Zn and Cd chemical species and, ultimately, the bioavailability of these micronutrient metals can be studied.

  4. Tuning the Properties of Molecular Magnets and Conductors Based on Lanthanide and Transition Metal Ions Bridged by TCNQ Derivatives or Cyanometallate Ligands by Varying the Dimensionality of the Structure and Metal Ion Identity

    E-print Network

    Lopez Cruz, Nazario

    2011-08-08

    framework of composition {[Mn2(TCNQF4)(CH3OH)7.5(H2O)0.5]-(TCNQF4)2•7.5CH3OH}?, as well as molecular magnets based on first row metal ions and TCNQF4 ligands of composition MII(TCNQF4)-•(TCNQF42-)0.5(CH3CN) (M = Mn, Co) were prepared. In addition...

  5. Novel synergism by complex ligands in solvent extraction of rare earth metals(III) with ?-diketones

    Microsoft Academic Search

    H. Imura; M. Ebisawa; M. Kato; K. Ohashi

    2006-01-01

    The extraction of rare earth metals(III) (RE) with hexafluoroacetylacetone (Hhfa) and 2-thenoyltrifluoroacetone (Htta) was studied in the presence of some cobalt(III) chelates such as tris(acetylacetonato)cobalt(III), tris(4-isopropyltropolonato)cobalt(III), tris(8-quinolinolato)cobalt(III), tris(8-quinolinethiolato)cobalt(III), and tris(diethyldithiocarbamato)cobalt(III) in benzene or toluene. The synergistic enhancement of the extraction of RE, especially of lanthanum(III) was found in all the systems. Therefore, those cobalt(III) chelates act as synergists or complex

  6. Assembly of two supramolecular structures by metal complexes with a urea-based pyridyl ligand

    Microsoft Academic Search

    Biao Wu; Xiaojuan Huang; Jianjun Liang; Yanyan Liu; Xiao-Juan Yang; Huai-Ming Hu

    2007-01-01

    The supramolecular structures of two metal complexes, [CuL4Cl2] (1) and [ZnL2Cl2] (2), where L=N-(2,6-dimethylphenyl)-N?-(3-pyridy1)urea, are reported. Complex 1 features infinite tapes formed by intermolecular N–H?Cl hydrogen bonds with an R21(6) motif, as well as a ?–? stacking interaction. The solid-state structure of 2 shows a 2D network held together by two types of N–H?O R21(6) motifs, and there is no

  7. Solution pH effects on arsenic removal by drinking water treatment residuals in presence of metals and ligands

    NASA Astrophysics Data System (ADS)

    Nagar, R.; Sarkar, D.; Datta, R.; Makris, K.

    2006-05-01

    Arsenic (As) is a Group A carcinogen whose presence in soils in higher than background concentrations has become a serious concern with increasing suburban encroachment on former agricultural lands. One of the most promising methods to decrease the mobility of As in soil and water environments is by promoting its adsorption onto amorphous Fe/Al hydroxides. Drinking water treatment residuals (WTRs) are cost-effective sources of such Fe/Al hydroxides, and generated during the drinking water treatment process as a byproduct. Preliminary work in our laboratory showed that the WTRs are characterized by large specific surface and a net positive charge, ideal for retention of oxyanions such as those of As. However, the overall magnitude of As retention by the WTRs is a function of solution factors such as pH, presence of competing ions and complexing metals. A comprehensive understanding of the aforementioned parameters is, therefore, needed to quantify As mobility and bioaccessibility. The primary objective of the studying progress is to determine the effect of solution pH (range: 3-10) on the amount of As sorbed by the WTRs in the presence of competing ligands such as phosphate, sulfate and silicate as well as complexing metals (e.g., calcium and lead). Experiments are being conducted at 3 solid/solution ratios- 1:5, 1:10 and 1:20 and four initial As loads (375, 750, 1500 and 3000 mgAs L-1). Sodium arsenate is used as the As source. Arsenate adsorption is expected to decrease with increasing pH because generally when solution pH is less than pH of the zero point of charge, the positively charged surface on the soil prefers to complex with the negatively charged arsenate oxyanions. Furthermore, phosphate, sulfate and silicate are expected to compete with arsenate for sorption sites because like arsenate, these ions are typically sorbed via formation of inner-sphere complexes with suface functional groups. On the other hand, the presence of metals like lead and calcium are expected to decrease As mobility due to their tendency to complex with As oxyanions, thereby promoting precipitation when the ion activity product (IAP) is equal to or higher then the solubility equilibrium constant (Ksp) of the respective mineral precipitate. Keywords: Adsorption, arsenic, water treatment residuals, oxyanions, complexing metals, competing ions.

  8. In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters.

    PubMed

    Anju, R S; Saha, Koushik; Mondal, Bijan; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

    2015-07-01

    Building upon our earlier results on the chemistry of diruthenium analogue of pentaborane (9) with heterocumulenes, we continued to investigate the reactivity of arachno-[(Cp*Ru)2(B3H8)(CS2H)], 1, (Cp* = ?(5)-C5Me5) towards group 7 and 8 transition metal carbonyl compounds under photolytic and thermolytic conditions. The metal carbonyl compounds show diverse reactivity pattern with arachno-1. For example, the photolysis of arachno-1 with [Re2(CO)10] yielded [(Cp*Ru)2B3H5(CH2S2){Re(CO)4}2], 2, [(Cp*RuCO)2(?-H)2(CH2S2){Re(CO)4}{Re(CO)3}], 3 and [(Cp*Ru)2(?-CO)(?-H)(CH2S2){Re(CO)3}], 4. The geometry of 2 with a nearly planar eight-membered ring containing heavier transition metals rhenium, ruthenium is unprecedented. Compounds 3 and 4 can be considered as M4-quadrilateral and M3-triangle with a methylenedithiolato ligand attached to the metal centres, respectively. [Mn2(CO)10], on the other hand, reacts with arachno-1 to yield heterometallic binuclear [(Cp*RuCO){Mn(CO)4}(?-H)(SCH3)], 5 and homocubane [(Cp*Ru)2{Mn(CO)3}-(CS2H2)B3H4], 6. In an attempt to generate group 8 analogues of 2-5, we performed the reaction of arachno-1 with [Fe2(CO)9] and [Ru3(CO)12]. Although, the objective of isolating analogous compounds was not achieved, the reaction with [Fe2(CO)9] led to novel tetrahedral cluster [(Cp*RuCO){(Fe(CO)3}2S(?-H)], 7. [Ru3(CO)12], in contrast, yielded known compounds [{Cp*Ru(CO)}2B2H6], 9 and [Cp*Ru(CO)2]2, 10. All the cluster compounds have been characterized by mass spectrometry, IR, and (1)H, (11)B, and (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis of 2-5 and 7. PMID:25723783

  9. Selective extraction of histidine derivatives by metal affinity with a copper(II)-chelating ligand complex in an aqueous two-phase system.

    PubMed

    Oshima, Tatsuya; Oshima, Chinatsu; Baba, Yoshinari

    2015-05-15

    Affinity extraction based on the interaction between a target molecule and a specific affinity ligand offers a novel separation system for biomolecules in an aqueous two-phase system, however, most of affinity ligands are expensive. In the present study, metal affinity extraction of histidine (His) derivatives using a complex between Cu(II) and a commercially available chelating ligand was studied in a poly(ethylene glycol) (PEG)/Li2SO4 ATPS. Alizarin complexone (3-[N,N-bis(carboxymethyl)amino methyl]-1,2-dihydroxy anthraquinone, AC) was selected as the chelating ligand because of the good extractability of Cu(II) into the upper PEG-rich phase. On the basis of coordinate bonding with Cu(II), the extraction of His in the presence of the Cu(II)-AC complex under neutral condition was 73%, which was much higher than that under Cu(II) free condition (13%). Among a series of divalent transition metal ions (Cu(II), Ni(II), Co(II), and Zn(II)), Cu(II) was the most effective for the extraction of His. Derivatives of His were selectively extracted in the presence of many other amino acids because of the specificity of the interaction between Cu(II) and imidazole group of His. Extracted His was quantitatively stripped from the Cu(II)-AC complex using competitive complexation with agents such as iminodiacetic acid and imidazole. PMID:25864007

  10. Two-dimensional metal-organic frameworks (MOFs) constructed from heterotrinuclear coordination units and 4,4'-biphenyldicarboxylate ligands.

    PubMed

    Wang, Yonghui; Bredenkötter, Björn; Rieger, Bernhard; Volkmer, Dirk

    2007-02-14

    Three novel metal-organic frameworks (MOFs) formulated as [Zn(2)M(BPDC)(3)(DMF)(2)].4DMF (M = Co(II), Ni(II) or Cd(II); BPDC = 4,4'-biphenyldicarboxylate; DMF = N,N'-dimethylformamide) have been prepared via solvothermal synthesis from mixtures of the corresponding transition metal salts and 4,4'-biphenyldicarboxylic acid (H(2)BPDC). The framework structures are characterized by single-crystal X-ray diffraction analysis, IR and UV-vis diffuse reflectance spectroscopy, thermogravimetric analysis (TGA), and X-ray powder diffraction (XRPD). All three compounds possess essentially the same 2-D layered coordination framework consisting of linear heterotrinuclear secondary building units (SBUs) connected by rigid bridging BPDC ligands. Crystal data: for (C(60)H(66)CoN(6)O(18)Zn(2)): monoclinic, space group P2(1)/n, M = 1348.86, a = 20.463(4), b = 14.819(3), c = 23.023(5) A, beta = 111.75(3) degrees , V = 6484(2) A(3), Z = 4, D(c) = 1.382 Mg m(-3). For (C(60)H(66)N(6)NiO(18)Zn(2)): monoclinic, space group P2(1)/n, M = 1348.64, a = 11.670(2), b = 14.742(3), c = 19.391(4) A, beta = 102.29(3) degrees , V = 3259.5(11) A(3), Z = 2, D(c) = 1.374 Mg m(-3). For (C(60)H(66)CdN(6)O(18)Zn(2)): monoclinic, space group P2(1)/n, M = 1402.33, a = 11.491(2), b = 14.837(3), c = 19.386(4) A, beta = 101.53(3) degrees , V = 3238.3(11) A(3), Z = 2, D(c) = 1.438 Mg m(-3). PMID:17268603

  11. Hydroxylated derivatives of dimethoxy-1,4-benzoquinone as redox switchable earth-alkaline metal ligands and radical scavengers

    NASA Astrophysics Data System (ADS)

    Gulaboski, Rubin; Bogeski, Ivan; Mir?eski, Valentin; Saul, Stephanie; Pasieka, Bastian; Haeri, Haleh H.; Stefova, Marina; Stanoeva, Jasmina Petreska; Mitrev, Saša; Hoth, Markus; Kappl, Reinhard

    2013-05-01

    Benzoquinones (BQ) have important functions in many biological processes. In alkaline environments, BQs can be hydroxylated at quinoid ring proton positions. Very little is known about the chemical reaction leading to these structural transformations as well as about the properties of the obtained hydroxyl benzoquinones. We analyzed the behavior of the naturally occurring 2,6-dimethoxy-1,4-benzoquinone under alkaline conditions and show that upon substitution of methoxy-groups, poly-hydroxyl-derivatives (OHBQ) are formed. The emerging compounds with one or several hydroxyl-substituents on single or fused quinone-rings exist in oxidized or reduced states and are very stable under physiological conditions. In comparison with the parent BQs, OHBQs are stronger radical scavengers and redox switchable earth-alkaline metal ligands. Considering that hydroxylated quinones appear as biosynthetic intermediates or as products of enzymatic reactions, and that BQs present in food or administered as drugs can be hydroxylated by enzymatic pathways, highlights their potential importance in biological systems.

  12. Carbon dioxide adsorption in amine-functionalized mixed-ligand metal-organic frameworks of UiO-66 topology.

    PubMed

    Ethiraj, Jayashree; Albanese, Elisa; Civalleri, Bartolomeo; Vitillo, Jenny G; Bonino, Francesca; Chavan, Sachin; Shearer, Greig C; Lillerud, Karl Petter; Bordiga, Silvia

    2014-12-01

    A series of mixed-ligand [1,4-benzenedicarboxylic acid (BDC)/2-amino-1,4-benzenedicarboxylic acid (ABDC)] UiO-66 metal-organic frameworks (MOFs) synthesized through two different methods (low (LT) and high temperature (HT)) have been investigated for their carbon dioxide adsorption properties from 0 to 1?bar to clarify the role of amino loading on carbon dioxide uptake. Volumetric CO2 isotherms show that the CO2 capacity (normalized to the Langmuir surface area) increases with a degree of functionalization of about 46%; for similar NH2 contents, the same values are found for both synthetic procedures. Microcalorimetric isotherms reveal that amino-functionalized materials have a larger differential heat of adsorption (q(diff) ) towards CO2 ; reaching 27(25) and 20(22)?kJ?mol(-1) on HT(LT)-UiO-66-NH2 and UiO-66, respectively, at the lowest equilibrium pressures used in this study. All experimental results are supported by values obtained through quantum mechanical calculations. PMID:25302675

  13. N-aryl pyrrolo-tetrathiafulvalene based ligands: synthesis and metal coordination.

    PubMed

    Balandier, Jean-Yves; Chas, Marcos; Dron, Paul I; Goeb, Sébastien; Canevet, David; Belyasmine, Ahmed; Allain, Magali; Sallé, Marc

    2010-03-01

    A straightforward general synthetic access to N-aryl-1,3-dithiolo[4,5-c]pyrrole-2-thione derivatives 6 from acetylenedicarbaldehyde monoacetal is depicted. In addition to their potentiality as precursors to dithioalkyl-pyrrole derivatives, thiones 6 are key building blocks to N-aryl monopyrrolo-tetrathiafulvalene (MPTTF) derivatives 10. X-ray structures of four of these thiones intermediates, reminiscent of the corresponding MPTTF derivatives, are provided. When the aryl group is a binding pyridyl unit, the MPTTF derivative 10a can coordinate M(II) salts (M = Pt, Pd). The first examples of metal-directed orthogonal MPTTF-based dimers 11-14, obtained through coordination of 10a to cis-blocked square planar Pt or Pd complexes are described. Studies on the parameters influencing the dimer construction are presented, as well as first recognition properties of the resulting electron-rich clip for C(60). PMID:20143799

  14. Growth modes of thin films of ligand-free metal clusters

    NASA Astrophysics Data System (ADS)

    Dollinger, A.; Strobel, C. H.; Bleuel, H.; Marsteller, A.; Gantefoer, G.; Fairbrother, D. H.; Tang, Xin; Bowen, K. H.; Kim, Young Dok

    2015-05-01

    Size-selected Mon-, Wn-, and Fen- cluster anions are deposited on a weakly interacting substrate (highly oriented pyrolytic graphite) and studied ex-situ using atomic force microscopy. Depending on size, three growth modes can be distinguished. Very small clusters consisting of less than 10-30 atoms behave similar to atoms and coalesce into 3-dimensional bulk-like islands. Medium sized clusters consisting of hundreds of atoms do not coalesce and follow a Stanski-Krastanov growth pattern. At low coverage, an almost perfect monolayer is formed. This is a new finding different from all previous studies on deposited metal clusters. For clusters with several thousands of atoms, the growth pattern again changes. At low coverage, the substrate is dotted with individual clusters, while at high coverage, the surface becomes extremely rough.

  15. Metalorganic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

    Microsoft Academic Search

    Everetr L. Shock; Carla M. Koretsky

    1995-01-01

    Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies (So) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of So provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to

  16. Influence of ligand type and solution pH on heavy metal ion complexation in cellulosic fibre: model calculations and experimental results

    Microsoft Academic Search

    Arunee Kongdee; Thomas Bechtold

    2009-01-01

    Complexation of heavy metal ions such as Cu2+, Zn2+ and Co2+ by cellulosic fibres cotton, lyocell and viscose was studied in the pH range from pH 7–13. Glycine and sodium D-gluconate complexes were studied. Complex formation in the cellulose matrix depends on ligand, solution pH, complex species\\u000a formed and type of cellulosic fibre. Species distribution in solution was calculated using

  17. Temporary anion states of. pi. -ligand transition-metal carbonyls studied by means of electron transmission spectroscopy and x. cap alpha. calculations

    SciTech Connect

    Modelli, A.; Distefano, G.; Guerra, M.; Jones, D.

    1987-07-22

    The resonances observed in the electron transmission spectra of (benzene)chromium tricarbonyl, (cyclopentadienyl)manganese tricarbonyl, (1,3-butadiene)iron tricarbonyl, and (cyclopentadienyl)cobalt dicarbonyl have been assigned with the aid of MS X..cap alpha.. calculations. In contrast with previous theoretical results, the present calculations on the neutral states show a large net electronic charge transfer from the ..pi.. ligand to the metal.

  18. Reactivity of CO2 Activated on Transition Metals and Sulfur Ligands.

    PubMed

    Kobayashi, Katsuaki; Tanaka, Koji

    2015-06-01

    Dicationic dicarbonyl [Ru(bpy)2(CO)2](2+) (bpy = 2,2'- bipyridyl) exists as equilibrium mixtures with [Ru(bpy)2(CO)(COOH)](+) and [Ru(bpy)2(CO)(CO2)](0) depending on the pH in H2O. Those three complexes work as the precursors to CO, HCOOH production, and CO2 carrier, respectively, in electro- and photochemical CO2 reduction in aqueous solutions. However, [Ru(bpy)2(CO)2](2+) loses the catalytic activity toward CO2 reduction under aprotic conditions because [Ru(bpy)2(CO)2](2+) is not regenerated from [Ru(bpy)2(CO)(CO2)](0) in the absence of proton sources. Analogous monocarbonylruthenium complexes such as [Ru(tpy)(bpy)(CO)](2+) and [Ru(bpy)2(qu)(CO)](2+) catalyze CO2 reduction in the absence and presence of proton sources. Both complexes are reproduced through oxide transfer from the corresponding Ru-CO2 to CO2 in CO2 reduction and produce the same amount of CO and CO3(2-) in the absence of proton donors. The reduction of CO2 catalyzed by polypyridylrhenium complexes in the presence of proton sources takes place via essentially the similar mechanism as that in the case of ruthenium complexes. On the other hand, CO evolution in CO2 reduction under aprotic conditions is ascribed to the dissociation of CO from a dimeric Re-C(O)OC(O)O-Re scaffold. Visible-light irradiation to a catalytic system composed of [Ru(bpy)2(CO)2](2+)/[Ru(bpy)3](2+)/Me2NH2(+)/Me2NH as the catalyst, photosensitizer, proton donor, and nucleophile in addition to the electron donor, respectively, in CO2-saturated CH3CN selectively produces N,N-dimethylformamide without concomitant CO and HCOOH formation. Structurally robust ?3-S of reduced metal-sulfur clusters provides a suitable site for reductive activation of CO2 with retention of the framework. Indeed, CO2 activated on ?3-S of [Fe6Mo2S8(SEt)3](5-) is fixed at the carbonyl carbon of thioesters trapped on a neighboring iron of the cluster, and ?-keto acids are produced catalytically. Furthermore, two-electron reduction of [(CpMen)3M3S3](2+) (n = 1, M = Co; n = 5, M = Rh, Ir) creates the catalytic ability to produce oxalate through the coupling of two CO2 molecules possibly activated on ?3-S and a metal ion. PMID:25978130

  19. Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters

    PubMed Central

    Kreutzer, Johannes; Puchberger, Michael; Artner, Christine; Schubert, Ulrich

    2015-01-01

    The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters.

  20. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(ii).

    PubMed

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-01

    Covalent tethering of P(Ph)2N(C6H4C[triple bond, length as m-dash]CH)2 ligands (P(Ph)2N(C6H4C[triple bond, length as m-dash]CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3?P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex. PMID:25811536

  1. Influence of PNIPAm on log?Kf of a copolymerized 2,2'-bipyridine: revised bifunctional ligand design for ratiometric metal-ion sensing.

    PubMed

    Massing, Justin O; Planalp, Roy P

    2015-07-14

    Here we describe the synthesis of a model compound (1) based upon a previously reported bifunctional 2,2'-bipyridine (2). Ligand pKa and thermodynamic stability constants were investigated by potentiometric titrations for 1 in order to assess the metal-binding capabilities of 2 following subsequent incorporation within a temperature-responsive polymer that functions as a fluorescent metal-ion indicator. While the log?KCu1 measured here was found to be 8.86 ± 0.05 at 25 °C, this value was previously seen to fall 2.8 orders of magnitude following copolymerization of 2 with poly(N-isopropylacrylamide) (PNIPAm). This drop in affinity was attributed to stabilization of the neutral ligand by the polymer environment and elevated temperatures at which metal-binding experiments were performed. ?H (-54.4 kJ mol(-1)) and ?S (-12.8 J K(-1) mol(-1)) were therefore determined through variable temperature titrations in order to establish the temperature dependence of log?KCu1. Doing so enabled elucidation of the overall effect that the polymer environment exerts on thermodynamic stability of copolymerized 2. Specifically, the polymer indicator was found to decrease the thermodynamic stability by 2.2 orders of magnitude, whereas elevated temperatures account for the additional 0.6 order of magnitude drop observed. This finding has implications regarding the design of future bifunctional ligands for ratiometric sensing within our temperature-responsive polymer indicator. PMID:26057502

  2. Studies with an immobilized metal affinity chromatography cassette system involving binuclear triazacyclononane-derived ligands: automation of batch adsorption measurements with tagged recombinant proteins.

    PubMed

    Petzold, Martin; Coghlan, Campbell J; Hearn, Milton T W

    2014-07-18

    This study describes the determination of the adsorption isotherms and binding kinetics of tagged recombinant proteins using a recently developed IMAC cassette system and employing automated robotic liquid handling procedures for IMAC resin screening. These results confirm that these new IMAC resins, generated from a variety of different metal-charged binuclear 1,4,7-triaza-cyclononane (tacn) ligands, interact with recombinant proteins containing a novel N-terminal metal binding tag, NT1A, with static binding capacities similar to those obtained with conventional hexa-His tagged proteins, but with significantly increased association constants. In addition, higher kinetic binding rates were observed with these new IMAC systems, an attribute that can be positively exploited to increase process productivity. The results from this investigation demonstrate that enhancements in binding capacities and affinities were achieved with these new IMAC resins and chosen NT1A tagged protein. Further, differences in the binding performances of the bis(tacn) xylenyl-bridged ligands were consistent with the distance between the metal binding centres of the two tacn moieties, the flexibility of the ligand and the potential contribution from the aromatic ring of the xylenyl group to undergo ?/? stacking interactions with the tagged proteins. PMID:24891160

  3. Blind-Anchor-Nut-Installation Fixture (BANIF)

    NASA Technical Reports Server (NTRS)

    Willey, Norman F., Jr.; Linker, James F.

    1994-01-01

    Blind-anchor-nut-installation fixture, BANIF, developed for replacing or installing anchor nuts in blind holes or other inaccessible places. Attachment of anchor nut to BANIF enables placement of anchor nut on blind side of component.

  4. New isostructural transition metal complexes with a non-innocent dithiolate ligand.

    PubMed

    Herich, Peter; Fronc, Marek; Ko?íšek, Jozef

    2015-02-01

    Three new complexes with 3,6-dichlorobenzene-1,2-dithiol (bdtCl2), namely methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-?(2)S,S')cobaltate(1-), (C19H18P)[Co(C6H2Cl2S2)2], (I), bis(methyltriphenylphosphonium) bis(3,6-dichlorobenzene-1,2-dithiolato-?(2)S,S')cuprate(2-) dimethyl sulfoxide disolvate, (C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS, (II), and methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-?(2)S,S')cuprate(1-), (C19H18P)[Cu(C6H2Cl2S2)2], (III), have been synthesized and characterized by single-crystal X-ray diffraction. The X-ray structure analyses of all three complexes confirm that the four donor S atoms form a slightly distorted square-planar coordination arrangement around the central metal atom. An interesting finding for both the Cu(II) and Cu(III) complexes, i.e. (II) and (III), respectively, is that the coordination polyhedra are principally the same and differ only slightly with respect to the interatomic distances. PMID:25652286

  5. Use of the Biotic Ligand Model to predict metal toxicity to aquatic biota in areas of differing geology

    USGS Publications Warehouse

    Smith, Kathleen S.

    2005-01-01

    This work evaluates the use of the biotic ligand model (BLM), an aquatic toxicity model, to predict toxic effects of metals on aquatic biota in areas underlain by different rock types. The chemical composition of water, soil, and sediment is largely derived from the composition of the underlying rock. Geologic source materials control key attributes of water chemistry that affect metal toxicity to aquatic biota, including: 1) potentially toxic elements, 2) alkalinity, 3) total dissolved solids, and 4) soluble major elements, such as Ca and Mg, which contribute to water hardness. Miller (2002) compiled chemical data for water samples collected in watersheds underlain by ten different rock types, and in a mineralized area in western Colorado. He found that each rock type has a unique range of water chemistry. In this study, the ten rock types were grouped into two general categories, igneous and sedimentary. Water collected in watersheds underlain by sedimentary rock has higher mean pH, alkalinity, and calcium concentrations than water collected in watersheds underlain by igneous rock. Water collected in the mineralized area had elevated concentrations of calcium and sulfate in addition to other chemical constituents. Miller's water-chemistry data were used in the BLM (computer program) to determine copper and zinc toxicity to Daphnia magna. Modeling results show that waters from watersheds underlain by different rock types have characteristic ranges of predicted LC 50 values (a measurement of aquatic toxicity) for copper and zinc, with watersheds underlain by igneous rock having lower predicted LC 50 values than watersheds underlain by sedimentary rock. Lower predicted LC 50 values suggest that aquatic biota in watersheds underlain by igneous rock may be more vulnerable to copper and zinc inputs than aquatic biota in watersheds underlain by sedimentary rock. For both copper and zinc, there is a trend of increasing predicted LC 50 values with increasing dissolved organic carbon (DOC) concentrations. Predicted copper LC 50 values are extremely sensitive to DOC concentrations, whereas alkalinity appears to have an influence on zinc toxicity at alkalinities in excess of about 100 mg/L CaCO 3 . These findings show promise for coupling the BLM (computer program) with measured water-chemistry data to predict metal toxicity to aquatic biota in different geologic settings and under different scenarios. This approach may ultimately be a useful tool for mine-site planning, mitigation and remediation strategies, and ecological risk assessment.

  6. Self-assembly of metal-organic coordination polymers constructed from a bent dicarboxylate ligand: diversity of coordination modes, structures, and gas adsorption.

    PubMed

    Yang, Wenbin; Lin, Xiang; Blake, Alexander J; Wilson, Claire; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2009-12-01

    We have synthesized five new metal-organic coordination polymers incorporating the bent ligand H(2)hfipbb [4,4'-(hexafluoroisopropylidene)bis(benzoic acid)] with different transition metal ions and co-ligands via solvothermal reactions to give [Zn(2)(hfipbb)(2)(py)(2)] x DMF (1), [Zn(2)(hfipbb)(2)(4,4'-bipy)(H(2)O)] (2), [Zn(2)(hfipbb)(2)(bpdab)].2DMF (3), [Cd(2)(hfipbb)(2)(DMF)(2)] x 2 DMF (4), and [Co(hfipbb)(dpp)] x MeOH (5) (py = pyridine, 4,4'-bipy = 4,4'-bipyridine, bpdab = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, dpp = 1,3-di(4-pyridyl)propane). Compound 1 displays a 2-fold 2D-->2D parallel interpenetrated layer network with one-dimensional (1D) helical channels, while 3 exhibits a three-dimensional pillared helical-layer open framework of alpha-Po topology based upon binuclear paddlewheel units. In compounds 2 and 5, binuclear motifs with double carboxylate bridges are linked by hfipbb(2-) ligands into a 1D ribbon, which are further assembled into two-dimensional non-interpenetrated (4,4) layers via bipyridyl co-ligands. However, the different bridging modes of hfipbb(2-) ligands and the different disposition of the coordinated co-ligands around metal ions result in subtle differences in the final architecture. Thus, 2 is based on a binuclear cluster node, double-stranded hfipbb(2-) linkers, and single-stranded 4,4'-bipy linkers, while 5 is based on a binuclear cluster node and hfipbb(2-) and dpp linkers which are both double-stranded. Among these compounds, the Cd(II) complex 4 is possibly the most interesting because it represents a rare example in which metal centers are linked by carboxylate groups into infinite chains further joined together by hfipbb(2-) spacers to form a 2D network with tubular helical channels. All these coordination polymers exhibit low solvent-accessible volumes. Both 3 and 4 retain structural integrity and permanent microporosity upon evacuation of guest molecules, with hydrogen uptakes of 0.57 and 0.78 wt %, respectively, at 20 bar and 77 K. PMID:19943692

  7. A comparative study of semiempirical, ab initio, and DFT methods in evaluating metal-ligand bond strength, proton affinity, and interactions between first and second shell ligands in Zn-biomimetic complexes.

    PubMed

    Frison, Gilles; Ohanessian, Gilles

    2008-02-01

    Although theoretical methods are now available which give very accurate results, often comparable to the experimental ones, modeling chemical or biological interesting systems often requires less demanding and less accurate theoretical methods, mainly due to computer limitations. Therefore, it is crucial to know the precision of such less reliable methods for relevant models and data. This has been done in this work for small zinc-active site models including O- (H(2)O and OH(-)) and N-donor (NH(3) and imidazole) ligands. Calculations using a number of quantum mechanical methods were carried out to determine their precision for geometries, coordination number relative stability, metal-ligand bond strengths, proton affinities, and interaction energies between first and second shell ligands. We have found that obtaining chemical accuracy can be as straightforward as HF geometry optimization with a double-zeta plus polarization basis followed by a B3LYP energy calculation with a triple-zeta quality basis set including diffuse and polarization functions. The use of levels as low as PM3 geometry optimization followed by a B3LYP single-point energy calculation with a double-zeta quality basis including polarization functions already yields useful trends in bond length, proton affinities or bond dissociation energies, provided that appropriate caution is taken with the optimized structures. The reliability of these levels of calculation has been successfully demonstrated for real biomimetic cases. PMID:17631650

  8. Science Sampler: Anchor activities

    NSDL National Science Digital Library

    Cindy Corlett

    2003-03-01

    What's the best way to keep students occupied when they have finished their work? An Anchor Activity Learning Station provides high-interest, educational options for students who have finished with required class assignments, labs, or investigations. A list of ideas is included.

  9. The tunable coordination architectures of a flexible multicarboxylate N-(4-carboxyphenyl)iminodiacetic acid via different metal ions, pH values and auxiliary ligand

    SciTech Connect

    Chai Xiaochuan [Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350108 (China); Zhang Hanhui, E-mail: zhanghh1840@hotmail.co [Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350108 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Zhang Shuai; Cao Yanning; Chen Yiping [Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350108 (China)

    2009-07-15

    {l_brace}[Pb{sub 3}(CPIDA){sub 2}(H{sub 2}O){sub 3}].H{sub 2}O{r_brace}{sub n}1, {l_brace}[Cd{sub 3}(CPIDA){sub 2}(H{sub 2}O){sub 4}].5H{sub 2}O{r_brace}{sub n}2, [Cd(HCPIDA)(bpy)(H{sub 2}O)]{sub n}3 (bpy=4,4'-bipyridine) and {l_brace}[Co{sub 3}(CPIDA){sub 2}(bpy){sub 3}(H{sub 2}O){sub 4}].2H{sub 2}O{r_brace}{sub n}4 were synthesized with N-(4-carboxyphenyl) iminodiacetic acid (H{sub 3}CPIDA). In 1, the CPIDA{sup 3-} ligands adopt chelating and bridging modes with Pb(II) to possess a 3D porous framework. In 2D-layer 2, the CPIDA{sup 3-} ligands display a simple bridging mode with Cd(II). The 2D layers have parallelogram-shaped channels along a axis. With bpy ligands, the HCPIDA{sup 2-} ligands in 3 show more abundant modes, but 3 still displays a 2D sheet on bc plane for the unidentate bpy molecules. However, in 3D-framework 4, the bpy ligands adopt bridging bidentate at a higher pH value and the CPIDA{sup 3-} ligands show bis-bidentate modes with Co(II). Additionally, 2D correlation analysis of FTIR was introduced to ascertain the characteristic adsorptions location of the carboxylate groups with different coordination modes in 4 with thermal and magnetic perturbation. Compounds 1, 2 and 4 exhibit the fluorescent emissions at room temperature. - Graphical abstract: A series of coordination polymers were synthesized with H{sub 3}CPIDA and transition metal ions at lower pH values. The figure displays a 3D porous framework with three parallel channels in compound 1.

  10. Synthesis, spectral and magnetic studies of mono- and bi-nuclear metal complexes of a new bis(tridentate NO2) Schiff base ligand derived from 4,6-diacetylresorcinol and ethanolamine.

    PubMed

    Shebl, Magdy

    2009-07-15

    A new bis(tridentate NO2) Schiff base ligand, H(4)L, was prepared by the reaction of the bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) with ethanolamine. The ligand reacted with iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), cerium(III) and uranyl(VI) ions, in absence and in presence of LiOH, to yield mono- and bi-nuclear complexes with different coordinating sites. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. In absence of LiOH, mononuclear complexes (2, 3 and 5-9) as well as binuclear complexes (1 and 4) were obtained. In mononuclear complexes, the ligand acted as a neutral, mono- and di-basic/bi- and tetra-dentate ligand while in binuclear complexes (1 and 4), the ligand acted as a bis(mono- or di-basic/tridentate) ligand. On the other hand, in presence of LiOH, only binuclear complexes (10-15) were obtained in which the ligand acted as a bis(dibasic tridentate) ligand. The metal complexes exhibited different geometrical arrangements such as octahedral, tetrahedral, square planar, square pyramidal and pentagonal bipyramidal arrangements. PMID:19345138

  11. Synthesis, spectral and magnetic studies of mono- and bi-nuclear metal complexes of a new bis(tridentate NO2) Schiff base ligand derived from 4,6-diacetylresorcinol and ethanolamine

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy

    2009-07-01

    A new bis(tridentate NO2) Schiff base ligand, H4L, was prepared by the reaction of the bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) with ethanolamine. The ligand reacted with iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), cerium(III) and uranyl(VI) ions, in absence and in presence of LiOH, to yield mono- and bi-nuclear complexes with different coordinating sites. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. In absence of LiOH, mononuclear complexes (2, 3 and 5-9) as well as binuclear complexes (1 and 4) were obtained. In mononuclear complexes, the ligand acted as a neutral, mono- and di-basic/bi- and tetra-dentate ligand while in binuclear complexes (1 and 4), the ligand acted as a bis(mono- or di-basic/tridentate) ligand. On the other hand, in presence of LiOH, only binuclear complexes (10-15) were obtained in which the ligand acted as a bis(dibasic tridentate) ligand. The metal complexes exhibited different geometrical arrangements such as octahedral, tetrahedral, square planar, square pyramidal and pentagonal bipyramidal arrangements.

  12. Formation of a Metal-to-Nitrogen Bond of Normal Length by a Neutral Sufonamide Group within a Tridentate Ligand. A New Approach to Radiopharmaceutical Bioconjugation

    PubMed Central

    Perera, Theshini; Abhayawardhana, Pramuditha; Marzilli, Patricia A.; Fronczek, Frank R.

    2014-01-01

    We demonstrate that a tertiary sulfonamide group, N(SO2R)R?2, can re-hybridize to form a M–N bond of normal length even when the group is in a linear tridentate ligand, such as in the new tridentate N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). N(SO2R)dpa ligands were used to prepare fac-[Re(CO)3(N(SO2R)dpa)](PF6 or BF4) complexes. Structural characterization of the new complexes established that the tertiary sulfonamide nitrogen atom binds to Re with concomitant sp2-to-sp3 re-hybridization, facilitating facial coordination. The new fac-[Re(CO)3(N(SO2R)dpa)]X structures provide the only examples for any metal with the sulfonamide as part of a noncyclic linear tridentate ligand and with a normal metal-to-nitrogen(tertiary sulfonamide) bond length. Rare previous examples of such normal M–N bonds have been found only in more constrained situations, such as with tripodal tetradentate ligands. Our long-term objectives for the new tridentate N(SO2R)dpa ligands are to develop the fundamental chemistry relevant to the eventual use of the fac-[MI(CO)3]+ core (M = 99mTc, 186/188Re) in imaging and therapy. The sulfonamide group uniquely contributes to two of our goals: expanding ways to conjugate the fac-[MI(CO)3]+ core to biological molecules and also developing new symmetrical tridentate ligands that can coordinate facially to this core. Tests of our conjugation method, conducted by linking the fac-[ReI(CO)3]+ core to a new tetraarylporphyrin (T(N(SO2C6H4)dpa)P) as well as to a dansyl (5-(dimethylamino)naphthalene-1-sulfonyl) group, demonstrate that large molecular fragments can be tethered via a coordinated tertiary sulfonamide linkage to this core. PMID:23421481

  13. Formation of a metal-to-nitrogen bond of normal length by a neutral sufonamide group within a tridentate ligand. A new approach to radiopharmaceutical bioconjugation.

    PubMed

    Perera, Theshini; Abhayawardhana, Pramuditha; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

    2013-03-01

    We demonstrate that a tertiary sulfonamide group, N(SO2R)R'2, can rehybridize to form a M-N bond of normal length even when the group is in a linear tridentate ligand, such as in the new tridentate N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). N(SO2R)dpa ligands were used to prepare fac-[Re(CO)3(N(SO2R)dpa)](PF6 or BF4) complexes. Structural characterization of the new complexes established that the tertiary sulfonamide nitrogen atom binds to Re with concomitant sp(2)-to-sp(3) rehybridization, facilitating facial coordination. The new fac-[Re(CO)3(N(SO2R)dpa)]X structures provide the only examples for any metal with the sulfonamide as part of a noncyclic linear tridentate ligand and with a normal metal-to-nitrogen(tertiary sulfonamide) bond length. Rare previous examples of such normal M-N bonds have been found only in more constrained situations, such as with tripodal tetradentate ligands. Our long-term objectives for the new tridentate N(SO2R)dpa ligands are to develop the fundamental chemistry relevant to the eventual use of the fac-[M(I)(CO)3](+) core (M = (99m)Tc, (186/188)Re) in imaging and therapy. The sulfonamide group uniquely contributes to two of our goals: expanding ways to conjugate the fac-[M(I)(CO)3](+) core to biological molecules and also developing new symmetrical tridentate ligands that can coordinate facially to this core. Tests of our conjugation method, conducted by linking the fac-[Re(I)(CO)3](+) core to a new tetraarylporphyrin (T(N(SO2C6H4)dpa)P) as well as to a dansyl (5-(dimethylamino)naphthalene-1-sulfonyl) group, demonstrate that large molecular fragments can be tethered via a coordinated tertiary sulfonamide linkage to this core. PMID:23421481

  14. Colloid/Solution Partitioning of Metal-Selective Organic Ligands, and its Relevance to Cu, Pb and Cd Cycling in the Firth of Clyde

    NASA Astrophysics Data System (ADS)

    Muller, F. L. L.

    1998-03-01

    The electrochemical lability of Cu, Pb and Cd and the complexation parameters (stability constants, ligand concentrations) of their organic ligands were determined by anodic stripping voltammetry (ASV) in 14 samples collected in April-May 1994 from the lower Clyde Estuary ( S<30·0), through the surface estuarine plume (30·0< S<32·4), and into the Clyde Sea. The titrations were applied to 0·4 ?m-filtered and cross-flow filtered (˜1 nm cut-off) fractions of each sample. In addition, the surface electrical properties of the colloidal matter (1 nmligands did take place in an adjoining loch, but their control on Cu speciation (up to 99·99% Cu in inert forms) remained localized. By contrast, organic complexation was sufficient to maintain pPb (pPb=-log [Pb 2+]) as high as 11·7-12·5. Lead in river runoff was extensively and strongly bound to organics. A unique class of ligands of in situorigin and belonging to the colloidal phase was detected at 40 m depth, i.e. under the plume. This colloidal material had limited affinity for Cd and no detectable affinity for Cu, and probably consisted of the remains of micro-organisms which must have been concentrated at this depth by the plume circulation. Despite some affinity for the above-mentioned colloidal ligands (resulting in 54-88% complexation) and for the dissolved ligands produced by phytoplankton (59-64 % complexation), Cd was generally poorly bound (0-30% complexation) and the ligands responsible were mostly of marine origin. Although a fraction of the particulate Pb (associated with Mn-rich particles) was removed from the surface plume by sedimentation, the major modification in the seaward flux seemed to occur at the leading edge of the plume. There was a change in the speciation of Pb across this frontal zone, from a dominance by colloids and macroparticles in the plume to a situation where most of Pb found in the 0·4 ?m-filtered fraction was also present in the <1 nm permeate. In contrast, Cu became less extensively associated with the dissolved phase away from the plume. When interpreted in combination, the ASV and DLS results show that two bulk properties of organic coatings on colloids (electrophoretic mobility and second acidity constant), important in the context of colloid stability, can explain some of the variability in the colloid-solution partitioning of metal-complexing ligands. What is more, the surface electrical state of the colloids appears to have a different effect on the adsorption of Pb-binding ligands than on that of Cu-binding ligands, supporting the conclusion reached from the spatial distribution of ligands that they are metal-selective.

  15. Bio-sensitive activities of coordination compounds containing 1,10-phenanthroline as co-ligand: synthesis, structural elucidation and dna binding properties of metal(II) complexes.

    PubMed

    Raman, Natarajan; Mahalakshmi, Rajkumar; Mitu, Liviu

    2014-10-15

    Present work reports the DNA binding and cleavage characteristics of a series of mixed-ligand complexes having the composition [M(L)(phen)2]Cl2 (where M=Cu(II), Ni(II), Co(II) and Zn(II) and phen as co-ligand) in detail. Their structural features and other properties have been deduced from their elemental analyses, magnetic susceptibility and molar conductivity as well as from IR, UV-Vis, (1)H NMR and EPR spectral studies. The UV-Vis, magnetic susceptibility and EPR spectral data of metal complexes suggest an octahedral geometry. The binding properties of these complexes with calf thymus DNA (CT-DNA) have been explored using electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry and differential pulse voltammetry. The DNA-binding constants for Cu(II), Ni(II), Co(II), and Zn(II) complexes are 6.14×10(5)M(-1), 1.8×10(5)M(-1), 6.7×10(4)M(-1) and 2.5×10(4)M(-1) respectively. Detailed analysis reveals that these complexes interact with DNA through intercalation binding. Nuclease activity has also been investigated by gel electrophoresis. Moreover, the synthesized Schiff base and its mixed-ligand complexes have been screened for antibacterial and antifungal activities. The data reveal that the complexes exhibit higher activity than the parent ligand. PMID:24835939

  16. Bio-sensitive activities of coordination compounds containing 1,10-phenanthroline as co-ligand: Synthesis, structural elucidation and DNA binding properties of metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Raman, Natarajan; Mahalakshmi, Rajkumar; Mitu, Liviu

    2014-10-01

    Present work reports the DNA binding and cleavage characteristics of a series of mixed-ligand complexes having the composition [M(L)(phen)2]Cl2 (where M = Cu(II), Ni(II), Co(II) and Zn(II) and phen as co-ligand) in detail. Their structural features and other properties have been deduced from their elemental analyses, magnetic susceptibility and molar conductivity as well as from IR, UV-Vis, 1H NMR and EPR spectral studies. The UV-Vis, magnetic susceptibility and EPR spectral data of metal complexes suggest an octahedral geometry. The binding properties of these complexes with calf thymus DNA (CT-DNA) have been explored using electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry and differential pulse voltammetry. The DNA-binding constants for Cu(II), Ni(II), Co(II), and Zn(II) complexes are 6.14 × 105 M-1, 1.8 × 105 M-1, 6.7 × 104 M-1 and 2.5 × 104 M-1 respectively. Detailed analysis reveals that these complexes interact with DNA through intercalation binding. Nuclease activity has also been investigated by gel electrophoresis. Moreover, the synthesized Schiff base and its mixed-ligand complexes have been screened for antibacterial and antifungal activities. The data reveal that the complexes exhibit higher activity than the parent ligand.

  17. Third-order NLO properties of metal complexes containing delocalized oxygen or sulphur donor ligands and mixed oxygen and sulphur donor ligands

    SciTech Connect

    Dhindsa, A.S.; Underhill, A.E. [Univ. of Wales, Gwynedd (United Kingdom). Dept. of Chemistry; Oliver, S.N.; Kershaw, S.V. [BTRL, Ipswich (United Kingdom)

    1995-12-31

    The third-order nonlinear susceptibility, {chi}{sup (3)}, for a series of complexes of 3,5-ditertbutyl-o-benzoquinone (dbsq), (M(dbsq){sub 2} where M = Pd or Pt), o-mercaptophenol (mp), ((TBA)[Ni(mp){sub 2}]), or 1,3-dithiol-2-thione-4,5-dithiol (dmit), ((TBA)[M(dmit){sub 2}] where M = Ni or Pd), have been measured in CH{sub 2}Cl{sub 2} solution by retroreflection DFWM technique at 1064 mn. The results indicate large {chi}{sup (3)} values of the order of 10{sup {minus}11} esu at concentration levels of 10{sup 18} molecules/cm{sup 3}. These values are up to two orders higher than those found for other sulphur donor dithiolenes and nitrogen donor ligand systems, although the linear absorption is also higher.

  18. Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: Synthesis, spectroscopic and antipathogenic studies

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-01-01

    2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X 2 and [Ni(L)X]X compositions (where L = ligand and X = NO 3-, Cl - and CH 3COO -) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Otomycosis in humans.

  19. Enhanced selectivity for actinides over lanthanides with CMPO ligands secured to a C(3)-symmetric triphenoxymethane platform.

    PubMed

    Peters, Matthew W; Werner, Eric J; Scott, Michael J

    2002-04-01

    A ligand system containing three preorganized carbamoylmethylphosphine oxide (CMPO) moieties anchored onto a rigid C(3)-symmetric triphenoxymethane platform has been developed for facile metal complexation and subsequent extraction from aqueous acidic nuclear waste streams. Intended to mimic the 3:1 CMPO-actinide stoichiometry of the extracted species in the TRUEX nuclear waste treatment process, the CMPO arms on this ligand are oriented such that all three CMPO moieties can cooperatively bind a metal ion. Extractions of simulated nuclear waste streams (10(-4) M metal in 1 M nitric acid) with solutions of this ligand in methylene chloride (10(-3) M) reveal a high affinity for the actinide thorium and a very low, but constant, affinity for the lanthanides across the series. Thorium and five lanthanide (lanthanum, cerium, neodymium, europium, and ytterbium) nitrate complexes of this ligand have been synthesized and fully characterized by X-ray crystallography, (1)H and (31)P NMR spectra, and FT-ICR-MS to elucidate the mechanism of this unique actinide selectivity. All six oxygen donors from the three CMPO arms of the ligand and one or two nitrate counterions coordinate these metals to afford 2+ cationic complexes in every case. Because of the large size of the ligand, both the thorium and lanthanide complexes present similarly charged and sized surfaces to the extraction solvents, but the thorium complex is extracted quantitatively over the lanthanide complexes. A possible rationale for this extraction behavior difference is presented and further illustrated by the extraction properties of this ligand system for the alkali metals (lithium, sodium, potassium, rubidium, and cesium) as picrate salts and by the solid- and solution-state structures of its lithium picrate complex. PMID:11925161

  20. Impact of Coordination Geometry, Bite Angle, and Trans Influence on Metal-Ligand Covalency in Phenyl-Substituted Phosphine Complexes of Ni and Pd.

    PubMed

    Donahue, Courtney M; McCollom, Samuel P; Forrest, Chelsie M; Blake, Anastasia V; Bellott, Brian J; Keith, Jason M; Daly, Scott R

    2015-06-15

    Despite the long-standing use of phosphine and diphosphine ligands in coordination chemistry and catalysis, questions remain as to their effects on metal-ligand bonding in transition metal complexes. Here we report ligand K-edge XAS, DFT, and TDDFT studies aimed at quantifying the impact of coordination geometry, diphosphine bite angle, and phosphine trans influence on covalency in M-P and M-Cl bonds. A series of four-coordinate NiCl2 and PdCl2 complexes containing PPh3 or Ph2P(CH2)nPPh2, where n = 1 (dppm), 2 (dppe), 3 (dppp), and 4 (dppb), was analyzed. The XAS data revealed that changing the coordination geometry from tetrahedral in Ni(PPh3)2Cl2 (1) to square planar in Ni(dppe)Cl2 (2) more than doubles the intensity of pre-edge features assigned to Ni-P and Ni-Cl 1s ? ?* transitions. By way of comparison, varying the diphosphine in Pd(dppm)Cl2 (4), Pd(dppp)Cl2 (6), and Pd(dppb)Cl2 (7) yielded Pd-P 1s ? ?* transitions with identical intensities, but a 10% increase was observed in the P K-edge XAS spectrum of Pd(dppe)Cl2 (5). A similar observation was made when comparing Ni(dppe)Cl2 (2) to Ni(dppp)Cl2 (3), and DFT and TDDFT calculations corroborated XAS results obtained for both series. Comparison of the spectroscopic and theoretical results to the diphosphine structures revealed that changes in M-P covalency were not correlated to changes in bite angles or coordination geometry. As a final measure, P and Cl K-edge XAS data were collected on trans-Pd(PPh3)2Cl2 (8) for comparison to the cis diphosphine complex Pd(dppe)Cl2 (5). Consistent with phosphine's stronger trans influence compared to chloride, a 35% decrease in the intensity of the Pd-P 1s ? ?* pre-edge feature and a complementary 34% increase in Pd-Cl 1s ? ?* feature was observed for 8 (trans) compared to 5 (cis). Overall, the results reveal how coordination geometry, ligand arrangement, and diphosphine structure affect covalent metal-phosphorus and metal-chloride bonding in these late transition metal complexes. PMID:25996554

  1. Evidence for metal to solvent charge transfer photooxidation of iron, cobalt, nickel and copper dithiocarbamato derivatives in poly(vinylchloride) matrices at ca. 90 K: New insights into the bonding of late transition metals with dithiocarbamate ligands through DFT modeling

    Microsoft Academic Search

    Thomas E. Bitterwolf

    2008-01-01

    Photolysis of FeL3, CoL3, NiL2, CuL2 and ZnL2, where L=S2CNEt2, in PVC matrices at ca. 90K results in photooxidation of the metal complexes through irreversible metal to solvent charge transfer. DFT quantum mechanical studies of the S2CNMe2 anion and the Ni, Cu and Zn derivatives were carried out, providing a more nuanced understanding of the bonding of the dithiocarbamate ligand

  2. Building complexity in O2-binding copper complexes. Site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand.

    PubMed

    Serrano-Plana, Joan; Costas, Miquel; Company, Anna

    2014-12-15

    A novel unsymmetric dinucleating ligand (L(N3N4)) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. L(N3N4) is able to discriminate between Cu(I) and a complementary metal (M' = Cu(I), Zn(II), Fe(II), Cu(II), or Ga(III)) so that pure heterodimetallic complexes with a general formula [Cu(I)M'(L(N3N4))](n+) are synthesized. Reaction of the dicopper(I) complex [Cu(I)2(L(N3N4))](2+) with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and (T)P) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM'(L(N3N4))](n+) with O2 at low temperature is used as a tool to determine the final position of the Cu(I) center in the system because only one of the two Cu2O2 species is formed. PMID:25424176

  3. Comparing three approaches in extending biotic ligand models to predict the toxicity of binary metal mixtures (Cu-Ni, Cu-Zn and Cu-Ag) to lettuce (Lactuca sativa L.).

    PubMed

    Liu, Yang; Vijver, Martina G; Peijnenburg, Willie J G M

    2014-10-01

    Metals are always found in the environment as mixtures rather than as solitary elements. However, effect models such as biotic ligand models (BLMs) are usually derived for toxicity prediction of single metals. Our study aimed at predicting mixture toxicity of Cu-Ni, Cu-Zn and Cu-Ag combinations to lettuce (Lactucasativa L.) by combining BLMs with three toxicity indexes: the toxic unit, the overall amounts of metal ions bound to the biotic ligands and the toxic equivalency factor. The accumulation of metal ions at the biotic ligands was used to determine the toxic potency of metals alone or in combination. On the basis of parameters derived from toxicity assessment of individual metals, these three extended BLMs appeared to be all acceptable (p<0.0001) in assessing toxicity of diverse metal mixtures. The BLM-based approaches integrated competition between metal ions in assessing mixture toxicity and showed different predictive ability for each metal combination. The outcome of modeling suggested that the combined toxicity depends on the specific components of the metal mixtures. The best developed models assist in identifying the type of underlying toxic mechanisms of diverse metal mixtures in terrestrial plants. PMID:25048917

  4. Formation and reactivity of metal-ligand bonds: platinum(I) dimers and cobalt and chromium alkyls

    SciTech Connect

    Blau, R.J.

    1985-01-01

    (Pt/sub 2/(..mu..-dppm)/sub 2/Cl(PPh/sub 3/))/sup +/ is formed from a rate-limiting bimolecular reaction of PPH/sub 3/ with (Pt(..mu..-dppm)/sub 2/Cl/sub 2/) in CH/sub 2/Cl/sub 2/. Alternatively, it and its bromo and chloro derivatives can be formed from the reaction of halides with (Pt(..mu..-dppm)/sub 2/-PPh/sub 3/)/sub 2/)/sup 2 +/ by (a) rate-limiting PPH/sub 3/ dissociation, or (b) rate-limiting Pt/sub 2/(..mu..-dppm) ring opening at a Pt-P bond. Formation of product by (b) occurs after the formation of two observable intermediates, one of which, (Pt/sub 2/)eta/sup 2/-dppm)(..mu..-dppm)X(PPh/sub 3/))/sup +/, is readily characterized by /sup 31/P(/sup 1/H) NMR spectroscopy. Rates of these ligand substitution reactions are very sensitive to the anions present in solution. Atropisomers due to hindered rotation around the Pt-PPh/sub 3/ bond of (Pt/sub 2/(..mu..-dppm)/sub 2/Cl(PPh/sub 3/))/sup +/ are caused by phenyl-phenyl repulsions and can be distinguished by /sup 31/P(H) NMR spectroscopy. Such repulsions also retard the rate of positional interchange of axial and equatorial substitutents on its Pt/sub 2/(..mu..-dppm)/sub 2/ ring as observed by /sup 1/H NMR spectroscopy. Several correlations between /sup 195/Pt-/sup 31/P coupling constants and Pt-P and Pt-Pt bond lengths were observed. The synthesis, characterization, and reactivity of((Pt/sub 2/(..mu..-dppm)/sub 2/Cl)(di-eta/sup 2/-P/sub 4/))/sup 2 +/ is reported. This complex is a dimer of platinum dimers bridged by tetra-phosphorus. One platinum of each dimer is bound to two phosphorus atoms of P/sub 4/. The formation and reactivity of the metal-carbon bonds in benzylcobalamin and chromium alkyls, ((H/sub 2/O)/sub 5/CrR/sup 2 +/; R = CH/sub 2/Ph, CH(CH/sub 3/)OC/sub 2/H/sub 5/, CH/sub 2/OCH/sub 9/), were also investigated.

  5. Metal Complexes: Preparation, Magnetic, Spectral, and Biocidal Studies of Some Mixed?Ligand Complexes with Schiff Bases Containing NO and NN Donor Atoms

    Microsoft Academic Search

    Prakash P. Dholakiya; M. N. Patel

    2004-01-01

    Metal complexes of the types [M(SB)2acphen] and [M(SB)2acphen] where M = Mn(II), Co(II), Ni(II), Cu(II), and Cd(II); HSB = 5?chlorosalicylidene?p?anisidine and HSB = 5?bromosalicylidene?p?anisidine have been prepared and characterized. Magnetic susceptibility measurements, elemental analyses, electro?nic, and infrared spectral data suggest six?coordinated octahedral structures for these complexes. The mixed?ligand complexes show higher activity against Saccharomyces cereuisae, Salmonella typhi, Fasarium oxysporum, and Lasiodiplodia theobromae as compared to the

  6. A Highly Porous and Robust (3,3,4)-Connected Metal?Organic Framework Assembled with a 90° Bridging-Angle Embedded Octacarboxylate Ligand

    SciTech Connect

    Lu, Weigang; Yuan, Daqiang; Makal, Trevor A.; Li, Jian-Rong; Zhou, Hong-Cai (TAM)

    2012-03-15

    A dicopper(II)-paddle-wheel-based metal-organic framework (PCN-80, see picture) with a rare (3,3,4)-connected topology has been synthesized by using a unique octatopic ligand featuring 90{sup o} bridging-angle dicarboxylate moieties. PCN-80 has Brunauer-Emmett-Teller (BET) and Langmuir surface areas of 3850 and 4150 m{sup 2}g{sup -1}, respectively. It exhibits high gas-uptake capacity for H{sub 2} and large adsorption selectivity of CO{sub 2} over N{sub 2}.

  7. Transition-Metal Derivatives of the Cyclopentadienylphosphine Ligands. 11. Reactivity of the Dinuclear Bridged Rhodium(II) Complexes toward Nitrogen-Containing Ligands.

    PubMed

    Iretskii, Alexei; Jennings, Michael C.; Poilblanc, René

    1996-02-28

    We report observations on the reactivity of the dinuclear bridged metal-metal-bonded carbonyl [Rh(II)(CO)(&mgr;-CpPPh(2))](2)(2+) (2(2+)) and of the bis(solvate) cations [Rh(II)(solv)(&mgr;-CpPPh(2))(2)](2)(2+) (3(2+)) with nitriles, amines and pyridine and in general with nitrosyl cation and nitrite anion. By reaction of nitriles and pyridine with 2(2+) we obtained monosubstituted [Rh(2)(CO)L(&mgr;-CpPPh(2))(2)](2+) (4(2+)) and disubstituted [Rh(L)(&mgr;-CpPPh(2))](2)(2+) (5(2+)) (L = MeCN, PhCN, pyridine). These complexes (5(2+)) were also obtained directly from 3(2+). In the reactions with 2(2+) the difference in reactivity of the two rhodium(II) sites suggests a specific role of the metal-metal bond. With secondary and primary amines, reductions of 2(2+) to [Rh(I)(CO)(&mgr;-CpPPh(2))](2) (1) were also observed, and the selectivity with respect to substitution or reduction was strongly solvent dependent. Lithium diisopropylamide induces quantitatively the reduction of 2(2+) to 1 and apparently the substitution of the solvent in 3a(2+). Finally, the new compounds [Rh(II)(THF)(&mgr;-CpPh(2))](2)(2+) (3a(2+)), [Rh(II)(&mgr;-H(2)NC(5)H(4)N)(&mgr;-CpPh(2))(2)](2+) (6(2+)) and [Rh(II)(NO(2))(&mgr;-CpPh(2))](2) (7(2+)) were obtained from 2(2+) and PhIO, from 3(2+) and aminopyridine, and from 2(2+) and nitrite anion, respectively. The compounds were characterized by elemental analysis and the usual spectroscopic methods including COSY NMR experiments. Reaction of NOBF(4) with 1 led efficiently to the compound 2(2+) again through a redox process, instead of a substitution. PMID:11666317

  8. Bellow seal and anchor

    DOEpatents

    Mansure, Arthur J. (Albuquerque, NM)

    2001-01-01

    An annular seal is made of a collapsible bellows. The bellows can function as an anchor or a seal and is easily set into position using relative component movement. The bellows folds can be slanted and their outer sealing edges can have different profiles to meet expected conditions. The bellows is expanded for insertion to reduce its outer dimension and sets by compaction as a result of relative movement. The bellows can be straight or tapered and is settable with a minimal axial force.

  9. The Glycophosphatidylinositol Anchor of the MCMV Evasin, m157, Facilitates Optimal Cell Surface Expression and Ly49 Receptor Recognition.

    PubMed

    Carlin, Lindsey E; Guseva, Natalya V; Shey, Michael R; Ballas, Zuhair K; Heusel, Jonathan W

    2013-01-01

    The murine cytomegalovirus-encoded protein m157 is a cognate ligand for both inhibitory and activating receptors expressed by natural killer cells. Additionally, m157 is expressed on the surface of infected cells by a glycophosphatidylinositol (GPI) anchor. Although endogenous GPI-anchored proteins are known to be ligands for the NK cell receptor, NKG2D, the contribution of the GPI anchor for viral m157 ligand function is unknown. To determine whether the GPI anchor for m157 is dispensable for m157 function, we generated m157 variants expressed as transmembrane fusion proteins and tested cells expressing transmembrane m157 for the capacity to activate cognate Ly49 receptors. We found that the GPI anchor is required for high-level cell surface expression of m157, and that the transmembrane m157 ligand retains the capacity to activate reporter cells and NK cells expressing Ly49H, as well as Ly49I(129) reporter cells, but with reduced potency. Importantly, target cells expressing the transmembrane form of m157 were killed less efficiently and failed to mediate Ly49H receptor downregulation on fresh NK cells compared to targets expressing GPI-anchored m157. Taken together, these results show that the GPI anchor for m157 facilitates robust cell surface expression, and that NK cells are sensitive to the altered cell surface expression of this potent viral evasin. PMID:23840655

  10. Consideration of the bioavailability of metal/metalloid species in freshwaters: experiences regarding the implementation of biotic ligand model-based approaches in risk assessment frameworks.

    PubMed

    Rüdel, Heinz; Díaz Muñiz, Cristina; Garelick, Hemda; Kandile, Nadia G; Miller, Bradley W; Pantoja Munoz, Leonardo; Peijnenburg, Willie J G M; Purchase, Diane; Shevah, Yehuda; van Sprang, Patrick; Vijver, Martina; Vink, Jos P M

    2015-05-01

    After the scientific development of biotic ligand models (BLMs) in recent decades, these models are now considered suitable for implementation in regulatory risk assessment of metals in freshwater bodies. The BLM approach has been described in many peer-reviewed publications, and the original complex BLMs have been applied in prospective risk assessment reports for metals and metal compounds. BLMs are now also recommended as suitable concepts for the site-specific evaluation of monitoring data in the context of the European Water Framework Directive. However, the use is hampered by the data requirements for the original BLMs (about 10 water parameters). Recently, several user-friendly BLM-based bioavailability software tools for assessing the aquatic toxicity of relevant metals (mainly copper, nickel, and zinc) became available. These tools only need a basic set of commonly determined water parameters as input (i.e., pH, hardness, dissolved organic matter, and dissolved metal concentration). Such tools seem appropriate to foster the implementation of routine site-specific water quality assessments. This work aims to review the existing bioavailability-based regulatory approaches and the application of available BLM-based bioavailability tools for this purpose. Advantages and possible drawbacks of these tools (e.g., feasibility, boundaries of validity) are discussed, and recommendations for further implementation are given. PMID:25750051

  11. Tuning the Formations of Metal–Organic Frameworks by Modification of Ratio of Reactant, Acidity of Reaction System, and Use of a Secondary Ligand

    SciTech Connect

    Gao, Qian; Xie, Ya-Bo; Li, Jian-Rong; Yuan, Daqiang; Yakovenko, Andrey A; Sun, Ji-Hong; Zhou, Hong-Cai

    2012-01-01

    Four porous coordination networks (PCNs), {[Zn?O(H?O)?(adc)?]·2(C?H?NH?)·2(DMF)·3(H?O)}n (PCN-131), Zn?(DMA)?(adc)?]·2(DMA)}n (PCN-132), {[Zn?O(DMF)(adc)?(4,4'-bpy)]·2(C?H?NH?)·S}n (PCN-131'), and {[Zn(adc)(4,4'-bpy)0.5]·S}n (PCN-132'), have been synthesized by the assembly of anthrancene-9,10-dicarboxylic acid (H?adc) with Zn(II) under different reaction conditions, including modifications of reactant ratio, acidity variations, and the use of a secondary ligand. Single-crystal X-ray diffraction studies reveal that PCN-131, obtained from the dimethylformamide (DMF) solution under acid condition, has a three-dimentional (3D) framework structure with one-dimensional (1D) honeycomb channels. PCN-132 isolated from dimethylacetamide (DMA) solution without adding acid in synthesis is a two-dimensional (2D) layer compound. By employing 4,4'-bipyridyl (4,4'-bpy) as a secondary ligand, PCN-131' and PCN-132' were synchronously synthesized as a mixture outcome with more PCN-131' than PCN-132'. In PCN-131', 4,4'-bpy acting as a secondary ligand is arranged inside the honeycomb channel of the 3D PCN-131, resulting in an effective improvement of thermal stability of the network, while in PCN-132', 4,4'-bpy ligands link 2D layers of PCN-132 to form a pillared-layer 3D framework. Gas adsorption has been performed for selected materials. The results show that the framework of PCN-131 is thermally unstable after removing the solvent molecules coordinated to their metal sites. While PCN-131' is stable for gas uptake, with an evaluated Langmuir surface area of 199.04 m² g–1, it shows a selective adsorption of CO? over CH?.

  12. A high power (>5 W) temperature stable RF MEMS metal-contact switch with orthogonal anchors and force-enhancing stoppers

    Microsoft Academic Search

    Chirag D. Patel; Gabriel M. Rebeiz

    2011-01-01

    This paper presents a temperature stable metal- contact RF MEMS switch capable of handling >5 W of RF power. The device achieves 0.7 - 1.5 mN of contact force for actuation voltages of 80 - 90 V, with a restoring force of 0.63 mN. Furthermore, the device is insensitive to stress effects and temperature. Temperature measurements showed excellent thermal stability

  13. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    PubMed Central

    Holby, Edward F.; Taylor, Christopher D.

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358

  14. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: role of *OH ligands.

    PubMed

    Holby, Edward F; Taylor, Christopher D

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358

  15. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    DOE PAGESBeta

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O? bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H?O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore »structures have the highest calculated activity to date.« less

  16. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    NASA Astrophysics Data System (ADS)

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  17. The influence of metals on the electronic system of biologically important ligands. Spectroscopic study of benzoates, salicylates, nicotinates and isoorotates. Review.

    PubMed

    Lewandowski, W; Kalinowska, M; Lewandowska, H

    2005-07-01

    This paper reviews the results of the intense experimental and theoretical studies on the influence of selected metals on the electronic system of biologically important molecules such as benzoic, 2-hydroxybenzoic and 3-pyridine carboxylic acids as well as 5-carboxyuracil. The research involved following techniques: infrared (FT-IR), Raman (FT-Raman), FT-IR Ar matrix, electronic absorption spectroscopy (UV/visible), nuclear magnetic resonance ((1)H, (13)C, (15)N, (17)O NMR), X-ray and quantum mechanical calculations. The influence of metals on the electronic system was examined through comparison of the changes in so called "logical series". The exemplary series are: Li-->Na-->K-->Rb-->Cs, Na(I)-->Ca(II)-->La(III)-->Th(IV); Na(I)-->Mg(II)-->Al(III) or long series of La(III) and fourteen lanthanides La(III)-->Ce(III)-->Lu(III). The correlation between the perturbation of the electronic system of ligands and the position of metals in the periodic table was found. The influence of the carboxylic anion structure and the effect of hydration on the perturbation of the electronic system of molecule were also discussed. The partial explanation in what way metals disturb and stabilize electronic system of studied ligands was done. It is necessary to carry out the physico-chemical studies of benzoates, salicylates, 3-pyridine carboxylates and isoorotates in order to understand the nature of the interactions of these compounds with their biological targets (e.g., receptors in the cell or important cell components). The results of this study make possible to predict some properties of a molecule, such as its reactivity, durability of complex compounds, and kinship to enzymes. PMID:15927261

  18. Synthesis, characterization, and antipathogenic studies of some transition metal complexes with N,O-chelating Schiff's base ligand incorporating azo and sulfonamide Moieties

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Bayoumi, Hoda A.; Ammar, Yousry A.; Aldhlmani, Sharah A.

    2013-03-01

    Chromium(III), Manganese(II), Cobalt(II), nickel(II), copper(II) and cadmium(II) complexes of 4-[4-hydroxy-3-(phenyliminomethyl)-phenylazo]benzenesulfonamide, were prepared and characterized on the basis of elemental analyses, spectral, magnetic, molar conductance and thermal analysis. Square planar, tetrahedral and octahedral geometries have been assigned to the prepared complexes. Dimeric complexes are obtained with 2:2 molar ratio except chromium(III) complex is monomeric which is obtained with 1:1 molar ratios. The IR spectra of the prepared complexes were suggested that the Schiff base ligand(HL) behaves as a bi-dentate ligand through the azomethine nitrogen atom and phenolic oxygen atom. The crystal field splitting, Racah repulsion and nepheloauxetic parameters and determined from the electronic spectra of the complexes. Thermal studies suggest a mechanism for degradation of HL and its metal complexes as function of temperature supporting the chelation modes. Also, the activation thermodynamic parameters, such as ?E*, ?H*, ?S* and ?G* for the different thermal decomposition steps of HL and its metal complexes were calculated. The pathogenic activities of the synthesized compounds were tested in vitro against the sensitive organisms Staphylococcus aureus (RCMB010027), Staphylococcus epidermidis (RCMB010024) as Gram positive bacteria, Klebsiella pneumonia (RCMB 010093), Shigella flexneri (RCMB 0100542), as Gram negative bacteria and Aspergillus fumigates (RCMB 02564), Aspergillus clavatus (RCMB 02593) and Candida albicans (RCMB05035) as fungus strain, and the results are discussed.

  19. Construction of Ligand Group Orbitals for Polyatomics and Transition-Metal Complexes Using an Intuitive Symmetry-Based Approach

    ERIC Educational Resources Information Center

    Johnson, Adam R.

    2013-01-01

    A molecular orbital (MO) diagram, especially its frontier orbitals, explains the bonding and reactivity for a chemical compound. It is therefore important for students to learn how to construct one. The traditional methods used to derive these diagrams rely on linear algebra techniques to combine ligand orbitals into symmetry-adapted linear…

  20. Supercritical carbon dioxide-soluble ligands for extracting actinide metal ions from porous solids (EMSP Project Number 64965)

    Microsoft Academic Search

    M. L. Dietz; Barrans Jr. R. E; A. W. Herlinger; J. F. Brennecke

    2000-01-01

    The objective of this project is to develop novel, substituted diphosphonic acid ligands that can be used for supercritical carbon dioxide extraction (SCDE) of actinide ions from solid wastes. Specifically, selected diphosphonic acids, which are known to form extremely stable complexes with actinides in aqueous and organic solution, are to be rendered carbon dioxide-soluble by the introduction of appropriate alkyl-

  1. Steady-state distribution of metals among metallothionein and other cytosolic ligands and links to cytotoxicity in bivalves living along a polymetallic gradient.

    PubMed

    Giguère, Anik; Couillard, Yves; Campbell, Peter G C; Perceval, Olivier; Hare, Landis; Pinel-Alloul, Bernadette; Pellerin, Jocelyne

    2003-07-16

    The present study was designed to assess the environmental effects of metals in a field setting. We explored exposure-->bioaccumulation-->effects relationships in freshwater molluscs exposed to metals in their natural habitat. Indigenous floater mussels (Pyganodon grandis) were collected from ten limnologically similar lakes located along a Cd, Cu and Zn gradient. Ambient free-metal ion concentrations were estimated as a measure of metal exposure. Metallothionein (MT) was measured in mussel gills and metal partitioning among the various cytosolic protein pools was determined by size exclusion chromatography. Various biomarkers were also measured, including malondialdehyde (MDA) concentrations in the gills and in the digestive gland, glutathione-peroxidase and glutathione-reductase activities in the digestive gland, and lipid concentrations in the gonad. Cadmium and MT concentrations in the gill cytosol increased along the contamination gradient, but Cu and Zn levels were independent of the ambient free-metal ion concentrations. The distribution of Cd among the various cytosolic complexes remained quite constant: 80% in the MT-like pool, 7% in the low molecular weight pool (LMW<1.8 kDa) and 13% in the high molecular weight pool (HMW>18 kDa). For these chronically exposed molluscs there was thus no threshold exposure concentration above which spillover of Cd occurred from the MT pool to other cytosolic ligands. However, the presence of Cd in the LMW and HMW fractions suggests that metal detoxification was imperfect, i.e. that P. grandis was subject to some Cd-related stress at low chronic exposure concentrations. Consistent with this suggestion, MDA concentrations, an indicator of oxidative stress, increased with gill cytosolic Cd. In the digestive gland, MDA concentrations were unrelated to any of the measured metals, but glutathione-peroxidase and glutathione-reductase activities increased with gill cytosolic copper. We speculate that cytosolic Cu catalyses the production of reactive oxygen species, to which the organism reacts by increasing activities of the two enzymes, thus preventing the accumulation of reactive oxygen species. Lipid concentrations in the gonad did not decrease with any of the measured toxicological parameters, suggesting that energy reserves for reproduction were not compromised in the metal-contaminated mussels. The results of the present study, where chronically exposed bivalves were collected from their natural habitat along a metal contamination gradient, contrast markedly with what would have been predicted on the basis of experimental metal exposures, and clearly demonstrate the need to study metal exposure-->bioaccumulation-->effects relationships in natural populations. PMID:12799111

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

    PubMed

    Liu, Fangwei; Anis, Reema; Hwang, Eunmi; Ovalle, Rafael; Varela-Ramírez, Armando; Aguilera, Renato J; Contel, María

    2011-01-01

    New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole) thioether ligand (N-methyl-4,5-diphenyl-2-imidazolyl)2C(OMe)C(CH3)2S(tert-Bu) ({BITOMe,StBu}, 2). The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI, AuIII, AgI, CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3), [Au{BITOMe,StBu}Cl] (4), [Ag{BITOMe,StBu}X] (X = OSO2CF3- 5, PF6- 6) and [Cu{BITOMe,StBu}Cl2] (7) have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the neutral dinuclear mixed AuIII-AuI species [Au2{BITOMe,S}Cl3] (8) were obtained and its crystal structure was determined by X-ray diffraction studies. The structure shows a AuIII center coordinated to the pincer ligand through one N and the S atom. The soft AuI center coordinates to the ligand through the same S atom that has lost the tert-butyl group, thus becoming a thiolate ligand. The short distance between the AuI-AuIII atoms (3.383 Å) may indicate a weak metal-metal interaction. Complexes 2-7 and the previously described CuI compound [Cu{BITOMe,StBu}]PF6 (9) have been evaluated in the oxidation of biphenyl ethylene with tert-butyl hydrogen peroxide (TBHP) as the oxidant. Results have shown that the AuI and AgI complexes 4 and 6 (at 10 mol % loading) are the more active catalysts in this oxidative cleavage. The antimicrobial activity of compounds 2-5, 7 and 9 against Gram-positive and Gram-negative bacteria and yeast has also been evaluated. The new gold and silver compounds display moderate to high antibacterial activity, while the copper derivatives are mostly inactive. The gold and silver complexes were also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing HeLa human cervical carcinoma cells. The compounds displayed a very low cytotoxicity on this cell line (5 to 10 times lower than cisplatin) and on normal primary cells derived from C57B6 mouse muscle explants, which may make them promising candidates as potential antimicrobial agents and safer catalysts due to low toxicity in human and other mammalian tissues. PMID:25134773

  3. Quantifying the density of surface capping ligands on semiconductor quantum dots

    NASA Astrophysics Data System (ADS)

    Zhan, Naiqian; Palui, Goutam; Merkl, Jan-Philip; Mattoussi, Hedi

    2015-03-01

    We have designed a new set of coordinating ligands made of a lipoic acid (LA) anchor and poly(ethylene glycol) (PEG) hydrophilic moiety appended with a terminal aldehyde for the surface functionalization of QDs. This ligand design was combined with a recently developed photoligation strategy to prepare hydrophilic CdSe-ZnS QDs with good control over the fraction of intact aldehyde (-CHO) groups per nanocrystal. We further applied the efficient hydrazone ligation to react aldehyde-QDs with 2-hydrazinopyridine (2-HP). This covalent modification produces QD-conjugates with a well-defined absorption feature at 350 nm ascribed to the hydrazone chromophore. We exploited this unique optical signature to accurately measure the number of aldehyde groups per QD when the fraction of LA-PEG-CHO per nanocrystal was varied. This allowed us to extract an estimate for the number of LA-PEG ligands per QD. These results suggest that hydrazone ligation has the potential to provide a simple and general analytical method to estimate the number of surface ligands for a variety of nanocrystals such as metal, metal oxide and semiconductor nanocrystals.

  4. Gas adsorption and gas mixture separations using mixed-ligand MOF material

    DOEpatents

    Hupp, Joseph T. (Northfield, IL); Mulfort, Karen L. (Chicago, IL); Snurr, Randall Q. (Evanston, IL); Bae, Youn-Sang (Evanston, IL)

    2011-01-04

    A method of separating a mixture of carbon dioxiode and hydrocarbon gas using a mixed-ligand, metal-organic framework (MOF) material having metal ions coordinated to carboxylate ligands and pyridyl ligands.

  5. Anchor bolt assembly

    SciTech Connect

    Simmons, W.J.

    1988-06-14

    This patent describes an anchor bolt assembly for securing a bolt in a bore hole having a settable bonding material therein comprising an elongated bolt having a head on one end and a threaded portion for receiving a nut at the other end, the improvement comprising in combination, (a) an essentially straight elongated rod for mixing the settable bonding material in a bore hole and (b) a bolt, the ends of the rod being attached to the bolt, (c) the rod being selectively releasable from attachment at one end when the bolt is rotated in a bore hole and subjected to increasing drag of the settable bonding material as the bonding material cures in the hole.

  6. Polyoxometalate-based organic-inorganic hybrid compounds containing transition metal mixed-organic-ligand complexes of N-containing and pyridinecarboxylate ligands.

    PubMed

    Zhao, De-Chuan; Hu, Yang-Yang; Ding, Hong; Guo, Hai-Yang; Cui, Xiao-Bing; Zhang, Xiao; Huo, Qi-Sheng; Xu, Ji-Qing

    2015-05-01

    Five new organic-inorganic hybrid compounds based on the Keggin-type polyoxoanion [SiW12O40](4-), namely [Cu3(2,2'-bpy)3(inic)(?2-OH)(H2O)][SiW12O40]·2H2O (), [Cu6(phen)6(?3-Cl)2(?2-Cl)2Cl2(inic)2][SiW12O40]·6H2O (), [Cu2(hnic)(2,2'-bpy)2Cl]2[H2SiW12O40] (), [Cu2(nic)(phen)2Cl2]2[SiW12O40] () and [Cu2(pic)(2,2'-bpy)2Cl]2[SiW12O40] () (inic = isonicotinic acid, hnic = 2-hydroxy-nicotinic acid, nic = nicotinic acid, pic = picolinic acid, 2,2'-bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by IR, UV-Vis, XPS, XRD, cyclic voltammetric measurements, photoluminescence analysis and single crystal X-ray diffraction analysis. Crystal analysis reveals that compound exhibits a 2-D double layered framework structure constructed from [SiW12O40](4-) and copper-aqua-2,2'-bipy-hydroxyl-isonicotinate complexes. Compound is a 0-D discrete structure formed by [SiW12O40](4-) and copper-chloro-isonicotinate-phenanthroline complexes. Compound shows a 1-D single chain structure based on the linkage of copper-2,2-bpy-chloro-2-hydroxy-nicotinate complexes and [SiW12O40](4-). Compounds and both contain polyoxometalate supported transition metal complexes, one is a polyoxometalate supported copper-chloro-nicotinate-phenanthroline complex in , and the other is a polyoxometalate supported copper-2,2-bpy-chloro-nicotinate complex in . It should be noted that nicotinic, isonicotinic and picolinic acids are structural isomers and 2-hydroxy-nicotinic acid is an in situ hydroxylated product of nicotinic acid. In addition, photocatalytic degradation of Rhodamine B (RhB) by compounds has been investigated in aqueous solutions. PMID:25882351

  7. Ligand-enabled multiple absolute stereocontrol in metal-catalysed cycloaddition for construction of contiguous all-carbon quaternary stereocentres

    NASA Astrophysics Data System (ADS)

    Ohmatsu, Kohsuke; Imagawa, Naomichi; Ooi, Takashi

    2014-01-01

    The development of a general catalytic method for the direct and stereoselective construction of contiguous all-carbon quaternary stereocentres remains a formidable challenge in chemical synthesis. Here, we report a highly enantio- and diastereoselective [3+2] annulation reaction of 5-vinyloxazolidinones and activated trisubstituted alkenes catalysed by a palladium complex bearing a newly devised phosphine ligand with a chiral ammonium salt component, which enables the single-step construction of three contiguous stereocentres, including vicinal all-carbon quaternary stereocentres, in a five-membered heterocyclic framework. This stereoselective cycloaddition protocol relies on the remarkable ability of the chiral ligand to rigorously control the absolute stereochemistry of each chiral centre associated with the multiple bond-forming events, and provides a reliable catalytic process for the asymmetric synthesis of densely functionalized pyrrolidines.

  8. Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.

    PubMed

    Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J; Arion, Vladimir B

    2015-06-15

    Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry. PMID:26030801

  9. Ligand displacement for fixing manganese: relevance to cellular metal ion transport and synthesis of polymeric coordination complexes.

    PubMed

    Sanchez-Ballester, Noelia M; Shrestha, Lok Kumar; Elsegood, Mark R J; Schmitt, Wolfgang; Ariga, Katsuhiko; Anson, Christopher E; Hill, Jonathan P; Powell, Annie K

    2013-02-28

    A dinuclear manganese(III) complex (1) of an N-(carboxymethyl)-N-[3,5-bis(?,?-dimethylbenzyl-2-hydroxybenzyl)]glycine (HDA) ligand (L) binds a manganese(II) species through displacement of its solvating ligands by appropriately dispositioned carbonyl groups of a dinuclear complex {[Mn(2)(L)(2)(OH)(OCH(3))][Mn(H(2)O)(3)(CH(3)OH)(3)], 2, triclinic P1, a = 13.172(3) Å, b = 15.897(3) Å, c = 19.059(4) Å, V = 3461.9(13) Å(3)} leading to a trinuclear complex {3, monoclinic P21/n, a = 11.7606(8) Å, b = 21.3505(8) Å, c = 26.7827(17) Å, V = 6722.7(7) Å(3)} with cyclization of two of the carboxy groups through the doubly-carboxy group coordinated Mn(2+) ion. The reaction is discussed in terms of its significance as an illustration of how Mn(2+) ions might be sequestered in biological systems. A similar solvato-ligand displacement reaction was used to synthesise coordination polymers of an HDA iron(III) complex involving polymerization through a bridging carboxylato group. Several isostructural polymers (5-7; for 5: orthorhombic Pbca, a = 9.411(5) Å, b = 16.390(8) Å, c = 37.968(19) Å, V = 5856(5) Å(3)) with different coordinated alcohols could be prepared indicating the potential synthetic uses of this method. PMID:23238775

  10. Granular Simulation of NEO Anchoring

    NASA Technical Reports Server (NTRS)

    Mazhar, Hammad

    2011-01-01

    NASA is interested in designing a spacecraft capable of visiting a Near Earth Object (NEO), performing experiments, and then returning safely. Certain periods of this mission will require the spacecraft to remain stationary relative to the NEO. Such situations require an anchoring mechanism that is compact, easy to deploy and upon mission completion, easily removed. The design philosophy used in the project relies on the simulation capability of a multibody dynamics physics engine. On Earth it is difficult to create low gravity conditions and testing in low gravity environments, whether artificial or in space is costly and therefore not feasible. Through simulation, gravity can be controlled with great accuracy, making it ideally suited to analyze the problem at hand. Using Chrono::Engine [1], a simulation package capable of utilizing massively parallel GPU hardware, several validation experiments will be performed. Once there is sufficient confidence, modeling of the NEO regolith interaction will begin after which the anchor tests will be performed and analyzed. The outcome of this task is a study with an analysis of several different anchor designs, along with a recommendation on which anchor is better suited to the task of anchoring. With the anchors tested against a range of parameters relating to soil, environment and anchor penetration angles/velocities on a NEO.

  11. Synthesis, Characterization of Some Transition-Metal Complexes of a New Heptadentate N5S2 Schiff-Base Ligand and the Effects of These Metal Complexes on U2OS Cells Cytotoxicity and DNA Cleavage Activity

    Microsoft Academic Search

    G. Uluçcam; N. Beynek; Z. Seller; G. Akal?n; G. Turan; K. Benkli

    2008-01-01

    Metal complexes of a heptadentate N5S2 donor Schiff-base ligand were synthesized by the template reaction between 2,6-bis(2-aminothiophenoxymethyl)pyridine and 2,2 ?-bipyridine-6,6 ?-dicarboxaldehyde in the presence of Zn(II), Cd(II), Hg(II) and Pb(II) perchlorate salts. The complexes were characterized by IR, H NMR, MS-FAB, and elemental analyses. The mitochondrial activity of U2OS cells after exposure to these complexes was determined by colorimetric assay,

  12. Coordination mode of pentadentate ligand derivative of 5-amino-1,3,4-thiadiazole-2-thiol with nickel(II) and copper(II) metal ions: synthesis, spectroscopic characterization, molecular modeling and fungicidal study.

    PubMed

    Chandra, Sulekh; Gautam, Seema; Kumar, Amit; Madan, Molly

    2015-02-01

    Complexes of nickel(II), and copper(II) were synthesized with pantadentate ligand i.e. 3,3'-thiodipropionicacid-bis(5-amino-1,3,4-thiadiazole-2-thiol) (L). The ligand was synthesized by the condensation of thiodipropionic acid and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio, respectively. Synthesized ligand was characterized by elemental analysis, mass, (1)H NMR, IR, and molecular modeling. All the complexes were characterized by elemental analysis, molar conductance, magnetic moment, IR, electronic spectra, ESR, and molecular modeling. The newly synthesized complexes possessed general composition [M(L)X2] where M = Ni(II), Cu(II), L = pantadentate ligand and X = Cl(-), CH3COO(-). The IR spectral data indicated that the ligand behaved as a pantadentate ligand and coordinated to the metal ion through N2S3 donor atoms. The molar conductance value of Ni(II), and Cu(II) complexes in DMSO corresponded to their electrolytic behavior. On the basis of spectral study, octahedral and tetragonal geometry was assigned for Ni(II) and Cu(II) complexes, respectively. In vitro fungicidal study of ligand and its complexes was investigated against fungi Candida albicans, Candida parapsilosis, Candidia krusei, and Candida tropicalis by means of well diffusion method. PMID:25448967

  13. Coordination mode of pentadentate ligand derivative of 5-amino-1,3,4-thiadiazole-2-thiol with nickel(II) and copper(II) metal ions: Synthesis, spectroscopic characterization, molecular modeling and fungicidal study

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gautam, Seema; Kumar, Amit; Madan, Molly

    2015-02-01

    Complexes of nickel(II), and copper(II) were synthesized with pantadentate ligand i.e. 3,3?-thiodipropionicacid-bis(5-amino-1,3,4-thiadiazole-2-thiol) (L). The ligand was synthesized by the condensation of thiodipropionic acid and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio, respectively. Synthesized ligand was characterized by elemental analysis, mass, 1H NMR, IR, and molecular modeling. All the complexes were characterized by elemental analysis, molar conductance, magnetic moment, IR, electronic spectra, ESR, and molecular modeling. The newly synthesized complexes possessed general composition [M(L)X2] where M = Ni(II), Cu(II), L = pantadentate ligand and X = Cl-, CH3COO-. The IR spectral data indicated that the ligand behaved as a pantadentate ligand and coordinated to the metal ion through N2S3 donor atoms. The molar conductance value of Ni(II), and Cu(II) complexes in DMSO corresponded to their electrolytic behavior. On the basis of spectral study, octahedral and tetragonal geometry was assigned for Ni(II) and Cu(II) complexes, respectively. In vitro fungicidal study of ligand and its complexes was investigated against fungi Candida albicans, Candida parapsilosis, Candidia krusei, and Candida tropicalis by means of well diffusion method.

  14. Ligand Field Theoretical Considerations

    Microsoft Academic Search

    Andreas Hauser

    The phenomenon of the thermal spin transition, as observed for octahedral transition metal complexes having a d 4 to d 7 electronic configuration, can be fully rationalised on the basis of ligand field theory. In order to arrive at a self-consistent description of the vibronic structure of spin crossover compounds, it is essential to take into account the fact that

  15. Unique (3,8)-connected lanthanide arenedisulfonate metal-organic frameworks containing benzimidazole-5,6-dicarboxylic acid co-ligand: Syntheses, structures and luminescence

    NASA Astrophysics Data System (ADS)

    Sun, Yan-Qiong; Liu, Qi; Zhong, Jie-Cen; Pan, Qun-Feng; Chen, Yi-Ping

    2013-10-01

    Two isostructural 3D lanthanide arenedisulfonate metal-organic frameworks (MOFs) [Ln(Hbidc)(nds)0.5(H2O)]n(Ln=Eu(1), La(2)) have been successfully synthesized by the hydrothermal reaction of lanthanide oxide with 2,6-naphthalenedisulfonate sodium (Na2nds) and an auxiliary ligand, 1H-benzimidazole-5,6-dicarboxylic acid (H3bidc). The two complexes are both constructed from 2D [Ln(Hbidc)]+ double layers pillared by nds2- ligands to generate 3D (3, 8)-connected open-framework structures with 1D long narrow channels running along the a axis. From topological point of view, the 3D framework is a (3, 8)-connected tfz-d net. The weak interactions including N-H⋯O, O-H⋯O hydrogen bonds and ?-? stacking are observed in 1. The 2D IR correlation spectroscopy was applied to study the molecular interactions induced by thermal perturbation. The emission spectra of 1 exhibit the characteristic transition of 5D0?7FJ(J=0-4) of Eu(III).

  16. Postsynthetic Metal and Ligand Exchange in MFU-4l: A Screening Approach toward Functional Metal-Organic Frameworks Comprising Single-Site Active Centers.

    PubMed

    Denysenko, Dmytro; Jelic, Jelena; Reuter, Karsten; Volkmer, Dirk

    2015-05-26

    The isomorphous partial substitution of Zn(2+) ions in the secondary building unit (SBU) of MFU-4l leads to frameworks with the general formula [Mx Zn(5-x) Cl4 (BTDD)3 ], in which x?2, M=Mn(II) , Fe(II) , Co(II) , Ni(II) , or Cu(II) , and BTDD=bis(1,2,3-triazolato-[4,5-b],[4',5'-i])dibenzo-[1,4]-dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU-4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis-NIR, TGA, and gas sorption measurements. Several MFU-4l derivatives show high catalytic activity in a liquid-phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co- and Cu derivatives with chloride side-ligands are the most active catalysts. Upon thermal treatment, several side-ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300?°C, Co(II) -azide units in the SBU of Co-MFU-4l are converted into Co(II) -isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of Cu(II) -fluoride units with H2 at 240?°C leads to Cu(I) and proceeds through the heterolytic cleavage of the H2 molecule. PMID:25882594

  17. Experimental investigations of a partial Ru-O bond during the metal-ligand bifunctional addition in Noyori-type enantioselective ketone hydrogenation.

    PubMed

    Takebayashi, Satoshi; Dabral, Nupur; Miskolzie, Mark; Bergens, Steven H

    2011-06-29

    The transition state for the metal-ligand bifunctional addition step in Noyori's enantioselective ketone hydrogenation was investigated using intramolecular trapping experiments. The bifunctional addition between the Ru dihydride trans-[Ru((R)-BINAP)(H)(2)((R,R)-dpen)] and the hydroxy ketone 4-HOCH(2)C(6)H(4)(CO)CH(3) at -80 °C exclusively formed the corresponding secondary ruthenium alkoxide trans-[Ru((R)-BINAP)(H)(4-HOCH(2)C(6)H(4)CH(CH(3))O)((R,R)-dpen)]. Combined with the results of control experiments, this observation provides strong evidence for the formation of a partial Ru-O bond in the transition state. PMID:21634401

  18. Synthesis and characterization of a three dimensional zinc(II) metal-organic framework constructed from flexible 1,2,3,4-tetra-(4-pyridyl)-butane ligand

    NASA Astrophysics Data System (ADS)

    Lin, Jianguo; Wu, Peiheng; Kang, Lin; Lu, Changsheng; Meng, Qingjin

    2011-08-01

    Employing the flexible tetrapodal ligand 1,2,3,4-tetra-(4-pyridyl)-butane (TPB) along with fumaric acid (H 2FMA) as the bridges, a metal-organic framework of [Zn(TPB)(FMA)·(2H 2O)] ( 1) was obtained and characterized by elemental analysis, spectral method (IR), single crystal X-ray diffraction, thermal gravimetric analysis (TGA) and fluorescent property. This polymer exhibits a three dimensional (3D) dense network with an interesting (4,4)-connected PtS topology. It also displays good thermal stability and strong photoluminescence in the blue region band. Thus it may serve as a candidate of thermally stable blue-light-emitting photoluminescent material.

  19. Phosphonate-anchored thin films on titanium and niobium oxide surfaces: Fabrication and characterization

    Microsoft Academic Search

    Racheli Adadi; Gilad Zorn; Reuven Brener; Irena Gotman; Elazar Y. Gutmanas; Chaim N. Sukenik

    2010-01-01

    Phosphonate-anchored thin films form on various metal oxide substrates. This paper compares structural details of these covalently anchored films on the oxidized surfaces of titanium, niobium and a Ti45Nb alloy. This is made possible by a sample configuration wherein the alkylphosphonates are coated onto a thin film of metal which is sputtered onto a double-side-polished silicon wafer and then oxidized.

  20. Ab initio and density functional theoretical design and screening of model crown ether based ligand (host) for extraction of lithium metal ion (guest): effect of donor and electronic induction.

    PubMed

    Boda, Anil; Ali, Sk Musharaf; Rao, Hanmanth; Ghosh, Sandip K

    2012-08-01

    The structures, energetic and thermodynamic parameters of model crown ethers with different donor, cavity and electron donating/ withdrawing functional group have been determined with ab initio MP2 and density functional theory in gas and solvent phase. The calculated values of binding energy/ enthalpy for lithium ion complexation are marginally higher for hard donor based aza and oxa crown compared to soft donor based thia and phospha crown. The calculated values of binding enthalpy for lithium metal ion with 12C4 at MP2 level of theory is in good agreement with the available experimental result. The binding energy is altered due to the inductive effect imparted by the electron donating/ withdrawing group in crown ether, which is well correlated with the values of electron transfer. The role of entropy for extraction of hydrated lithium metal ion by different donor and functional group based ligand has been demonstrated. The HOMO-LUMO gap is decreased and dipole moment of the ligand is increased from gas phase to organic phase because of the dielectric constant of the solvent. The gas phase binding energy is reduced in solvent phase as the solvent molecules weaken the metal-ligand binding. The theoretical values of extraction energy for LiCl salt from aqueous solution in different organic solvent is validated by the experimental trend. The study presented here should contribute to the design of model host ligand and screening of solvent for metal ion recognition and thus can contribute in planning the experiments. PMID:22318713

  1. Nickel/lanthanide single-molecule magnets: {Ni(3)Ln} "stars" with a ligand derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions.

    PubMed

    Efthymiou, Constantinos G; Stamatatos, Theocharis C; Papatriantafyllopoulou, Constantina; Tasiopoulos, Anastasios J; Wernsdorfer, Wolfgang; Perlepes, Spyros P; Christou, George

    2010-11-01

    Unusual {Ni(II)(3)Ln(III)(?-OR)(6)}(3+) complexes with a "star" topology have been prepared with ligands derived from the metal-promoted reduction of di-2-pyridyl ketone under solvothermal conditions; the Dy(III) member shows weak single-molecule-magnet behavior. PMID:20873852

  2. Ir Spectroscopy of Au-...(CO2)n Clusters: Strong Cluster Size Dependence of Metal-Ligand Interaction

    NASA Astrophysics Data System (ADS)

    Knurr, Benjamin J.; Weber, J. Mathias

    2012-06-01

    Gold is a widely used catalyst in many reactions. For example, negatively charged gold clusters have been shown to catalyze the oxidation of CO to CO2 [1], although the precise role of negative charge has not been understood. A previous study from our laboratory has shown that the binary complex [AuCO2]- has the CO2 ligand covalently bound to the gold, leading to significant charge transfer onto the CO2 unit and concomitant decrease of the OCO bond angle and weakening of the CO bonds [2]. The structure of this aurylformate anion is reminiscent of structural motifs assumed to play a role in a recent approach towards production of solar fuels using reductive activation of CO2 [3]. We report infrared spectra of Au-...(CO2)n clusters highlighting solvation mediated changes in the infrared signatures of the ligands. These results are discussed in the framework of quantum chemistry calculations. 1. U. Heiz and W.D. Schneider, J. Phys. D - Appl. Phys., 33 (2000) R85- R102. 2. A.D. Boese, H. Schneider, A.N. Gloess, and J.M. Weber, J. Chem. Phys., 122 (2005) 154301. 3. E.E. Barton, D.M. Rampulla, and A.B. Bocarsly, J. Am. Chem. Soc., 130 (2008) 6342.

  3. Metal-organic coordination architectures of azole heterocycle ligands bearing acetic acid groups: Synthesis, structure and magnetic properties

    SciTech Connect

    Hu Bowen; Zhao Jiongpeng; Yang Qian; Hu Tongliang; Du Wenping [Department of Chemistry, Nankai University, Tianjin 300071 (China); Bu Xianhe, E-mail: buxh@nankai.edu.c [Department of Chemistry, Nankai University, Tianjin 300071 (China)

    2009-10-15

    Four new coordination complexes with azole heterocycle ligands bearing acetic acid groups, [Co(L{sup 1}){sub 2}]{sub n} (1), [CuL{sup 1}N{sub 3}]{sub n} (2), [Cu(L{sup 2}){sub 2}.0.5C{sub 2}H{sub 5}OH.H{sub 2}O]{sub n} (3) and [Co(L{sup 2}){sub 2}]{sub n} (4) (here, HL{sup 1}=1H-imidazole-1-yl-acetic acid, HL{sup 2}=1H-benzimidazole-1-yl-acetic acid) have been synthesized and structurally characterized. Single-crystal structure analysis shows that 3 and 4 are 2D complexes with 4{sup 4}-sql topologies, while another 2D complex 1 has a (4{sup 3}){sub 2}(4{sup 6})-kgd topology. And 2 is a 3D complex composed dinuclear mu{sub 1,1}-bridging azido Cu{sup II} entities with distorted rutile topology. The magnetic properties of 1 and 2 have been studied. - Graphical Abstract: The synthesis, crystal structure, and magnetic properties of the new coordination complexes with azole heterocycle ligands bearing acetic acid groups are reported.

  4. Large shape-persistent metal-invertible 15-Nsp(2)-donor-atom macrocycles functioning as trinucleating ligands.

    PubMed

    Stadler, Adrian-Mihail; Jiang, Ji-Jun; Wang, Hai-Ping; Bailly, Corinne

    2013-05-01

    Reaction of 4,6-dihydrazinopyrimidines with 2,6-dicarbonylpyridines produces, under metal-free or template conditions, a new class of [3 + 3] macrocycles with 15 Nsp(2) donor atoms. Nine Nsp(2) atoms are on the external circumference of the macrocycle. The macrocycle can bind metal ions and produce trinuclear complexes along with the motion of the nine outer Nsp(2) atoms to inner positions (a motion of inversion of the macrocycle). PMID:23546549

  5. Synthesis and characterization of d{sup 10} metal complexes with mixed 1,3-di(1H-imidazol-4-yl)benzene and multicarboxylate ligands

    SciTech Connect

    Chen, Zhi-Hao; Zhao, Yue; Chen, Shui-Sheng; Wang, Peng; Sun, Wei-Yin, E-mail: sunwy@nju.edu.cn

    2013-06-15

    Seven new coordination polymers [Zn(H{sub 2}L)(mbdc)] (1), [Zn(H{sub 3}L)(btc)] (2), [Zn(H{sub 2}L)(Hbtc)] (3), [Zn(H{sub 2}L)(Hbtc)]·H{sub 2}O (4), [Zn{sub 2}(H{sub 2}L)(btc)(?{sub 2}-OH)] (5), [Cd(H{sub 2}L)(mbdc)] (6) and [Cd{sub 3}(H{sub 2}L){sub 2}(btc){sub 2}(H{sub 2}O)]·5H{sub 2}O (7) were synthesized by reactions of the corresponding metal salt with rigid ligand 1,3-di(1H-imidazol-4-yl)benzene (H{sub 2}L) and different carboxylic acids of 1,3-benzenedicarboxylic acid (H{sub 2}mbdc) and benzene-1,3,5-tricarboxylic acid (H{sub 3}btc), respectively. The results of X-ray crystallographic analysis indicate that complex 1 is 1D chain while 2 is a (3,3)-connected 2D network with Point (Schläfli) symbol of (4,8{sup 2}). Complexes 3 and 6 are 2D networks, 4 is a 3-fold interpenetrating 3D framework with Point (Schläfli) symbol of (6{sup 5},8) and 5 is a (3,8)-connected 2D network with Point (Schläfli) symbol of (3,4{sup 2}){sub 2}(3{sup 4},4{sup 6},5{sup 6},6{sup 8},7{sup 3},8), while 7 is a (3,10)-connected 3D net with Schläfli symbol of (3,4,5){sub 2}(3{sup 4},4{sup 8},5{sup 18},6{sup 12},7{sup 2},8). The thermal stability and photoluminescence of the complexes were investigated. Furthermore, DFT calculations were performed for 2–4 to discuss the temperature controlled self-assembly of the complexes. - Graphical abstract: Seven new coordination polymers with multicarboxylate and rigid ditopic 4-imidazole containing ligands have been obtained and found to show different structures and topologies. - Highlights: • Metal complexes with diverse structures of 1D chain, 2D network and 3D framework. • Mixed ligands of 1,3-di(1H-imidazol-4-yl)benzene and multicarboxylate. • Photoluminescence property.

  6. Mixed-ligand complexes of zinc(II), cobalt(II) and cadmium(II) with sulfur, nitrogen and oxygen ligands. Analysis of the solid state structure and solution behavior. Implications for metal ion substitution in alcohol dehydrogenase

    Microsoft Academic Search

    Agnieszka Pladzyk; Katarzyna Baranowska; Dietrich Gudat; Sylwia Godlewska; Monika Wieczerzak; Jaros?aw Chojnacki; Mateusz Bulman; Katarzyna Januszewicz; Anna Do??ga

    2011-01-01

    In this paper we characterize new, mixed ligand complexes of zinc(II), cobalt(II) and cadmium(II) with tri-tert-butoxysilanethiolate and 2-(2?-hydroxyethyl)pyridine ligands. Due to the chelating versus non-chelating behavior of 2-(2?-hydroxyethyl)pyridine ligand we have obtained an interesting structural variety in the studied system. The presented coordination patterns together with the results of NMR studies have been used to illustrate a rapid chemical exchange

  7. 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

    2014-04-01

    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 the design of a catalyst. PMID:24649877

  8. The effects of phosphorous donor ligand substitution on the reactivity of anionic group 6 transition metal carbonyl hydrides 

    E-print Network

    Lusk, Richard Jay

    1986-01-01

    of this solution does proceed at 60'C after 36 hours. One haunting aspect of the above decompositon of HN(CO)&L is the vanishing act of half of the hydride ligands. The aggr egation reactions shown below and carried out in apr otic solvents do not immediately.... 4 3 CQlllQE)Lld Na HIV(CO)4P(OMe)3 22 -20 -60 -5. 37 -5. 13 -4. 83 50 -5. 44 30. 89 3. 52 31. 62 3. 50 30. 60 3. 48 32. 56 3. 44 2~~3 d~ 11. 43 55. 74 11. 43 56 30 6. 18 986 51 98 PPN H(V(CQ)4P(QMe)3 50 22 -20 -60 -4. 32 -434...

  9. In situ metal imaging and Zn ligand-speciation in a soil-dwelling sentinel: complementary electron microprobe and synchrotron microbeam X-ray analyses.

    PubMed

    Morgan, A J; Mosselmans, J F W; Charnock, J M; Bennett, A; Winters, C; O'Reilly, M; Fisher, P; Andre, J; Turner, M; Gunning, P; Kille, P

    2013-01-15

    Understanding the relationships between accumulated metal speciation in cells and tissues of ecologically significant taxa such as earthworms will improve risk assessments. Synchrotron-based ?-focus X-ray spectroscopy was used to detect, localize, and determine ligand-speciation of Zn and Pb in thin sections of two epigeic earthworm species collected from a Pb/Zn-mine soil. The findings indicated that Zn and Pb partition predominantly as typical hard acids (i.e., strong affinities for O-donors) within liverlike chloragocytes. Moreover, Zn speciation was very similar in the chloragog and intestinal epithelia but differed subtly in the kidneylike nephridial tubules; neither Zn nor Pb was detectable in the ventral nerve cord. High resolution X-ray mapping of high pressure-frozen, ultrathin, freeze-substituted sections in a transmission electron microscope (TEM), combined with conventional TEM structural analysis, identified a new cell type packed with highly organized rough endoplasmic reticulum and containing deposits of Cd (codistributed with S); there was no evidence that these cells are major depositories of Zn or Pb. These data may be used in a systems biology approach to assist in the interpretation of metal-evoked perturbations in whole-worm transcriptome and metabolome profiles. PMID:23198708

  10. Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex

    SciTech Connect

    Witte, Jonathon [Department of Chemistry, University of California, Berkeley, California 94720 (United States) [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States) [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2014-03-14

    Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO{sub 2} binding to benzene. We begin by clarifying the geometry of the CO{sub 2}–benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ?CCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Møller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ?B97X-V, perform with similar accuracy for this system, as do ?B97X and M06-L.

  11. Glycosylphosphatidylinositol anchors regulate glycosphingolipid levels[S

    PubMed Central

    Loizides-Mangold, Ursula; David, Fabrice P. A.; Nesatyy, Victor J.; Kinoshita, Taroh; Riezman, Howard

    2012-01-01

    Glycosylphosphatidylinositol (GPI) anchor biosynthesis takes place in the endoplasmic reticulum (ER). After protein attachment, the GPI anchor is transported to the Golgi where it undergoes fatty acid remodeling. The ER exit of GPI-anchored proteins is controlled by glycan remodeling and p24 complexes act as cargo receptors for GPI anchor sorting into COPII vesicles. In this study, we have characterized the lipid profile of mammalian cell lines that have a defect in GPI anchor biosynthesis. Depending on which step of GPI anchor biosynthesis the cells were defective, we observed sphingolipid changes predominantly for very long chain monoglycosylated ceramides (HexCer). We found that the structure of the GPI anchor plays an important role in the control of HexCer levels. GPI anchor-deficient cells that generate short truncated GPI anchor intermediates showed a decrease in very long chain HexCer levels. Cells that synthesize GPI anchors but have a defect in GPI anchor remodeling in the ER have a general increase in HexCer levels. GPI-transamidase-deficient cells that produce no GPI-anchored proteins but generate complete free GPI anchors had unchanged levels of HexCer. In contrast, sphingomyelin levels were mostly unaffected. We therefore propose a model in which the transport of very long chain ceramide from the ER to Golgi is regulated by the transport of GPI anchor molecules. PMID:22628614

  12. A study of the removal of heavy metals from aqueous solutions by Moringa oleifera seeds and amine-based ligand 1,4-bis[N,N-bis(2-picoyl)amino]butane.

    PubMed

    Obuseng, Veronica; Nareetsile, Florence; Kwaambwa, Habauka M

    2012-06-12

    Uptake for lead, copper, cadmium, nickel and manganese from aqueous solution using the Moringa oleifera seeds biomass (MOSB) and amine-based ligand (ABL) was investigated. Experiments on two synthetic multi-solute systems revealed that MOSB performed well in the biosorption and followed the decreasing orders Pb(II)>Cu(II)>Cd(II)>Ni(II)>Mn(II) and Zn(II)>Cu(II)>Ni(II). The general trend of the heavy metal ions uptake by the amine-based ligand followed decreased in the order Mn>Cd>Cu>Ni>Pb, which is the reverse trend for what was observed for MOSB. Comparing the single- and multi-metal solutions, there was no clear effect in the biosorption capacity of MOSB suggesting the presence of sufficient active binding sites for all metal ions studied. The MOSB performance is also not affected by pH in the range 3.5-8. PMID:22632049

  13. Synthesis and Study of Boron and Antimony Lewis Acids as Small Anion Receptors and Ligands Towards Transition Metals 

    E-print Network

    Wade, Casey

    2012-02-14

    of tetraorganostibonium ions (R4Sb+) and cationic transition metal-triarylstibine complexes (R3SbM+) to complex fluoride. Finally, the electropositivity of antimony and its ability to form stable compounds in both the +3 and +5 oxidation states have led us to begin...

  14. Unique (3,8)-connected lanthanide arenedisulfonate metal-organic frameworks containing benzimidazole-5,6-dicarboxylic acid co-ligand: Syntheses, structures and luminescence

    SciTech Connect

    Sun, Yan-Qiong, E-mail: sunyq@fzu.edu.cn [College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002 (China); State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Liu, Qi; Zhong, Jie-Cen; Pan, Qun-Feng; Chen, Yi-Ping [College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002 (China)

    2013-10-15

    Two isostructural 3D lanthanide arenedisulfonate metal-organic frameworks (MOFs) [Ln(Hbidc)(nds){sub 0.5}(H{sub 2}O)]{sub n}(Ln=Eu(1), La(2)) have been successfully synthesized by the hydrothermal reaction of lanthanide oxide with 2,6-naphthalenedisulfonate sodium (Na{sub 2}nds) and an auxiliary ligand, 1H-benzimidazole-5,6-dicarboxylic acid (H{sub 3}bidc). The two complexes are both constructed from 2D [Ln(Hbidc)]{sup +} double layers pillared by nds{sup 2?} ligands to generate 3D (3, 8)-connected open-framework structures with 1D long narrow channels running along the a axis. From topological point of view, the 3D framework is a (3, 8)-connected tfz-d net. The weak interactions including N–H?O, O–H?O hydrogen bonds and ?–? stacking are observed in 1. The 2D IR correlation spectroscopy was applied to study the molecular interactions induced by thermal perturbation. The emission spectra of 1 exhibit the characteristic transition of {sup 5}D{sub 0}?{sup 7}F{sub J}(J=0–4) of Eu(III). - Graphical abstract: Two isostructural 3D (3,8)-connected lanthanide arenedisulfonates were hydrothermally synthesized. The 2D IR correlation spectroscopy was applied to study the molecular interactions induced by thermal perturbation. Display Omitted - Highlights: • The first lanthanide arenedisulfonates incorporating fused-ring aromatic carboxylic acid. • Three-dimensional (3,8)-connected framework with tfz-d network topology. • The emission spectra of 1 exhibit the characteristic transition of {sup 5}D{sub 0}?{sup 7}F{sub J} (J=0–4) of Eu(III). • The 2D IR correlation spectroscopy was applied to study the molecular interactions.

  15. Functionalized adamantane tectons used in the design of mixed-ligand copper(II) 1,2,4-triazolyl/carboxylate metal-organic frameworks.

    PubMed

    Senchyk, Ganna A; Lysenko, Andrey B; Krautscheid, Harald; Rusanov, Eduard B; Chernega, Alexander N; Krämer, Karl W; Liu, Shi-Xia; Decurtins, Silvio; Domasevitch, Konstantin V

    2013-01-18

    Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr(2)pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H(4)-adtc) platform for the construction of neutral heteroleptic copper(II) metal-organic frameworks. Two coordination polymers, [{Cu(4)(OH)(2)(H(2)O)(2)}{Cu(4)(OH)(2)}(tr(2)pr)(2)(H-adtc)(4)]·2H(2)O (1) and [Cu(4)(OH)(2)(tr(2)ad)(2)(H-adtc)(2)(H(2)O)(2)]·3H(2)O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N(1),N(2)-1,2,4-triazolyl (tr) and ?(3)-OH(-) groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu(4)(OH)(2)} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu(4)(OH)(2)} secondary building block and trideprotonated carboxylate H-adtc(3-) can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing ?(3)- or ?(4)-binding patterns, introduce additional integrating links between the neighboring {Cu(4)(OH)(2)} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J(1) = -109 cm(-1) and J(2) = -21 cm(-1)), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = -2.5 cm(-1)). PMID:23294097

  16. Synthesis, Structural Characterization and Biological Activity of Novel Cyclohexane-1,3-dione Ligands and Their Metal Complexes.

    PubMed

    Turan, Nevin; Körkoca, Hanifi; Adigüzel, Rag?p; Çolak, Naki; Buldurun, Kenan

    2015-01-01

    Some new Zn(II) and Cu(II) complexes [Cu(L1)(OAc)2]?H2O, [Cu(L1)(NO3)H2O]?NO3?3.5H2O, [Zn(L1)(NO3)2]?4.5H2O, [Zn(L1)(OAc)2(H2O)2]?3H2O, [Cu2(L2)(OAc)4]?2H2O?2DMF, [Cu(L2)2]?2NO3?1.5DMF?H2O, [Zn(L2)2(NO3)2]?DMF and [Zn2(L2)(OAc)4(H2O)4]?5H2O; L1 = 2-[2-(2-methoxyphenyl)hydrazono]cyclohexane-1,3-dione and L2 = 2-[2-(3-nitrophenyl)hydrazono]cyclohexane-1,3-dione were synthesized and characterized by IR, 1H-NMR,13C-NMR and ultraviolet (UV-Vis.) spectroscopy, elemental analysis, magnetic susceptibility, mass spectrometry and thermogravimetry-differential thermal analysis (TGA-DTA). The synthesized ligands and their complexes were tested for antibacterial activity against Escherichia coli ATCC 25922, Enterococcus faecalis ATCC 29212, Staphylococcus aureus ATCC 25923, and Salmonella typhimurium CCM 583. Some of complexes showed medium-level antibacterial activity against the test bacteria compared with ampicillin. PMID:26007185

  17. Metal and ligand binding to the HIV-RNase H active site are remotely monitored by Ile556

    PubMed Central

    Zheng, Xunhai; Mueller, Geoffrey A.; DeRose, Eugene F.; London, Robert E.

    2012-01-01

    HIV-1 reverse transcriptase (RT) contains a C-terminal ribonuclease H (RH) domain on its p66 subunit that can be expressed as a stable, although inactive protein. Recent studies of several RH enzymes demonstrate that substrate binding plays a major role in the creation of the active site. In the absence of substrate, the C-terminal helix E of the RT RNase H domain is dynamic, characterized by severe exchange broadening of its backbone amide resonances, so that the solution characterization of this region of the protein has been limited. Nuclear magnetic resonance studies of 13C-labeled RH as a function of experimental conditions reveal that the ?1 methyl resonance of Ile556, located in a short, random coil segment following helix E, experiences a large 13C shift corresponding to a conformational change of Ile556 that results from packing of helix E against the central ?-sheet. This shift provides a useful basis for monitoring the effects of various ligands on active site formation. Additionally, we report that the RNase H complexes formed with one or both divalent ions can be individually observed and characterized using diamagnetic Zn2+ as a substitute for Mg2+. Ordering of helix E results specifically from the interaction with the lower affinity binding to the A divalent ion site. PMID:22941642

  18. Spectroscopic and thermal properties of short wavelength metal (II) complexes containing ?-isoxazolylazo-?-diketones as co-ligands

    Microsoft Academic Search

    Fuxin Huang; Yiqun Wu; Donghong Gu; Fuxi Gan

    2005-01-01

    Two new azo dyes of ?-isoxazolylazo-?-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from

  19. Anchored in the Florida Current

    NASA Astrophysics Data System (ADS)

    Brooks, David A.

    I once spent a week aboard a vessel anchored in the Florida current, in water 830 m deep, far from the sight of land. We were there to measure transport variations, and I recall the numbing hourly routine of profiling the current with an instrument that traveled down a weighted line suspended from the ship. In much sharper focus I remember the mighty current that ceaselessly swept past the vessel. The current raised a foaming bow wave and strummed the anchor cable with a note that permeated the quiet ship, giving the strange experience of being underway with silent engines while going nowhere.

  20. An equilibrium model for ligand-modified micellar-enhanced ultrafiltration, selective separation of metal ions using iminoacetic substituted polyamines and a theoretical model for the titration behavior of polyamines

    SciTech Connect

    Dharmawardana, U.R.

    1992-12-31

    This thesis consists of three chapters. Chapter 1, An equilibrium model for ligand-modified micellar-enhanced ultrafiltration, describes a theoretical model and experimental investigations which used the semi-equilibrium-dialysis method with N-n-dodecyl iminodiacetic acid as the ligand. In Chapter 2, Selective separation of metal ions using iminoacetic substituted polyamines, polyamines with a substituted ligand group are synthesized and used in investigating selective separation of copper ions from aqueous solution. In Chapter 3, A theoretical model for the titration behavior of polyamines, a novel approach to explain the titration behavior of polymeric amines based on the binding behavior of counterions is described. The application of this study is to the investigation of inexpensive and efficient methods of industrial waste water treatment.

  1. Bone Anchored Hearing Aid

    PubMed Central

    2002-01-01

    Executive Summary Objective The objective of this health technology policy assessment was to determine the effectiveness and cost-effectiveness of bone-anchored hearing aid (BAHA) in improving the hearing of people with conduction or mixed hearing loss. The Technology The (BAHA) is a bone conduction hearing device that includes a titanium fixture permanently implanted into the mastoid bone of the skull and an external percutaneous sound processor. The sound processor is attached to the fixture by means of a skin penetrating abutment. Because the device bypasses the middle ear and directly stimulates the cochlea, it has been recommended for individuals with conduction hearing loss or discharging middle ear infection. The titanium implant is expected to last a lifetime while the external sound processor is expected to last 5 years. The total initial device cost is approximately $5,300 and the external sound processor costs approximately $3,500. Review of BAHA by the Medical Advisory Secretariat The Medical Advisory Secretariat’s review is a descriptive synthesis of findings from 36 research articles published between January 1990 and May 2002. Summary of Findings No randomized controlled studies were found. The evidence was derived from level 4 case series with relative small sample sizes (ranging from 30-188). The majority of the studies have follow-up periods of eight years or longer. All except one study were based on monaural BAHA implant on the side with the best bone conduction threshold. Safety Level 4 evidence showed that BAHA has been be implanted safely in adults and children with success rates of 90% or higher in most studies. No mortality or life threatening morbidity has been reported. Revision rates for tissue reduction or resiting were generally under 10% for adults but have been reported to be as high as 25% in pediatric studies. Adverse skin reaction around the skin penetration site was the most common complication reported. Most of these conditions were successfully treated with antibiotics, and only 1% to 2% required surgical revision. Less than 1% required removal of the fixture. Other complications included failure to osseointegrate and loss of fixture and/or abutment due to trauma or infection. Effectiveness Studies showed that BAHAs were implanted in people who have conduction or mixed hearing loss, congenital atresia or suppurative otitis media who were not candidates for surgical repair, and who cannot use conventional bone conduction hearing aids. The need for BAHA is not age- related. Objective audiometric measures and subjective patient satisfaction surveys showed that BAHA significantly improved the unaided and aided free field and sound field thresholds as well as speech discrimination in quiet and in noise for former users of conventional bone conduction hearing aids. The outcomes were ambiguous for former users of air conduction hearing aids. BAHA has been shown to reduce the frequency of ear infection and reduce the discharge particularly among patients with suppurative otitis media. Patients have reported that BAHA improved their quality of life. Reported benefits were improved speech intelligibility, better sound comfort, less pressure on the head, less skin irritation, greater cosmetic acceptance and increase in confidence. Main reported shortcomings were wind noise, feedback and difficulty in using the telephone. Experts and the BAHA manufacturer recommended that recipients of a BAHA implant be at least 5 years old. Challenges associated with the implantation of BAHA in pediatric patients include thin bone, soft bone, higher rates of fixture loss due to trauma, psychological problems, and higher revision rates due to rapid bone growth. The overall outcomes are comparable to adult BAHA. The benefits of pediatric BAHA (e.g. on speech development) appear to outweigh the disadvantages. Screening according to strict eligibility criteria, preoperative counselling, close monitoring by a physician with BAHA expertise and on-going follow-up were identified as critical factors for long-ter

  2. Cubane-type Cu(II)4 and Mn(II)2Mn(III)2 complexes based on pyridoxine: a versatile ligand for metal assembling.

    PubMed

    Marino, Nadia; Armentano, Donatella; Mastropietro, Teresa F; Julve, Miguel; De Munno, Giovanni; Martínez-Lillo, José

    2013-10-21

    By using Vitamin B6 in its monodeprotonated pyridoxine form (PN-H) [PN = 3-hydroxy-4,5-bis(hydroxymethyl)-2-methylpyridine], two tetranuclear compounds of formula [Mn4(PN-H)4(CH3CO2)3Cl2]Cl·2CH3OH·2H2O (1) and [Cu4(PN-H)4Cl2(H2O)2]Cl2 (2) have been synthesized and magneto-structurally characterized. 1 crystallizes in the triclinic system with space group P1 whereas 2 crystallizes in the orthorhombic system with Fdd2 as space group. They exhibit Mn(II)2Mn(III)2 (1) and Cu(II)4 (2) cubane cores containing four monodeprotonated pyridoxine groups simultaneously acting as chelating and bridging ligands (1 and 2), three bridging acetate ligands in the syn-syn conformation (1), and two terminally bound chloride anions (1 and 2) plus two coordinated water molecules (2). The electroneutrality is achieved by the presence of chloride counterions in both compounds. Tri- [Mn(1) and Mn(3)] and divalent [Mn(2) and Mn(4)] manganese centers coexist in 1, all being six-coordinate with distorted Mn(1/3)O6 and Mn(2/4)O5Cl octahedral surroundings, respectively, the equatorial Mn-O bonds being about 0.2 Å shorter at the former ones. The two crystallographically independent copper(II) ions in 2 are five-coordinate in somewhat distorted CuO5 [Cu(1)] and CuO4Cl [Cu(2)] square pyramidal geometries. The values of the intracore metal-metal separation cover the ranges 3.144(1)-3.535(1) (1) and 2.922(6)-3.376(1) Å (2). The magnetic properties of 1 and 2 were investigated in the temperature range 1.9-300 K, and they correspond to an overall antiferromagnetic behavior with susceptibility maxima at 5.0 (1) and 65.0 K (2). The analysis of the magnetic susceptibility data showed the coexistence of intracore antiferro- and ferromagnetic interactions in the two compounds. Their values compare well with those existing in the literature for the parent systems. PMID:24074249

  3. "Directed" assembly of metallacalix[n]arenes with pyrimidine nucleobase ligands of low symmetry: interchanging metals in mixed-metal metallacalix[4]arenes and incorporating additional metals at the exocyclic groups.

    PubMed

    Khutia, Anupam; Sanz Miguel, Pablo J; Lippert, Bernhard

    2011-04-01

    The pyrimidine (pym) nucleobase cytosine (H(2)C) forms cyclic ring structures ("metallacalix[n]arenes") when treated with square-planar cis-a(2)M(II) entities (M=Pt, Pd; a=NH(3) or a(2)=diamine). The number of possible linkage isomers for a given n and the number of possible rotamers can be substantially reduced if a "directed" approach is pursued. Hence, two cytosine ligands are bonded in a defined way to a kinetically robust platinum corner stone. In the accompanying paper (Part I: A. Khutia, P. J. Sanz?Miguel, B. Lippert, Chem. Eur. J. 2010, 17, DOI: 10.1002/chem.2010002722) we have demonstrated this principle by allowing cis-[Pta(2)(H(2)C-N3)(2)](2+) to react with (en)Pd(II) to give cycles of (N1,N3?N3,N1?)(x) (with x=2 or 3; ? represents Pt(II) and ? represents Pd(II)). In an extension of this work we have now prepared cis-[Pta(2)(HC-N1)(2)] (1; HC=monoanion of cytosine) and treated it with (bpy)Pd(II) (bpy=2,2'-bipyridine) to give the Pt(2) Pd(2) cycle cis-[{Pt(NH(3))(2)(N1-HC-N3)(2)Pd(bpy)}(2)](NO(3))(4) ?13H(2)O (5) with the coordination sites of the metals inverted; hence, platinum is bonded to N1 and palladium is bonded to N3 sites. Again, not only the expected single linkage isomer is formed, but at the same time the solid-state structure and (1)H?NMR spectroscopy reveal the preferential occurrence of a single rotamer (1,3-alternate). The addition of (bpy)Pd(II) to 5 led to the formation of Pd(6) Pt(2) complex 6 in which the exocyclic N4H(2) groups of the cytosine ligands have undergone deprotonation and chelate four more (bpy)Pd(II) entities through the O2 and N4H sites. With a large excess of (bpy)Pd(II) over 5 (4:1), cis-(NH(3))(2) Pt(II) is eventually substituted by (bpy)Pd(II) to give the Pd(8) complex 7. In both 6 and 7 stacks of three (bpy)Pd(II) entities occur. The linkage isomer of 5,cis-[{Pt(NH(3))(2)(N3-HC-N1)(2)Pd(bpy)}(2)](NO(3))(4) ?9H(2)O (8), has been structurally characterized and the two complexes compared. The acid/base properties of cis-[Pt(NH(3))(2)(H(2)C-N1)(2)] (1) have been determined and compared with those of the corresponding N3 isomer. The complexation of AgCl by 1 is reported. PMID:21387424

  4. Nanopatterned anchoring layers for liquid crystals

    E-print Network

    Gear, Christopher S. (Christopher Stanwood)

    2014-01-01

    This thesis describes the theory and fabrication of inhomogeneous Liquid Crystal anchoring layers. While chemical anchoring techniques have proved useful for many applications, especially Liquid Crystal Displays, they have ...

  5. Anchors Aweigh: A Demonstration of Cross-Modality Anchoring and Magnitude Priming

    ERIC Educational Resources Information Center

    Oppenheimer, Daniel M.; LeBoeuf, Robyn A.; Brewer, Noel T.

    2008-01-01

    Research has shown that judgments tend to assimilate to irrelevant "anchors." We extend anchoring effects to show that anchors can even operate across modalities by, apparently, priming a general sense of magnitude that is not moored to any unit or scale. An initial study showed that participants drawing long "anchor" lines made higher numerical…

  6. Ligand Symmetry Modulation for Designing a Mesoporous Metal-Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization.

    PubMed

    Du, Miao; Wang, Xi; Chen, Min; Li, Cheng-Peng; Tian, Jia-Yue; Wang, Zhuo-Wei; Liu, Chun-Sen

    2015-06-26

    A promising alternative strategy for designing mesoporous metal-organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn8 (ad)4 ] (ad=adeninate) clusters and C3 -symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8?nm) and hexagonal mesoporous (ca., 3.0?nm) 1D channels. Moreover, the resulting 446-MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of Co(II) or Ni(II) on the Zn(II) centers in 446-MOF can enhance the sorption capacities of CO2 and CH4 (16-21?%), whereas the impregnation of Eu(III) and Tb(III) in the channels of 446-MOF will result in adjustable light-emitting behaviors. PMID:26013160

  7. Anchored phosphatases modulate glucose homeostasis

    E-print Network

    Scott, John D.

    EMBO open Anchored phosphatases modulate glucose homeostasis Simon A Hinke1 , Manuel F Navedo2 principally controls glucose homeostasis. Nutrient-induced exocytosis of insulin granules from pancreatic b signalling events that facilitate insulin secretion and glucose homeostasis may be set by AKAP150 associated

  8. Anchored phosphatases modulate glucose homeostasis

    PubMed Central

    Hinke, Simon A; Navedo, Manuel F; Ulman, Allison; Whiting, Jennifer L; Nygren, Patrick J; Tian, Geng; Jimenez-Caliani, Antonio J; Langeberg, Lorene K; Cirulli, Vincenzo; Tengholm, Anders; Dell'Acqua, Mark L; Santana, L Fernando; Scott, John D

    2012-01-01

    Endocrine release of insulin principally controls glucose homeostasis. Nutrient-induced exocytosis of insulin granules from pancreatic ?-cells involves ion channels and mobilization of Ca2+ and cyclic AMP (cAMP) signalling pathways. Whole-animal physiology, islet studies and live-?-cell imaging approaches reveal that ablation of the kinase/phosphatase anchoring protein AKAP150 impairs insulin secretion in mice. Loss of AKAP150 impacts L-type Ca2+ currents, and attenuates cytoplasmic accumulation of Ca2+ and cAMP in ?-cells. Yet surprisingly AKAP150 null animals display improved glucose handling and heightened insulin sensitivity in skeletal muscle. More refined analyses of AKAP150 knock-in mice unable to anchor protein kinase A or protein phosphatase 2B uncover an unexpected observation that tethering of phosphatases to a seven-residue sequence of the anchoring protein is the predominant molecular event underlying these metabolic phenotypes. Thus anchored signalling events that facilitate insulin secretion and glucose homeostasis may be set by AKAP150 associated phosphatase activity. PMID:22940692

  9. INFLATION STABILIZATION AND NOMINAL ANCHORS

    Microsoft Academic Search

    GUILLERMO A. CALVO; CARLOS A. VÉGH

    1994-01-01

    This paper analyzes the choice of a nominal anchor in disinflation programs in chronic inflation countries. Both theory and evidence suggest several conclusions. (i) The recessionary effects associated with disinflation appear in the early stages of money-based programs but only in the late stages of exchange rate-based programs. (ii) Lack of credibility is more disruptive under fixed exchange rates than

  10. Synthesis and Characterization of Organo-Rare-Earth Metal Monoalkyl Complexes Supported by Carbon ?-Bonded Indolyl Ligands: High Specific Isoprene 1,4-Cis Polymerization Catalysts.

    PubMed

    Guo, Liping; Zhu, Xiancui; Zhang, Guangchao; Wei, Yun; Ning, Lixin; Zhou, Shuangliu; Feng, Zhijun; Wang, Shaowu; Mu, Xiaolong; Chen, Jun; Jiang, Yuzhe

    2015-06-15

    A series of N-protected 3-imino-functionalized indolyl ligands 1-R-3-(R'N?CH)C8H5N [R = Bn, R' = 2,6-(i)Pr2C6H3 (HL(1)); R = CH3, R' = 2,6-(i)Pr2C6H3 (HL(2)); R = Bn, R' = (t)Bu (HL(3))] and 1-CH3-2-(2,6-(i)Pr2C6H3N?CH)C8H5N (HL(4)) was prepared via reactions of N-protected indolyl aldehydes with corresponding amines. The C-H ?-bond metathesis followed by alkane elimination reactions between RE(CH2SiMe3)3(thf)2 and HL(1)-HL(3) afforded the carbon ?-bonded indolyl-ligated rare-earth metal monoalkyl complexes. Reactions of RE(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) or HL(2) gave the carbon ?-bonded indolyl-ligated rare-earth metal monoalkyl complexes L(1)2RECH2SiMe3 (RE = Y(1), Er(2), Dy(3)) and L(2)2RECH2SiMe3 (RE = Y(5), Er(6), Dy(7), Yb(8)), while reaction of Yb(CH2SiMe3)3(thf)2 with 2 equiv of HL(1) afforded the ytterbium dialkyl complex L(1)Yb(CH2SiMe3)2(thf)2 (4). Reactions of RE(CH2SiMe3)3(thf)2 with HL(3) gave the tris(heteroaryl) rare-earth metal complexes L(3)3RE (RE = Y(9), Er(10)). In the presence of cocatalysts, the rare-earth metal monoalkyl complexes initiated isoprene polymerization with a high activity (90% conversion of 1000 equiv of isoprene in 25 min) producing polymers with high regio- and stereoselectivity (1,4-cis polymers up to 99%). PMID:25996643

  11. INVESTIGATIONS OF CONCRETE BOREHOLES FOR BONDED ANCHORS

    Microsoft Academic Search

    Roland Unterweger; Konrad Bergmeister

    1998-01-01

    SUMMARY The use of chemical bonded anchors has increased over the last years due to diminished costs, time and simply of installation. The present paper considers the modelling of chemical bonded anchors. It consists of two parts: the first part describes the common types of chemical anchor - systems. The second part concerns the influence of environmental conditions on the

  12. Heterogeneous anchoring in dichotomous choice valuation framework

    E-print Network

    Paris-Sud XI, Université de

    Heterogeneous anchoring in dichotomous choice valuation framework by Emmanuel Flachaire Ces of anchoring in contingent valuation surveys that use the double-bounded elicitation format. Anchoring occurs when responses to the follow-up dichotomous choice valuation question are influenced by the bid

  13. 33 CFR 401.15 - Stern anchors.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 2010-07-01 false Stern anchors. 401.15 Section 401.15 Navigation...Condition of Vessels § 401.15 Stern anchors. (a) Every ship of more than 110m...1975, shall be equipped with a stern anchor. (b) Every integrated tug...

  14. Knowledge Representation and Reasoning for Perceptual Anchoring

    Microsoft Academic Search

    Jonas Melchert; Silvia Coradeschi; Amy Loutfi

    2007-01-01

    In this work we report results on the use of symbolic knowledge representation and reasoning (KRR) for perceptual anchoring. Anchoring is the creation and maintenance of a connection between the symbolic and perceptual description that refer to the same physical object in the environment. We extend the anchoring framework to manage the symbolic information in a KRR system, and to

  15. Development of a Membrane-anchored Chemerin Receptor Agonist as a Novel Modulator of Allergic Airway Inflammation and Neuropathic Pain*

    PubMed Central

    Doyle, Jamie R.; Krishnaji, Subrahmanian T.; Zhu, Guangli; Xu, Zhen-Zhong; Heller, Daniel; Ji, Ru-Rong; Levy, Bruce D.; Kumar, Krishna; Kopin, Alan S.

    2014-01-01

    The chemerin receptor (CMKLR1) is a G protein-coupled receptor found on select immune, epithelial, and dorsal root ganglion/spinal cord neuronal cells. CMKLR1 is primarily coupled to the inhibitory G protein, G?i, and has been shown to modulate the resolution of inflammation and neuropathic pain. CMKLR1 is activated by both lipid and peptide agonists, resolvin E1 and chemerin, respectively. Notably, these ligands have short half-lives. To expedite the development of long acting, stable chemerin analogs as candidate therapeutics, we used membrane-tethered ligand technology. Membrane-tethered ligands are recombinant proteins comprised of an extracellular peptide ligand, a linker sequence, and an anchoring transmembrane domain. Using this technology, we established that a 9-amino acid-tethered chemerin fragment (amino acids 149–157) activates both mouse and human CMKLR1 with efficacy exceeding that of the full-length peptide (amino acids 21–157). To enable in vivo delivery of a corresponding soluble membrane anchored ligand, we generated lipidated analogs of the 9-amino acid fragment. Pharmacological assessment revealed high potency and wash resistance (an index of membrane anchoring). When tested in vivo, a chemerin SMAL decreased allergic airway inflammation and attenuated neuropathic pain in mice. This compound provides a prototype membrane-anchored peptide for the treatment of inflammatory disease. A parallel approach may be applied to developing therapeutics targeting other peptide hormone G protein-coupled receptors. PMID:24659779

  16. Development of a membrane-anchored chemerin receptor agonist as a novel modulator of allergic airway inflammation and neuropathic pain.

    PubMed

    Doyle, Jamie R; Krishnaji, Subrahmanian T; Zhu, Guangli; Xu, Zhen-Zhong; Heller, Daniel; Ji, Ru-Rong; Levy, Bruce D; Kumar, Krishna; Kopin, Alan S

    2014-05-01

    The chemerin receptor (CMKLR1) is a G protein-coupled receptor found on select immune, epithelial, and dorsal root ganglion/spinal cord neuronal cells. CMKLR1 is primarily coupled to the inhibitory G protein, G?i, and has been shown to modulate the resolution of inflammation and neuropathic pain. CMKLR1 is activated by both lipid and peptide agonists, resolvin E1 and chemerin, respectively. Notably, these ligands have short half-lives. To expedite the development of long acting, stable chemerin analogs as candidate therapeutics, we used membrane-tethered ligand technology. Membrane-tethered ligands are recombinant proteins comprised of an extracellular peptide ligand, a linker sequence, and an anchoring transmembrane domain. Using this technology, we established that a 9-amino acid-tethered chemerin fragment (amino acids 149-157) activates both mouse and human CMKLR1 with efficacy exceeding that of the full-length peptide (amino acids 21-157). To enable in vivo delivery of a corresponding soluble membrane anchored ligand, we generated lipidated analogs of the 9-amino acid fragment. Pharmacological assessment revealed high potency and wash resistance (an index of membrane anchoring). When tested in vivo, a chemerin SMAL decreased allergic airway inflammation and attenuated neuropathic pain in mice. This compound provides a prototype membrane-anchored peptide for the treatment of inflammatory disease. A parallel approach may be applied to developing therapeutics targeting other peptide hormone G protein-coupled receptors. PMID:24659779

  17. Spectroscopic studies and biological evaluation of some transition metal complexes of azo Schiff-base ligand derived from (1-phenyl-2,3-dimethyl-4-aminopyrazol-5-one) and 5-((4-chlorophenyl)diazenyl)-2-hydroxybenzaldehyde

    NASA Astrophysics Data System (ADS)

    Anitha, C.; Sheela, C. D.; Tharmaraj, P.; Sumathi, S.

    2012-10-01

    A series of metal(II) complexes of VO(II), Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized from the azo Schiff base ligand 4-((E)-4-((E)-(4-chlorophenyl)diazenyl)-2-hydroxybenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (CDHBAP) and characterized by elemental analysis, spectral (IR, UV-Vis, 1H NMR, ESR and EI-mass), magnetic moment measurements, molar conductance, DNA, SEM, X-ray crystallography and fluorescence studies. The electronic absorption spectra and magnetic susceptibility measurements of the complexes indicate square pyramidal geometry for VO(II) and octahedral geometry for all the other complexes. The important infrared (IR) spectral bands corresponding to the active groups in the ligand and the solid complexes under investigation were studied and implies that CDHBAP is coordinated to the metal ions in a neutral tridentate manner. The redox behavior of copper(II) and vanadyl(II) complexes have been studied by cyclic voltammetry. The nuclease activity of the above metal(II) complexes shows that the complexes cleave DNA. All the synthesized complexes can serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The antibacterial and antifungal activities of the synthesized ligand and its metal complexes were screened against bacterial species (Staphylococcus aureus, Salmonella typhi, Escherichia coli, Bacillus subtilis, Shigella sonnie) and fungi (Candida albicans, Aspergillus niger, Rhizoctonia bataicola). Amikacin and Ketoconozole were used as references for antibacterial and antifungal studies. The activity data show that the metal complexes have a promising biological activity comparable with the parent Schiff base ligand against bacterial and fungal species. The second harmonic generation (SHG) efficiency of the ligand was measured and the NLO (non-linear optical) properties of the ligand are expected to result in the realization of advanced optical devices in optical fiber communication (OFC) and optical computing. The SEM image of the copper(II) complex implies that the size of the particles is 1 ?m.

  18. Mixed ligand chelate therapy for plutonium and toxic metals from energy power production. Final report, April 15, 1977-October 14, 1980. [Mice

    SciTech Connect

    Schubert, J.

    1980-10-14

    The results of experiments are summarized on the ability of combinations of chelating agents to modify the genotoxicity or tissue distributions. The mutagenicities of Cr and of chelating agents were determined. The metals described in the report are Pu(IV), Cd(II), Cr(III), and Cr(VI). Accurate measurements were made of the ability of CaNa/sub 2/EDTA, CaNa/sub 3/DTPA, and DMPS to reduce mortality in mice given doses (i.p.) of CdCl/sub 2/ well above the 100% lethal level. The efficacy in terms of the mmoles/kg needed to reduce the mortality was: DTPA > EDTA > DMPS. The combination of DTPA + DMPS proved most promising though little evidence for mixed complex formation was noted. Potentiometric titration studies the case of Pu(IV) a few combinations proved effective, but only when given shortly after Pu administration and then only in the liver but not the skeleton. It is recommended that metabolically stable chelating agents be used in combinations, especially for those combinations which may form very stable mixed ligand chelates.

  19. Novel Asymmetric Tetradentate Schiff Base Ligands Derived from 6-Metwia-Formyl4Hydroxy2-(1H)-Quinolone and Their Metal Complexes

    Microsoft Academic Search

    Adel A. A. Emara

    1999-01-01

    Novel asymmetric, tetradentate, dibasic Schiff base ligands were synthesized by the condensation of the half-unit Schiff base ligand 3-[o-aminophenyliminomethyl]-4-hydroxy-6-methyl-2-(1H)-quinolone with acetylacetone and salicylaldehyde. Cu(II), Ni(II), UO2 (VI) and Fe(III) complexes of both ligands were prepared using different salts in the case of Cu(II) and Ni(II) cations The structures of the ligands and the complexes were elucidated by chemical analyses, IR,

  20. Pendant Ancillary Ligand Switches Off Auto-Oxidation of Group 13 Metal Alkyl Compounds Bearing Non-Bulky Alkyl Groups

    PubMed Central

    Kobrsi, Issam

    2014-01-01

    The reaction of 3,5-di-2-pyridyl-1,2,4-triazole with excess Al(CH3)3 and Ga(CH3)3 afforded (3,5-di-2-pyridyl-1,2,4-triazolate)Al(CH3)2•3Al(CH3)3 (1) and (3,5-di-2-pyridyl-1,2,4-triazolate) Ga(CH3)2•3Ga(CH3)3 (2) respectively. 1 and 2 reacted with oxygen gas to produce (CH3)2M(µ-3,5-di-2-pyridyl-1,2,4-triazolate)(µ-OCH3)M(CH3)2 (M?=?Al, 3; M?=?Ga, 4). 3 and 4 contain the non-bulky dimethylalumino moiety, yet they are indefinitely stable in the presence of oxygen gas. This increased stability towards oxygen is due to ancillary 2-pyridyl groups bonding to the metal centers producing a pseudo-trigonal pyramidal Al and Ga environments. This environment blocks oxygen from further inserting into the M–C bond. The Al–N(pyridine) and Ga–N(pyridine) bonds reported herein are extremely elongated yet inactive towards dissociation due to the chelate effect. PMID:24945752

  1. Physiochemical characterization and antimicrobial evaluation of phenylthiourea-formaldehyde polymer (PTF) based polymeric ligand and its polymer metal complexes.

    PubMed

    Ahamad, Tansir; Alshehri, Saad M

    2013-05-01

    Phenylthiourea-formaldehyde polymer (PTF) has been synthesized via polycondensation of phenylthiourea and formaldehyde in basic medium and its corresponding metal complexes [PTF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) ions. The synthesized polymers have been characterized by elemental analysis, magnetic susceptibility, UV-visible, FT-IR, (1)H NMR, (13)C NMR, ESR spectroscopy and thermogravimetric analysis (TGA). Elemental analysis, electronic spectra and magnetic moment measurement indicate that PTF-Mn(II), PTF-Co(II) and PTF-Ni(II) show octahedral geometry, while PTF-Cu(II) and PTF-Zn(II) show square planar and tetrahedral geometry, respectively. The results of TGA ascribed that all the PTF-M(II) showed better heat-resistance properties than PTF resin. In vitro antimicrobial activities were performed against several bacteria and fungi using agar well diffusion method. The results of microbial activity were compared with Kanamycin and Miconazole as standard antibiotics for antibacterial and antifungal activities respectively. PMID:23454711

  2. Physiochemical characterization and antimicrobial evaluation of phenylthiourea-formaldehyde polymer (PTF) based polymeric ligand and its polymer metal complexes

    NASA Astrophysics Data System (ADS)

    Ahamad, Tansir; Alshehri, Saad M.

    2013-05-01

    Phenylthiourea-formaldehyde polymer (PTF) has been synthesized via polycondensation of phenylthiourea and formaldehyde in basic medium and its corresponding metal complexes [PTF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) ions. The synthesized polymers have been characterized by elemental analysis, magnetic susceptibility, UV-visible, FT-IR, 1H NMR, 13C NMR, ESR spectroscopy and thermogravimetric analysis (TGA). Elemental analysis, electronic spectra and magnetic moment measurement indicate that PTF-Mn(II), PTF-Co(II) and PTF-Ni(II) show octahedral geometry, while PTF-Cu(II) and PTF-Zn(II) show square planar and tetrahedral geometry, respectively. The results of TGA ascribed that all the PTF-M(II) showed better heat-resistance properties than PTF resin. In vitro antimicrobial activities were performed against several bacteria and fungi using agar well diffusion method. The results of microbial activity were compared with Kanamycin and Miconazole as standard antibiotics for antibacterial and antifungal activities respectively.

  3. SOLVENT EXTRACTION OF THE RARE-EARTH METAL IONS BY A CONE-SHAPED CALDC[4]ARENE SUBSTITUTED AT THE LOWER RTM BY FOUR CH2P(O)Ph2 LIGANDS

    Microsoft Academic Search

    M. R. Yaftian; M. Burgard; D. Matt; C. B. Dieleman; F. Rastegar

    1997-01-01

    The extraction properties of cone-5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(diphenylphosphinoylmethoxy)calix[4]arene (1) in 1,2-dichloroethane towards rare-earth metal ions at 25 °C have been investigated. The slope analysis showed a 1:1 metal\\/ligand ratio for the extracted species (La, Eu, Er and Y). The distribution coefficients increase with the polarity of the diluents : chloroform ? dichioromethane ? 1,2-dichloroethane ? nitrobenzene. In the competitive extraction of 11 rare-earth

  4. Independent control of polar and azimuthal anchoring.

    PubMed

    Anquetil-Deck, C; Cleaver, D J; Bramble, J P; Atherton, T J

    2013-07-01

    Monte Carlo simulation, experiment, and continuum theory are used to examine the anchoring exhibited by a nematic liquid crystal at a patterned substrate comprising a periodic array of rectangles that, respectively, promote vertical and planar alignment. It is shown that the easy axis and effective anchoring energy promoted by such surfaces can be readily controlled by adjusting the design of the pattern. The calculations reveal rich behavior: for strong anchoring, as exhibited by the simulated system, for rectangle ratios ?2 the nematic aligns in the direction of the long edge of the rectangles, the azimuthal anchoring coefficient changing with pattern shape. In weak anchoring scenarios, however, including our experimental systems, preferential anchoring is degenerate between the two rectangle diagonals. Bistability between diagonally aligned and edge-aligned arrangement is predicted for intermediate combinations of anchoring coefficient and system length scale. PMID:23944468

  5. Distinct and Overlapping Expression Patterns of Ligands for Eph-Related Receptor Tyrosine Kinases during Mouse Embryogenesis

    Microsoft Academic Search

    Ann M. Flenniken; Nicholas W. Gale; George D. Yancopoulos; David G. Wilkinson

    1996-01-01

    Recent studies have implicated Eph-related receptor tyrosine kinases and their membrane-bound ligands in restricting or stimulating the movement of cells and axons. Members of these large families of receptors and ligands fall into two major binding specificity classes, in which the GPI-anchored subgroup of ligands can each bind to all members of a subgroup of receptors, whereas the transmembrane ligands

  6. New concept to remove heavy metals from liquid waste based on electrochemical pH-switchable immobilized ligands

    NASA Astrophysics Data System (ADS)

    Pascal, Viel; Laetitia, Dubois; Joël, Lyskawa; Marc, Sallé; Serge, Palacin

    2007-01-01

    Absorption on resins is often used as secondary step in the treatment of water-based effluents, in order to reach very low concentrations. The separation of the trapped effluents from the resins and the regeneration of the resins for further use create wide volumes of secondary effluents coming from the washings of the resins with chemical reagents. We propose an alternative solution based on a "surface strategy" through adsorption phenomena and electrical control of the expulsion stage. The final goal is to limit or ideally to avoid the use of chemical reagents at the expulsion (or regeneration) stage of the depolluting process. Heavy metal ions were captured on active filters composed by a conducting surface covered by poly-4-vinylpyridine (P 4VP). Due to pyridine groups those polymer films have chelating properties for copper ions. Our strategy for electrical triggering of the copper expulsion in aqueous medium is based on pH sensitive chelating groups. Applying moderate electro-oxidizing conditions generates acidic conditions in the vicinity of the electrode, i.e. "inside" the polymer film. This allows a "switch-off" of the complexing properties of the film from the basic form of pyridine to pyridinium. Interestingly, no buffer washing is necessary to restore (or "switch-on") the complexing properties of the polymer film because the pH of the external medium is left unchanged by the electrochemical effect that affects only the vicinity of the electrode. Switch-on/switch-off cycles are followed and attested by IR spectroscopy and EQCM method.

  7. Thermodynamics of the interaction of Pd(dmen)(H2O)22+ with bio-relevant ligands with reference to the deactivation of metal-based drug by thiol ligands

    NASA Astrophysics Data System (ADS)

    Shehata, Mohamed R.; Shoukry, Mohamed M.; Ali, Sara

    2012-06-01

    Pd(dmen)Cl2 complex was synthesized and characterized, where dmen = N,N-dimethylethylenediamine. Stoichiometry and stability constants of the complexes formed between [Pd(dmen)(H2O)2]2+ and various biologically relevant ligands such as amino acids, peptides and dicarboxylic acids are investigated at 25 °C and at constant 0.1 M ionic strength. The concentration distribution diagrams of the various species formed are evaluated. The equilibrium constants for the displacement of coordinated ligands as inosine, glycine or methionine by cysteine are calculated. The results are expected to contribute to the chemistry of tumour therapy.

  8. Anchoring bias in online voting

    NASA Astrophysics Data System (ADS)

    Yang, Zimo; Zhang, Zi-Ke; Zhou, Tao

    2012-12-01

    Voting online with explicit ratings could largely reflect people's preferences and objects' qualities, but ratings are always irrational, because they may be affected by many unpredictable factors like mood, weather and other people's votes. By analyzing two real systems, this paper reveals a systematic bias embedding in the individual decision-making processes, namely people tend to give a low rating after a low rating, as well as a high rating following a high rating. This so-called anchoring bias is validated via extensive comparisons with null models, and numerically speaking, the extent of bias decays with voting interval in a logarithmic form. Our findings could be applied in the design of recommender systems and considered as important complementary materials to previous knowledge about anchoring effects on financial trades, performance judgments, auctions, and so on.

  9. New Designs of Rigid Pincer Complexes with PXP Ligands and Late Transition Metals and sp3 C-F Bond Activation with Silylium and Alumenium Species 

    E-print Network

    Gu, Weixing

    2012-02-14

    complexes are presented. In Chapter II, the design and synthesis of P2Si= and PBP ligand precursors is described. BrC6H4PR2 is shown to be a useful building block for PXP type of ligands with o-arylene backbone. RLi reagents displayed high chemoselectivity...

  10. The first metal complex containing a silylated ?-diketonate ligand: bis(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionato) copper(II)

    Microsoft Academic Search

    Kulbinder K. Banger; Andrei Kornilov; Rolf U. Claessen; Eric T. Eisenbraun; Alain E. Kaloyeros; Paul J. Toscano; John T. Welch

    2001-01-01

    A facile preparation of 2,2,6,6-tetramethyl-2-sila-3,5-heptanedione (tmshdH), exemplar of a new class of ligands, the sila-?-diketones, has been developed. Silicon substitution in the ligands has profound effects on the volatility, thermal properties, crystal packing, and electronic spectrum of the homoleptic Cu(II) complex, Cu(tmshd)2.

  11. Anchor for Fiberglas Guy Rod

    NASA Technical Reports Server (NTRS)

    Wilson, A. H.

    1982-01-01

    Solution to problem of anchoring fiberglas guy rods to install nut with threads on outer circumference, followed by aluminum sleeve. Sleeve has opening oval at upper and round at bottom end. End of rod is split so fiberglas wedge can be inserted to form V-shaped end. Spread end of rod fits into tapered hole in sleeve and threaded aluminum coupling is put over rod and sleeve.

  12. A universal rule for organic ligand exchange.

    PubMed

    You, Hongjun; Wang, Wenjin; Yang, Shengchun

    2014-11-12

    Most synthetic routes to high-quality nanocrystals with tunable morphologies predominantly employ long hydro-carbon molecules as ligands, which are detrimental for electronic and catalytic applications. Here, a rule is found that the adsorption energy of an organic ligand is related to its carbon-chain length. Using the density functional theory method, the adsorption energies of some commonly used ligand molecules with different carbon-chain lengths are calculated, including carboxylate, hydroxyl, and amine molecules adsorbed on metal or metal oxide crystal surface. The results indicate that the adsorption energy of the ligand molecule with a long carbon chain is weaker than that of a smaller molecule with same functional group. This rule provides a theoretical support for a new kind of ligand exchange method in which large organic ligand molecules can be exchanged by small molecules with same functional group to improve the catalytic properties. PMID:25335915

  13. Smart FBG-based FRP anchor

    NASA Astrophysics Data System (ADS)

    Zhou, Zhi; Zhang, Zhichun; Wang, Chuan; Ou, Jinping

    2006-03-01

    FRP ( Fiber Reinforced Polymer ) has become the popular material to alternate steel in civil engineering under harsh corrosion environment. But due to its low shear strength ability, the anchor for FRP is most important for its practical application. However, the strain state of the surface between FRP and anchor is not fully understood due to that there is no proper sensor to monitor the inner strain in the anchor by traditional method. In this paper, a new smart FBG-based FRP anchor is brought forward, and the inner strain distribution of FRP anchor has been monitored using FRP-OFBG sensors, a smart FBG-embedded FRP rebar, which is pre-embedded in the FRP rod and cast in the anchor. Based on the strain distribution information the bonding shear stress on the surface of FRP rod along the anchor can also be obtained. This method can supply important information for FRP anchor design and can also monitor the anchorage system, which is useful for the application of FRP in civil engineering. The experimental results also show that the smart FBG-based FRP anchor can give direct information of the load and damage of the FRP anchor.

  14. Probing pore constriction in a ligand-gated ion channel by trapping a metal ion in the pore upon agonist dissociation.

    PubMed

    Pittel, Ilya; Witt-Kehati, Dvora; Degani-Katzav, Nurit; Paas, Yoav

    2010-08-20

    Eukaryotic pentameric ligand-gated ion channels (pLGICs) are receptors activated by neurotransmitters to rapidly transport ions across cell membranes, down their electrochemical gradients. Recent crystal structures of two prokaryotic pLGICs were interpreted to imply that the extracellular side of the transmembrane pore constricts to close the channel (Hilf, R. J., and Dutzler, R. (2009) Nature 457, 115-118; Bocquet, N., Nury, H., Baaden, M., Le Poupon, C., Changeux, J. P., Delarue, M., and Corringer, P. J. (2009) Nature 457, 111-114). Here, we utilized a eukaryotic acetylcholine (ACh)-serotonin chimeric pLGIC that was engineered with histidines to coordinate a metal ion within the channel pore, at its cytoplasmic side. In a previous study, the access of Zn(2+) ions to the engineered histidines had been explored when the channel was either at rest (closed) or active (open) (Paas, Y., Gibor, G., Grailhe, R., Savatier-Duclert, N., Dufresne, V., Sunesen, M., de Carvalho, L. P., Changeux, J. P., and Attali, B. (2005) Proc. Natl. Acad. Sci. U.S.A. 102, 15877-15882). In this study, the interactions of Zn(2+) with the pore were probed upon agonist (ACh) dissociation that triggers the transition of the receptor from the active conformation to the resting conformation (i.e. during deactivation). Application of Zn(2+) onto ACh-bound open receptors obstructed their pore and prevented ionic flow. Removing ACh from its extracellular binding sites to trigger deactivation while Zn(2+) is still bound led to tight trapping of Zn(2+) within the pore. Together with single-channel recordings, made to explore single pore-blocking events, we show that dissociation of ACh causes the gate to shut on a Zn(2+) ion that effectively acts as a "foot in the door." We infer that, upon deactivation, the cytoplasmic side of the pore of the ACh-serotonin receptor chimera constricts to close the channel. PMID:20466725

  15. Heteronuclear, mixed-metal Ag(I)-Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties.

    PubMed

    Bikas, Rahman; Hosseini-Monfared, Hassan; Vasylyeva, Vera; Sanchiz, Joaquín; Alonso, Javier; Barandiaran, Jose Manuel; Janiak, Christoph

    2014-08-21

    Mixed-metal dicyanoargentate-bridged coordination polymers of Ag(i)-Mn(ii) have been prepared and their structure and magnetic properties were determined. Reaction of manganese(ii) chloride and potassium dicyanoargentate(i) with (X)(pyridin-2-ylmethylene)isonicotinohydrazide ligands (HL(1) X = Ph, HL(2) X = Me, HL(3) X = H) produced the coordination polymer 2D-[Mn(?-L(1))(Cl)(?-NCAgCN)Mn0.5(CH3OH)]n (), 1D-{[Mn(L(2))(Cl)(?-NCAgCN)Mn0.5(CH3OH)]CH3OH}n () and [Mn(L(3))(Cl)(?-NCAgCN)Mn0.5(CH3OH)]n () in good yields. Trinuclear {Mn(?-L(1))Mn(?-L(1))Mn} and [Ag(CN)2](-) building units form a two-dimensional slab in and 1D strands in . Variable temperature magnetic susceptibility measurements showed that despite the long distance among the high spin Mn(ii) ions [10.4676(12) Å and 10.522(1) Å, for and , respectively], weak antiferromagnetic coupling takes place through the long NC-Ag-CN bridge. The best fit parameters to the model led to the magnetic coupling constant of J = -0.1 and J = -0.47 cm(-1) for and , respectively. The photoluminescence behaviour of compounds and was studied. The spectrum of compound shows a broad emission centered at about 450 nm and two excitation maxima at 270 and 310 nm. PMID:24967880

  16. Ligand Identification Scoring Algorithm (LISA)

    PubMed Central

    Zheng, Zheng; Merz, Kenneth M.

    2011-01-01

    A central problem in de novo drug design is determining the binding affinity of a ligand with a receptor. A new scoring algorithm is presented that estimates the binding affinity of a protein-ligand complex given a three-dimensional structure. The method, LISA (Ligand Identification Scoring Algorithm), uses an empirical scoring function to describe the binding free energy. Interaction terms have been designed to account for van der Waals (VDW) contacts, hydrogen bonding, desolvation effects and metal chelation to model the dissociation equilibrium constants using a linear model. Atom types have been introduced to differentiate the parameters for VDW, H-bonding interactions and metal chelation between different atom pairs. A training set of 492 protein-ligand complexes was selected for the fitting process. Different test sets have been examined to evaluate its ability to predict experimentally measured binding affinities. By comparing with other well known scoring functions, the results show that LISA has advantages over many existing scoring functions in simulating protein-ligand binding affinity, especially metalloprotein-ligand binding affinity. Artificial Neural Network (ANN) was also used in order to demonstrate that the energy terms in LISA are well designed and do not require extra cross terms. PMID:21561101

  17. Anchoring transition in confined discotic columnar liquid crystal films

    NASA Astrophysics Data System (ADS)

    Brunet, Thomas; Thiebaut, Olivier; Charlet, Émilie; Bock, Harald; Kelber, Julien; Grelet, Éric

    2011-01-01

    We report the achievement of ultrathin films (down to 25 nm thick) of thermotropic columnar liquid crystals in homeotropic alignment (columns normal to the interface) confined between a glass slide and a thin metallic electrode (about 150 nm thick). The face-on orientation of the discotic compound is obtained by anchoring transition of a columnar liquid crystalline phase from a degenerate planar orientation to the homeotropic alignment without any phase transition to the isotropic liquid phase. The kinetic dependence on temperature of such anchoring transition is investigated revealing various diffusive growth regimes of the homeotropic domains. Finally, confining effects are also considered by varying the thickness of the columnar liquid crystal film to reach the typical value required in organic solar cells thus demonstrating the reliability of such alignment process in a photovoltaic context.

  18. Endocytosis of glycosylphosphatidylinositol-anchored proteins

    Microsoft Academic Search

    Shaheen E Lakhan; Shefali Sabharanjak; Ananya De

    2009-01-01

    Glycosylphosphatidylinositol-anchored proteins (GPI-APs) represent an interesting amalgamation of the three basic kinds of cellular macromolecules viz. proteins, carbohydrates and lipids. An unusually hybrid moiety, the GPI-anchor is expressed in a diverse range of organisms from parasites to mammalian cells and serves to anchor a large number of functionally diverse proteins and has been the center of attention in scientific debate

  19. A lunar/Martian anchor emplacement system

    NASA Astrophysics Data System (ADS)

    Clinton, Dustin; Holt, Andrew; Jantz, Erik; Kaufman, Teresa; Martin, James; Weber, Reed

    On the Moon or Mars, it is necessary to have an anchor, or a stable, fixed point able to support the forces necessary to rescue a stuck vehicle, act as a stake for a tent in a Martian gale, act as a fulcrum in the erection of general construction poles, or support tent-like regolith shields. The anchor emplacement system must be highly autonomous. It must supply the energy and stability for anchor deployment. The goal of the anchor emplacement system project is to design and build a prototype anchor and to design a conceptual anchor emplacement system. Various anchors were tested in a 1.3 cubic meter test bed containing decomposed granite. A simulated lunar soil was created by adjusting the moisture and compaction characteristics of the soil. We conducted tests on emplacement torque, amount of force the anchor could withstand before failure, anchor pull out force at various angles, and soil disturbances caused by placing the anchor. A single helix auger anchor performed best in this test bed based on energy to emplace, and the ultimate holding capacity. The anchor was optimized for ultimate holding capacity, minimum emplacement torque, and minimum soil disturbance in sandy soils yielding the following dimensions: helix diameter (4.45 cm), pitch (1.27 cm), blade thickness (0.15 cm), total length (35.56 cm), shaft diameter (0.78 cm), and a weight of 212.62 g. The experimental results showed that smaller diameter, single-helix augers held more force than larger diameter augers for a given depth. The emplacement system consists of a flywheel and a motor for power, sealed in a protective box supported by four legs. The flywheel system was chosen over a gear system based on its increased reliability in the lunar environment.

  20. Synthesis, XAFS and X-ray structural studies of mono- and binuclear metal-chelates of N,O,O(N,O,S) tridentate Schiff base pyrazole derived ligands

    NASA Astrophysics Data System (ADS)

    Burlov, Anatolii S.; Uraev, Ali I.; Garnovskii, Dmitrii A.; Lyssenko, Konstantin A.; Vlasenko, Valery G.; Zubavichus, Yan V.; Murzin, Vadim Yu.; Korshunova, Eugenie V.; Borodkin, Gennadii S.; Levchenkov, Sergey I.; Vasilchenko, Igor S.; Minkin, Vladimir I.

    2014-05-01

    The syntheses of a series of novel N,O,O and N,O,S donor tridentate Schiff base ligands H2L1 and H2L2via the condensation of 1-phenyl-3-methyl-4-formylpyrazol-5-ol(thiol) with 2-hydroxymethylaniline and their Co(II), Ni(II), Cu(II), Fe(III), and Mn(II) complexes are reported. The compounds are characterized by the C, H, N, S, metal elemental analysis, IR spectroscopy; 1H NMR data for ligands, low-temperature magnetic measurements, X-ray absorption spectroscopy. The crystal structures for Ni(II) and Cu(II) coordination compounds with the compositions NiL21 and CuL21 are established by X-ray crystallography.

  1. Syntheses, structures, and properties of two new zinc(II) metal-organic frameworks based on flexible 1,6-bis(2-methyl-imidazole-1-yl)hexane ligand

    NASA Astrophysics Data System (ADS)

    Jin, Jun-Cheng; Fu, Ai-Yun; Li, Dian; Chang, Wen-Gui; Wu, Ju; Yang, Mei; Xie, Cheng-Gen; Xu, Guang-Nian; Cai, An-Xing; Wu, Ai-Hua

    2014-11-01

    Two new zinc(II) metal-organic compounds of [Zn(ADC)(bimh)]n (1) and [Zn(ADA)(bimh)]n (2) (H2ADC = 1,3-adamantanedicarboxylic acid, H2ADA = 1,3-adamantanediacetic acid, bimh = 1,6-bis(2-methyl-imidazole-1-yl)-hexane, have been structurally characterized by X-ray diffraction analysis. In compound 1, the zinc(II) ions are bridged by ADC and bimh ligands to form a 1D looped chain. In compound 2, the ADA molecules alternately bridge Zn(II) atoms to form infinite chains, and then the 1D chain is connected through the bimh ligand resulting in an undulating infinite two-dimensional (2D) polymeric network. Additionally, TG analysis, XRPD and fluorescent properties for compounds 1 and 2 are also measured and discussed.

  2. The first tritopic bridging ligand 1,3,5-tris(4-carboxyphenyl)-benzene (H3BTB) functionalized porous polyoxometalate-based metal-organic framework (POMOF): from design, synthesis to electrocatalytic properties.

    PubMed

    Dong, Bao-Xia; Chen, Lu; Zhang, Shi-Yang; Ge, Jun; Song, Liang; Tian, Hui; Teng, Yun-Lei; Liu, Wen-Long

    2015-01-21

    Replacing the metal ions (or metal clusters) in routine MOFs with size-matched polyoxoanions to construct POM-based MOF materials (POMOF) combining well-defined crystalline structures, high surface area, regular and tunable cavities is the great challenge in the current POM chemistry area. In this work, we report a 2-fold interpenetrated porous POMOF, [TBA]6[H3PMo12O40]2[Zn8(BTB)2]·(?35H2O), which exhibits effective catalytic activity towards bromate reduction, using the methodology of extension for the reduced transition-metal-grafted ?-Keggin polyoxoanions with an expanded tripodal bridging ligand of H3BTB. The simultaneous TGA/DSC-MS technique was applied in this work to identify the evolved gases and was proved to be an effective method for analysing the decomposition process. PMID:25428699

  3. GPI-Anchored Cell-Surface Molecules Complexed to Protein Tyrosine Kinases

    Microsoft Academic Search

    Irena Stefanova; Vaclav Horejsi; Ignacio J. Ansotegui; Walter Knapp; Hannes Stockinger

    1991-01-01

    Binding of ligand or antibody to certain cell-surface proteins that are anchored to the membrane by glycophosphatidylinositol (GPI) can cause activation of leukocytes. However, it is not known how these molecules, which lack intracellular domains, can transduce signals. The GPI-linked human molecules CD59, CD55, CD48, CD24, and CD14 as well as the mouse molecules Thy-1 and Ly-6 were found to

  4. Dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in ?-?(2) :?(1) :?(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

    2015-02-01

    Two series of new dinuclear rare-earth metal alkyl complexes supported by indolyl ligands in novel ?-?(2) :?(1) :?(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-[(?-?(2) :?(1) :?(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 ?-?(2) :?(1) :?(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-[(?-?(2) :?(1) :?(1) -3-{tBuNCH2 }Ind)Yb(thf)(CH2 SiMe3 )]2 (major) and cis-[(?-?(2) :?(1) :?(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. PMID:25490879

  5. Hindsight bias as a function of anchor distance and anchor plausibility

    Microsoft Academic Search

    Oliver Hardt; Rüdiger Pohl

    2003-01-01

    This study explored the influence of anchor distance on hindsight bias and how the subjective plausibility of different anchors moderates this relation. In addition to the standard memory design used in hindsight bias research, participants were asked to indicate the range of values for possible answers to difficult almanac questions. Varying anchor distance on the basis of each participant's individual

  6. FRP-to-concrete joint assemblages anchored with multiple FRP anchors

    Microsoft Academic Search

    H. W. Zhang; S. T. Smith

    Mechanical anchorage can enhance the strain capacity of externally bonded fibre-reinforced polymer (FRP) composite plates which are used for the strengthening of concrete members. Anchors made from FRP, which are known as FRP anchors or spike anchors, are an effective anchorage because they can be applied to a wide variety of FRP-strengthened structural elements such as beams and slabs. Limited

  7. Anchored Instruction and Anchored Assessment: An Ecological Approach to Measuring Situated Learning.

    ERIC Educational Resources Information Center

    Young, Michael F.; Kulikowich, Jonna M.

    Anchored instruction and anchored assessment are described and illustrated through a mathematics problem from the Jasper problem solving series developed at Vanderbilt University in Nashville (Tennessee). Anchored instruction is instruction situated in a context complex enough to provide meaning and reasons for why information is useful. Problems…

  8. A-kinase Anchoring Protein 79/150 Recruits Protein Kinase C to Phosphorylate Roundabout Receptors.

    PubMed

    Samelson, Bret K; Gore, Bryan B; Whiting, Jennifer L; Nygren, Patrick J; Purkey, Alicia M; Colledge, Marcie; Langeberg, Lorene K; Dell'Acqua, Mark L; Zweifel, Larry S; Scott, John D

    2015-05-29

    Anchoring proteins direct protein kinases and phosphoprotein phosphatases toward selected substrates to control the efficacy, context, and duration of neuronal phosphorylation events. The A-kinase anchoring protein AKAP79/150 interacts with protein kinase A (PKA), protein kinase C (PKC), and protein phosphatase 2B (calcineurin) to modulate second messenger signaling events. In a mass spectrometry-based screen for additional AKAP79/150 binding partners, we have identified the Roundabout axonal guidance receptor Robo2 and its ligands Slit2 and Slit3. Biochemical and cellular approaches confirm that a linear sequence located in the cytoplasmic tail of Robo2 (residues 991-1070) interfaces directly with sites on the anchoring protein. Parallel studies show that AKAP79/150 interacts with the Robo3 receptor in a similar manner. Immunofluorescent staining detects overlapping expression patterns for murine AKAP150, Robo2, and Robo3 in a variety of brain regions, including hippocampal region CA1 and the islands of Calleja. In vitro kinase assays, peptide spot array mapping, and proximity ligation assay staining approaches establish that human AKAP79-anchored PKC selectively phosphorylates the Robo3.1 receptor subtype on serine 1330. These findings imply that anchored PKC locally modulates the phosphorylation status of Robo3.1 in brain regions governing learning and memory and reward. PMID:25882844

  9. Pyrazolate-Bridging Dinucleating Ligands Containing Hydrogen-Bond Donors: Synthesis and Structure of Their Cobalt Analogues

    E-print Network

    Hendrich, Mike

    Pyrazolate-Bridging Dinucleating Ligands Containing Hydrogen-Bond Donors: Synthesis and Structure to new urea-pyrazolate dinucleating ligands are described. Metal complexes of these ligands have hydrogen

  10. Resin reinforced expansion anchor system

    SciTech Connect

    Clark, C.A.; Wright, R.L.

    1988-08-16

    An expansion anchor assembly is described in combination with a dual compartment resin and cartridge inserted into a mine roof opening, the anchor assembly including: (a) an elongated bolt having a head at one end and threaded for a portion of its length at the other end; (b) an expansion member engaged with the threaded end of the bolt; (c) the expansion member including an expansion shell having a plurality of leaf segments; (d) a first means for engaging the expansion shell with the elongated bolt; (e) a wedge threaded on the elongated bolt for engagement with the expansion shell to urge the latter into gripping engagement with the mine roof; (f) a first resin passageway means on the outer surface of the wedge for permitting resin to gravitate therethrough; (g) the leaf segments of the expansion shell being separated to form a second resin passageway means aligned with the first resin passageway means, whereby resin may gravitate downwardly through substantially the entire length of the assembly, and (h) a second means within the first passageway and engageable with one of the leaf segments to prevent relative rotation of the wedge member with respect to the expansion shell; (i) the resin being mixed upon rotation of the bolt and expansion member and gravitating downwardly through the first and second passageway means into engagement with that portion of the mine roof defining the mine roof opening.

  11. Upper bound analysis for drag anchors in soft clay

    E-print Network

    Kim, Byoung Min

    2007-04-25

    parameter studies were carried out varying the properties of the anchor, anchor line, and soil. The UBM show good agreement with six full-scale tests covering several different anchor types and centrifuge model tests....

  12. Crossed ring anchored disk resonator for self-alignment of the anchor.

    PubMed

    Baghelani, Masoud; Ghavifekr, Habib Badri; Ebrahimi, Afshin

    2014-01-01

    Misalignment is a problematic challenge in RF MEMS resonators. It causes asymmetry in the ultra symmetric radial contour mode disk resonators and degrades their performance by increasing the insertion loss and decreasing their quality factors (Q). Self-alignment method seems to be a good solution for misalignment problem, but it cannot be directly applied on high performance ring shape anchored resonators. This paper discusses misalignment effects for the ring shape anchored resonators and proposes a method for reconfiguring its anchor to be compatible with self-alignment process. Simulation results validate that the crossed ring anchor structure has the same resonance characteristics with the complete ring shape anchored resonator. PMID:25685477

  13. Large-ring chain and sheet polymeric metal complexes of extended-reach siloxypyridine ligands of type O[ iPr 2SiO(CH 2) n py] 2

    Microsoft Academic Search

    David M. L Goodgame; Paul D Lickiss; Stephanie J Rooke; Andrew J. P White; David J Williams

    2003-01-01

    The preparations are reported of a range of metal complexes of Mn(II), Co(II), Ni(II) and Zn(II) with the ‘extended reach’ ligands O[iPr2SiO(CH2)npy]2 (n=0, 1 or 3, I–III) and with Cu(II), Cd(II) and Ag(I) for II; six of them have been shown by X-ray studies to have polymeric structures. The compounds M[O(iPr2SiOpy)2]2Cl2 (M=Co, Cu) form chains of 24-membered macrocycles, as does

  14. Anchor Nodes Placement for Effective Passive Localization

    E-print Network

    Akl, Robert

    Anchor Nodes Placement for Effective Passive Localization Robert Akl, Karthik Pasupathy Department after deployment. Localization is a process used to locate sensor nodes' positional coordinates, which is vital information. The localization is generally assisted by anchor nodes that are also sensor nodes

  15. Research Article The Anchoring-and-Adjustment

    E-print Network

    used to explain such diverse phenomena as preference reversals, the hindsight bias, subadditivity intuitive judgments, and insufficient adjustment is commonly in- voked to explain judgmental biases. However, despite extensive research on anchoring effects, evidence for adjustment-based anchoring biases has only

  16. Anchoring of proteins to lactic acid bacteria

    Microsoft Academic Search

    Girbe Buist; Kees Leenhouts; Jan Kok

    1999-01-01

    The anchoring of proteins to the cell surface of lactic acid bacteria (LAB) using genetic techniques is an exciting and emerging research area that holds great promise for a wide variety of biotechnological applications. This paper reviews five different types of anchoring domains that have been explored for their efficiency in attaching hybrid proteins to the cell membrane or cell

  17. Smart FBG-based FRP anchor

    Microsoft Academic Search

    Zhi Zhou; Zhichun Zhang; Chuan Wang; Jinping Ou

    2006-01-01

    FRP ( Fiber Reinforced Polymer ) has become the popular material to alternate steel in civil engineering under harsh corrosion environment. But due to its low shear strength ability, the anchor for FRP is most important for its practical application. However, the strain state of the surface between FRP and anchor is not fully understood due to that there is

  18. Anchoring International sets new water depth record

    Microsoft Academic Search

    1983-01-01

    Santa Barbara Channel has a history steeped in firsts in techniques for the production of offshore oil. Landscaped drilling and production islands, production piers, and directional drilling from land rigs to production under the channel, to name a few. The latest such project was handled by Anchoring International, Inc., a pipe line anchoring company headquartered in Houston, Texas. Contracted by

  19. Knowledge Representation and Reasoning for Perceptual Anchoring

    Microsoft Academic Search

    Jonas Melchert; Silvia Coradeschi; Amy Loutfi

    2007-01-01

    In this work we report results on the use of symbolic knowledge representation and reasoning (KRR) for percep- tual anchoring. This is the creation and maintenance of a connection between symbolic and perceptual description that refer to the same physical object in the environment. We extend an anchoring framework to manage the symbolic information in a KRR system, and to

  20. The effect of accuracy motivation on anchoring and adjustment: do people adjust from provided anchors?

    PubMed

    Simmons, Joseph P; LeBoeuf, Robyn A; Nelson, Leif D

    2010-12-01

    Increasing accuracy motivation (e.g., by providing monetary incentives for accuracy) often fails to increase adjustment away from provided anchors, a result that has led researchers to conclude that people do not effortfully adjust away from such anchors. We challenge this conclusion. First, we show that people are typically uncertain about which way to adjust from provided anchors and that this uncertainty often causes people to believe that they have initially adjusted too far away from such anchors (Studies 1a and 1b). Then, we show that although accuracy motivation fails to increase the gap between anchors and final estimates when people are uncertain about the direction of adjustment, accuracy motivation does increase anchor-estimate gaps when people are certain about the direction of adjustment, and that this is true regardless of whether the anchors are provided or self-generated (Studies 2, 3a, 3b, and 5). These results suggest that people do effortfully adjust away from provided anchors but that uncertainty about the direction of adjustment makes that adjustment harder to detect than previously assumed. This conclusion has important theoretical implications, suggesting that currently emphasized distinctions between anchor types (self-generated vs. provided) are not fundamental and that ostensibly competing theories of anchoring (selective accessibility and anchoring-and-adjustment) are complementary. PMID:21114351

  1. Hindsight bias as a function of anchor distance and anchor plausibility.

    PubMed

    Hardt, Oliver; Pohl, Rüdiger F

    2003-01-01

    This study explored the influence of anchor distance on hindsight bias and how the subjective plausibility of different anchors moderates this relation. In addition to the standard memory design used in hindsight bias research, participants were asked to indicate the range of values for possible answers to difficult almanac questions. Varying anchor distance on the basis of each participant's individual range of possible answers showed (1) that anchor plausibility decreased with increasing anchor distance following a non-linear monotone function, (2) that size of hindsight bias initially increased with increasing anchor distance but, from a certain distance, started to decrease, and (3) that hindsight bias was found to be always higher for plausible than for implausible anchors. PMID:14562869

  2. A New Six-Connected Double-Layer MetalOrganic Framework Directed by Carboxylate and N-Containing Donor Co-Ligands

    Microsoft Academic Search

    Jian-Qiang Liu

    2011-01-01

    A new polymer, [Co(fipbb)(bpt).DMF]n (1) (H2fipbb = 4,4?-(hexafluoroisopropylidene)bis(benzoic acid) and bpt = 2,5-bis (4-pyridyl)-1,3,4-thiadiazole), has been synthesized and characterized. The polymer presents a two-dimensional (2D) bilayer structure containing dimeric [Co2(COO)4] units. In the 2D network, each Co(II) atom is coordinated by four carboxylate oxygen atoms from three different fipbb ligands and two nitrogen atoms from two bpt ligands. The thermogravimetric

  3. The structures of the isomorphous potassium and rubidium salts of 4-nitrobenzoic acid and an overview of the metal complex stereochemistries of the alkali metal salt series with this ligand.

    PubMed

    Smith, Graham

    2015-06-01

    4-Nitrobenzoic acid (PNBA) has proved to be a useful ligand for the preparation of metal complexes but the known structures of the alkali metal salts of PNBA do not include the rubidium salt. The structures of the isomorphous potassium and rubidium polymeric coordination complexes with PNBA, namely poly[?2-aqua-aqua-?3-(4-nitrobenzoato)-potassium], [K(C7H4N2O2)(H2O)2]n, (I), and poly[?3-aqua-aqua-?5-(4-nitrobenzoato)-rubidium], [Rb(C7H4N2O2)(H2O)2]n, (II), have been determined. In (I), the very distorted KO6 coordination sphere about the K(+) centres in the repeat unit comprise two bridging nitro O-atom donors, a single bridging carboxylate O-atom donor and two water molecules, one of which is bridging. In Rb complex (II), the same basic MO6 coordination is found in the repeat unit, but it is expanded to RbO9 through a slight increase in the accepted Rb-O bond-length range and includes an additional Rb-Ocarboxylate bond, completing a bidentate O,O'-chelate interaction, and additional bridging Rb-Onitro and Rb-Owater bonds. The comparative K-O and Rb-O bond-length ranges are 2.7352?(14)-3.0051?(14) and 2.884?(2)-3.182?(2)?Å, respectively. The structure of (II) is also isomorphous, as well as isostructural, with the known structure of the nine-coordinate caesium 4-nitrobenzoate analogue, (III), in which the Cs-O bond-length range is 3.047?(4)-3.338?(4)?Å. In all three complexes, common basic polymeric extensions are found, including two different centrosymmetric bridging interactions through both water and nitro groups, as well as extensions along c through the para-related carboxylate group, giving a two-dimensional structure in (I). In (II) and (III), three-dimensional structures are generated through additional bridges involving the nitro and water O atoms. In all three structures, the two water molecules are involved in similar intra-polymer O-H...O hydrogen-bonding interactions to both carboxylate and water O-atom acceptors. A comparison of the varied coordination behaviour of the full set of Li-Cs salts with 4-nitrobenzoic acid is also made. PMID:26044333

  4. Metal flux and dynamic speciation at (bio)interfaces. Part V: The roles of simple, fulvic and aggregate complexes on Pb flux in freshwater ligand mixtures, computed at planar consuming interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Zeshi; Buffle, Jacques

    2009-03-01

    The computations of metal flux in aquatic systems, at consuming interfaces like oganism membranes are of major importance in ecotoxicology and dynamic risk assessment. In this paper, the flux of Pb(II), at a planar consuming interface in natural waters, is studied. The system includes (a) simple ligands (OH -, CO32-); (b) fulvics and (c) aggregates, as complexants, i.e. those which may play the major roles in controlling the metal flux in aquatic media. The effects of various physico-chemical factors, in particular, the diffusion layer thickness, the stability constants of fulvic and aggregate complexes, the complexing site distribution of fulvics and the size distribution of aggregates, are studied in details.

  5. Synthesis and characterization of a series of transition metal complexes with a new symmetrical polyoxaaza macroacyclic Schiff base ligand: X-ray crystal structure of cobalt(II) and nickel(II) complexes and their antibacterial properties.

    PubMed

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Valencia, Laura

    2013-01-15

    A new symmetrical [N4O2] hexadentate Schiff base ligand, (E)-N-(pyridin-2-ylmethylene)-2-(3-(2-((E)-pyridin-2-lmethyleneamino)phenoxy)naphthalen-2-yloxy)benzenamine, abbreviated to L, and its complexes of Ni(II), Cu(II), Zn(II), Co(II), Cd(II) and Mn(II) have been synthesized in the presence of metal ions. The complexes were structurally characterized by elemental analyses, IR, UV-Vis, NMR and molar conductivity. The crystal structures of two complexes, [NiL(ONO2)2]·2H2O and [CoLCl2]CH3OH·0.5H2O, have been determined by a single crystal X-ray diffraction study. In these complexes, the ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms. The metal ions complete their six coordination with two coordinated nitrate or chloride ions, forming a distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epid and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The activity data show that the complexes are more potent antibacterials than the parent Schiff base. PMID:23099161

  6. 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. PMID:25325719

  7. Synthesis, Characterization, Antioxidant, and Antibacterial Studies of Some Metal(II) Complexes of Tetradentate Schiff Base Ligand: (4E)-4-[(2-{(E)-[1-(2,4-Dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one

    PubMed Central

    Ejidike, Ikechukwu P.; Ajibade, Peter A.

    2015-01-01

    Co(II), Ni(II), Cu(II), and Zn(II) complexes of (4E)-4-[(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one have been synthesized and characterized by elemental analyses, molar conductance, electronic and IR spectral studies, and XRD. FTIR confirmed the ligand coordinates the metal ion to form mononuclear complex via the oxygen and nitrogen atoms of the phenolic group and azomethine group, respectively. Tetrahedral geometry is proposed for Co(II) complex and square-planar geometry for Ni(II) and Cu(II) complexes. The antibacterial studies of the compounds were determined and they show that the metal complexes are more active than the free ligands. The antioxidant activity by DPPH and ABTS method was examined and it shows Cu(II); IC50 = 2.31 ± 1.54?µM for DPPH and Co(II); IC50 = 1.83 ± 1.08?µM for ABTS were the most active.

  8. Synthesis and spectroscopic studies of homo-binuclear, alkoxo bridged homo- and hetero-tetranuclear metal complexes of a bis-N2O4 Schiff base ligand derived from ethanolamine and macroacyclic tetranaphthaldehyde.

    PubMed

    Karao?lu, Kaan; Baran, Talat; De?irmencio?lu, Ismail; Serbest, Kerim

    2011-09-01

    Three new homo-binuclear Ni(II), Cu(II), Zn(II) complexes (2-4), homo-tetranuclear Cu(II) complex (5), and hetero-tetranuclear Cu(II)-Ni(II) complex (6) of a macroacyclic potentially bis-hexadentate N2O4 Schiff base have been synthesized. The imino-alcohol ligand, H4L was obtained by the condensation of ethanolamine with 2,2'-[2,3-bis(1-formyl-2-naphthyloxymethyl)-but-2-ene-1,4-diyldioxy]bis(naphthalene-1-carbaldehyde). The structures of both the Schiff base and its complexes have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The ligand has two similar compartments to bind first primary two metal ions, and acts bi- or tetra-negative, bis-tetradentate forming five membered chelate ring. However, secondary two metal ions (either Cu2+ or Ni2+) are ligated with dianionic oxygen atoms of the alcohol groups and are linked to the 1,10-phenanthroline-nitrogen atoms in the tetranuclear complexes (5 and 6). PMID:21550297

  9. Synthesis and spectroscopic studies of homo-binuclear, alkoxo bridged homo- and hetero-tetranuclear metal complexes of a bis-N 2O 4 Schiff base ligand derived from ethanolamine and macroacyclic tetranaphthaldehyde

    NASA Astrophysics Data System (ADS)

    Karao?lu, Kaan; Baran, Talat; De?irmencio?lu, ?smail; Serbest, Kerim

    2011-09-01

    Three new homo-binuclear Ni(II), Cu(II), Zn(II) complexes ( 2-4), homo-tetranuclear Cu(II) complex ( 5), and hetero-tetranuclear Cu(II)-Ni(II) complex ( 6) of a macroacyclic potentially bis-hexadentate N 2O 4 Schiff base have been synthesized. The imino-alcohol ligand, H 4L was obtained by the condensation of ethanolamine with 2,2'-[2,3-bis(1-formyl-2-naphthyloxymethyl)-but-2-ene-1,4-diyldioxy]bis(naphthalene-1-carbaldehyde). The structures of both the Schiff base and its complexes have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The ligand has two similar compartments to bind first primary two metal ions, and acts bi- or tetra-negative, bis-tetradentate forming five membered chelate ring. However, secondary two metal ions (either Cu 2+ or Ni 2+) are ligated with dianionic oxygen atoms of the alcohol groups and are linked to the 1,10-phenanthroline-nitrogen atoms in the tetranuclear complexes ( 5 and 6).

  10. Synlett 2001 No. 3, 391393 ISSN 0936-5214 Thieme Stuttgart New York New Bifunctional Chelating Phosphine Ligands for Immobilization of Metal

    E-print Network

    Bluemel, Janet

    , and recycle, are much easier to tailor and fine tune than heterogeneous catalysts, and remain as active and se detach from the phosphine linkers, if the catalyst is recycled.6 In order to attach the complexes firmly Achiwa's important work on highly efficient chiral bisphosphine ligands in rhodi- um-catalyzed asymmetric

  11. A highly robust metal-organic framework based on an aromatic 12-carboxyl ligand with highly selective adsorption of CO2 over CH4.

    PubMed

    He, Hongming; Song, Yang; Zhang, Chuanqi; Sun, Fuxing; Yuan, Rongrong; Bian, Zheng; Gao, Lianxun; Zhu, Guangshan

    2015-05-26

    A highly robust MOF based on a 12-carboxyl dendritic aromatic ligand and two Cd clusters is successfully synthesized. This activated MOF exhibits high heat of absorption of CO2 and highly selective adsorption of CO2 over CH4. Especially, a new type of topology () is presented. PMID:25959840

  12. Method and apparatus for anchoring roof bolts

    SciTech Connect

    Hipkins, E.C.; Locotos, F.M.; Comfort, J.D.

    1987-04-07

    This patent describes an anchor bolt assembly of the type used in mine roofs and the like in which the anchor bolt assembly is positioned in a bore hole of a rock formation. The bolt assembly includes an elongated bolt shaft with a head on one end and threads on the other end, and with a mechanical expansion anchor including a spreader on the threaded end. A quick-setting resin cartridge is positioned in the bore hole above the threaded end of the bolt shaft. The anchor bolt assembly is secured to the rock formation by both the expansion anchor and the quick-setting resin. The improvement described here comprises a stop connected to the bolt shaft immediately below the expansion anchor and an elongated helical coil having an upper end attached to the stop and positioned external of and surrounding a substantial length along the bolt shaft. The coil has a direction of coil so as to urge resin upwardly toward the threaded end while the spreader moves downwardly and while the bolt shaft is rotated in one continuous direction to achieve mixing of the resin and to secure the mechanical anchor to the rock formation.

  13. Polymerization catalysts containing electron-withdrawing amide ligands

    DOEpatents

    Watkin, John G. (Los Alamos, NM); Click, Damon R. (Bloomington, IN)

    2002-01-01

    The present invention describes methods of making a series of amine-containing organic compounds which are used as ligands for group 3-10 and lanthanide metal compounds. The ligands have electron-withdrawing groups bonded to them. The metal compounds, when combined with a cocatalyst, are catalysts for the polymerization of olefins.

  14. Auger anchors produce major cost savings

    SciTech Connect

    Webb, B.C.

    1981-10-01

    To meet specific-gravity standards, a 42-in.-diam, 0.598-in.-wall-thickness pipeline being installed in a glacial area full of potholes, peat swamps, and low-lying sections required 425 lb/ft of anchor hold-down. In spots where the underlying soil had an acceptable shear strength, the crew installed auger anchors (costing only $8/ft of pipeline) instead of the concrete set-on weights (at $80/ft) required in areas where the auger anchors would not hold; the savings amounted to about $380,000/mile of line laid.

  15. Strength of anchor bolts in masonry

    NASA Astrophysics Data System (ADS)

    Whitlock, A. R.; Brown, R. H.

    1983-08-01

    The strength properties of bent bar bolts in masonry were evaluated. The variables studied include bolt size, loading direction, embedment substrate, and bolt location. It is found that bolt strength increases with bolt size up to the point where failure is controlled by masonry strength. The loading direction, substrate, and location of bolts are shown to be significant factors in the strength of anchors. Previously developed empirical and analytical design equations for anchor bolts in reinforced concrete and masonry are investigated and compared to the study results. The equations are found to accurately predict the mean strengths of anchor bolts.

  16. Spectroscopic and biological studies of new binuclear metal complexes of a tridentate ONS hydrazone ligand derived from 4-amino-6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one and 4,6-diacetylresorcinol

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.; Emara, Adel A. A.

    2014-11-01

    The binuclear hydrazone, H2L, ligand derived from 4-amino-6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one and 4,6-diacetylresorcinol, in the molar ratio 2:1, and its copper(II), nickel(II), cobalt(II), zinc(II), cadmium(II), cerium(III), iron(III), oxovanadium(IV) and dioxouranium(VI) complexes have been synthesized. Structures of the ligand and its metal complexes were characterized by elemental analyses, spectral (infrared, electronic, mass, 1H NMR and ESR) data, magnetic susceptibility, molar conductivity measurements and thermal gravimetric analysis (TGA). The ligand acts as dibasic with two ONS tridentate sites. The bonding sites are the azomethine nitrogen, phenolate oxygen and sulfur atoms. The metal complexes exhibit different geometrical arrangements such as square planer, tetrahedral and octahedral. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. The ligand and its metal complexes showed antimicrobial activity towards Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus). Structural parameters of the ligand and its metal complexes were theoretically computed on the basis of semiempirical PM3 level, and the results were correlated with their experimental data.

  17. Spectroscopic and biological studies of new binuclear metal complexes of a tridentate ONS hydrazone ligand derived from 4-amino-6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one and 4,6-diacetylresorcinol.

    PubMed

    Adly, Omima M I; Emara, Adel A A

    2014-11-11

    The binuclear hydrazone, H2L, ligand derived from 4-amino-6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one and 4,6-diacetylresorcinol, in the molar ratio 2:1, and its copper(II), nickel(II), cobalt(II), zinc(II), cadmium(II), cerium(III), iron(III), oxovanadium(IV) and dioxouranium(VI) complexes have been synthesized. Structures of the ligand and its metal complexes were characterized by elemental analyses, spectral (infrared, electronic, mass, 1H NMR and ESR) data, magnetic susceptibility, molar conductivity measurements and thermal gravimetric analysis (TGA). The ligand acts as dibasic with two ONS tridentate sites. The bonding sites are the azomethine nitrogen, phenolate oxygen and sulfur atoms. The metal complexes exhibit different geometrical arrangements such as square planer, tetrahedral and octahedral. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. The ligand and its metal complexes showed antimicrobial activity towards Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus). Structural parameters of the ligand and its metal complexes were theoretically computed on the basis of semiempirical PM3 level, and the results were correlated with their experimental data. PMID:24858350

  18. The biotic ligand model: a historical overview

    Microsoft Academic Search

    Paul R. Paquin; Joseph W. Gorsuch; Simon Apte; Graeme E. Batley; Karl C. Bowles; Peter G. C. Campbell; Charles G. Delos; Dominic M. Di Toro; Robert L. Dwyer; Fernando Galvez; Robert W. Gensemer; Gregory G. Goss; Christer Hogstrand; Colin R. Janssen; James C. McGeer; Rami B. Naddy; Richard C. Playle; Robert C. Santore; Uwe Schneider; William A. Stubblefield; Chris M. Wood; Kuen Benjamin Wu

    2002-01-01

    During recent years, the biotic ligand model (BLM) has been proposed as a tool to evaluate quantitatively the manner in which water chemistry affects the speciation and biological availability of metals in aquatic systems. This is an important consideration because it is the bioavailability and bioreactivity of metals that control their potential to cause adverse effects. The BLM approach has

  19. Numerical modelling of anchor bolts under pullout and relaxation tests

    Microsoft Academic Search

    F. Delhomme; G. Debicki

    2010-01-01

    The anchoring of structure elements in a reinforced concrete foundation is often performed by means of cast-in-place anchors. Their main function is to transfer normal loads, tension and compression, and possible shear loads according to the force transferred to the base of the structure. This study is limited to the study of long and smooth anchor rods with an anchor

  20. The Use of Comics-Based Cases in Anchored Instruction

    ERIC Educational Resources Information Center

    Kneller, Matthew F.

    2009-01-01

    The primary purpose of this research was to understand how comics fulfill the role of anchor in an anchored instruction learning environment. Anchored instruction addresses the inert knowledge problem through the use of realistic multimedia stories, or "anchors," that embed a problem and the necessary data to solve it within the narrative. In the…

  1. A New Series of Complexes Possessing Rare “Tertiary” Sulfonamide Nitrogen-to-Metal Bonds of Normal Length: fac-[Re(CO)3(N(SO2R)dien)]PF6 Complexes with Hydrophilic Sulfonamide Ligands

    PubMed Central

    Abhayawardhana, Pramuditha L.; Marzilli, Patricia A.; Fronczek, Frank R.

    2014-01-01

    Tertiary sulfonamide nitrogen-to-metal bonds of normal length are very rare. We recently discovered such a bond in one class of fac-[Re(CO)3(N(SO2R)(CH2Z)2)]n complexes (Z = 2-pyridyl) with N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). fac-[M(CO)3(N(SO2R)(CH2Z)2)]n agents (M = 186/188Re, 99mTc) could find use as radiopharmaceutical bioconjugates when R is a targeting moiety. However, the planar, electron-withdrawing 2-pyridyl groups of N(SO2R)dpa destabilize the ligand to base and create relatively rigid chelate rings, raising the possibility that the rare M– N(sulfonamide) bond is an artifact of a restricted geometry. Also, the hydrophobic 2-pyridyl groups could cause undesirable accumulation in the liver, limiting future use in radiopharmaceuticals. Our goal is to identify a robust, hydrophilic, and flexible N(CH2Z)2 chelate framework. New C2-symmetric ligands, N(SO2R)(CH2Z)2 with (Z = CH2NH2; R = Me, dmb, or tol), were prepared by treating N(H)dien(Boc)2, a protected diethylenetriamine (N(H)dien) derivative, with methanesulfonyl chloride (MeSO2Cl), 3,5-dimethylbenzenesulfonyl chloride (dmbSO2Cl), and 4-methylbenzenesulfonyl chloride (tolSO2Cl). Treatment of fac-[Re(CO)3(H2O)3]+ with these ligands, designated as N(SO2R)dien, afforded new fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes. Comparing the fac-[Re(CO)3(N(SO2Me)dien)]PF6 and fac-[Re(CO)3(N(SO2Me)dpa)]PF6 complexes, we find that the ReI–N(sulfonamide) bonds are normal in length and statistically identical and that the methyl 13C NMR signal has an unusually upfield shift compared to that in the free ligand. We attribute this unusual upfield shift to the fact that the sulfonamide N undergoes an sp2-to-sp3 rehybridization upon coordination to ReI in both complexes. Thus, the sulfonamide N of N(SO2R)dien ligands is a good donor, even though the chelate rings are conformationally flexible. Addition of the strongly basic and potentially monodentate ligand, 4-dimethylaminopyridine, did not affect the fac-[Re(CO)3(N(SO2tol)dien)]PF6 complex, even after several weeks. This complex is also stable to heat in aqueous solution. These results indicate that N(SO2R)dien ligands form fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes sufficiently robust to be utilized for radiopharmaceutical development. PMID:24400928

  2. Complexes possessing rare "tertiary" sulfonamide nitrogen-to-metal bonds of normal length: fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes with hydrophilic sulfonamide ligands.

    PubMed

    Abhayawardhana, Pramuditha L; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

    2014-01-21

    Tertiary sulfonamide nitrogen-to-metal bonds of normal length are very rare. We recently discovered such a bond in one class of fac-[Re(CO)3(N(SO2R)(CH2Z)2)](n) complexes (Z = 2-pyridyl) with N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). fac-[M(CO)3(N(SO2R)(CH2Z)2)](n) agents (M = (186/188)Re, (99m)Tc) could find use as radiopharmaceutical bioconjugates when R is a targeting moiety. However, the planar, electron-withdrawing 2-pyridyl groups of N(SO2R)dpa destabilize the ligand to base and create relatively rigid chelate rings, raising the possibility that the rare M-N(sulfonamide) bond is an artifact of a restricted geometry. Also, the hydrophobic 2-pyridyl groups could cause undesirable accumulation in the liver, limiting future use in radiopharmaceuticals. Our goal is to identify a robust, hydrophilic, and flexible N(CH2Z)2 chelate framework. New C2-symmetric ligands, N(SO2R)(CH2Z)2 with (Z = CH2NH2; R = Me, dmb, or tol), were prepared by treating N(H)dien(Boc)2, a protected diethylenetriamine (N(H)dien) derivative, with methanesulfonyl chloride (MeSO2Cl), 3,5-dimethylbenzenesulfonyl chloride (dmbSO2Cl), and 4-methylbenzenesulfonyl chloride (tolSO2Cl). Treatment of fac-[Re(CO)3(H2O)3](+) with these ligands, designated as N(SO2R)dien, afforded new fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes. Comparing the fac-[Re(CO)3(N(SO2Me)dien)]PF6 and fac-[Re(CO)3(N(SO2Me)dpa)]PF6 complexes, we find that the Re(I)-N(sulfonamide) bonds are normal in length and statistically identical and that the methyl (13)C NMR signal has an unusually upfield shift compared to that in the free ligand. We attribute this unusual upfield shift to the fact that the sulfonamide N undergoes an sp(2)-to-sp(3) rehybridization upon coordination to Re(I) in both complexes. Thus, the sulfonamide N of N(SO2R)dien ligands is a good donor, even though the chelate rings are conformationally flexible. Addition of the strongly basic and potentially monodentate ligand, 4-dimethylaminopyridine, did not affect the fac-[Re(CO)3(N(SO2tol)dien)]PF6 complex, even after several weeks. This complex is also stable to heat in aqueous solution. These results indicate that N(SO2R)dien ligands form fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes sufficiently robust to be utilized for radiopharmaceutical development. PMID:24400928

  3. Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

    NASA Technical Reports Server (NTRS)

    Miskowski, Vincent M.; Houlding, Virginia H.

    1989-01-01

    Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

  4. Tightening procedures for large diameter anchor bolts 

    E-print Network

    Abraham, Ryan Charles

    1997-01-01

    judgment concerning how tight to tighten the nuts on the anchor bolt system. Recent bolt failures have raised concerns about nut tightening procedures. When the nuts of a double nut system are not tightened sufficiently, fatigue loading, and even impact...

  5. 50 CFR 622.432 - Anchoring restriction.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ...ADMINISTRATION, DEPARTMENT OF COMMERCE FISHERIES OF THE CARIBBEAN, GULF OF MEXICO, AND SOUTH ATLANTIC Reef Fish Fishery of Puerto Rico and the U.S. Virgin Islands § 622.432 Anchoring restriction. (a) The owner or...

  6. 50 CFR 622.432 - Anchoring restriction.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ...ADMINISTRATION, DEPARTMENT OF COMMERCE FISHERIES OF THE CARIBBEAN, GULF OF MEXICO, AND SOUTH ATLANTIC Reef Fish Fishery of Puerto Rico and the U.S. Virgin Islands § 622.432 Anchoring restriction. (a) The owner or...

  7. Oblique anchoring at a free nematic surface

    NASA Astrophysics Data System (ADS)

    Braun, F. N.; Sluckin, T. J.; Velasco, E.; Mederos, L.

    1996-01-01

    We generalize earlier density functional theories of the interface between an ordered nematic liquid crystal and its vapor to consider oblique anchoring. This is achieved by including a term with the symmetry of the electrostatic quadrupole in the model molecular interaction potential. As the bulk triple point of the liquid crystal is approached, the model exhibits the second-order oblique to homeotropic anchoring transition observed experimentally by Chiarelli et al. The result constitutes a thermodynamically consistent demonstration of this phenomenon using a microscopic theory. We plot the relevant anchoring phase diagrams, and compare them with constrained treatments of the density functional. By means of this comparison we assess to what extent the commonly adopted strategy of decoupling interfacial structure from anchoring is justified.

  8. Why Is There an “Inert” Metal Center in the Active Site of Nitrile Hydratase? Reactivity and Ligand Dissociation from a Five-Coordinate Co(III) Nitrile Hydratase Model

    PubMed Central

    Shearer, Jason; Kung, Irene Y.; Lovell, Scott; Kaminsky, Werner; Kovacs, Julie A.

    2015-01-01

    To determine how a substitutionally inert metal can play a catalytic role in the metalloenzyme nitrile hydratase (NHase), a reactive five-coordinate CoIII thiolate complex ([CoIII(S2Me2N3(Pr,Pr))](PF6) (1)) that resembles the active site of cobalt containing nitrile hydratase (Co NHase) was prepared. This was screened for reactivity, by using low-temperature electronic absorption spectroscopy, toward a number of biologically relevant “substrates”. It was determined 1 will react with azide, thiocyanate, and ammonia, but is unreactive toward nitriles, NO, and butyrate. Substrate-bound 1 has similar spectroscopic and structural properties as [CoIII(ADIT2)](PF6) (2). Complex 2 is a six-coordinate CoIII complex containing cis-thiolates and imine nitrogens, and has properties similar to the cobalt center of Co NHase. Substrate binding to 1 is reversible and temperature-dependent, allowing for the determination of the thermodynamic parameters of azide and thiocyanate binding and the rates of ligand dissociation. Azide and thiocyanate bind trans to a thiolate, and with similar entropies and enthalpies (thiocyanate: ?H = ?7.5 ± 1.1 kcal/mol, ?S = ?17.2 ± 3.2 eu; azide: ?H = ?6.5 ± 1.0 kcal/mol, ?S = ?12.6 ± 2.4 eu). The rates of azide and thiocyanate displacement from the metal center are also comparable to one another (kd = (7.22 ± 0.04) × 10?1 s?1 for thiocyanate and kd = 2.14 ± 0.50) × 10?2 s?1 for azide), and are considerably faster than one would expect for a low-spin d6 six-coordinate CoIII complex. These rates are comparable to those of an analogous Fe(III) complex, demonstrating that Co(III) and Fe(III) react at comparable rates when in this ligand environment. This study therefore indicates that ligand displacement from a low-spin CoIII center in a ligand environment that resembles NHase is not prohibitivly slow so as to disallow catalytic action in nonredox active cobalt metalloenzymes. PMID:11456548

  9. SYNTHESIS, CHARACTERIZATION, ANTIMICROBIAL AND CYTOTOXIC STUDIES ON SOME NOVEL TRANSITION METAL COMPLEXES OF SCHIFF BASE LIGAND DERIVED FROM SULFADIAZINE WITH MOLECULAR ORBITAL CALCULATIONS

    Microsoft Academic Search

    Badr A. Elsayed; A. A. Elhenawy

    2014-01-01

    Some selected solid complexes of the Schiff base ligand HL derived from Sulfadiazine with Co(II), Ni(II) and Cu(II) ions were synthesized and characterized by Micro-analysis, FTIR, Electronic, Mass, and ESR Spectral Analyses, Magnetic susceptibility and Molar Conductance Measurements. The disappearance of ?(O-H) hydroxyl band of the phenolic and the lowering shift of the stretching frequency of the ?(CH=N) azomethine band

  10. Current state of laser synthesis of metal and alloy nanoparticles as ligand-free reference materials for nano-toxicological assays

    PubMed Central

    Rehbock, Christoph; Jakobi, Jurij; Gamrad, Lisa; van der Meer, Selina; Tiedemann, Daniela; Taylor, Ulrike; Kues, Wilfried; Rath, Detlef

    2014-01-01

    Summary Due to the abundance of nanomaterials in medical devices and everyday products, toxicological effects related to nanoparticles released from these materials, e.g., by mechanical wear, are a growing matter of concern. Unfortunately, appropriate nanoparticles required for systematic toxicological evaluation of these materials are still lacking. Here, the ubiquitous presence of surface ligands, remaining from chemical synthesis are a major drawback as these organic residues may cause cross-contaminations in toxicological studies. Nanoparticles synthesized by pulsed laser ablation in liquid are a promising alternative as this synthesis route provides totally ligand-free nanoparticles. The first part of this article reviews recent methods that allow the size control of laser-fabricated nanoparticles, focusing on laser post irradiation, delayed bioconjugation and in situ size quenching by low salinity electrolytes. Subsequent or parallel applications of these methods enable precise tuning of the particle diameters in a regime from 4–400 nm without utilization of any artificial surface ligands. The second paragraph of this article highlights the recent progress concerning the synthesis of composition controlled alloy nanoparticles by laser ablation in liquids. Here, binary and ternary alloy nanoparticles with totally homogeneous elemental distribution could be fabricated and the composition of these particles closely resembled bulk implant material. Finally, the model AuAg was used to systematically evaluate composition related toxicological effects of alloy nanoparticles. Here Ag+ ion release is identified as the most probable mechanism of toxicity when recent toxicological studies with gametes, mammalian cells and bacteria are considered. PMID:25247135

  11. Steady-state distribution of metals among metallothionein and other cytosolic ligands and links to cytotoxicity in bivalves living along a polymetallic gradient

    Microsoft Academic Search

    Anik Giguère; Yves Couillard; Peter G. C Campbell; Olivier Perceval; Landis Hare; Bernadette Pinel-Alloul; Jocelyne Pellerin

    2003-01-01

    The present study was designed to assess the environmental effects of metals in a field setting. We explored exposure?bioaccumulation?effects relationships in freshwater molluscs exposed to metals in their natural habitat. Indigenous floater mussels (Pyganodon grandis) were collected from ten limnologically similar lakes located along a Cd, Cu and Zn gradient. Ambient free-metal ion concentrations were estimated as a measure of

  12. Homoleptic nickel(II) complexes of redox-tunable pincer-type ligands.

    PubMed

    Hewage, Jeewantha S; Wanniarachchi, Sarath; Morin, Tyler J; Liddle, Brendan J; Banaszynski, Megan; Lindeman, Sergey V; Bennett, Brian; Gardinier, James R

    2014-10-01

    Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)2 complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett ?(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)2](BF4)n (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)2](BF4)2, is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)2](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)2](2+). PMID:25222027

  13. Coordination chemistry of two heavy metals: I, Ligand preferences in lead(II) complexation, toward the development of therapeutic agents for lead poisoning: II, Plutonium solubility and speciation relevant to the environment

    SciTech Connect

    Neu, M.P. [Lawrence Berkeley Lab., CA (United States)

    1993-11-01

    The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK{sub a}s and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK{sub a} = 5.94, log{beta}{sub 120} = 10.92; acetohydroxamic acid, pK{sub a} = 9.34, log{beta}{sub l20} = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is log{beta}{sub 110} = 41.7. The solubility limited speciation of {sup 242}Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods.

  14. Theoretical analysis on pullout of anchor from anchor–mortar–concrete anchorage system

    Microsoft Academic Search

    Shutong Yang; Zhimin Wu; Xiaozhi Hu; Jianjun Zheng

    2008-01-01

    Theoretical studies on pullout of an anchor from an anchor–adhesive\\/mortar–concrete anchorage system have been carried out with the wide application of this anchorage system in civil engineering. Most of them focused on one interfacial debonding crack propagation from the loading end similar to the theoretical method on fiber pullout from matrix, or adopting a uniform interfacial shear stress model to

  15. Two new metal-organic coordination polymers of lead with O-, N-donor ligands: Synthesis, characterization, luminescence and thermal behavior

    SciTech Connect

    Rana, Abhinandan; Kumar Jana, Swapan; Bera, Madhusudan; Hazari, Debdoot; Sankar Chowdhuri, Durga [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India); Zangrando, Ennio [Dipartimento di Scienze Chimiche e Farmaceutiche, University of Trieste, 34127 Trieste (Italy); Dalai, Sudipta, E-mail: sudipta@mail.vidyasagar.ac.in [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India)

    2013-01-15

    The synthesis of two new lead(II) coordination polymers, [Pb{sub 2}(picOH){sub 4}]{center_dot}H{sub 2}O (1) and [Pb{sub 3}(Sip){sub 2}(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (2) has been reported, where HpicOH=3-hydroxypicolinic acid and NaH{sub 2}Sip=5-sulfoisophthalic acid monosodium salt. Both the complexes were structurally characterized by X-ray single crystal diffraction analysis. Complex 1, where the 3-hydroxypicolinate ligand is used for the first time in conjunction with Pb(II), revealed to be a 1D polymeric array. Complex 2 showed a 3D structure with 5-sulfoisophthalate ligand adopting two novel binding modes of high denticity ({eta}{sup 6}{mu}{sub 6} and {eta}{sup 7}{mu}{sub 7}). The photoluminescence and thermal properties of the two complexes have been studied. - Graphical abstract: 1D and 3D inorganic organic hybrid luminescent material of Pb(II) have been synthesized by using 3-hydroxypicolinate and 5-sulfoisophthalate anions. The 5-sulfoisophthalate ligand shows two novel binding modes with high denticity. Highlights: Black-Right-Pointing-Pointer 3-hydroxypicolinic acid is used for first time with Pb{sup 2+} in a MOF. Black-Right-Pointing-Pointer 5-sulfoisophthalic acid displays two novel binding modes of high denticity. Black-Right-Pointing-Pointer Complex 1 shows high thermal stability (up to 167 Degree-Sign C). Black-Right-Pointing-Pointer MLCT is present in both the complexes.

  16. Spectroscopic studies and biological evaluation of some transition metal complexes of Schiff-base ligands derived from 5-arylazo-salicylaldehyde and thiosemicarbazide

    Microsoft Academic Search

    Moamen S. Refat; Ibrahim M. El-Deen; Zeinab M. Anwer; Samir El-Ghol

    2009-01-01

    Synthesis and spectroscopic characterization of Schiff-base complexes of Cu(II), Ni(II), and Mn(II) resulting from condensation of salicylaldehyde derivatives with thiosemicarbazide [PHBT = 1-(5-(2-phenyldiazenyl)-2-hydroxybenzylidene)thiosemicarbazide, CHBT = 1-(5-(2-(2-chlorophenyl)diazenyl)-2-hydroxybenzylidene)thiosemicarbazide, and MHBT = 1-(5-(2-p-tolyldiazenyl)-2-hydroxybenzylidene)thiosemicarbazide] are discussed. The solid complexes were confirmed by elemental analysis (CHN), molar conductance, and mass spectra. Important infrared (IR) spectral bands corresponding to the active groups in the three ligands,

  17. Structural, spectral and biological studies of binuclear tetradentate metal complexes of N 3O Schiff base ligand synthesized from 4,6-diacetylresorcinol and diethylenetriamine

    Microsoft Academic Search

    Adel A. A. Emara

    2010-01-01

    The binuclear Schiff base, H2L, ligand was synthesized by reaction of 4,6-diacetylresorcinol with diethylenetriamine in the molar ratio 1:2. The coordination behavior of the H2L towards Cu(II), Ni(II), Co(II), Zn(II), Fe(III), Cr(III), VO(IV) and UO2(VI) ions has been investigated. The elemental analyses, magnetic moments, thermal studies and IR, electronic, 1H NMR, ESR and mass spectra were used to characterize the

  18. Tp*Cu(I)-CN-SiL2-NC-Cu(I)Tp*--a hexacoordinate Si-complex as connector for redox active metals via ?-conjugated ligands.

    PubMed

    Kämpfe, Alexander; Brendler, Erica; Kroke, Edwin; Wagler, Jörg

    2015-03-14

    Hexacoordinate silicon complexes L2SiX2 (L = a 2-benzoylpyrrol-1-yl derivative, X = CN, NCS) were synthesized from L2SiCl2 by ligand exchange with trimethylsilyl reagents Me3SiX. In the presence of [Tp*CuNCMe] and Me3SiCN the silicon complex L2Si(NC(CuTp*))2 was obtained, which contains a linear Cu-CN-Si-NC-Cu unit (Tp* = hydrotris(3,5-dimethylpyrazolyl)borato). PMID:25665985

  19. Ligand-to-metal charge-transfer quenching of the Eu 3+( 5D 1) state in europium-doped tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium (III)

    Microsoft Academic Search

    Yizhe An; Garrett E. Schramm; Mary T. Berry

    2002-01-01

    Rate constants for the decay of the Eu3+(5D1) state in dilute Eu3+-doped tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium(III) are reported for a temperature range 50–315K. A temperature-independent contribution of 1.3×106s?1 is attributed to carbonyl mediated 5D1?5D0 relaxation. A temperature-dependent contribution, that has been parameterized as kCT=Ae?Ea\\/kT with Ea=2540±140cm?1 and A=1.3×1012s?1 is attributed to quenching of 5D1 by a low-lying ligand-to-metal charge-transfer state (CTS). The height

  20. Binding of hydrocarbons and other extremely weak ligands to transition metal complexes that coordinate hydrogen: Investigation of cis-interactions and delocalized bonding involving sigma bonds

    SciTech Connect

    Kubas, G.J.; Eckert, J.; Luo, X.L. [and others

    1997-07-01

    This is the final report of a three-year Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). At the forefront of chemistry are efforts to catalytically transform the inert C-H bonds in alkanes to more useful products using metal compounds. The goal is to observe binding and cleavage of alkane C-H bonds on metals or to use related silane Si-H bonding as models, analogous to the discovery of hydrogen (H{sub 2}) binding to metals. Studies of these unique sigma complexes (M{hor_ellipsis}H-Y; Y{double_bond}H, Si, C) will aid in developing new catalysts or technologies relevant to DOE interest, e.g., new methods for tritium isotope separation. Several transition metals (Mo, W, Mn, and Pt) were found to reversibly bind and cleave H{sub 2}, silanes, and halocarbons. The first metal-SiH{sub 4} complexes, thus serving as a model for methane reactions. A second goal is to study the dynamics and energetics of H-Y bonds on metals by neutron scattering, and evidence for interactions between bound H-Y and nearby H atoms on metal complexes has been found.

  1. COORDINATION AND BIOINORGANIC CHEMISTRY OF ARYL-APPENDED TRIS(2-PYRIDYLMETHYL)AMINE LIGANDS

    Microsoft Academic Search

    Lisa M. Berreau

    2007-01-01

    Aryl-appended tris(2-pyridylmethyl)amine ligands are a relatively new class of chelate ligands in coordination and synthetic bioinorganic chemistry. As outlined herein, to date, coordination complexes of such ligands have been prepared and characterized for first row metal ions from groups 7–12. These studies revealed key coordination properties for this family of ligands. Aryl-appended tris(2-pyridylmethyl)amine ligands have been recently employed in synthetic,

  2. The anchor subperiosteal forehead lift.

    PubMed

    Ramirez, O M

    1995-05-01

    The coronal incision used for brow lift procedure has a high rate of localized alopecia, widening, and depression of the scar at the suture line. Other sequelae of the standard coronal brow lift incision procedure are "stretch-back" with a recurrent brow ptosis, poor brow elevation, and numbness beyond the incision line. Factors causing alopecia are tension, use of a monopolar cautery, use of key sutures with undue tension, one-layer closure, and sutures left too long. Recurrent brow ptosis may be due to anterior displacement of the posterior scalp flap, stretching of the anterior frontal skin flap, or insufficient power of the weakened frontalis muscle. Poor brow elevation may be due to unsatisfactory dissection on the glabella and orbital rims. Numbness and itching beyond the incision line are due to a low coronal incision. To avoid these problems, the following principles were followed: (1) If not contraindicated, the incision is made high on the vertex of the head, posterior to a biauricular line. (2) The pericranium is included in the frontal flap starting at the incision lines. (3) The subperiosteal dissection is continued down to the orbital rims and nasal bones. (4) The release of the periosteum at the arcus marginalis or just above allows repositioning of the brow structures. (5) The inelastic pericranium maintains the position of the elevated structures and avoids stretching of the frontal skin. (6) The integrity of the frontalis muscle is maintained completely. (7) Two large triangles of scalp resected in the posterior flaps allow fixing the position of the posterior scalp and match better the length of the anterior flap. (8) The galea periosteal rim flap allows anchoring of the frontal flap to the undersurface of the posterior scalp flap. This stabilizes the closure with minimal tension on the hair-bearing portion of the scalp. The wide surface of contact avoids depression and widening at the suture line. (9) Closure with skin staples avoids constriction of the hair follicles. (10) Hemostasis is done with a bipolar cautery. (11) No through-and-through key sutures are used. Some of these principles were introduced to the endoscopic subperiosteal forehead lift. The modifications mentioned above have been used in 92 open brow/face lift procedures with excellent aesthetic and functional results and minimal complications. PMID:7732147

  3. Bond strength of glass fiber reinforced plastics (GFRP) grouted anchors

    SciTech Connect

    Bellavance, E.; Xu, H.; Benmokrane, B. [Univ. of Sherbrooke, Quebec (Canada). Dept. of Civil Engineering

    1995-11-01

    This paper describes the results of laboratory and field pull-out tests on cement grouted glass fiber reinforced plastic (GFRP) anchors. As an alternative for grouted steel anchors, GFRP bars have many advantages over steel tendons, and can avoid corrosion and some difficulties in transportation, handling, and installation. Three types of 36 GFRP anchors and 20 steel anchors installed in three types of host media: steel pipe, concrete block, and rock mass were tested in the laboratory as well as in the field. The bond strength, load carrying capacity, load-displacement behavior, and critical bond length of cement grouted GFRP anchors were examined in comparison with conventional steel anchors.

  4. Ultimate load capacities of expansion anchor bolts

    SciTech Connect

    Czarnecki, R.M. (URS Consultants, San Francisco, CA (United States)); Manrique, M.A. (ABB Impell Corp., San Ramon, CA (United States)); Samaddar, S.K. (Westinghouse Savannah River Co., Aiken, SC (United States))

    1993-08-01

    A summary of available experimental expansion anchor bolt test data is presented. These data were collected as part of programs by the nuclear industry to address generic issues related to verification of seismic adequacy of equipment in nuclear power plants. Some of the data presented are suitable for use in seismic probabilistic risk assessments. For example, mean values of ultimate strength, along with their standard deviation and coefficients of variation, for a range of most typical expansion anchor bolt sizes are presented. Effects of interaction between shear and tension, edge distance, spacing, and cracking of the concrete are presented in a manner that is more suitable for use in deterministic evaluations. Related industry programs to derive anchor bolt capacities are briefly discussed. Recommendations for areas of further investigation are also presented.

  5. Multiple magnetic microrobot control using electrostatic anchoring

    NASA Astrophysics Data System (ADS)

    Pawashe, Chytra; Floyd, Steven; Sitti, Metin

    2009-04-01

    Addressing power and control to individual untethered microrobots is a challenge for small-scale robotics. We present a 250×130×100 ?m3 magnetic robot wirelessly driven by pulsed external magnetic fields. An induced stick-slip motion results in translation speeds over 8 mm/s. Control of multiple robots is achieved by an array of addressable electrostatic anchoring pads on the surface, which selectively fixes microrobots, preventing translation. We demonstrate control of two microrobots in both uncoupled individual motion and coupled symmetric motion. An estimated anchoring force of 23.0 ?N is necessary to effectively fix each microrobot.

  6. Influence of ligand structures on methanol electro-oxidation by mixed catalysts based on platinum and organic metal complexes for DMFC

    Microsoft Academic Search

    Morihiro Saito; Hidenobu Shiroishi; Chisato Ono; Seiji Tsuzuki; Tatsuhiro Okada; Yoshiharu Uchimoto

    2006-01-01

    In order to investigate the influence of mixing organic metal complexes with various metal coordination structure on Pt\\/C catalyst for methanol oxidation reaction (MOR) in acidic media, N,N?-mono-8-quinolyl-o-phenylenediamine (mqph), N,N?-bis(anthranilidene)ethylenediamine (anthen) and N,N?-bis(salicylidene)ethylenediamine (salen), coordinating to Co(II) and Ni(II), were examined as the model compounds. M(mqph), M(anthen) and M(salen) have MN3, MN4 and MN2O2 moiety as the catalytic active sites,

  7. Undrained behavior of plate anchors subjected to general loading 

    E-print Network

    Yang, Ming

    2010-01-14

    This study presents a method for predicting the undrained behavior of plate anchors, including out-of-plane loading of simple plates and performance of suction embedded plate anchors (SEPLA). Three dimensional finite element ...

  8. 9. CABLE ANCHORAGE DETAIL, NORTHWEST ABUTMENT (NOTE MOSSCOVERED CONCRETE ANCHOR ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    9. CABLE ANCHORAGE DETAIL, NORTHWEST ABUTMENT (NOTE MOSS-COVERED CONCRETE ANCHOR LEFT OF ANCHOR BOLTS) - Nisqually Suspension Bridge, Spanning Nisqually River on Service Road, Longmire, Pierce County, WA

  9. Plastic Limit Analysis of Offshore Foundation and Anchor 

    E-print Network

    Chi, Chao-Ming

    2010-10-12

    This study presents the applications of plastic limit analysis to offshore foundations and anchors, including the drag embedment anchors (DEAs) for mobile offshore drilling units (MODU’s) and spudcan foundations for jack-up ...

  10. Standardization of test methodology: a comparison between three suture anchors 

    E-print Network

    Jonnalagadda, Silpa P.

    2005-08-29

    Suture anchors have been used successfully in many applications in orthopedics. They have been in the forefront of research in the recent years. Most of the studies, though, have focused on human suture anchors. This research concentrates...

  11. 30 CFR 56.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 false Anchoring stationary sizing devices. 56.9311 Section 56.9311...Sites § 56.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  12. 30 CFR 57.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 false Anchoring stationary sizing devices. 57.9311 Section 57.9311...Sites § 57.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  13. 30 CFR 56.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 false Anchoring stationary sizing devices. 56.9311 Section 56.9311...Sites § 56.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  14. 30 CFR 56.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 false Anchoring stationary sizing devices. 56.9311 Section 56.9311...Sites § 56.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  15. 30 CFR 57.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...2013-07-01 false Anchoring stationary sizing devices. 57.9311 Section 57.9311...Sites § 57.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  16. 30 CFR 56.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 false Anchoring stationary sizing devices. 56.9311 Section 56.9311...Sites § 56.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  17. 30 CFR 57.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...2012-07-01 false Anchoring stationary sizing devices. 57.9311 Section 57.9311...Sites § 57.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  18. 30 CFR 57.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...2011-07-01 false Anchoring stationary sizing devices. 57.9311 Section 57.9311...Sites § 57.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  19. 30 CFR 56.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...2014-07-01 false Anchoring stationary sizing devices. 56.9311 Section 56.9311...Sites § 56.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  20. 30 CFR 57.9311 - Anchoring stationary sizing devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...2010-07-01 false Anchoring stationary sizing devices. 57.9311 Section 57.9311...Sites § 57.9311 Anchoring stationary sizing devices. Grizzlies and other stationary sizing devices shall be securely...

  1. Experimental and Theoretical Investigations of Anion-pi Interactions Metallacyclic Architectures of First-Row Transition Metals and N-Heteroaromatic Ligands 

    E-print Network

    Giles, Ian

    2012-07-16

    metallacycles. The extension of metallacycles of bptz to CoII and FeII demonstrates the ability to tune the size of the metallacyclic cavity by simply changing the metal ion and results in the surprising encapsulation of two [SbF6]- anions in [Fe5(bptz)5(NCCH3...

  2. Concentration, Complexation and Chemical Speciation of Zinc and Cadmium in the Western North Pacific Ocean : Exploring Sources and Transport of Trace Metals and Complexing Ligands

    Microsoft Academic Search

    G. G. Carrasco; P. L. Morton; J. R. Donat

    2008-01-01

    We determined Zn and Cd total dissolved (0.45 µm-filtered) concentrations, organic complexation and chemical speciation in surface water samples collected along the transect of the 2002 IOC Baseline Contaminant Survey expedition in the Western North Pacific and in vertical profile water samples at nine stations. The goals of this work were (1) to compare and contrast various trace metal sources,

  3. Behavior of 10 full-scale ground anchors installed in stiff clay

    E-print Network

    Powers, William Francis

    1993-01-01

    Anchors 2. 3 Ground Anchor Design Practice 2, 4 Load Testing of Ground Anchors 2. 4. 1 Testing Equipment 2. 4. 2 Components of Ground Anchor Movements 2. 4. 3 Proof Tests. . . . . . . . . . . . . . . . . . 2. 4. 4 Performance Tests 2. 4. 5 Creep... Tests 3 GROUND ANCHOR BEHAVIOR 3. 1 Load Distribution in Ground Anchors 3. 2 Creep Behavior of Ground Anchors. . . . . . . . . . . . . . 3. 3 Mechanisms Contributing to Ground Anchor Failure 3. 3. 1 Failure of the Grout-Tendon Bond...

  4. Use of bone anchors in female urology

    Microsoft Academic Search

    J. Christian Winters; Harriette M Scarpero; Rodney A Appell

    2000-01-01

    Stress urinary incontinence remains one of the most prevalent conditions encountered by urologists. In many cases, surgical correction of this condition is carried out using a pubovaginal sling procedure. Bone anchors were initially used in transvaginal needle suspension procedures to improve stabilization of the bladder neck. This technology has been extended to sling procedures, allowing completion of these procedures by

  5. Polysaccharide-anchored fatty acid liposome.

    PubMed

    Tan, Hsiao Wei; Misran, Misni

    2013-01-30

    In this study, the preparation of N-pamitoyl chitosan (ChP) anchored oleic acid (OA) liposome was demonstrated. Two different types of water-soluble ChPs with different degrees of acylation (DA) were selected for this study. The presence of ChPs on the surface of OA liposome was confirmed with their micrographs and physicochemical properties. The "peeling off" effect on the surface of the ChP-anchored OA (OAChP) liposomes was observed on the atomic force microscope micrographs and confirmed the presence of the ChPs layer on the liposome surface. The surface tension of the OAChPs liposome solution was found to be higher than that of the OA liposome solution. This result indicated the removal of OA monomer by ChPs from the air-water interface. The increase in the minimum area per headgroup (A(min)) of the OA with the presence of ChPs has further proved the interaction between OA monomer and the hydrophobic moieties of the ChPs. The ChPs anchored onto the OA monolayer increased the curvature of the OAChP liposomes monolayer and reduced the liposome size. The size of the OAChP liposomes was reduced by 30 nm as compared with the unmodified OA liposome. Results revealed that the anchored ChPs can improve the integrity and rigidity of the OA liposome. PMID:23174410

  6. Pultruded CFRP rods for ground anchor application

    Microsoft Academic Search

    Akira Sumitani; Masao Kikuchi; Manabu Sotooka; Haruhito Akimoto; Nobuyuki Ozawa

    1998-01-01

    Carbon fiber reinforced plastic (CFRP) rods with spiral surface indentations have been developed as tension elements in prestressed concrete and as anchor tendons in place of conventional prestressing steels. The indented type CFRP rods have sufficient bonding strength to concrete without sacrificing the high tensile strength. As a low cost manufacturing process of the advanced composite, the pultrusion processing method

  7. Inhibition of glycosylphosphatidylinositol anchor formation by mannosamine.

    PubMed

    Pan, Y T; Kamitani, T; Bhuvaneswaran, C; Hallaq, Y; Warren, C D; Yeh, E T; Elbein, A D

    1992-10-15

    Many eucaryotic cell surface proteins are anchored to the plasma membrane via a glycosylphosphatidylinositol (GPI), of which the core region is highly conserved from protozoa to mammalian cells. Previous studies (Lisanti, M. P., Field, M. C., Caras, I. W., Menon, A. K., and Rodiguez-Boulan, E. (1991) EMBO J. 10, 1969-1977) showed that mannosamine blocked the expression of a recombinant GPI-anchored protein in Madin-Darby canine kidney cells and converted this protein to an unpolarized secretory product. In the present study, we examined the effect of mannosamine on the formation of the glycan portion of the GPI anchor precursors. This amino sugar inhibited the incorporation of mannose into the glycan portion, and the inhibition was dose-dependent. Mannosamine was shown to be incorporated into the glycan as mannosamine, probably mostly in the second mannose position and thereby to block the further addition of mannose and other anchor components. The products formed in the presence of this drug were characterized by gel filtration and high resolution TLC both before and after deamination with nitrous acid and dephosphorylation by HF. Galactosamine and trehalosamine were inactive in this system, whereas glucosamine also inhibited mannose incorporation into GPI intermediates. PMID:1400435

  8. Weighing Anchor in the "Ragged Times"

    ERIC Educational Resources Information Center

    Perry, Tonya B.

    2012-01-01

    In today's middle school classroom, grouping is an essential learning tool that enhances students' ability to collaborate with others and deepen their own thinking. Implementing group work effectively, though, can be a challenge, especially since groups tend to end their work at "ragged" or staggered times. Creating "anchor activities"--respectful…

  9. Centrosome composition and microtubule anchoring mechanisms

    Microsoft Academic Search

    Michel Bornens

    2002-01-01

    Centrosomes of animal cells and spindle pole bodies of fungi are the major microtubule nucleating centers. Recent studies indicate that their capacity to organize microtubule arrays rests on elaborate control of the anchoring and release of the nucleated microtubules. Although common molecular mechanisms are likely to be involved in both cases, the centrosome from animal cells shows considerable complexity and

  10. Anchoring the Panic Disorder Severity Scale

    ERIC Educational Resources Information Center

    Keough, Meghan E.; Porter, Eliora; Kredlow, M. Alexandra; Worthington, John J.; Hoge, Elizabeth A.; Pollack, Mark H.; Shear, M. Katherine; Simon, Naomi M.

    2012-01-01

    The Panic Disorder Severity Scale (PDSS) is a clinician-administered measure of panic disorder symptom severity widely used in clinical research. This investigation sought to provide clinically meaningful anchor points for the PDSS both in terms of clinical severity as measured by the Clinical Global Impression-Severity Scale (CGI-S) and to extend…

  11. Multifunctional ligand for use as a diagnostic or therapeutic pharmaceutical

    DOEpatents

    Katti, K.V.; Volkert, W.A.; Ketring, A.R.; Singh, P.R.

    1996-05-14

    A compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical are revealed. The ligand comprises either a phosphorous or germanium core and at least two hydrazine groups forming a ligand for bonding to a metal extending from the phosphorous or germanium core.

  12. Anchoring and Adjustment in Software Estimation Jorge Aranda

    E-print Network

    Easterbrook, Steve

    @cs.toronto.edu ABSTRACT Anchoring and adjustment is a form of cognitive bias that affects judgments under uncertainty, Experimentation. Keywords Effort estimation, cognitive bias, anchoring and adjustment, empirical software in cognitive psychology. Its effects consist of biasing the answer to a complex question towards an anchor (an

  13. Centrifuge tests on installation of suction anchors in soft clay

    Microsoft Academic Search

    Knut H. Andersen; Philippe Jeanjean; Dirk Luger; Hans Petter Jostad

    2005-01-01

    Three centrifuge model tests were performed in normally consolidated Speswhite Kaolin to study the penetration of suction anchors in soft clay. The suction anchors could be penetrated by means of underpressure to a depth of about 12.4 to a little more than 14.5 times the diameter. When the anchors were penetrated by underpressure, all clay displaced by the skirt moved

  14. STUDY ON ANCHOR BEHAVIOR OF CFRP PLATE TO CONCRETE

    Microsoft Academic Search

    Kentaro MATSUNAGA; Tsutomu YANO; Hiroyuki NAKAMURA; Nobuhiro HISABE; Toshiyuki KANAKUBO

    In this study, direct shear type bond test is conducted to examine the anchor behavior of CFRP plate to concrete. CFRP plate is bonded to concrete and anchored by five types of anchor method. In case of anchorage method by carbon fiber sheet, the debonding of CFRP plate is restrained after maximum load. In case of anchorage method by multilayer

  15. Pull-out behavior of an imperfectly bonded anchor system

    Microsoft Academic Search

    Yiming Zhao; Mijia Yang

    2011-01-01

    A theoretical model of imperfectly bonded anchorage system was analyzed and validated using the ABAQUS code. Based on the proposed model, the axial stress in the anchor and shear stress at the anchor–epoxy interface along the embedded direction have been obtained. Then the slope of the axial stress in anchor along the embedded direction was analyzed and showed a steep

  16. Career Paths, Images and Anchors: A Study with Brazilian Professionals

    ERIC Educational Resources Information Center

    Kilimnik, Zelia Miranda; de Oliveira, Luiz Claudio Vieira; Sant'anna, Anderson De Souza; Barros, Delba Teixeira Rodrigues

    2011-01-01

    This article analyses career anchors changes associated to images and professionals trajectories. Its main question: Do anchors careers change through time? We conducted twelve interviews involving professionals from the Administration Area, applying Schein's Career Anchors Inventory (1993). We did the same two years later. In both of them, the…

  17. 33 CFR 401.14 - Anchor marking buoys.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 2010-07-01 2010-07-01 false Anchor marking buoys. 401.14 Section 401.14...Regulations Condition of Vessels § 401.14 Anchor marking buoys. A highly visible anchor marking buoy of a type approved by the...

  18. Standardization of test methodology: a comparison between three suture anchors

    E-print Network

    Jonnalagadda, Silpa P.

    2005-08-29

    whether suture anchor failure due to eyelet cut-out or suture wear-out resulting from the sharp edges of the eyelet is the major cause of failure of bone-suture anchor-bone complexes. Cyclic loading of suture anchors during testing for durability has...

  19. Spectral, magnetic, biocidal screening, DNA binding and photocleavage studies of mononuclear Cu(II) and Zn(II) metal complexes of tricoordinate heterocyclic Schiff base ligands of pyrazolone and semicarbazide/thiosemicarbazide based derivatives

    NASA Astrophysics Data System (ADS)

    Raman, N.; Selvan, A.; Manisankar, P.

    2010-07-01

    We depict the synthesis and characterization of copper(II) and zinc(II) coordination compounds of 4-(3',4'-dimethoxybenzaldehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-semicarbazone ( 1a), 4-(3',4'-dimethoxybenzaldehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-thiosemicarbazone ( 1b), 4-(3'-hydroxy-4'-nitrobenzaldehydene)2-3-dimeth yl-1-phenyl-3-pyrazolin-5-semicarbazone ( 1c) and 4-(3'-hydroxy-4'-nitrobenzal dehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-thiosemicarbazone ( 1d). All the remote compounds have the general composition [ML 2] (M = Cu(II) and Zn(II)); L = Schiff base ( 1a- 1d). All the complexes were characterized by elemental analysis, molar conductivity, IR, 1H NMR, UV-vis, ESI-Mass, magnetic susceptibility measurements, cyclic voltammetric measurements, and EPR spectral studies. It has been originated that the Schiff bases with Cu(II) and Zn(II) ions form mononuclear complexes on 1:2 (metal:ligand) stoichiometry. Distorted octahedral environment is suggested for the metal complexes. The conductivity data confirm the non-electrolytic nature of the complexes. The interaction of CuL 21a- 1d complexes with CT DNA was investigated by spectroscopic, electrochemical and viscosity measurements. Results suggest that the copper complexes bind to DNA via an intercalative mode. Moreover, the complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The Schiff bases and their metal complexes were screened for their antifungal and antibacterial activities against different species of pathogenic fungi and bacteria and their biopotency has been discussed.

  20. Comparative reliability of numerically anchored versus job-task anchored rating scales

    Microsoft Academic Search

    David L. Peters; Ernest J. McCormick

    1966-01-01

    Compared the effectiveness with which job-task anchored equal-appearing interval scales could be used in contrast with scales anchored only by simple numerical benchmarks. 2 groups of judges rated identical lists of job-task statements in terms of both types of scales. Ratings were made on 5 sensory\\/physical dimensions of job activities. The reliabilities of ratings for all scales were computed by

  1. Naked eye sensing of toxic metal ions in aqueous medium using thiophene-based ligands and its application in living cells.

    PubMed

    Udhayakumari, Duraisamy; Suganya, Sivalingam; Velmathi, Sivan; MubarakAli, Davoodbasha

    2014-03-01

    Thiophene-based diimine (R1) and monoimine (R2) were synthesized in a single step, and their cation binding affinity was tested using colorimetric and UV-vis spectral studies. R1 selectively shows a colorimetric turn-on response for Pb(2+), Hg(2+) ions and colorimetric turn-off with Sn(2+) ions, and R2 shows visual response for Cu(2+) and Hg(2+) over other examined metal ions in aqueous medium. R1 forms 1:1 complex with Pb(2+), Hg(2+), and Sn(2+) and exhibits fluorescence quenching, whereas R2 shows 2:1 complex with Hg(2+), Cu(2+) and shows fluorescence enhancement. The structural and electronic properties of the sensors and their metal complexes were also investigated using Density Functional Theory calculations. R2 was also successfully demonstrated as a fluorescent probe for detecting Cu(2+) ions in living cells. PMID:24446379

  2. Synthesis and Characterization of Transition Metal Complexes with N,O; N,N and S,N-donor Schifff Base Ligands

    Microsoft Academic Search

    Y. Prashanthi; Shiva Raj

    2010-01-01

    The Schiff bases namely MIMFMA, MIMTMA and MIPMA have been prepared by reacting 3-amino-5-methyl isoxazole with 5-methyl furan-2-carboxyaldehyde, 5-methyl thiphene-2-carboxaldehyde and pyridine-2-carboxaldehyde. The Cu(II), Ni(II), Co(II), Zn(II) and VO(IV) have been prepared by reacting metal chlorides with those Schiff bases in an alchololic medium. The complexes are electrolytes in DMSO. These have been characterized by using elemental analysis, IR, UV-VIS,

  3. Second-sphere ligand field effects on oxygen ligator atoms and experimental evidence—the transition metal–oxygen bond in oxidic solids

    Microsoft Academic Search

    Dirk Reinen; Michail Atanasov; Show-Ling Lee

    1998-01-01

    The properties of the M–O bond in oxidic solids, where M is a low-valent 3d transition metal ion such as NiII, CuII, CoII or CrIII, are very variable depending on the structure and constitution of the respective compound, and are studied by optical and EPR spectroscopy. Specifically, high-valent cations in the cationic coordination of the oxygen ligator atoms beside M

  4. Targeting of AIDS related encephalopathy using phenylalanine anchored lipidic nanocarrier.

    PubMed

    Vyas, Anil; Jain, Ankit; Hurkat, Pooja; Jain, Ashish; Jain, Sanjay K

    2015-07-01

    Transport of the anti-HIV agents across the blood-brain barrier (BBB) is a prerequisite to treat acquired immunodeficiency syndrome (AIDS) related encephalopathy. In the present study, we explored facilitated transport of efavirenz (EFV, a non-nucleoside reverse transcriptase inhibitor) across BBB using phenylalanine anchored solid lipid nanoparticles (PA-SLN). PA (amino acid micro-nutrient) was used as a ligand which facilitated carrier mediated transport (CMT) via l-amino acid transporter i.e. LAT1 to traverse BBB. PA was coupled to SLN via amide linkage using carbodiimide chemistry and coupling was confirmed by comparative infrared spectroscopic analysis. SLNs (SLN and PA-SLN) were nanometric in size (around 150nm) and possessed good entrapment efficiency (around 70%). In vitro drug release revealed controlled release pattern for more than 24h. In vivo studies showed 2-3-folds and 7-8-folds accumulation of PA-SLN in brain as compared to SLN and EFV, respectively. Further, transcytosis studies confirmed capability of PA-SLN to cross BBB i.e. 10-fold higher transcytosis potential as compared to EFV. Fluorescence microscopic imaging reassured enhanced brain localization of PA-SLN. Thus, PA-SLN improved the EFV bioavailability and maintained therapeutic levels in the brain for an extended period of time that can result in significant eradication of the viral load therein. Such nutrient mediated drug targeting could bring forth advances in biocompatible and biodegradable drug delivery systems. PMID:25988279

  5. Formation of Supported and Anchored Phospholipid Bilayers by Fusion of Unilamellar Vesicles: An AFM Study.

    NASA Astrophysics Data System (ADS)

    Reviakine, Ilya; Brisson, Alain

    2000-03-01

    The process of formation of supported phospholipid bilayers (SPBs) on the surface of mica from unilamellar vesicles prepared by sonication or extrusion was investigated by AFM. The effect of liposome size and of Ca2+ on the SPB formation was studied. Intact surface-adsorbed liposomes of various sizes could be visualized. The results obtained in this study were compared with the theoretical model of Seifert et al (1) and with the experimental results obtained by other groups (2),(3). 2-dimensional (2D) crystals formed on SPBs (4) present a surface with significantly different properties than that of mica. Phospholipid vesicles can be anchored to them via specific (ligand-receptor) interactions, forming Anchored Vesicular Layers (AVLs, by analogy with Supported Vesicular Layers, or SVLs (5)). The formation of Anchored Phospholipid Bilayers (APBs) from AVLs was also investigated (6). 1. Seifert, U. Adv. Phys. (1997), 46, 13. 2. Keller, C.A., Kasemo, B. Biophys. J. (1998), 75, 1397. 3. Reviakine and Brisson, Langmuir, in press. 4. Reviakine, I., Bergsma-Schutter, W., Brisson, A. J.Struct. Biol. (1998), 121, 356. 5. Nollert, P., Kiefer, H., Jähnig, F. Biophys. J. (1995), 69, 1447. 6. Reviakine and Brisson, Langmuir, submitted.

  6. Complexes of trivalent metal ions with potentially heptadentate N{sub 4}O{sub 3} Schiff base and amine phenol ligands of varying rigidity

    SciTech Connect

    Yang, L.W.; Liu, S.; Wong, E.; Rettig, S.J.; Orvig, C. [Univ. of British Columbia, Vancouver (Canada)

    1995-04-12

    The synthesis and characterization of several potentially heptadentate N{sub 4}O{sub 3} Schiff bases and amine phenols, as well as a series of their mononuclear and dinuclear complexes with indium and the lanthanides are reported. Schiff bases containing imidazolidine rings were the products of the known condensation reaction of triethylenetetramine with 3 equiv of 5-substituted salicylaldehydes to form H{sub 3}api (5-H-substituent), H{sub 3}Clapi (5-Cl-substituent), or H{sub 3}Brapi (5-Br-substituent); KBH{sub 4} reduction of these Schiff bases gave the appropriate isomeric N{sub 4}O{sub 3} amine phenols H{sub 3}(1,2,4-btt) and H{sub 3}(1,1,4-btt), as well as an acetone adduct, H{sub 3}(1,2,4-ahi). The Schiff bases reacted with 1 equiv of a lanthanide (Ln{sup 3+}) nitrate to produce mononuclear nine-coordinated [Ln(H{sub 3}Xapi)-(NO{sub 3}){sub 3}] complex wherein the ligand adopts a tridentate capping coordination mode, whereas the amine phenols formed mononuclear seven-coordinate complexes with the lanthanides and indium; homodinuclear complexes [LnL]{sub 2} were also obtained with the Schiff bases. The X-ray structures of the Schiff bases H{sub 3}api and H{sub 3}Clapi, the mononuclear amine phenol complexes Yb(1,2,4-btt){center_dot}0.5CH{sub 3}OH and In(1,1,4-btt), and the homodinuclear Schiff base complex [La(Brapi)]{sub 2}{center_dot}2CHCl{sub 3} have been determined.

  7. PEGylated N-Heterocyclic Carbene Anchors Designed To Stabilize Gold Nanoparticles in Biologically Relevant Media.

    PubMed

    MacLeod, Michelle J; Johnson, Jeremiah A

    2015-07-01

    N-Heterocyclic carbenes (NHCs) have emerged as versatile ligands for surface functionalization. Their ease of synthesis and ability to form strong bonds with a range of substrates provide a unique complement to traditional surface modification methods. Gold nanoparticles (NPs) are a particularly useful class of materials whose applications intimately depend on surface functionalization. Here we report the development of PEGylated-NHC ligands for Au-NP surfaces and the first example of NHC-functionalized NPs that are compatible with biologically relevant conditions. Our PEGylated-NHC-Au-NPs are stable toward aggregation in aqueous solutions in the pH range of 3-14, in <250 mM electrolyte solutions, at high and low temperatures (95 and -78 °C), in cell culture media, and in aqueous H2O2 solutions. This work demonstrates for the first time that NHCs can serve as anchors for water-soluble Au-NPs and opens the door to potential biomedical applications of NHC surface anchors. PMID:26081724

  8. Optical and electronic properties of pyrite nanocrystal thin films: the role of ligands.

    PubMed

    Li, Wei; Dittrich, Thomas; Jäckel, Frank; Feldmann, Jochen

    2014-03-26

    Pyrite nanocrystals are currently considered as a promising material for large scale photovoltaic applications due to their non-toxicity and large abundance. While scalable synthetic routes for phase-pure and shape controlled colloidal pyrite nanocrystals have been reported, their use in solar cells has been hampered by the detrimental effects of their surface defects. Here, we report a systematic study of optical and electronic properties of pyrite nanocrystal thin films employing a series of different ligands varying both the anchor and bridging group. The effect of the ligands on the optical and electronic properties is investigated by UV-vis/NIR absorption spectroscopy, current voltage characteristic measurements and surface photovoltage spectroscopy. We find that the optical absorption is mainly determined by the anchor group. The absorption onset in the thin films shifts up to ?100 meV to the red. This is attributed to changes in the dielectric environment induced by different anchors. The conductivity and photoconductivity, on the other hand, are determined by combined effects of anchor and bridging group, which modify the effective hopping barrier. Employing different ligands, the differential conductance varies over four orders of magnitude. The largest redshift and differential conductance are observed for ammonium sulfides and thiolated aromatic linkers. Pyridine and long chain amines, on the other hand, lead to smaller modifications. Our findings highlight the importance of surface functionalization and interparticle electronic coupling in the use of pyrite nanocrystals for photovoltaic devices. PMID:24395590

  9. An analytical method for positioning drag anchors in seabed soils

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Liu, Hai-xiao; Li, Xin-zhong; Li, Qing-ping; Cao, Jing

    2015-03-01

    Positioning drag anchors in seabed soils are strongly influenced not only by the properties of the anchor and soil, but also by the characteristics of the installation line. The investigation on the previous prediction methods related to anchor positioning demonstrates that the prediction of the anchor position during dragging has inevitably introduced some key and unsubstantiated hypotheses and the applicability of these methods is limited. In the present study, the interactional system between the drag anchor and installation line is firstly introduced for the analysis of anchor positioning. Based on the two mechanical models for embedded lines and drag anchors, the positioning equations for drag anchors have been derived both for cohesive and noncohesive soils. Since the drag angle at the shackle is the most important parameter in the positioning equations, a novel analytical method that can predict both the variation and the exact value of the drag angle at the shackle is proposed. The analytical method for positioning drag anchors which combines the interactional system between the drag anchor and the installation line has provided a reasonable theoretic approach to investigate the anchor behaviors in soils. By comparing with the model flume experiments, the sensitivity, effectiveness and veracity of the positioning method are well verified.

  10. The effects of phosphorous ligands on the gas phase ligand exchange reactions of dichromium ionic cluster fragments

    E-print Network

    Nguyen, Hanh Duc

    1991-01-01

    on the steric effect. For Cr, (CO), ' the metal-metal bond cleavage depends on both steric and electronic effects. Also in this study, the rate constants for disappearance of Cr, (CO), ' are greater than those of Cr, (CO), '. Finally, Cr, (CO), ' tends... Table I. Cone angles and CO stretching frequencies of phosphorus ligands. , Page . . 11 II. The relative rate constants for disappearance of Cr, (CO), ' for ligand exchange reaction with phosphorusligands. 14 vu LIST OF FIGURES Figure Page 1...

  11. Rational design of class I MHC ligands

    NASA Astrophysics Data System (ADS)

    Rognan, D.; Scapozza, L.; Folkers, G.; Daser, Angelika

    1995-04-01

    From the knowledge of the three-dimensional structure of a class I MHC protein, several non natural peptides were designed in order to either optimize the interactions of one secondary anchor amino acid with its HLA binding pocket or to substitute the non interacting part with spacer residues. All peptides were synthesized and tested for binding to the class I MHC protein in an in vitro reconstitution assay. As predicted, the non natural peptides present an enhanced binding to the HLA-B27 molecule with respect to their natural parent peptides. This study constitutes the first step towards the rational design of non peptidic MHC ligands that should be very promising tools for the selective immunotherapy of autoimmune diseases.

  12. On the Metal Ion Selectivity of Oxoacid Extractants

    SciTech Connect

    Hay, Benjamin [ORNL; Chagnes, Alexandre [Chimie ParisTech; Cote, Gerard [Chimie ParisTech

    2013-01-01

    Relationships between metal chelate stability, ligand basicity, and metal ion acidity are reviewed and the general applicability is illustrated by linear correlations between aqueous stability constants and ligand pKa values for 35 metals with 26 ligands. The results confirm that most individual ligands of this type exhibit a stability ordering that correlates with the Lewis acidity of the metal ion. It is concluded that the general metal ion selectivity exhibited by liquid-liquid oxoacid extractants such as carboxylic acids, -diketones, and alkylphosphoric acids reflects the intrinsic affinity of the metal ion for the negative oxygen donor ligand.

  13. Precursors in the preparation of transition metal nitrides and transition metal carbonitrides and their reaction intermediates

    SciTech Connect

    Maya, L.

    1991-06-11

    This patent describes a composition comprising: a transition metal bound to; a first ligand selected from the group inorganic amide and imide ligands; and a second ligand being acetylide ligands. This patent also describes a process for making ceramics comprising: pyrolyzing the precursor in an inert atmosphere.

  14. Surface anchoring on liquid crystalline polymer brushes

    E-print Network

    Harald Lange; Friederike Schmid

    2002-05-15

    We present a Monte Carlo study of the surface anchoring of a nematic fluid on swollen layers of grafted liquid crystalline chain molecules. The liquid crystalline particles are modeled by soft repulsive ellipsoids, and the chains are made of the same particles. An appropriately modified version of the configurational bias Monte Carlo algorithm is introduced, which removes and redistributes chain bonds rather than whole monomers. With this algorithm, a wide range of grafting densities could be studied. The substrate is chosen such that it favors a planar orientation (parallel to the surface). Depending on the grafting density, we find three anchoring regimes: planar, tilted, and perpendicular alignment. At low grafting densities, the alignment is mainly driven by the substrate. At high grafting densities, the substrate gradually loses its influence and the alignment is determined by the structure of the interface between the brush and the pure solvent instead.

  15. MFR PAPER 1070 Anchor tags show ment

    E-print Network

    was initiated to test the efAclency of th e anchor tag o n ki ng crabs u nder Aeld conditi o ns a nd o n Tanner-It 14- Inch J...lng crah pot\\. 1 hc pot. Ihelr tunncl entrance\\ c\\owJ With hanJ \\C\\\\ n n\\ Ion nell In g. A shown in Table I. 37 crab re- mai ned in the pots after 125 days. Only five known mortalities were ob

  16. International Lunar Network (ILN) Anchor Nodes

    NASA Technical Reports Server (NTRS)

    Cohen, Barbara A.

    2008-01-01

    This slide presentation reviews what we know about the interior and surface of the moon and the need to establish a robotic set of geophysical monitoring stations on the surface of the Moon for the purpose of providing significant scientific value to the exploration of the Moon. The ILN Anchor Nodes will provide the backbone of the network in a way that accomplishes new science and allows other nodes to be flexible contributors to the network.

  17. Developing Ligands for Palladium(II)-Catalyzed C–H Functionalization: Intimate Dialogue between Ligand and Substrate

    PubMed Central

    Engle, Keary M.; Yu, Jin-Quan

    2013-01-01

    Homogeneous transition metal–catalyzed reactions are indispensable to all facets of modern chemical synthesis. It is thus difficult to imagine that for much of the early 20th century, the reactivity and selectivity of all known homogeneous metal catalysts paled in comparison to their heterogeneous and biological counterparts. In the intervening decades, advances in ligand design bridged this divide, such that today some of the most demanding bond-forming events are mediated by ligand-supported homogeneous metal species. While ligand design has propelled many areas of homogeneous catalysis, in the field of Pd(II)-catalyzed C–H functionalization, suitable ligand scaffolds are lacking, which has hampered the development of broadly practical transformations based on C–H functionalization logic. In this review, we offer an account of our research employing three ligand scaffolds, mono-N-protected amino acids, 2,6-disubstituted pyridines, and 2,2?-bipyridines, to address challenges posed by several synthetically versatile substrate classes. Drawing on this work, we discuss principles of ligand design, such as the need to match a ligand to a particular substrate class, and how ligand traits such as tunability and modularity can be advantageous in reaction discovery. PMID:23565982

  18. Anchor bolt behavior and strength during earthquakes

    SciTech Connect

    Klingner, R.E. [Univ. of Texas, Austin, TX (United States); Graves, H.L. [Nuclear Regulatory Commission, Washington, DC (United States)

    1994-10-01

    The Seismic Qualification Utility Group (SQUG), a utility group, has developed a Generic Implementation Plant (GIP) including criteria and walkdown procedures that will be used to resolve the concerns of USI A-46. Following NRC approach of the GIP, each utility will conduct a walkdown of its nuclear facilities using the GIP criteria and procedures. The criteria and procedures specified for anchorage walkdown in the GIP contain specific information relating to bolt strength under dynamic conditions. The GIP including criteria and walkdown procedures has been reviewed and accepted by the NRC. However, very little test data are available regarding the behavior and strength of anchor bolts under dynamic conditions (cyclic loads) to validate the criteria in the GIP. It is usually assumed that behavior and strength of anchor bolts under static loads do not differ much from that of earthquake conditions. The adequacy of this assumption has never been adequately verified. The goal of this contract is to verify, by testing, the adequacy of the assumption used in the U.S. nuclear power plant designs that the behavior and strength of anchor bolts (cast-in-place, expansion and bearing-type undercut) and their supporting concrete under seismic loads do not differ significantly from those for static conditions.

  19. The Use of Anchored Agonists of Phagocytic Receptors for Cancer Immunotherapy: B16-F10 Murine Melanoma Model

    PubMed Central

    Janotová, Tereza; Jalovecká, Marie; Auerová, Marie; Švecová, Ivana; Bruzlová, Pavlína; Maierová, Veronika; Kumžáková, Zuzana; ?unátová, Št?pánka; Vl?ková, Zuzana; Caisová, Veronika; Rozsypalová, Petra; Luká?ová, Katarína; Vácová, Nikol; Wachtlová, Markéta; Salát, Ji?í; Lieskovská, Jaroslava; Kopecký, Jan; Ženka, Jan

    2014-01-01

    The application of the phagocytic receptor agonists in cancer immunotherapy was studied. Agonists (laminarin, molecules with terminal mannose, N-Formyl-methioninyl-leucyl-phenylalanine) were firmly anchored to the tumor cell surface. When particular agonists of phagocytic receptors were used together with LPS (Toll-like receptor agonist), high synergy causing tumour shrinkage and a temporary or permanent disappearance was observed. Methods of anchoring phagocytic receptor agonists (charge interactions, anchoring based on hydrophobic chains, covalent bonds) and various regimes of phagocytic agonist/LPS mixture applications were tested to achieve maximum therapeutic effect. Combinations of mannan/LPS and f-MLF/LPS (hydrophobic anchors) in appropriate (pulse) regimes resulted in an 80% and 60% recovery for mice, respectively. We propose that substantial synergy between agonists of phagocytic and Toll-like receptors (TLR) is based on two events. The TLR ligand induces early and massive inflammatory infiltration of tumors. The effect of this cell infiltrate is directed towards tumor cells, bearing agonists of phagocytic receptors on their surface. The result of these processes was effective killing of tumor cells. This novel approach represents exploitation of innate immunity mechanisms for treating cancer. PMID:24454822

  20. 2D?3D polycatenated and 3D?3D interpenetrated metal-organic frameworks constructed from thiophene-2,5-dicarboxylate and rigid bis(imidazole) ligands

    NASA Astrophysics Data System (ADS)

    Erer, Hakan; Ye?ilel, Okan Zafer; Ar?c?, Mürsel; Keskin, Seda; Büyükgüngör, Orhan

    2014-02-01

    Hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H2tdc) in the presence of Zn(II) and Cd(II) salts in H2O produced three new metal-organic frameworks, namely, [Zn(?-tdc)(H2O)(?-dib)]n (1), [Cd(?-tdc)(H2O)(?-dib)]n (2), and {[Cd2(?3-tdc)2(?-dimb)2]·(H2O)}n(3). These MOFs were characterized by FT-IR spectroscopy, elemental, thermal (TG, DTA, DTG and DSC), and single-crystal X-ray diffraction analyses. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D?3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 66. Molecular simulations were used to assess the potentials of the complexes for H2 storage application. Moreover, these coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature.

  1. Ligand deconstruction: Why some fragment binding positions are conserved and others are not

    PubMed Central

    Kozakov, Dima; Hall, David R.; Jehle, Sefan; Luo, Lingqi; Ochiana, Stefan O.; Jones, Elizabeth V.; Pollastri, Michael; Allen, Karen N.; Whitty, Adrian; Vajda, Sandor

    2015-01-01

    Fragment-based drug discovery (FBDD) relies on the premise that the fragment binding mode will be conserved on subsequent expansion to a larger ligand. However, no general condition has been established to explain when fragment binding modes will be conserved. We show that a remarkably simple condition can be developed in terms of how fragments coincide with binding energy hot spots—regions of the protein where interactions with a ligand contribute substantial binding free energy—the locations of which can easily be determined computationally. Because a substantial fraction of the free energy of ligand binding comes from interacting with the residues in the energetically most important hot spot, a ligand moiety that sufficiently overlaps with this region will retain its location even when other parts of the ligand are removed. This hypothesis is supported by eight case studies. The condition helps identify whether a protein is suitable for FBDD, predicts the size of fragments required for screening, and determines whether a fragment hit can be extended into a higher affinity ligand. Our results show that ligand binding sites can usefully be thought of in terms of an anchor site, which is the top-ranked hot spot and dominates the free energy of binding, surrounded by a number of weaker satellite sites that confer improved affinity and selectivity for a particular ligand and that it is the intrinsic binding potential of the protein surface that determines whether it can serve as a robust binding site for a suitably optimized ligand. PMID:25918377

  2. Mechanokinetics of receptor-ligand interactions in cell adhesion

    NASA Astrophysics Data System (ADS)

    Li, Ning; Lü, Shouqin; Zhang, Yan; Long, Mian

    2015-05-01

    Receptor-ligand interactions in blood flow are crucial to initiate such biological processes as inflammatory cascade, platelet thrombosis, as well as tumor metastasis. To mediate cell adhesion, the interacting receptors and ligands must be anchored onto two apposing surfaces of two cells or a cell and a substratum, i.e., two-dimensional (2D) binding, which is different from the binding of a soluble ligand in fluid phase to a receptor, i.e., three-dimensional (3D) binding. While numerous works have been focused on 3D kinetics of receptor-ligand interactions in the immune system, 2D kinetics and its regulations have been less understood, since no theoretical framework or experimental assays were established until 1993. Not only does the molecular structure dominate 2D binding kinetics, but the shear force in blood flow also regulates cell adhesion mediated by interacting receptors and ligands. Here, we provide an overview of current progress in 2D binding and regulations, mainly from our group. Relevant issues of theoretical frameworks, experimental measurements, kinetic rates and binding affinities, and force regulations are discussed.

  3. Mechanokinetics of receptor-ligand interactions in cell adhesion

    NASA Astrophysics Data System (ADS)

    Li, Ning; Lü, Shouqin; Zhang, Yan; Long, Mian

    2015-04-01

    Receptor-ligand interactions in blood flow are crucial to initiate such biological processes as inflammatory cascade, platelet thrombosis, as well as tumor metastasis. To mediate cell adhesion, the interacting receptors and ligands must be anchored onto two apposing surfaces of two cells or a cell and a substratum, i.e., two-dimensional (2D) binding, which is different from the binding of a soluble ligand in fluid phase to a receptor, i.e., three-dimensional (3D) binding. While numerous works have been focused on 3D kinetics of receptor-ligand interactions in the immune system, 2D kinetics and its regulations have been less understood, since no theoretical framework or experimental assays were established until 1993. Not only does the molecular structure dominate 2D binding kinetics, but the shear force in blood flow also regulates cell adhesion mediated by interacting receptors and ligands. Here, we provide an overview of current progress in 2D binding and regulations, mainly from our group. Relevant issues of theoretical frameworks, experimental measurements, kinetic rates and binding affinities, and force regulations are discussed.

  4. Coordination chemistry with pyrazole-based chelating ligands: molecular structural aspects

    Microsoft Academic Search

    Rabindranath Mukherjee

    2000-01-01

    Pyrazole-based chelating ligands form a variety of coordination complexes with a number of metal ions, providing varying coordination geometry and nuclearity. Recent years have seen considerable interest in the designing of various pyrazole-based ligands and to study their structural properties to serve specific stereochemical requirement of a particular metal-binding site. Using over 120 pyrazole-based chelating ligands, the stereochemical properties of

  5. Engineered liquid crystal anchoring energies with nanopatterned surfaces.

    PubMed

    Gear, Christopher; Diest, Kenneth; Liberman, Vladimir; Rothschild, Mordechai

    2015-01-26

    The anchoring energy of liquid crystals was shown to be tunable by surface nanopatterning of periodic lines and spaces. Both the pitch and height were varied using hydrogen silsesquioxane negative tone electron beam resist, providing for flexibility in magnitude and spatial distribution of the anchoring energy. Using twisted nematic liquid crystal cells, it was shown that this energy is tunable over an order of magnitude. These results agree with a literature model which predicts the anchoring energy of sinusoidal grooves. PMID:25835840

  6. Failure Mode of Suture Anchors as a Function of Insertion Depth

    Microsoft Academic Search

    C. Kelly Bynum; Steven Lee; Andrew Mahar; James Tasto; Robert Pedowitz

    2005-01-01

    Background: Surgeons can control not only the angle but also the depth of suture anchor placement during arthroscopic rotator cuff repair, although the tendency may be to place suture anchors on the deep side to avoid damage from prominent anchor eyelets. However, little information is available regarding possible effects of suture anchor depth on construct failure mechanisms.Hypothesis: Anchor depth affects

  7. New Retrievable Coil Anchors: Preliminary In Vivo Experiences in Swine

    SciTech Connect

    Konya, A., E-mail: akonya@mdanderson.org; Wright, K.C. [University of Texas M.D. Anderson Cancer Center, Section of Interventional Radiology, Division of Diagnostic Imaging (United States)

    2005-04-15

    Purpose. To design and test retrievable coil anchors to improve the safety and efficacy of coil embolization. Methods. Fifty-two 0.038-inch homemade retrievable stainless steel coils were equipped with one of four different pre-shaped nitinol anchors and tested in 38 pigs. All coils with the anchor were completely retrieved and redeployed 3-18 times (median 7 times) prior to release. Types 1 and 2 anchored coils were acutely deployed in the external iliac arteries (n = 10 each), and chronically tested (1 week) in the common carotid arteries (n = 6 each). Larger type 1 (n = 4), type 3 (n = 6), and type 4 (n = 4) anchored coils were acutely deployed in the abdominal aorta. The largest type 1 anchors (n = 6) were acutely tested in the inferior vena cava. Results. All anchored coils were successfully retrieved and repositioned several times. All but two coils formed a compact plug and there was no coil migration except with two mechanically defective type 3 anchors. Conclusion. The use of retrievable anchors allowed the coils to be retrieved and repositioned, prevented coil migration, and enabled compact coil configuration.

  8. Use of lug anchors to related pavement movement

    NASA Astrophysics Data System (ADS)

    Oakey, S. A.

    1980-04-01

    Minnesota Department of Transporatation's policy is that grades in the 3 to 5 percent and greater range are steep and may require lug anchors. Standard lug anchor spacing varies from 150 feet, center to center, for 3 percent grades to 75 feet, center to center, for 5 percent and greater grades. Conclusions are: (1) that lug anchors do prevent the downhill movement of the concrete pavement; (2) that when lug anchors are used a perforated pipe system also be built to collect the surface water that enters the pavement structure thus eliminating the anticipated base pumping and pavement settlement.

  9. Infrastructure anchor bolt inspection program with NDE applications

    NASA Astrophysics Data System (ADS)

    Fish, Philip E.

    1996-11-01

    In 1990, Wisconsin Department of Transportation found a high mast light pole with two of six anchor bolts failed. This failure along with published reports from Michigan DOT about anchor bolt failures on cantilever sign structures, raised concern about the quality and condition of anchor bolts on the Wisconsin DOT system. Wisconsin Department of Transportation implemented an Anchor Bolt Inspection Program in 1990 for cantilever sign structures, high mast light towers, interstate light towers, and signal masts. The program requires an experienced inspection team and a practical inspection approach. Inspection preparation includes review of all background information such as design plans, design computations, construction plans, shop plans, and maintenance history. An inspection plan is developed. Special emphasis is placed on determining material type, cut or rolled threads, and type of coating for anchor bolts. Inspection emphasis are on "hands on" and Nondestructive evaluation. Special emphasis is placed on visual conditions of anchor bolts (cut or rolled threads, straightness, corrosion, nut tension etc.) along with ultrasonic inspection. This program places a strong emphasis on Non Destructive Testing (NDT), especially ultrasonic. Procedures and inspection calibrations are developed from similar anchor bolt geometry and material type. Cut notches are placed in the anchor bolts at locations of possible failure. NDT inspection calibrations are performed from these bolts. Report documentation includes all design plans, pictorial documentation of structural deficiencies, sketches, nondestructive evaluation reports, conclusions, and recommendations. This program has been successful in locating failed anchor bolts and critical cracks before failure of an entire structure.

  10. Specific inhibition of GPI-anchored protein function by homing and self-association of specific GPI anchors.

    PubMed

    Nicholson, Thomas B; Stanners, Clifford P

    2006-11-20

    The functional specificity conferred by glycophosphatidylinositol (GPI) anchors on certain membrane proteins may arise from their occupancy of specific membrane microdomains. We show that membrane proteins with noninteractive external domains attached to the same carcinoembryonic antigen (CEA) GPI anchor, but not to unrelated neural cell adhesion molecule GPI anchors, colocalize on the cell surface, confirming that the GPI anchor mediates association with specific membrane domains and providing a mechanism for specific signaling. This directed targeting was exploited by coexpressing an external domain-defective protein with a functional protein, both with the CEA GPI anchor. The result was a complete loss of signaling capabilities (through integrin-ECM interaction) and cellular effect (differentiation blockage) of the active protein, which involved an alteration of the size of the microdomains occupied by the active protein. This work clarifies how the GPI anchor can determine protein function, while offering a novel method for its modulation. PMID:17101695

  11. BAHA: Bone-Anchored Hearing Aid

    PubMed Central

    Hagr, Abdulrahman

    2007-01-01

    Bone-Anchored Hearing Aid (BAHA) has proven performance and advantages for patients with aural atresia or chronic ear drainage who cannot wear air-conduction hearing aids. The BAHA has both cosmetic and acoustic advantages over most conventional hearing aids and hence is becoming increasingly popular. Moreover, BAHA improves the quality of life and has also significantly reduces ear discharge. This extensive review of the literature pertaining to BAHA discus the history, the indications, the advantages, the prediction of the outcome and the complications of this device as well as comparing it to the conventional hearing aids. PMID:21475438

  12. Equation helps select refractory anchor system

    SciTech Connect

    Crowley, M.S.

    1982-08-30

    An equation for calculating the breaking strength of anchorage systems, giving results of tests on a series of lining designs, cost factors and advantages of various independent anchors is investigated. Refractory concrete linings are used in most refining and chemical process vessels operating above 1,000F to protect the vessel shell and to conserve heat. Erosion resistance, as well as thermal protection, can be obtained by selecting the proper concrete and securing it to the shell with appropriate anchorage. Tables with test variables and model of lining design strength are presented.

  13. Structural diversity and magnetic properties of six metal-organic polymers based on semirigid tricarboxylate ligand of 3,5-bi(4-carboxyphenoxy)benzoic acid.

    PubMed

    Fan, Liming; Fan, Weiliu; Song, Weikuo; Sun, Liming; Zhao, Xian; Zhang, Xiutang

    2014-11-14

    Solvothermal reactions of the semirigid 3,5-bi(4-carboxyphenoxy)benzoic acid (H3BCP) and transitional metal cations with the help of three ancillary bridging imidazole linkers afforded six coordination polymers, namely, [Co(HBCP)(1,4-bib)0.5]n (), {[Mn1.5(BCP)(1,4-bib)0.5(?2-H2O)(H2O)2]·(1,4-bib)0.5}n (), {[Mn0.5(1,4-bib)(H2O)]·(H2BCP)}n (), {[Fe(BCP)0.5(HCOO)0.5(4,4'-bibp)0.5]·2H2O}n (), [Ni2.5(HBCP)(BCP)(4,4'-bibp)2(?2-H2O)(H2O)2]n (), and [Ni(HBCP)(1,4-bidb)1.5(H2O)2]n (), (1,4-bib = 1,4-bis(1H-imidazol-4-yl)benzene, 1,4-bidb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene, 4,4'-bibp = 4,4'-bis(imidazol-1-yl)biphenyl). Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses, thermogravimetric analyses (TGA), and X-ray photoelectron spectroscopy (XPS). Complex displays unusual 2D + 2D?2D parallel entangled networks consisting of (3,4)-connected 3,4L83 sheets. Complex exhibits an interesting 2-fold interpenetrated framework with a trinodal (4,4,6)-connected (3·4·5·6(2)·7)2(3·6·7(4))2(3(2)·4(2)·5(2)·6(2)·7(6)·9) topology. The host network of complex is a 2D 4-connected (4(4)·6(2))-sql sheet. Complex affords unprecedented 3D (4,6,6)-coordinated framework with point symbol of (4(5)·6)(4(8)·6(7))(4(9)·6(3)·8(3))2, in which the 1D helix water chains occupy the void channels. Complex can be regarded as a novel self-penetrating (4,4,4,5)-coordinated framework with point symbol of (4·5(4)·6)2(4·6(5)·7·8(3))2(5·6·7·8(3))2(5(2)·8(3)·9(2)), which contains two interpenetrated (3,4,4,5)-coordinated (4·5(4)·6)2(4·6(5)·7·8(3))2(5·6·7)2(5(2)·8(3)·9(2)) subnets linked by ?2-H2O. Complex shows a 1D ladder chain, which are further assembled into a 3D supramolecular structure via O-HO and ?? interactions. Moreover, magnetic studies indicate that both complex and show antiferromagnetic properties. PMID:25233393

  14. Nonrotating, self-centering anchor assembly for anchoring a bolt in a borehole

    SciTech Connect

    Bevan, John E.; King, Grant W.

    1997-12-01

    An expandable anchor assembly is provided for anchoring the threaded end portion of an elongated roof bolt in a borehole. The anchoring assembly includes a hollow outer sleeve in the form of a plurality of symmetrically arranged, longitudinal segmented wall portions with exterior gripping teeth and an inner expander sleeve in the form of a corresponding plurality of longitudinal wall portions symmetrically arranged about a central axis to define an inner threaded cylindrical section. The inner sleeve is captured within and moveable axially relative to the outer sleeve. As the threaded end portion of the elongated bolt is inserted into the inner threaded cylindrical section of the inner sleeve from the trailing end to the leading end thereof, the inner sleeve expands over and clamps around the threaded end portion of the elongated bolt. Thereafter, partial withdrawal of the elongated bolt from the borehole causes the inner sleeve to axially move relative to the outer sleeve from the leading end toward the trailing end of the outer sleeve in a wedging action to cause the outer sleeve to radially expand and force engagement of the gripping teeth against the sidewall of the borehole to thereby secure the expandable anchor assembly and therewith the threaded end portion of the elongated bolt within the borehole.

  15. A simultaneous electrochemical multianalyte immunoassay of high sensitivity C-reactive protein and soluble CD40 ligand based on reduced graphene oxide-tetraethylene pentamine that directly adsorb metal ions as labels.

    PubMed

    Yuan, Guolin; Yu, Chao; Xia, Chunyong; Gao, Liuliu; Xu, Wailan; Li, Wenjuan; He, Junlin

    2015-10-15

    A simplified electrochemical multianalyte immunosensor for the simultaneous detection of high sensitivity C-reactive protein (hsCRP) and soluble CD40 ligand (sCD40L) that uses reduced graphene oxide-tetraethylene pentamine (rGO-TEPA) that directly adsorbs metal ions as labels is reported. rGO-TEPA contains a large number of amino groups and has excellent conductivity, making it an ideal template for the loading of Pb(2+) and Cu(2+), which greatly amplifies the detection signals. The signals could be directly detected in a single run through differential pulse voltammetry (DPV), and each biorecognition event produces a distinct voltammetric peak. The position and size of each peak reflects the identity and the level of the corresponding antigen. Primarily designed for an application in a sandwich-type immunoassay based on Pb(2+) and Cu(2+) labels, two main challenges are accomplished with the herein presented nanosheets: fabrication of the template and the amination process for Pb(2+) and Cu(2+) adsorption. To further improve the analytical performance of the immunosensor, Au@bovine serum albumin (BSA) nanospheres synthesized through a "green" synthesis route were used as a sensor platform, which not only provides a biocompatible microenvironment for the immobilization of antibodies but also amplifies the electrochemical signals. Under optimal conditions, hsCRP and sCD40L could be assayed in the range of 0.05 to 100ng mL(-1) with detection limits of 16.7 and 13.1pgmL(-1) (S/N=3), respectively. The assay results on clinical serum samples with the proposed immunosensor were in acceptable agreement with those using the standard single-analyte test of the enzyme-linked immunosorbent assay (ELISA). This novel immunosensing system provides a simple, sensitive and low-cost approach for a multianalyte immunoassay. PMID:25985199

  16. Multivalent & multifunctional ligands to beta-amyloid.

    PubMed

    Kim, YoungSoo; Lee, Ji Hoon; Ryu, Jiyeon; Kim, Dong Jin

    2009-01-01

    Ligands selectively targeting beta-amyloid in the living brain are promising candidates of therapeutics and early diagnosis tools for Alzheimer's disease. Among the major stages of beta-amyloid aggregation, monomers and oligomers are excellent targets to reduce neurotoxic brain damages for prevention of the disease progression, while oligomers and fibrils, abundant in the late stage of the disease, are pathological objectives to develop reliable imaging probes. So far, there have been many efforts to develop a wide variety of monovalent beta-amyloid ligands such as thioflavin T, PIB, FDDNP, curcumin, and tramiprosate. However, pathology of Alzheimer's disease is not fully understood yet so that there is currently no cure and further investigations on Alzheimer's disease are needed. For past several years, multivalent beta-amyloid ligands have offered an alternative route by enhancing binding affinity of drug candidates. In addition, it has been revealed that not only neurotoxicity due to the protein misfolding but also other factors are involved in the beta-amyloid cascade such as oxidative stress, inflammation, metal chelation, and several types of neurotransmitters. Thus, there have been numerous studies to improve binding affinities of single beta-amyloid ligands via adopting multivalent effects or to develop drug candidates targeting multiple stages of the pathological cascade. In this review, multivalent and multifunctional beta-amyloid ligands and their promising aspects as an alternative approach to Alzheimer's disease are discussed. PMID:19199987

  17. Hexadentate N[sub 3]O[sub 3] amine phenol ligands for group 13 metal ions: Evidence for intrastrand and interstrand hydrogen-bonds in polydentate tripodal amine phenols

    SciTech Connect

    Liu, Shuang; Wong, E.; Rettig, S.J.; Orvig, C. (Univ. of British Columbia, Vancouver (Canada))

    1993-09-29

    There is currently considerable interest in the design of polydentate chelating ligand systems, which form stable complexes with group 13 metal ions, either for the treatment of Al overload or for the development of Ga and In radiopharmaceuticals. Several N[sub 3]O[sub 3] amine phenols (H[sub 3]L1 = 1,2,3-tris(2-hydroxybenzyl)amino)propane; H[sub 3]L2 = 1,2,3-tris((5-chloro-2-hydroxybenzyl) amino) propane; H[sub 3]L3 = 1.2.3-tris((2-hydroxy-5-methoxybenzyl)amino)propane; H[sub 3]L4 = 1,2,3-tris((3,5-dichloro-2-hydroxybenzyl)amino)pane were prepared and characterized by various spectroscopic methods (IR,FAB-MS, NMR). The N[sub 3]O[sub 3] amine phenols are KBH[sub 4] reduction products of the corresponding Schiff bases derived from the condensation reactions of tap (tap = 1,2,3-triaminopropane) with 3 equiv of either salicylaldehyde or ring-substituted salicylaldehydes. Neutral binary metal complexes, [M(L)] (M = Al, L = L2, L4; M = Ga, In, L = L1-L4), were obtained from the reactions of Al[sup 3+], Ga[sup 3+], or In[sup 3+] with N[sub 3]O[sub 3] amine phenols in the presence of 3 equiv of a base (acetate or hydroxide). The molecular structure of [Ga(L3)][sm bullet]2CH[sub 3]OH was determined by X-ray methods. Crystals of [Ga(L3)][sm bullet]2CH[sub 3]OH are monoclinic, of space group P2[sub 1]/n, with a = 13.115(3) [angstrom], b = 15.674(2) [angstrom], c = 14.439(2) [angstrom] [beta] = 100.62(1)[degrees], and Z = 4. The structure of [Ga(L3)][sm bullet]2CH[sub 3]OH was solved by the Patterson method and was refined by full-matrix least-squares procedures to R = 0.028 for 4529 reflections with I [ge] 3[sigma](I). In [Ga(L3)][sm bullet]2CH[sub 3]OH, the Ga atom is coordinated by six (N[sup 3]O[sub 3]) donor atoms in a slightly distorted octahedral coordination geometry.

  18. First principles investigations on the electronic structure of anchor groups on ZnO nanowires and surfaces

    SciTech Connect

    Dominguez, A.; Lorke, M.; Rosa, A. L.; Frauenheim, Th. [BCCMS, Universität Bremen, Am Fallturm 1, 28359 Bremen (Germany); Schoenhalz, A. L.; Dalpian, G. M. [CCNH, Universidade Federal do ABC, Av. dos Estados 5001, Santo André (Brazil); Rocha, A. R. [IFT, Universidade Estadual Paulista, R. Dr. Bento Teobaldo Ferraz, 271, São Paulo (Brazil)

    2014-05-28

    We report on density functional theory investigations of the electronic properties of monofunctional ligands adsorbed on ZnO-(1010) surfaces and ZnO nanowires using semi-local and hybrid exchange-correlation functionals. We consider three anchor groups, namely thiol, amino, and carboxyl groups. Our results indicate that neither the carboxyl nor the amino group modify the transport and conductivity properties of ZnO. In contrast, the modification of the ZnO surface and nanostructure with thiol leads to insertion of molecular states in the band gap, thus suggesting that functionalization with this moiety may customize the optical properties of ZnO nanomaterials.

  19. Halfpipe Anchoring: An Efficient Technique for Multiple Connection Handoff Ravi Kokku

    E-print Network

    Vin, Harrick M.

    Half­pipe Anchoring: An Efficient Technique for Multiple Connection Handoff£ Ravi Kokku present half-pipe anchoring, a technique that enables multiple connection handoff mechanisms utilization and improved scalability. More importantly, half-pipe anchoring supports the only connection

  20. 75 FR 2152 - Certificate of Alternative Compliance for the Anchor Handling Tug Supply Vessel HOLIDAY

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-01-14

    ...Certificate of Alternative Compliance for the Anchor Handling Tug Supply Vessel HOLIDAY AGENCY...Alternative Compliance was issued for the anchor handling tug supply vessel HOLIDAY as...INFORMATION: Background and Purpose The anchor handling tug supply vessel HOLIDAY...